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WO2019194136A1 - Photosensitive composition, cured film, method for manufacturing color filter, color filter, solid-state imaging element, and image display device - Google Patents

Photosensitive composition, cured film, method for manufacturing color filter, color filter, solid-state imaging element, and image display device Download PDF

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Publication number
WO2019194136A1
WO2019194136A1 PCT/JP2019/014488 JP2019014488W WO2019194136A1 WO 2019194136 A1 WO2019194136 A1 WO 2019194136A1 JP 2019014488 W JP2019014488 W JP 2019014488W WO 2019194136 A1 WO2019194136 A1 WO 2019194136A1
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Prior art keywords
group
ring
photosensitive composition
compound
substituent
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PCT/JP2019/014488
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French (fr)
Japanese (ja)
Inventor
土村　智孝
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富士フイルム株式会社
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Priority to JP2020512238A priority Critical patent/JP7072638B2/en
Publication of WO2019194136A1 publication Critical patent/WO2019194136A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • C07D219/10—Nitrogen atoms attached in position 9
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/18—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B19/00—Oxazine dyes
    • C09B19/02—Bisoxazines prepared from aminoquinones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes

Definitions

  • the present invention relates to a photosensitive composition. More specifically, the present invention relates to a photosensitive composition containing a cyclic oxime compound and a polymerizable compound. Moreover, this invention relates to the cured film obtained using the above-mentioned photosensitive composition. The present invention also relates to a method for producing a color filter using the above-described photosensitive composition, a color filter, a solid-state imaging device, and an image display device.
  • a cured film used for a color filter or the like is formed using a photosensitive composition containing a polymerizable compound and a photopolymerization initiator.
  • photopolymerization initiators for example, oxime compounds described in Patent Documents 1 to 3 are known.
  • One of the characteristics required for the photosensitive composition is high sensitivity during exposure. In recent years, further improvement in the sensitivity of the photosensitive composition has been desired.
  • the objective of this invention is providing the photosensitive composition excellent in the sensitivity, a cured film, the manufacturing method of a color filter, a color filter, a solid-state image sensor, and an image display apparatus.
  • the present invention provides the following. ⁇ 1> a cyclic oxime moiety having a cyclic structure formed including an oxime group, a cyclic oxime compound each having an electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more, a polymerizable compound,
  • a photosensitive composition comprising: ⁇ 2> The photosensitive composition according to ⁇ 1>, wherein the cyclic oxime compound has an electron-withdrawing group having a Taft ⁇ * constant value of 4 or more.
  • ⁇ 3> The photosensitive composition according to ⁇ 1> or ⁇ 2>, wherein the electron withdrawing group is at least one selected from a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group.
  • ⁇ 4> The photosensitive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the cyclic oxime moiety of the cyclic oxime compound is represented by the following formula (a-1): In the formula, R 1 represents a substituent, A represents a ring formed including an oxime group, and n represents 0 or 1.
  • ⁇ 5> The photosensitivity according to any one of ⁇ 1> to ⁇ 4>, wherein the cyclic oxime compound has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the cyclic oxime moiety.
  • Composition. ⁇ 6> The photosensitive composition according to any one of ⁇ 1> to ⁇ 5>, wherein the cyclic oxime compound has a structure in which a condensed ring including a carbazole ring or a dibenzothiophene ring is bonded to the cyclic oxime moiety.
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may be bonded to a ring represented by R 2 , R 3 , or B to form a ring
  • R 1 to R 3 Each independently represents a substituent
  • L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ⁇ CR L2 —
  • R L1 and R L2 each independently represent a hydrogen atom or a substituent
  • B Represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring
  • o R 2 3 When o is 2 or more, o R 2 3 may be the same or different, and two R 3 may be bonded to each other to form a ring. When q is 2 or more, q Z 1 are the same. It may be different.
  • o1 R 3a When o1 is 2 or more, o1 R 3a may be the same or different, and 2 R 3a may be bonded to each other to form a ring.
  • o2 R 3b When o2 is 2 or more, o2 R 3b may be the same or different, and two R 3b may be May be bonded to form a ring, and when q1 is 2 or more, q1 Z 1a may be the same or different, and when q2 is 2 or more, q2 Z 1a 1b may be the same or different.
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3c to form a ring
  • Y 2 represents —CR Y21 R Y22 —, —NR Y23— or —S—, wherein R Y21 to R Y23 each independently represents a hydrogen atom or a substituent
  • X 2 represents> CR X10 -or> N-, and R x10 represents a hydrogen atom or a substituent;
  • N represents 0 or 1
  • m represents 0 or 1
  • p, q3 and q4 each independently represents an integer of 0 or more, and at least one of q3 and q4 is an integer of 1 or more
  • p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring.
  • the o3 R 3c s may be the same or different, and the two R 3c s May be bonded to form a ring, and when o4 is 2 or more, o4 R 3d may be the same or different, and two R 3d may be bonded to each other to form a ring.
  • q3 Z 1c When q3 is 2 or more, q3 Z 1c may be the same or different, and when q4 is 2 or more, q4 Z 1d is the same It may be different.
  • ⁇ 10> The photosensitive composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a resin.
  • ⁇ 11> The photosensitive composition according to any one of ⁇ 1> to ⁇ 10>, further containing a coloring material.
  • ⁇ 12> The photosensitive composition according to ⁇ 11>, wherein the color material contains a pigment.
  • ⁇ 13> The photosensitive composition according to ⁇ 11> or ⁇ 12>, wherein the color material includes at least one selected from a chromatic colorant, a white colorant, a black colorant, and a near-infrared absorbing dye.
  • the photosensitive composition according to any one of ⁇ 1> to ⁇ 13> which is a composition for forming a pixel of a color filter.
  • ⁇ 16> A step of forming a photosensitive composition layer by applying the photosensitive composition according to any one of ⁇ 1> to ⁇ 14> on a support, and exposing the photosensitive composition layer in a pattern
  • the manufacturing method of a color filter including the process and the process of developing the photosensitive composition layer after exposure, and forming a pattern.
  • ⁇ 17> A color filter having the cured film according to ⁇ 15>.
  • ⁇ 18> A solid-state imaging device having the cured film according to ⁇ 15>.
  • ⁇ 19> An image display device having the cured film according to ⁇ 15>.
  • the photosensitive composition excellent in the sensitivity, a cured film, the manufacturing method of a color filter, a color filter, a solid-state image sensor, and an image display apparatus can be provided.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acrylic and “(meth) acrylic”.
  • "Acryloyl” represents both and / or acryloyl and methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • a weight average molecular weight and a number average molecular weight are the polystyrene conversion values measured by GPC (gel permeation chromatography) method.
  • near infrared light refers to light having a wavelength of 700 to 2500 nm.
  • the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • the photosensitive composition of the present invention comprises a cyclic oxime compound having a cyclic oxime moiety formed containing an oxime group, and an electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more; And a polymerizable compound.
  • the photosensitive composition of this invention is excellent in the sensitivity at the time of exposure.
  • the reason why such an effect is obtained is presumed to be as follows.
  • the cyclic oxime compound contained in the photosensitive composition of the present invention has a cyclic oxime moiety having a cyclic structure formed by containing an oxime group. That is, this cyclic oxime compound has a structure in which an oxime group is incorporated into a ring structure. By incorporating the oxime group into the ring structure, it is presumed that the structure around the oxime group became rigid, thereby sharpening the absorption spectrum of the cyclic oxime compound and increasing the absorbance.
  • the cyclic oxime compound contains such a cyclic oxime moiety, so that it is possible to suppress the deactivation path in the excited state of the oxime compound, and it is presumed that the decomposition efficiency by light irradiation can be increased.
  • this cyclic oxime compound further has an electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more, thereby increasing the maximum absorption wavelength of the cyclic oxime compound. It is presumed that shifting to the long wavelength side facilitates matching with the wavelength of light emitted from the light source during exposure.
  • this cyclic oxime compound can generate a radical efficiently at the time of exposure.
  • the cyclic oxime compound has the above-described predetermined electron-withdrawing group, so that the cyclic oxime compound and a component such as a polymerizable compound easily interact in the film, and the cyclic oxime compound is polymerizable.
  • radicals can be generated in the vicinity of components such as compounds and in the vicinity of these components. Therefore, by exposing the photosensitive composition of the present invention to light, the cyclic oxime compound is efficiently decomposed to generate radicals, and further, radicals are efficiently produced in the vicinity of components such as polymerizable compounds. It is presumed that it can be generated well, and as a result, it is presumed that excellent sensitivity could be obtained.
  • hardenability of the cured film obtained can also be improved, for example, the cured film excellent in characteristics, such as solvent resistance, can also be obtained.
  • this photosensitive composition is excellent in sensitivity, it is also possible to form a pattern excellent in adhesion, rectangularity, linearity, and the like. In particular, a fine pattern with excellent adhesion can be formed.
  • the photosensitive composition of the present invention has excellent sensitivity and storage stability. The reason why such an effect can be obtained is presumed that the decomposition of the oxime compound with time, such as hydrolysis, could be suppressed by the rigid structure of the oxime. In addition, when the sensitivity of the photosensitive composition is high, the storage stability generally tends to decrease. However, the photosensitive composition of the present invention is sensitive and preserved by using the above-mentioned predetermined cyclic oxime compound. Stability can be achieved at a higher level than before.
  • the photosensitive composition of the present invention can be preferably used as a composition for forming a pixel of a color filter or a composition for forming a light shielding film such as a black matrix.
  • the photosensitive composition contains the predetermined cyclic oxime compound according to the present invention.
  • excellent sensitivity can be maintained even with a photosensitive composition having low light transmittance.
  • a light-transmitting photosensitive composition for example, when a film having a thickness of 2.0 ⁇ m after drying is formed using the photosensitive composition, examples thereof include a photosensitive composition having spectral characteristics such that an optical density with respect to light having a wavelength of 365 nm is 1.5 or more (preferably 1.8 or more, more preferably 2.1 or more).
  • the upper limit of the optical density is not particularly limited, but can be 5.0 or less.
  • the optical density (OD) is a value expressed by the logarithm of the degree of light absorption, and is a value defined by the following equation.
  • OD ( ⁇ ) Log 10 [T ( ⁇ ) / I ( ⁇ )] ⁇ represents a wavelength
  • T ( ⁇ ) represents a transmitted light amount at the wavelength ⁇
  • I ( ⁇ ) represents an incident light amount at the wavelength ⁇ .
  • the photosensitive composition having low light transmittance when a film having a film thickness after drying of 4.0 ⁇ m is formed using the photosensitive composition, the wavelength 360 of the film described above is used. And a photosensitive composition having a spectral characteristic in which the maximum value of transmittance in the range of ⁇ 700 nm is less than 40% (preferably less than 30%, more preferably less than 20%, and still more preferably less than 10%).
  • the photosensitive composition of the present invention includes a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light shielding film, a refractive index adjustment film, a photosensitive layer of a lithographic printing plate precursor, a protective film, an ultraviolet curable ink, various types Photoresists, various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coats, electrical components, magnetic recording materials, micromechanical components, waveguides, optical switches, masking for plating, It can be used in color proofing systems, glass fiber cable coatings, stencils for screen printing, three-dimensional objects by stereolithography, image recording materials for holographic recording, microelectronic circuits, healthcare materials and the like.
  • the color filter examples include a filter having a colored pixel that transmits light of a specific wavelength, and at least one colored pixel selected from a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel. It is preferable that the filter has The color filter can be formed using a photosensitive composition containing a chromatic colorant.
  • the near-infrared cut filter examples include a filter having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm.
  • the near-infrared cut filter is preferably a filter having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and more preferably a filter having a wavelength range of 700 to 1000 nm.
  • the transmittance of the near infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • the absorbance Amax / absorbance A550 which is the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500. 70 to 450 is more preferable, and 100 to 400 is particularly preferable.
  • the near-infrared cut filter can be formed using a photosensitive composition containing a near-infrared absorbing dye.
  • the near-infrared transmission filter is a filter that transmits at least part of the near-infrared ray.
  • the near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that blocks at least part of visible light and transmits at least part of near-infrared light. Also good.
  • the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm is Minimum value is 70% or more
  • a filter that satisfies the spectral characteristics (preferably 75% or more, more preferably 80% or more) is preferable.
  • the near-infrared transmission filter is preferably a filter satisfying any of the following spectral characteristics (1) to (4).
  • the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the photosensitive composition of the present invention When the photosensitive composition of the present invention is used as a composition for a near infrared transmission filter, the photosensitive composition of the present invention has a minimum absorbance Amin in a wavelength range of 400 to 640 nm and a wavelength in a range of 1100 to 1300 nm. It is preferable that Amin / Bmax, which is a ratio with the maximum absorbance Bmax, satisfies a spectral characteristic of 5 or more. Amin / Bmax is more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ ⁇ log (T ⁇ / 100) (1)
  • a ⁇ is the absorbance at the wavelength ⁇
  • T ⁇ is the transmittance (%) at the wavelength ⁇ .
  • the absorbance value may be a value measured in a solution state or may be a value in a film formed using a photosensitive composition.
  • the photosensitive composition is applied on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a film prepared by drying at 100 ° C. for 120 seconds.
  • the photosensitive composition of the present invention When the photosensitive composition of the present invention is used as a composition for a near-infrared transmission filter, the photosensitive composition of the present invention must satisfy any of the following spectral characteristics (11) to (14). More preferred. (11): Amin1 / Bmax1 which is a ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm and the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 640 nm and transmitting light having a wavelength of 720 nm or more.
  • Amin2 / Bmax2 which is a ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm and the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 750 nm and transmitting light having a wavelength of 850 nm or more.
  • Amin3 / Bmax3 which is a ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm and the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 850 nm and transmitting light having a wavelength of 940 nm or more.
  • Amin4 / Bmax4 which is a ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm and the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 950 nm and transmitting light having a wavelength of 1040 nm or more.
  • the photosensitive composition of the present invention is excellent in sensitivity and can form a fine pattern, it can be preferably used as a photosensitive composition for a color filter. Specifically, it can be preferably used as a photosensitive composition for forming a pixel of a color filter, and can be more preferably used as a photosensitive composition for forming a pixel of a color filter used in a solid-state imaging device.
  • the photosensitive composition of the present invention includes a cyclic oxime compound having a cyclic oxime moiety having an oxime group and an electron withdrawing group having a Taft ⁇ * constant value of 3.5 or more.
  • this cyclic oxime compound is also referred to as cyclic oxime compound A). That is, the cyclic oxime compound A is a compound having a cyclic oxime moiety and the electron withdrawing group in the same molecule.
  • electron-withdrawing group A having a Taft ⁇ * constant value of 3.5 or more in the cyclic oxime compound A will be described.
  • the value of Taft ⁇ * constant of the electron-withdrawing group A of the cyclic oxime compound A interacts with the polymerizable compound and the like contained in the photosensitive composition so that the cyclic oxime compound A is closer to the polymerizable compound.
  • it is preferably 4 or more, more preferably 4.2 or more.
  • the upper limit is preferably 10 or less from the viewpoint of the stability of the compound.
  • the Taft ⁇ * constant is a parameter representing the polarity of a substituent. In the present specification, the value of Taft's ⁇ * constant is given in Table A of “DD Perrin, B.
  • a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group are preferable because the polymerizable compound and the like contained in the photosensitive composition and the cyclic oxime compound A are more likely to interact with each other.
  • Nitro group, alkylsulfonyl group and arylsulfonyl group are more preferable, and nitro group is particularly preferable.
  • the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoyl group.
  • Examples include a sulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, a perfluoroalkylsulfonyl group, and the like.
  • the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples include phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3- Chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4- Examples thereof include a methylsulfanyl
  • Examples of the onium group include an ammonium group, a sulfonium group, and a phosphonium group, and an ammonium group is preferable.
  • Examples of the ammonium group include a group represented by -N + (Ro 1 ) (Ro 2 ) (Ro 3 ).
  • Ro 1 to Ro 3 each independently represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group or an aryl group, and more preferably an alkyl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • the cyclic oxime compound preferably has a counter anion.
  • Counter anions include halogen ions (Cl ⁇ , Br ⁇ , I ⁇ ), sulfonate anions, carboxylate anions, sulfonylimide anions, PF 6 ⁇ , BF 4 ⁇ , ClO 4 ⁇ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF 3 SO 2 ) 3 C ⁇ ), di (halogenoalkylsulfonyl) imide anion (for example (CF 3 SO 2 ) 2 N ⁇ ), tetraaryl borate anion, tetracyanoborate anion and the like can be mentioned.
  • the cyclic oxime compound A may have only one electron withdrawing group A, or may have two or more (preferably 2 to 5, more preferably 2 to 3). .
  • it has only one electron withdrawing group A, it is easy to improve solvent solubility.
  • it has two or more said electron withdrawing groups A, it is easy to raise radical generating efficiency more.
  • the plurality of electron withdrawing groups A may be the same or different. From the viewpoint of ease of synthesis, the plurality of electron withdrawing groups A are preferably the same.
  • the cyclic oxime compound A includes a cyclic oxime moiety having a cyclic structure formed including an oxime group. More specifically, the cyclic oxime compound A includes a cyclic oxime moiety having a cyclic structure formed by including a carbon atom directly connected to a nitrogen atom of the oxime group. That is, the cyclic oxime compound A has a structure in which an oxime group is incorporated into a ring structure.
  • the cyclic oxime moiety is preferably a 5- to 8-membered cyclic structure, more preferably a 5- to 7-membered cyclic structure, and a 5- or 6-membered cyclic structure for reasons of stability of the compound. More preferably it is.
  • the cyclic oxime moiety may include a hetero atom as an atom constituting the ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the cyclic oxime moiety has a carbonyl group directly connected to the carbon atom of the oxime group, and the oxime group and the carbonyl group may be incorporated into the ring structure.
  • a ring structure examples include a structure in which n is 1 in formula (a-1) described later. According to this aspect, more excellent optical bleaching properties are easily obtained. Further, when the cyclic oxime moiety does not contain the above-mentioned carbonyl group (that is, when n is 0 in formula (a-1) described later), higher sensitivity can be expected.
  • the cyclic oxime moiety may contain two or more oxime groups. In the case where the cyclic oxime moiety contains two or more oxime groups, it is easier to increase the radical generation efficiency. Further, when the cyclic oxime moiety contains only one oxime group, it is easier to improve the solvent solubility.
  • the cyclic oxime moiety preferably has a structure represented by the following formula (a-1).
  • A represents a ring formed including an oxime group.
  • the ring represented by A is preferably a 5- to 8-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring from the viewpoint of the stability of the compound.
  • the ring represented by A may contain a hetero atom as an atom constituting the ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the ring represented by A may contain two or more oxime groups.
  • n 0 or 1. From the viewpoint of increasing sensitivity, n is preferably 0. Further, n is preferably 1 from the viewpoint of optical bleaching property.
  • R 1 represents a substituent.
  • substituent represented by R 1 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and phosphinoyl.
  • These groups may further have a substituent.
  • Additional substituents include halogen groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, acyloxy groups, acyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylamino groups, dialkylamino groups, arylamino groups.
  • an alkyl group having 1 to 30 carbon atoms is preferable.
  • the aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms.
  • a phenyl group a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, or a 9-phenanthryl group.
  • the alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.
  • the alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
  • the alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms.
  • the arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms.
  • the alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group.
  • the arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group
  • the acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms.
  • acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group benzoyl group, 1-naphthoyl group Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl
  • the alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyl group.
  • alkoxycarbonyl group having 2 to 20 carbon atoms
  • Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.
  • the aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group.
  • the phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group.
  • a phosphinoyl group having 2 to 50 carbon atoms for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group.
  • the heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
  • thienyl group benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group
  • alkylthiocarbonyl group which may have a substituent include, for example, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.
  • the arylthiocarbonyl group which may have a substituent includes 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Bon
  • dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.
  • dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.
  • R 1 in formula (a-1) is preferably an acyl group which may have a substituent from the viewpoint of increasing sensitivity, and more preferably an acetyl group, a propionyl group, a benzoyl group, or a toluyl group.
  • the cyclic oxime compound A preferably has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the above-described cyclic oxime moiety. More specifically, it is preferable to have a condensed ring containing a cyclic oxime moiety formed by condensing at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring at the cyclic oxime moiety described above. By using the cyclic oxime compound A having such a structure, higher sensitivity can be achieved.
  • the electron withdrawing group A is preferably bonded to the aromatic hydrocarbon ring or heterocyclic ring.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthracene ring, an azulene ring, and a fluorene ring.
  • the heterocyclic ring may be a single ring or a condensed ring.
  • the heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, More preferably, it is an aromatic or aliphatic heterocyclic ring containing a nitrogen atom.
  • heterocyclic ring examples include pyrrole ring, furan ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, piperazine ring, pyran ring, chroman ring, imidazole ring, thiazole ring, pyrazole ring, morpholine ring, Examples thereof include carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring and condensed rings containing these rings, pyrrole ring, furan ring, thiophene ring, carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring are preferable, A thiophene ring, a carbazole ring, a thianthrene ring, a dihydrophenazine ring, and a dibenzo
  • the cyclic oxime compound A preferably has a structure in which a condensed ring containing a carbazole ring or a dibenzothiophene ring is bonded to the above-mentioned cyclic oxime moiety because it is easy to achieve higher sensitivity.
  • the cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (1).
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may be bonded to a ring represented by R 2 , R 3 , or B to form a ring
  • R 1 to R 3 Each independently represents a substituent
  • L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ⁇ CR L2 —
  • R L1 and R L2 each independently represent a hydrogen atom or a substituent
  • B Represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring
  • Z 1 represents an electron-withdrawing group having a Taf
  • the electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more represented by Z 1 in the formula (1) has the same meaning as the above-described electron-withdrawing group A, and the preferred range is also the same.
  • X 1 in the formula (1) represents —O—, —CR x1 R x2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4 , where R x1 to R x4 represent Independently represents a hydrogen atom or a substituent.
  • X 1 is preferably —O—, —CR x1 R X2 —, or —S— because it is easier to increase the photolysis efficiency.
  • substituent represented by R x1 to R x3 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. Details of these groups are the same as those described for R 1 in formula (a-1).
  • Examples of the substituent represented by R x4 include an alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl.
  • R x1 and R x3 may combine with the ring represented by R 2 , R 3 , or B to form a ring.
  • the ring formed may be an aliphatic ring or an aromatic ring.
  • R 1 to R 3 in the formula (1) each independently represent a substituent.
  • the substituent represented by R 1 has the same meaning as the range described for R 1 in formula (a-1).
  • Examples of the substituent represented by R 2 and R 3 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Details of these groups are the same as those described for R 1 in formula (a-1).
  • L in Formula (1) represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ⁇ CR L2 —, and R L1 and R L2 each independently represent a hydrogen atom or a substituent.
  • the alkylene represented by L is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 1 carbon atom.
  • the alkylene group represented by L may have a substituent. Examples of the substituent that the alkylene group represented by L may have include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, a heterocyclic group, and an alkylidene group.
  • halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
  • the alkylidene group is preferably an alkylidene group having 1 to 10 carbon atoms, and examples thereof include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, and a butylidene group.
  • alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).
  • Examples of the substituent represented by R L1 and R L2 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group.
  • Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
  • Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).
  • B in the formula (1) represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthracene ring, an azulene ring, and a fluorene ring.
  • the heterocyclic ring may be a single ring or a condensed ring.
  • the heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, More preferably, it is an aromatic or aliphatic heterocyclic ring containing a nitrogen atom.
  • heterocyclic ring examples include pyrrole ring, furan ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, piperazine ring, pyran ring, chroman ring, imidazole ring, thiazole ring, pyrazole ring, morpholine ring, Examples thereof include carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring and condensed rings containing these rings, pyrrole ring, furan ring, thiophene ring, carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring are preferable, A thiophene ring, a carbazole ring, a thianthrene ring, a dihydrophenazine ring, and a dibenzo
  • N in the formula (1) represents 0 or 1. From the viewpoint of increasing sensitivity, n is preferably 0. M in the formula (1) represents 0 or 1. Q in the formula (1) represents an integer of 1 or more, and 1 or 2 is preferable.
  • o and p each independently represent an integer of 0 or more, preferably 0 to 2, more preferably 0 to 1.
  • p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring.
  • o R 3 s may be the same or different, and two R 3 may be bonded to each other to form a ring.
  • the ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.
  • the cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (2).
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent
  • R x1 and R x3 may combine with R 2 or R 3a to form a ring
  • R L1 and R L2 each independently represent a hydrogen atom or a substituent
  • R 1 , R 2 , R 3a and R 3b each independently represent a substituent
  • Z 1a and Z 1b independently represents an electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more
  • Y 1 represents —CR Y1 R Y2
  • o1 R 3a When o1 is 2 or more, o1 R 3a may be the same or different, and 2 R 3a may be bonded to each other to form a ring.
  • o2 R 3b When o2 is 2 or more, o2 R 3b may be the same or different, and two R 3b may be May be bonded to form a ring, and when q1 is 2 or more, q1 Z 1a may be the same or different, and when q2 is 2 or more, q2 Z 1a 1b may be the same or different.
  • X 1, L, R 1, R 2, m and n of formula (2) has the same meaning as X 1, L, R 1, R 2, m and n of formula (1), the preferred range is also the same is there.
  • R 3a and R 3b in the formula (2) have the same meaning as R 3 in the formula (1), and preferred ranges thereof are also the same.
  • O1 and o2 in the formula (2) have the same meaning as o in the formula (1), and the preferred range is also the same.
  • o1 amino R 3a may be the same or different, they may form a ring together two R 3a is bonded to when the o2 is 2 or more, o2 one R 3b may be the same or different, two R 3b may be bonded to each other to form a ring.
  • the ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.
  • the electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more represented by Z 1a and Z 1b in the formula (2) is synonymous with the above-described electron-withdrawing group A, and the preferred range is also the same. is there.
  • q1 and q2 each independently represent an integer of 0 or more, and at least one of q1 and q2 represents an integer of 1 or more.
  • q1 and q2 are each independently preferably 0 to 2, more preferably 0 or 1.
  • q1 Z 1a may be the same or different
  • q2 Z 1b may be the same Well, it can be different.
  • Y 1 in the formula (2) represents —CR Y1 R Y2 —, —NR Y3 — or —S—
  • R Y1 to R Y3 each independently represents a hydrogen atom or a substituent.
  • the substituent represented by R Y1 to R Y3 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group.
  • the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
  • alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).
  • the cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (3a) or (3b). These compounds have more excellent sensitivity and are particularly preferably used.
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3c to form a ring
  • Y 2 represents —CR Y21 R Y22 —, —NR Y 23 — or —S—, R Y21 to R Y23 each independently represents a hydrogen atom or a substituent
  • X 2 represents> CR X10 — or> N—
  • R x10 Represents a hydrogen atom or a substituent
  • L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ⁇ CR L2 —
  • R L1 and R L2 each independently represents a hydrogen atom or a substituent
  • Z 1c and Z 1d are each independently Represents an electron-attracting group having a Taft ⁇ * constant value of 3.5 or more
  • n represents 0 or 1
  • m represents 0 or 1
  • o3, o4 p
  • q3 and q4 represent Each independently represents an integer of 0 or more, at least one of q3 and q4 represents an integer of 1 or more, and when p is 2 or more, p R 2 s may be the same or different, may have two R 2 are bonded to each other to form a ring, for o3 is 2 or more, o3 one R 3c may be the same or different, two R 3c They may be bonded to each other to form a ring.
  • o4 R 3d When o4 is 2 or more, o4 R 3d are the same, Or two R 3d's may be bonded to each other to form a ring.
  • q3 Z 1c's When q3 is 2 or more, q3 Z 1c's may be the same or different. In the case where q4 is 2 or more, q4 Z 1d may be the same or different.
  • X 1, L, R 1, R 2, m and n of formula (3a) have the same meanings as X 1, L, R 1, R 2, m and n of formula (1), the preferred range is also the same is there.
  • Y 2 in the formula (3a) represents —CR Y21 R Y22 —, —NR Y23 — or —S—
  • R Y21 to R Y23 each independently represents a hydrogen atom or a substituent.
  • the substituent represented by R Y21 to R Y23 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group.
  • the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
  • alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).
  • R 1, R 2, m and n are as defined for L, R 1, R 2, m and n Equation (1), and preferred ranges are also the same.
  • R x10 represents a hydrogen atom or a substituent.
  • substituent represented by R x10 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group.
  • the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
  • alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).
  • R 3c and R 3d in formula (3a) and formula (3b) have the same meaning as R 3 in formula (1), and the preferred ranges are also the same.
  • o3 and o4 have the same meaning as o in the formula (1), and preferred ranges thereof are also the same.
  • o3 one R 3c may be the same or different, form two R 3c are bonded to each other ring
  • o4 R 3d s may be the same or different, and two R 3d may be bonded to each other to form a ring.
  • the ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.
  • the electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more represented by Z 1c and Z 1d in the formulas (3a) and (3b) has the same meaning as the electron-withdrawing group A described above, The preferable range is also the same.
  • q3 and q4 each independently represent an integer of 0 or more, and at least one of q3 and q4 represents an integer of 1 or more.
  • q3 and q4 are each independently preferably 0 to 2, more preferably 0 or 1.
  • Formula (3a) and Formula In (3b) when q3 is 2 or more, q3 Z 1c may be the same or different, and when q4 is 2 or more, q4 Z 1d may be the same , May be different.
  • the cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (4a) or formula (4b). When these compounds are used, it is easier to improve the temporal stability of the photosensitive composition.
  • X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C ⁇ N—O—R x4
  • R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3a to form a ring
  • R 1 , R 3e and R 3f each independently represent a substituent
  • Z 1e and Z 1f each independently represent Taft's ⁇ * constant value of 3.5
  • o5, o6, q5 and q6 each independently represents an integer of 0 or more, at least one of q5 and q6 represents an integer of 1 or more, and o5 is 2 or more
  • o5 amino R 3e may be the same or different, may form two R 3e are bonded to each other ring
  • X 1 and R 1 of formula (4a) has the same meaning as X 1 and R 1 of formula (1), and preferred ranges are also the same.
  • R 1 in formula (4b) has the same meaning as R 1 in formula (1), and the preferred range is also the same.
  • R 3e and R 3f in formula (4a) and formula (4b) have the same meaning as R 3 in formula (1), and the preferred ranges are also the same.
  • o5 and o6 have the same meaning as o in formula (1), and the preferred range is also the same.
  • o5 R 3e s when o5 is 2 or more, o5 R 3e s may be the same or different, and two R 3e may be bonded to each other to form a ring.
  • o6 R 3f may be the same or different, and two R 3f may be bonded to each other to form a ring.
  • the ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.
  • the electron-withdrawing group having a Taft ⁇ * constant value of 3.5 or more represented by Z 1e and Z 1f in the formulas (4a) and (4b) has the same meaning as the electron-withdrawing group A described above, The preferable range is also the same.
  • q5 and q6 each independently represent an integer of 0 or more, and at least one of q5 and q6 represents an integer of 1 or more.
  • q5 and q6 are each independently preferably 0 to 2, more preferably 0 or 1.
  • Formula (4a) and Formula In (4b) when q5 is 2 or more, q5 Z 1e may be the same or different, and when q6 is 2 or more, q6 Z 1f may be the same , May be different.
  • cyclic oxime compound A examples include compounds having the following structure.
  • the cyclic oxime compound A preferably has a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the cyclic oxime compound A at a wavelength of 365 nm or a wavelength of 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, and still more preferably 20,000 to 200,000.
  • the molar extinction coefficient of the cyclic oxime compound A can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • the content of the cyclic oxime compound A is preferably 0.1 to 30% by mass in the total solid content of the photosensitive coloring composition.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 2% by mass or more.
  • the upper limit is more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the cyclic oxime compound A may be used alone or in combination of two or more. When using 2 or more types of cyclic oxime compounds A together, it is preferable that those total amounts become the said range.
  • the photosensitive composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated group.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound is preferably a compound that can be polymerized by a radical (radical polymerizable compound).
  • the polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, and further preferably 250 or more.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. More preferably, it is a compound containing one.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.)
  • Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.)
  • dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Compound for example, commercially available from Sartomer
  • oligomer types can also be used.
  • NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by KAYARAD RP-1040
  • DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
  • examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy modified tri (meth).
  • trifunctional (meth) acrylate compound such as acrylate or pentaerythritol tri (meth) acrylate.
  • commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.
  • the polymerizable compound may have an acid group.
  • the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable.
  • examples of commercially available radical polymerizable compounds having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
  • a preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling.
  • the polymerizable compound is also preferably a compound having a caprolactone structure.
  • Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
  • the polymerizable compound is also preferably a compound having an alkyleneoxy group.
  • the polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups.
  • a tri- to hexa-functional (meth) acrylate compound is more preferable.
  • Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 which is an acrylate.
  • Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238.
  • the content of the polymerizable compound is preferably from 0.1 to 50% by mass in the total solid content of the photosensitive coloring composition.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
  • a polymeric compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that those total amount becomes the said range.
  • the photosensitive composition of the present invention preferably contains a color material.
  • the color material include chromatic colorants, white colorants, black colorants, and near infrared absorbing dyes.
  • the kind of color material can be appropriately selected according to the use of the photosensitive composition.
  • the colorant may be a pigment or a dye, but is preferably a pigment because it is easy to obtain a film with more excellent light resistance.
  • the chromatic colorant examples include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the chromatic colorant may be a pigment or a dye.
  • a pigment is preferable.
  • the average particle diameter (r) of the pigment is preferably 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and still more preferably 30 nm ⁇ r ⁇ 200 nm.
  • the “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated.
  • the particle size distribution of secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ⁇ 100 nm are 70% by mass or more of the total. It is preferable that it is 80% by mass or more.
  • the pigment is preferably an organic pigment.
  • the following are mentioned as an organic pigment.
  • C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 22
  • a metal comprising at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomer structure thereof, two or more metal ions, and a melamine compound Azo pigments can also be used.
  • R 1 and R 2 are each independently —OH or —NR 5 R 6
  • R 3 and R 4 are each independently ⁇ O or ⁇ NR 7
  • R 5 to R 7 Each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent.
  • the substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an amino group.
  • R 1 and R 2 are preferably —OH.
  • R 3 and R 4 are preferably ⁇ O.
  • the melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).
  • R 11 to R 13 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
  • the alkyl group may have a substituent.
  • the substituent is preferably a hydroxy group.
  • at least one of R 11 ⁇ R 13 is a hydrogen atom, more preferably all of R 11 ⁇ R 13 is a hydrogen atom.
  • the metal azo pigment includes a metal ion containing at least one anion selected from the azo compound represented by the formula (I) and an azo compound having a tautomer structure thereof, and at least Zn 2+ and Cu 2+ And a metal azo pigment comprising an melamine compound.
  • the total amount of Zn 2+ and Cu 2+ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment.
  • the content is preferably 99.9 to 100 mol%, more preferably 100 mol%.
  • the metal azo pigment further contains a divalent or trivalent metal ion other than Zn 2+ and Cu 2+. (Hereinafter also referred to as metal ion Me1).
  • the content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment. More preferably it is.
  • paragraph numbers 0011 to 0062 and 0137 to 0276 in JP-A-2017-171912 paragraph numbers 0010 to 0062 and 0138 to 0295 in JP-A-2017-171913, and JP-A-2017-171914.
  • the descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the publication and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used.
  • a compound is preferably a compound represented by the formula (DPP1), and more preferably a compound represented by the formula (DPP2).
  • R 11 and R 13 each independently represent a substituent
  • R 12 and R 14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
  • n11 and n13 each independently
  • X 12 and X 14 each independently represents an oxygen atom, a sulfur atom or a nitrogen atom
  • m12 represents 1, If 12 is a nitrogen atom, m12 represents 2, if X 14 is an oxygen atom or a sulfur atom, m14 represents 1, if X 14 is a nitrogen atom, m14 represents 2.
  • Examples of the substituent represented by R 11 and R 13 include alkyl group, aryl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, amide group, cyano group, nitro group, trifluoro group.
  • a methyl group, a sulfoxide group, a sulfo group and the like are preferable examples.
  • a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 is used. You can also. Specific examples include the compounds described in International Publication No. WO2015 / 118720.
  • the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment.
  • Specific examples include compounds described in paragraphs 0022 to 0030 of JP2012-247491A and paragraph 0047 of JP2011-157478A.
  • dye there is no restriction
  • pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dyes. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
  • the white colorant includes not only pure white but also a light gray (for example, grayish white or light gray) colorant close to white.
  • the white colorant may be a pigment or a dye.
  • White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow Examples include resin particles and zinc sulfide.
  • the white colorant is preferably a particle having a titanium atom, and more preferably titanium oxide.
  • Titanium oxide preferably has a titanium dioxide (TiO 2 ) content (purity) of 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.
  • the titanium oxide preferably has a content of low-order titanium oxide, titanium oxynitride or the like represented by Ti n O 2n-1 (where n represents a number of 2 to 4) of 30% by mass or less, The content is more preferably no more than mass%, and even more preferably no more than 15 mass%.
  • titanium oxide there is no restriction
  • isotropic shapes for example, spherical shape, polyhedral shape, etc.
  • anisotropic shapes for example, needle shape, rod shape, plate shape, etc.
  • irregular shapes and the like can be mentioned.
  • the hardness (Mohs' hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5.
  • the true specific gravity (density) of titanium oxide is preferably 1.0 to 6.0 g / cm 3 , and more preferably 3.9 to 4.5 g / cm 3 .
  • the bulk specific gravity of titanium oxide is preferably 0.1 g / cm 3 to 1.0 g / cm 3 , and more preferably 0.2 g / cm 3 to 0.4 g / cm 3 .
  • a commercially available white colorant can be used.
  • Commercial products may be used as they are or may be used after classification.
  • Commercially available products of titanium oxide include, for example, trade names of Taipei R-550, R-580, R-630, R-670, R-680, R-780, R-780-2 manufactured by Ishihara Sangyo Co., Ltd.
  • titanium oxides described in paragraph numbers 0025 to 0027 of JP-A-2015-67794 can also be used.
  • strontium titanate examples include SW-100 (manufactured by Titanium Industry Co., Ltd.).
  • barium sulfate examples include BF-1L (manufactured by Sakai Chemical Industry Co., Ltd.).
  • zinc oxide examples include Zincox Super F-1 (manufactured by Hakutech Co., Ltd.).
  • examples of commercially available zirconium oxide include Z-NX (manufactured by Taiyo Mining Co., Ltd.).
  • titanium oxide described in “Titanium oxide physical properties and applied technology, Kiyono Manabu, pages 13 to 45, published on June 25, 1991, published by Gihodo Publishing” can also be used.
  • the white colorant may be not only a single inorganic material but also particles combined with other materials. For example, particles having pores or other materials inside, particles having a large number of inorganic particles attached to the core particles, cores composed of polymer particles and shell layers composed of inorganic nanoparticles are used, and shell composite particles. It is preferable.
  • core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles can refer to, for example, the descriptions in paragraph numbers 0012 to 0042 of JP-A-2015-47520, This content is incorporated herein.
  • hollow inorganic particles can be used as the white colorant.
  • the hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and means an inorganic particle having a cavity surrounded by an outer shell.
  • Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Laid-Open No. 2011-75786, International Publication WO2013-61621, Japanese Patent Application Laid-Open No. 2015-164881, and the like, the contents of which are incorporated herein. It is.
  • Black colorants include inorganic black colorants (inorganic black pigments) such as carbon black, titanium black, zirconium oxynitride, vanadium oxynitride, niobium oxynitride, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. Organic black colorant.
  • inorganic black colorants such as carbon black, titanium black, zirconium oxynitride, vanadium oxynitride, niobium oxynitride, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc.
  • organic black colorant organic black colorant.
  • the inorganic black colorant is preferably titanium black.
  • Titanium black is a black particle containing a titanium atom, and is preferably low-order titanium oxide or titanium oxynitride.
  • the surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation.
  • the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water repellent material as disclosed in JP-A-2007-302836 is also possible. Titanium black preferably has a small primary particle size and average primary particle size for each particle. Specifically, the average primary particle diameter is preferably 10 to 45 nm.
  • Titanium black can also be used as a dispersion.
  • the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
  • Commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D (trade name) : Ako Kasei Co., Ltd.).
  • carbon black described in paragraph 0149 of JP2013-249471A can be used.
  • the organic black colorant is preferably a bisbenzofuranone compound or a perylene compound.
  • the bisbenzofuranone compounds include compounds described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
  • perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
  • the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
  • the bisbenzofuranone compound is preferably a compound represented by any of the following formulas or a mixture thereof.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent
  • R 3 and R 4 each independently represent a substituent
  • a and b each independently represent an integer of 0 to 4
  • the plurality of R 3 may be the same or different
  • the plurality of R 3 may be bonded to form a ring
  • b is 2 or more
  • the plurality of R 4 may be the same or different, and the plurality of R 4 may be bonded to form a ring.
  • the substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , —COOR 303 , —OCOR 304 , —NR 305 R 306 , —NHCOR 307 , —CONR 308 R 309 , —NHCONR 310 R 311 , —NHCOOR 312 , —SR 313 , —SO 2 R 314 , —SO 2 OR 315 , —NHSO 2 R 316 or —SO 2 NR 317 R 318 , each of R 301 to R 318 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group
  • the near infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and a wavelength of 700 to 1000 nm. It is more preferable that the compound has a maximum absorption wavelength in the range. Also, near infrared absorber, that the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength in the wavelength 500nm is preferably 0.08 or less, 0.04 or less More preferred.
  • Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, oxytitanium phthalocyanine described in JP2006-343631, paragraph Nos. 0013 to 0029 of JP2013-195480A. And the vanadium phthalocyanine described in Japanese Patent No. 6081771, the contents of which are incorporated herein.
  • Examples of the naphthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein.
  • the near-infrared absorbing dye the compounds described in JP-A-2016-146619 can also be used.
  • Examples of the pyrrolopyrrole compound include a compound represented by the formula (PP).
  • R 1a and R 1b each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R 2 and R 3 are They may combine with each other to form a ring
  • each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 4A R 4B , or a metal atom
  • R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded
  • R 4A and R 4B each independently represent a substituent.
  • R 4A and R 4B may be bonded to each other to form a ring.
  • PP formula (PP)
  • R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in paragraph numbers 0020 to 0022 of JP-A-2009-263614 and the following substituent T.
  • an alkyl group preferably an alkyl group having 1 to 30 carbon atoms
  • an alkenyl group preferably an alkenyl group having 2 to 30 carbon atoms
  • an alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
  • an aryl group preferably Aryl group having 6 to 30 carbon atoms
  • amino group preferably amino group having 0 to 30 carbon atoms
  • alkoxy group preferably alkoxy group having 1 to 30 carbon atoms
  • An aryloxy group preferably an aryloxy group having 6 to 30 carbon atoms
  • an acyl group preferably an acyl group having 1 to 30 carbon atoms
  • an alkoxycarbonyl group Preferably an alkoxycarbonyl group having 2 to 30 carbon atoms
  • an aryloxycarbonyl group Preferably an aryloxycarbonyl group having 7 to 30 carbon atoms
  • an acyloxy group preferably an acy
  • R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxy group as a substituent, and an aryl group having an acyloxy group as a substituent.
  • R 2 and R 3 each independently represents a hydrogen atom or a substituent.
  • the substituent include the above-described substituent T.
  • At least one of R 2 and R 3 is preferably an electron withdrawing group.
  • the electron withdrawing group include a cyano group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group, and a cyano group is preferable. .
  • R 2 represents an electron withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and even more preferably a single ring or a condensed ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • Two R 2 in the formula (PP) may be the same or different.
  • two R ⁇ 3 > in Formula (PP) may be the same, and may differ.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR 4A R 4B , and preferably a hydrogen atom, an alkyl group, an aryl group or —BR A group represented by 4A R 4B is more preferred, and a group represented by —BR 4A R 4B is more preferred.
  • the substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Particularly preferred. These groups may further have a substituent.
  • Two R 4 s in the formula (PP) may be the same or different.
  • R 4A and R 4B may be bonded to each other to form a ring.
  • pyrrolopyrrole compound examples include compounds described in Examples described later.
  • examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph Nos. 0037 to 0052 of JP-A-2011-68731, and international publication WO2015 / 166873.
  • Examples include compounds described in paragraph numbers 0010 to 0033 of the publication, and the contents thereof are incorporated in the present specification.
  • the squarylium compound is preferably a compound represented by the following formula (SQ1).
  • As 1 and As 2 each independently represent an aryl group, a heterocyclic group or a group represented by the formula (As-1);
  • * represents a bond
  • Rs 1 to Rs 3 each independently represents a hydrogen atom or an alkyl group
  • As 3 represents a heterocyclic group
  • n s1 represents an integer of 0 or more
  • Rs 1 and Rs 2 may be bonded to each other to form a ring
  • Rs 1 and As 3 may be bonded to each other to form a ring
  • Rs 2 and Rs 3 may be bonded to each other to form a ring.
  • n s1 is 2 or more
  • a plurality of Rs 2 and Rs 3 may be the same or different.
  • the number of carbon atoms of the aryl group represented by As 1 and As 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.
  • the heterocyclic group represented by As 1 , As 2 and As 3 is preferably a 5-membered or 6-membered heterocyclic group.
  • the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4.
  • a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable.
  • hetero atom constituting the ring of the heterocyclic group examples include a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom and a sulfur atom are preferable.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.
  • Rs 1 to Rs 3 in the formula (As-1) each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group represented by Rs 1 to Rs 3 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • Rs 1 to Rs 3 are preferably hydrogen atoms.
  • n s1 represents an integer of 0 or more. n s1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • Rs 1 and Rs 2 may be bonded to each other to form a ring, and Rs 1 and As 3 may be bonded to each other to form a ring, and Rs 2 and Rs 2 3 may be bonded to each other to form a ring.
  • the linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. .
  • the alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.
  • the group represented by As 1 and As 2 preferably has a substituent.
  • substituents include the above-described substituent T.
  • As 1 and As 2 are each independently an aryl group or a heterocyclic group, or As 1 and As 2 are each independently a group represented by the formula (As-1) Preferably there is.
  • the squarylium compound include compounds described in JP-A-2011-208101, paragraphs 0044 to 0049, compounds described in JP-A-6065169, paragraphs 0060 to 0061, and international publication WO2016 / 181987.
  • the compound described in Paragraph No. 0040, the compound described in International Publication WO2013 / 133099, the compound described in International Publication WO2014 / 088063, the compound described in JP2014-126642A, JP2016-146619A Compounds described in Japanese Laid-Open Patent Publication No. 2015-176046, compounds described in Japanese Patent Laid-Open No. 2017-25311, compounds described in International Publication No. WO2016 / 154787, compounds described in Japanese Patent No. 5884953 , Patent 603
  • a compound according to 689 JP-compound described in Japanese Patent No. 5810604 can be mentioned compounds described in JP-A-2017-068120, the contents of which are incorporated herein.
  • the cyanine compound is preferably a compound represented by the formula (Cy1).
  • Rcy 1 to Rcy 5 each independently represents a hydrogen atom or a substituent, and two of Rcy 1 to Rcy 5 may combine to form a ring.
  • n cy1 represents an integer of 0 to 2, and when n cy1 is 2, a plurality of Rcy 4 and Rcy 5 may be the same or different.
  • Acy 1 and Acy 2 each independently represents an aryl group or a heterocyclic group.
  • Rcy 1 to Rcy 5 each independently represents a hydrogen atom or a substituent.
  • substituents include the above-described substituent T.
  • the linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. .
  • the alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.
  • n cy1 represents an integer of 0 to 2, preferably 0 or 1.
  • the plurality of Rcy 4 and Rcy 5 may be the same or different.
  • the number of carbon atoms of the aryl group represented by Acy 1 and Acy 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.
  • the heterocyclic group represented by Acy 1 and Acy 2 is preferably a 5-membered or 6-membered heterocyclic group.
  • the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4.
  • a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable.
  • the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom, and an oxygen atom and a sulfur atom are preferable.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.
  • the groups represented by Acy 1 and Acy 2 may have a substituent. Examples of the substituent include the above-described substituent T.
  • Counter anions include halogen ions (Cl ⁇ , Br ⁇ , I ⁇ ), sulfonate anions, carboxylate anions, sulfonylimide anions, PF 6 ⁇ , BF 4 ⁇ , ClO 4 ⁇ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF 3 SO 2 ) 3 C ⁇ ), di (halogenoalkylsulfonyl) imide anion (for example (CF 3 SO 2 ) 2 N ⁇ ), tetraaryl borate anion, tetracyanoborate anion and the like can be mentioned.
  • cyanine compound examples include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040, and JP-A No. 2015-172004.
  • the croconium compound is preferably a compound represented by the following formula (Cr1).
  • Ac 1 and Ac 2 each independently represent an aryl group, a heterocyclic group or a group represented by the formula (Ac-1);
  • * represents a bond
  • Rc 1 to Rc 3 each independently represents a hydrogen atom or an alkyl group
  • Ac 3 represents a heterocyclic group
  • n c1 represents an integer of 0 or more
  • Rc 1 and Rc 2 may be bonded to each other to form a ring
  • Rc 1 and Ac 3 may be bonded to each other to form a ring
  • Rc 2 and Rc 3 may be bonded to each other to form a ring.
  • the plurality of Rc 2 and Rc 3 may be the same or different.
  • the number of carbon atoms of the aryl group represented by Ac 1 and Ac 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.
  • the heterocyclic group represented by Ac 1 , Ac 2 and Ac 3 is preferably a 5-membered or 6-membered heterocyclic group.
  • the heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4.
  • a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable.
  • hetero atom constituting the ring of the heterocyclic group examples include a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom and a sulfur atom are preferable.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.
  • Rc 1 to Rc 3 in formula (Ac-1) are each independently a hydrogen atom or an alkyl group Represents.
  • the alkyl group represented by Rc 1 to Rc 3 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • Rc 1 to Rc 3 are preferably hydrogen atoms.
  • N c1 in formula (Ac-1) represents an integer of 0 or more.
  • n c1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.
  • Rc 1 and Rc 2 may combine with each other to form a ring
  • Rc 1 and Ac 3 may combine with each other to form a ring
  • Rc 2 and Rc 2 3 may be bonded to each other to form a ring.
  • the linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof.
  • the alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.
  • the groups represented by Ac 1 and Ac 2 preferably have a substituent.
  • substituents include the above-described substituent T.
  • Ac 1 and Ac 2 are each independently an aryl group or a heterocyclic group, or Ac 1 and Ac 2 are each independently a group represented by Formula (Ac-1) Preferably there is.
  • croconium compound examples include the compounds described in JP-A-5-155145 and the compounds described in JP-A-2007-31644, the contents of which are incorporated herein.
  • the iminium compound is preferably a compound represented by the following formula (Im).
  • each of R 11 to R 18 independently represents an alkyl group or an aryl group
  • each of V 11 to V 15 independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group
  • X represents a counter anion
  • c represents a number necessary for balancing the charge
  • n1 to n5 are each independently 0 to 4.
  • R 11 to R 18 each independently represents an alkyl group or an aryl group.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T.
  • V 11 to V 15 each independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group or a cyano group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • n1 to n5 are each independently 0 to 4.
  • n1 to n4 are preferably 0 to 2, and more preferably 0 or 1.
  • n5 is preferably 0 to 3, and more preferably 0 to 2.
  • X represents a counter anion.
  • Counter anions include halogen ions (Cl ⁇ , Br ⁇ , I ⁇ ). , Sulfonate anion, carboxylate anion, sulfonylimide anion, PF 6 ⁇ , BF 4 ⁇ , ClO 4 ⁇ , tris (halogenoalkylsulfonyl) methide anion (eg, (CF 3 SO 2 ) 3 C ⁇ ), di (halogenoalkyl) (Sulfonyl) imide anion (for example, (CF 3 SO 2 ) 2 N ⁇ ), tetraarylborate anion, tetracyanoborate anion and the like.
  • c represents a number necessary for balancing the electric charge, and is preferably 2, for example.
  • iminium compound examples include a compound described in JP-T-2008-528706, a compound described in JP-A-2012-012399, and a compound described in JP-A-2007-92060. Are incorporated herein.
  • a commercial item can also be used for the near-infrared absorbing dye.
  • Commercially available near-infrared absorbing dyes include SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), e-ex color IR-14, e-ex color IR-10A, e-ex color TX-EX-801B, e-ex color TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 And PRO-JET825LDI (manufactured by FUJIFILM Corporation), NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.
  • the content of the coloring material in the total solid content of the photosensitive composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more.
  • the content is more preferably at least 50% by mass, even more preferably at least 40% by mass, and even more preferably at least 50% by mass.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
  • the color material used in the photosensitive composition of the present invention preferably contains at least one selected from a chromatic colorant, a black colorant, and a white colorant, and at least selected from a chromatic colorant and a black colorant. It is more preferable to include one type, and it is more preferable to include a chromatic colorant. Further, the content of the chromatic colorant and the black colorant in the total mass of the colorant is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass or more. Is more preferable. The upper limit can be 100% by mass, or 90% by mass or less.
  • the photosensitive composition of the present invention is used as a composition for a color filter (more specifically, a composition for forming a colored pixel of a color filter), chromatic coloring in the total solid content of the photosensitive composition.
  • the content of the agent is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
  • the content of the chromatic colorant in the total mass of the coloring material is preferably 25% by mass or more, more preferably 45% by mass or more, and further preferably 65% by mass or more.
  • the upper limit can be 100% by mass, or 75% by mass or less.
  • the white colorant is contained in the total solid content of the photosensitive composition.
  • the amount is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
  • the content of the white colorant in the total mass of the coloring material is preferably 25% by mass or more, more preferably 45% by mass or more, and further preferably 65% by mass or more.
  • the upper limit can be 100% by mass, or 75% by mass or less.
  • a black colorant preferably an inorganic black colorant
  • the content of is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
  • the content of the black colorant in the total mass of the coloring material is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.
  • the upper limit can be 100% by mass, or 90% by mass or less.
  • the color material used in the present invention preferably satisfies at least one of the following requirements (1) to (3).
  • Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants. It is preferable that black is formed by a combination of two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant and a green colorant.
  • Examples of the preferred combination of the above aspect (1) include the following.
  • (1-1) An embodiment containing a red colorant and a blue colorant.
  • (1-2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant.
  • (1-3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
  • (1-4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
  • (1-5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
  • (1-6) An embodiment containing a red colorant, a blue colorant, and a green colorant.
  • (1-7) An embodiment containing a yellow colorant and a purple colorant.
  • a chromatic colorant By using the organic black colorant and the chromatic colorant in combination, excellent spectral characteristics can be easily obtained.
  • the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
  • the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass with respect to 100 parts by mass of the organic black colorant.
  • the content of the near-infrared absorbing dye in the total mass of the coloring material is preferably 5 to 40% by mass.
  • the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.
  • the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • the photosensitive composition of the present invention can contain a resin.
  • the resin refers to an organic compound other than a color material and having a molecular weight of 3000 or more.
  • Resin is mix
  • a resin mainly used for dispersing particles such as pigment is also referred to as a dispersant.
  • such use of the resin is an example, and it can be used for purposes other than such use.
  • the weight average molecular weight (Mw) of the resin is preferably 3000-2 million.
  • the upper limit is preferably 1000000 or less, and more preferably 500000 or less.
  • the lower limit is preferably 4000 or more, and more preferably 5000 or more.
  • Resins include (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.
  • a resin having an acid group as the resin.
  • the developability of the photosensitive composition can be improved, and a pixel having excellent rectangularity can be easily formed.
  • the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxyl group is preferable.
  • the resin having an acid group can be used as an alkali-soluble resin, for example.
  • the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of a repeating unit having an acid group in the side chain in the total repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
  • the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a repeating unit derived from the component.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the details of the formula (ED2) can be referred to the description of JP 2010-168539 A, the content of which is incorporated herein.
  • paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
  • the resin used in the present invention contains a repeating unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
  • the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
  • the upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
  • the weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100,000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.
  • Examples of the resin having an acid group include a resin having the following structure.
  • the photosensitive composition of the present invention can also contain a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred.
  • the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • the resin used as the dispersant preferably contains a repeating unit having an acid group.
  • the resin used as the dispersant contains a repeating unit having an acid group, the generation of a development residue can be further suppressed when a pattern is formed by a photolithography method.
  • the resin used as the dispersant is also preferably a graft resin.
  • Details of the graft resin can be referred to the descriptions in paragraph numbers 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein.
  • Specific examples of the graft resin include resins having the following structure.
  • the resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa 14 or less, and a side chain containing a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain A resin having a basic nitrogen atom is preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein.
  • Specific examples of the polyimine dispersant include resins having the following structure.
  • the resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core.
  • a resin include dendrimers (including star polymers).
  • dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP2013-043662A and compounds having the following structures.
  • alkali-soluble resin can be used as a dispersant.
  • resin used as a dispersing agent is resin containing the repeating unit which has an ethylenically unsaturated bond group in a side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol% in all repeating units of the resin. % Is more preferable.
  • Dispersants are also available as commercial products, and specific examples thereof include BYPER Chemie's DISPERBYK series (for example, DISPERBYK-111, 161, etc.), Nippon Lubrizol Corporation Solsperse series ( For example, Solsperse 76500).
  • pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
  • the resin described as the dispersant can be used for purposes other than the dispersant. For example, it can be used as a binder.
  • the content of the resin in the total solid content of the photosensitive composition is preferably 5 to 50% by mass.
  • the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
  • the content of the resin having an acid group in the total solid content of the photosensitive composition is preferably 5 to 50% by mass.
  • the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
  • the content of the resin having an acid group in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, because excellent developability is easily obtained. 80 mass% or more is particularly preferable.
  • the upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.
  • the total content of the polymerizable compound and the resin in the total solid content of the photosensitive composition is preferably 15 to 65% by mass from the viewpoints of curability, developability and film property.
  • the lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more.
  • the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
  • the resin is preferably contained in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the polymerizable compound.
  • the lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more.
  • the upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.
  • the photosensitive composition of the present invention can contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group.
  • the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule.
  • the upper limit of the epoxy group can be, for example, 10 or less, or 5 or less.
  • the lower limit of the epoxy group is preferably 2 or more.
  • Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A.
  • the described compounds and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
  • the compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
  • an epoxy resin can be preferably used as the compound having an epoxy group.
  • the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type.
  • the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.
  • Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corp.), EPICLON N-695 (manufactured by DIC Corp.), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, manufactured by NOF Corporation, epoxy group-containing polymer).
  • the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably from 0.1 to 20% by mass.
  • the lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the compound having a cyclic ether group may be only one type or two or more types. In the case of two or more types, the total amount thereof is preferably in the above range.
  • the photosensitive composition of this invention may contain other photoinitiators (henceforth other photoinitiators) other than the cyclic oxime compound mentioned above.
  • Other photopolymerization initiators include, for example, trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazole dimers.
  • Onium compounds benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, coumarin compounds, etc., oxime compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, Acylphosphine compounds are preferable, and oxime compounds and ⁇ -aminoketone compounds are more preferable.
  • Examples of the oxime compound as another photopolymerization initiator include the oxime compound having no cyclic oxime moiety described above and the oxime compound having no electron withdrawing group described above. For details of other photopolymerization initiators, paragraphs 0013 to 0031 of JP-A No. 2017-126044 can be referred to, the contents of which are incorporated herein.
  • Examples of commercially available ⁇ -hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF).
  • Examples of commercially available ⁇ -aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF).
  • Examples of commercially available acylphosphine compounds include IRGACURE-819, DAROCUR-TPO (manufactured by BASF).
  • Examples of oxime compounds include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. These compounds can be used.
  • Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • J.H. C. S. Perkin II (1979, pp. 1653-1660) J. MoI. C.
  • oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-14052 A), Adeka Arcles NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation) Etc.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a fluorine atom can also be used.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Compound (C-3). This content is incorporated herein.
  • an oxime compound having a nitro group can be used as another photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
  • a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator.
  • active species such as two or more radicals are generated from one molecule of the photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered and the solubility in a solvent or the like is improved, the precipitation with time is less likely to occur, and the temporal stability of the composition can be improved.
  • photopolymerization initiator examples include paragraphs 0417 to 0412 in JP2010-527339A, JP2011-524436A, International Publication WO2015 / 004565, and JP2016-532675A.
  • the content of the other photopolymerization initiator is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the cyclic oxime compound A described above.
  • the lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more.
  • the upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less.
  • the photosensitive composition of the present invention contains substantially no other photopolymerization initiator. According to this aspect, it is easier to suppress variation in the degree of curing of the obtained film.
  • the content of the other photopolymerization initiator in the total solid content of the photosensitive composition is 0.1 or less. In other words, it is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably no other photopolymerization initiator.
  • the photosensitive composition of the present invention may further contain a sensitizer for the purpose of improving the radical generation efficiency of the cyclic oxime compound A and increasing the photosensitive wavelength.
  • Sensitizers include polynuclear aromatic compounds (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthene compounds (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal) ), Thioxanthone compounds (eg, isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanine compounds (eg, thiacarbocyanine, oxacarbocyanine) , Merocyanine compounds (eg merocyanine, carbomerocyanine), phthalocyanine compounds, thiazine compounds (eg
  • the sensitizer is preferably a compound having a maximum absorption wavelength in the wavelength range of 300 to 450 nm.
  • Specific examples of the sensitizer include compounds described in Examples described later and compounds described in paragraph numbers 0172 to 0222 of JP2013-249471A.
  • the content of the sensitizer in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one sensitizer or two or more sensitizers may be used. In the case of two or more types, the total amount thereof is preferably in the above range.
  • the photosensitive composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable.
  • the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • functional groups other than hydrolyzable groups include vinyl groups, (meth) allyl groups, (meth) acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups.
  • a phenyl group, and an amino group, a (meth) acryloyl group and an epoxy group are preferable.
  • Specific examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph Nos. 0056 to 0066 of JP-A-2009-242604. Is incorporated herein by reference.
  • the content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass.
  • the upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.
  • Pigment derivative When the photosensitive composition of this invention contains a pigment, it is preferable to contain a pigment derivative further.
  • the pigment derivative include a compound having a structure in which a part of the chromophore is substituted with an acid group, a basic group or a phthalimidomethyl group.
  • the chromophores constituting the pigment derivatives include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone skeleton.
  • a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
  • a basic group which a pigment derivative has an amino group is preferable and a tertiary amino group is more preferable.
  • the pigment derivative for example, the description of paragraph numbers 0162 to 0183 in JP 2011-252065 A can be referred to, the contents of which are incorporated herein.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the photosensitive composition of this invention may contain only 1 type of pigment derivatives, and may contain 2 or more types. When two or more kinds of pigment derivatives are contained, the total amount thereof is preferably within the above range.
  • the photosensitive composition of the present invention preferably contains a solvent.
  • the solvent include organic solvents.
  • the solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
  • the organic solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Regarding these details, paragraph number 0223 of International Publication No. WO2015 / 166779 can be referred to, the contents of which are incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like.
  • the organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are preferable from the viewpoint of improving solubility.
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • aromatic hydrocarbons as a solvent may be better reduced for environmental reasons or the like (for example, 50 ppm by weight per part of organic solvent). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a solvent having a mass ppt (parts per trill) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.
  • the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the solvent in the photosensitive composition is preferably 10 to 95% by mass.
  • the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more. It is preferably 60% by mass or more.
  • the upper limit is preferably 90% by mass.
  • the photosensitive composition of this invention does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation.
  • “substantially containing no environmentally regulated substance” means that the content of the environmentally regulated substance in the photosensitive composition is 50 mass ppm or less, and is 30 mass ppm or less. Preferably, it is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like.
  • REACH Registration Evaluation Authorization and Restriction of Chemicals
  • PRTR Policy Release and Transfer Register
  • VOC Volatile Organic Registered
  • the method is strictly regulated.
  • These compounds may be used as a solvent when producing each component used in the photosensitive composition of the present invention, and may be mixed into the photosensitive composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and consideration for the environment.
  • As a method for reducing the environmentally regulated substances there is a method of heating and depressurizing the system so as to make it equal to or higher than the boiling point of the environmentally regulated substances to distill off the environmentally regulated substances from the system.
  • distilling off a small amount of environmentally regulated substances it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase efficiency.
  • a polymerization inhibitor or the like is added and the solvent is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding during the vacuum distillation and causing cross-linking between molecules. May be.
  • These distillation methods can be performed either at the raw material stage, the product obtained by reacting the raw material (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a composition stage prepared by mixing these compounds. It is also possible in stages.
  • the photosensitive composition of the present invention can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.001 to 5% by mass.
  • the photosensitive composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
  • the surfactant is preferably a fluorosurfactant.
  • a fluorosurfactant in the photosensitive composition, liquid properties (particularly, fluidity) can be further improved, and liquid-saving properties can be further improved.
  • a film with small thickness unevenness can be formed.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactant examples include surfactants described in paragraph Nos. 0060 to 0064 of JP-A No. 2014-41318 (paragraph Nos. 0060 to 0064 of the corresponding International Publication No. 2014/17669) and JP-A No. 2011-2011.
  • the surfactants described in paragraph Nos. 0117 to 0132 of No. 132503 are listed, the contents of which are incorporated herein.
  • Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heat is applied. It can be used suitably.
  • a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21.
  • the fluorine-based surfactant is also preferably a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a fluorosurfactant can be referred to the description in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can be used. Examples thereof include compounds described in JP2011-89090A.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.
  • a fluoropolymer having an ethylenically unsaturated bond group in the side chain can also be used.
  • Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like.
  • the fluorine-based surfactant compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BASF) Etsu Chemical Co., Ltd.), SOLSPERSE 20000 (manufactured by Lubrizol Japan (Ltd.)), NCW-101, NCW-1001, NCW-1002 (Wako
  • Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.) Olfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.) Manufactured).
  • silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
  • the content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. In the case of two or more types, the total amount is preferably within the above range.
  • the photosensitive composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, aminodiene compound, salicylate compound, benzophenone compound, benzotriazole compound, acrylonitrile compound, hydroxyphenyltriazine compound, indole compound, triazine compound, or the like can be used. Details of these are described in paragraph numbers 0052 to 0072 in JP2012-208374A, paragraph numbers 0317 to 0334 in JP2013-68814A, and paragraph numbers 0061 to 0080 in JP2016-162946A. Which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structure.
  • UV-503 manufactured by Daito Chemical Co., Ltd.
  • MYUA series Chemical Industry Daily, February 1, 2016
  • the content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
  • only 1 type may be used for an ultraviolet absorber and 2 or more types may be used for it.
  • 2 or more types it is preferable that a total amount becomes the said range.
  • the photosensitive composition of the present invention can contain an antioxidant.
  • the antioxidant include a phenol compound, a phosphite compound, and a thioether compound.
  • the phenol compound any phenol compound known as a phenol-based antioxidant can be used.
  • Preferable phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferred.
  • the aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule.
  • phosphorus antioxidant can also be used suitably for antioxidant.
  • phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
  • antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO-80.
  • Adeka Stub AO-330 (above, ADEKA Co., Ltd.) and the like.
  • the content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the photosensitive composition of the present invention may be a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, etc.) as necessary.
  • auxiliary agents for example, conductive particles, fillers, antifoaming agents, flame retardants, etc.
  • Properties such as film properties can be adjusted by appropriately containing these components. These components are described in, for example, paragraph No. 0183 of JP2012-003225A or later (paragraph No. 0237 of US Patent Application Publication No. 2013/0034812), paragraph of JP2008-250074, for example.
  • the photosensitive composition of this invention may contain a latent antioxidant as needed.
  • the latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • a compound that functions as an antioxidant due to elimination of the protecting group can be mentioned.
  • Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Unexamined Patent Publication No. 2017-008219.
  • Examples of commercially available products include ADEKA ARKLES GPA-5001 (manufactured by ADEKA Corporation).
  • the viscosity (23 ° C.) of the photosensitive composition of the present invention is preferably 1 to 100 mPa ⁇ s, for example, when a film is formed by coating.
  • the lower limit is more preferably 2 mPa ⁇ s or more, and further preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • a storage container of the photosensitive composition of this invention A well-known storage container can be used.
  • a container for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin, and a bottle having six types of resin and a seven layer structure are used. It is also preferable to use it. Examples of such a container include a container described in JP-A-2015-123351.
  • the voltage holding ratio of the liquid crystal display element provided with the color filter formed of the photosensitive composition of the present invention is 70. % Or more is preferable, and 90% or more is more preferable.
  • Known means for obtaining a high voltage holding ratio can be appropriately incorporated. Typical examples include the use of high-purity materials (for example, reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. Is mentioned.
  • the voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP2011-008004A and paragraphs 0123 to 0129 of JP2012-224847A.
  • the photosensitive composition of the present invention can be prepared by mixing the aforementioned components. In preparing the photosensitive composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the photosensitive composition. If necessary, two or more solutions in which each component is appropriately blended or A dispersion liquid may be prepared in advance, and these may be mixed at the time of use (at the time of application) to prepare a photosensitive composition.
  • the photosensitive composition of this invention contains particle
  • the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion.
  • the particles may be refined in the salt milling process.
  • materials, equipment, processing conditions, etc. used in the salt milling process for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.
  • a filter for the purpose of removing foreign substances or reducing defects.
  • a filter if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
  • fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
  • PP polypropylene
  • a filter using a material such as polyolefin resin.
  • polypropylene including high density polypropylene
  • nylon are preferable.
  • the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m. If the hole diameter of a filter is the said range, a fine foreign material can be removed reliably. It is also preferable to use a fiber-shaped filter medium.
  • the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber.
  • filter cartridges of SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno Co., Ltd. may be mentioned.
  • a filter When using a filter, you may combine a different filter (For example, a 1st filter, a 2nd filter, etc.). In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. Further, filtration with the first filter may be performed only on the dispersion, and after mixing other components, filtration may be performed with the second filter.
  • a different filter For example, a 1st filter, a 2nd filter, etc.
  • filtration with each filter may be performed only once or may be performed twice or more.
  • filtration with the first filter may be performed only on the dispersion, and after mixing other components, filtration may be performed with the second filter.
  • the cured film of the present invention is a cured film obtained from the above-described photosensitive composition of the present invention.
  • the cured film of the present invention includes a color filter, a near infrared transmission filter, a near infrared cut filter, a black matrix, a light shielding film, a refractive index adjusting film, a photosensitive layer of a lithographic printing plate precursor, a protective film, a UV curable ink, and various photoresists.
  • Various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coats, electrical components, magnetic recording materials, micromechanical components, waveguides, optical switches, masking for plating, color calibration It can be used in systems, glass fiber cable coatings, screen printing stencils, stereolithographic three-dimensional objects, image recording materials for holographic recording, microelectronic circuits, healthcare materials and the like.
  • the film thickness can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the method for producing a color filter of the present invention includes a step of forming a photosensitive composition layer by applying the above-described photosensitive composition of the present invention on a support, and a step of exposing the photosensitive composition layer in a pattern. And a step of developing the photosensitive composition layer after exposure to form a pattern.
  • a step of forming a photosensitive composition layer by applying the above-described photosensitive composition of the present invention on a support and a step of exposing the photosensitive composition layer in a pattern.
  • a step of developing the photosensitive composition layer after exposure to form a pattern will be described.
  • the photosensitive composition of the present invention is applied on a support to form a photosensitive composition layer.
  • a support body there is no limitation in particular as a support body, According to a use, it can select suitably. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate.
  • CMOS complementary metal oxide semiconductor
  • a black matrix for isolating each pixel is formed on the silicon substrate.
  • the silicon substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the substrate surface.
  • a known method can be used as a method for applying the photosensitive composition.
  • a dropping method drop casting
  • a slit coating method for example, a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A).
  • Methods described in the publication inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods transfer methods using a mold or the like; nanoimprint methods and the like.
  • the photosensitive composition layer formed on the support may be dried (prebaked).
  • the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower.
  • the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
  • the pre-bake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 2200 seconds.
  • Pre-baking can be performed with a hot plate, an oven, or the like.
  • pattern exposure can be performed by exposing the photosensitive composition layer formed on the support through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the photosensitive composition layer of an exposure part can be hardened.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can be used. Examples of the light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. A long wave light source of 300 nm or more can also be used. Various LED and LD light sources can also be used. In addition, radiation sources such as EB and EUV can be used.
  • exposure may be performed by continuously irradiating light, or by irradiating in pulses.
  • Pulse exposure is an exposure method in which exposure is performed by repeatedly irradiating and pausing light in a short cycle (for example, a millisecond level or less).
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, but may be 1 phenomsecond (fs) or more, and may be 10 phenomseconds or more.
  • the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less.
  • Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
  • the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
  • the pulse width is the time during which light is irradiated in the pulse period.
  • the frequency is the number of pulse periods per second.
  • the maximum instantaneous illuminance is the average illuminance within the time during which light is irradiated in the pulse period.
  • the pulse period is a period in which light irradiation and pause in pulse exposure are one cycle.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be selected as appropriate.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially It may be exposed in an oxygen-free manner, or may be exposed in a high oxygen atmosphere (for example, 22%, 30%, or 50% by volume) in which the oxygen concentration exceeds 21% by volume.
  • the exposure illuminance can be appropriately set, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). Can do.
  • Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the photosensitive composition layer after exposure is developed to form a pattern (development process). More specifically, a pattern is formed by developing and removing the photosensitive composition layer in the unexposed area.
  • the development removal of the photosensitive composition layer of an unexposed part can be performed using a developing solution. Thereby, the photosensitive composition layer of an unexposed part elutes in a developing solution, and only the photocured part remains on a support body.
  • the temperature of the developer is preferably 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds.
  • the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • the developer is preferably an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water.
  • alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide.
  • Organic compounds such as ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene
  • Alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate.
  • the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • surfactant the surfactant mentioned above is mentioned, A nonionic surfactant is preferable.
  • the developer may be once manufactured as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of convenience of transportation and storage.
  • the dilution factor is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to rinse (rinse) with pure water after development.
  • the rinsing is preferably performed by supplying a rinsing liquid to the photosensitive coloring composition layer after development while rotating the support on which the photosensitive coloring composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the periphery of the support. At this time, when moving from the central part of the support body of the nozzle to the peripheral part, the nozzle may be moved while gradually decreasing the moving speed of the nozzle. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.
  • post-baking is a heat treatment after development for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .
  • a pattern (pixel) can be formed through the above steps.
  • a color filter having two or more color pixels is manufactured, a color filter having a plurality of color pixels can be manufactured by repeating the above steps for the desired number of hues.
  • the embodiment using the photosensitive composition of the present invention when forming the pixel of the color filter has been mainly described.
  • the present invention is not limited to this embodiment. Absent.
  • the photosensitive composition of the present invention can also be applied to the formation of a black matrix that isolates pixels of each color constituting a color filter. That is, a black matrix (black pattern) can be formed on the support by performing the above steps.
  • the color filter of the present invention has the above-described cured film of the present invention.
  • the cured film of this invention contains a chromatic colorant. That is, the cured film of the present invention is preferably formed using a photosensitive composition containing a chromatic colorant.
  • the thickness of the cured film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
  • the color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.
  • the solid-state imaging device of the present invention has the above-described cured film of the present invention.
  • the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
  • the substrate has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.)). And a device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to cover only the entire surface of the light shielding film and the photodiode light receiving portion. And having a color filter on the device protective film.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • the device has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the color filter (on the side close to the substrate) on the device protective film, or a constitution having the condensing means on the color filter.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a lattice shape.
  • the partition walls preferably have a low refractive index for each colored pixel.
  • Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
  • the image pickup apparatus including the solid-state image pickup device of the present invention can be used for an in-vehicle camera and a monitoring camera in addition to a digital camera and an electronic apparatus (such as a mobile phone) having an image pickup function.
  • the image display device of the present invention has the above-described cured film of the present invention.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • the image display device for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junaki Ibuki, Industrial Book ( (Issued in 1989)).
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the photopolymerization initiator used in each of the following test examples is a compound having the following structure.
  • OX-1 to OX-21 are cyclic oxime compounds (cyclic oxime compound A) according to the present invention.
  • OX-R1 to OX-R4 are comparative compounds.
  • a photosensitive composition of Example 1-1 was prepared by mixing 16 g of cyclohexanone. The obtained photosensitive composition was applied onto a glass substrate with a spin coater and dried at 40 ° C. for 10 minutes to form a coating film having a thickness of 1.5 ⁇ m.
  • a 21-step gray scale film (made by Kodak) was placed on this coating film, and an exposure machine (USHIO Inc., “UVC-2534 / 1MNLC3-AA08”, one 120 W / cm 2 metal halide lamp) was placed.
  • the sample was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm 2 and then impregnated in toluene for 60 seconds for development.
  • the sensitivity was 6 steps.
  • a sensitivity shows that a sensitivity is so high that a number is large.
  • Example 1-1 (Examples 1-2 to 1-21, Comparative Examples 1-1 to 1-4)
  • the procedure was exactly the same as Example 1-1, except that 0.08 mmol of compound OX-1 as a photopolymerization initiator was replaced with 0.08 mmol of the compounds shown in the following table, respectively.
  • photosensitive compositions of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 were prepared, and the number of sensitivity steps was evaluated in the same manner as Example 1-1.
  • the evaluation results of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 are shown in the following table together with the evaluation results of Example 1-1.
  • the photosensitive compositions of the examples had higher sensitivity than the photosensitive compositions of the comparative examples.
  • the raw materials used for the production of each dispersion are as follows.
  • PR254 C.I. I. Pigment Red254 (red pigment)
  • PR264 C.I. I. Pigment Red 264 (red pigment)
  • PY139 C.I. I. Pigment Yellow 139 (yellow pigment)
  • PY150 C.I. I. Pigment Yellow 150 (yellow pigment)
  • PY185 C.I. I. Pigment Yellow 185 (yellow pigment)
  • PG36 C.I. I. Pigment Green 36 (green pigment)
  • PG58 C.I. I. Pigment Green 58 (green pigment)
  • PB15 6: C.I. I. Pigment Blue 15: 6 (blue pigment)
  • PV23 C.I. I. Pigment Violet 23 (purple pigment)
  • Pc1 zinc halide phthalocyanine pigment (green pigment) produced by the following method Sulfuryl chloride (45.5 parts by mass), anhydrous aluminum chloride (54.5 parts by mass) and sodium chloride (7 parts by mass) were mixed at 40 ° C., and zinc phthalocyanine pigment (15 parts by mass) was added. Bromine (35 parts by mass) was added dropwise thereto, and the temperature was raised to 130 ° C. over 19.5 hours and held for 1 hour. Thereafter, the reaction mixture was taken out into water, and a halogenated zinc phthalocyanine crude pigment was precipitated.
  • This aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% aqueous sodium hydrogen sulfate, washed with hot water at 60 ° C., dried at 90 ° C., and 2.7 parts by weight of a purified zinc halide phthalocyanine crude pigment A was obtained.
  • Purified zinc halide phthalocyanine crude pigment A (1 part by mass), crushed sodium chloride (10 parts by mass) and diethylene glycol (1 part by mass) were charged into a double-arm kneader and kneaded at 100 ° C. for 8 hours.
  • the obtained zinc halide phthalocyanine pigment had an average composition of ZnPcBr 9.8 Cl 3.1 H 3.1 from mass analysis and halogen content analysis by flask combustion ion chromatography. Pc is an abbreviation for phthalocyanine.
  • PP1, PP2 Compounds having the following structure (near infrared absorbing dyes)
  • IBk Irgaphor Black (manufactured by BASF, black colorant)
  • PBk32 C.I. I. Pigment Black 32 (black colorant)
  • TTO-80A Titanium oxide (TTO-80A, manufactured by Ishihara Sangyo Co., Ltd., white pigment)
  • N—Ti Titanium oxynitride-containing particles (black pigment) produced by the method described below.
  • the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used. Specifically, titanium oxynitride using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (Fukushin Kogyo Co., Ltd.) is used. Containing particles were produced. First, the air in the vacuum chamber was exhausted by an exhaust pump.
  • helium (He) gas purity 99.99%) and argon gas mixed gas (mixing ratio 50/50% by volume in a standard state) are set in a vacuum chamber at a pressure of 600 Torr (79.99 kPa).
  • a tungsten electrode formed into a hollow rod having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm was used.
  • the arrangement of the discharge electrodes was the same as that shown in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of 6 each. The distance between the upper stage and the lower stage was about 160 mm.
  • the discharge electrode having a hollow structure is connected to a raw material supply device so that the source gas can be supplied from the hollow portion of the discharge electrode into the vacuum chamber.
  • the discharge is started in a state where the tips of the discharge electrodes are in contact with each other while applying alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to the discharge electrodes.
  • alternating current voltage 20 to 40 V, current 70 to 100 A
  • the tip of each discharge electrode was moved outward so as to be separated, and the arc discharge was continued by setting the distance between the tips of adjacent discharge electrodes to be 5 to 10 mm. .
  • the supply tank of the raw material supply apparatus was heated, and the source gas was introduced into the vacuum chamber.
  • NH 3 gas (liquefied ammonium ECOAN, Showa Denko KK) 0.5 atm
  • H 2 gas hydrogen gas, Showa Denko Gas Products
  • Ar gas argon gas, Taiyo Nippon Sanso
  • TiCl 4 gas TiCl 4 gas (TLT-1, manufactured by Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm.
  • a fine sulfur powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Co., Ltd.) was supplied with nitrogen gas using a powder supply device TP-99010 FDR (manufactured by JEOL Ltd.).
  • the supply amount is the sulfur atom detected by fluorescent X-ray analysis, where T E (mass%) is the sulfur-based mass reference content detected by X-ray photoelectron spectroscopy in the obtained titanium oxynitride-containing particles.
  • the ratio (T E / T X ) between the two based on the mass-based content of T x (mass%) was adjusted to be less than 1.1.
  • N-Zr Zirconium oxynitride-containing particles (black pigment) prepared by the following method In the production of the titanium oxynitride-containing particles, instead of introducing TiCl 4 gas, the above-mentioned acid was used except that zirconium powder (zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.) was introduced with a powder supply device TP-99010 FDR (manufactured by JEOL Ltd.). Zirconium oxynitride-containing particles were produced in the same manner as the titanium nitride-containing particles.
  • NV Vanadium oxynitride-containing particles (black pigment) prepared by the following method
  • vanadium powder metal vanadium powder VHO manufactured by Taiyo Mining Co., Ltd.
  • a powder feeder TP-99010 FDR manufactured by JEOL
  • Vanadium oxynitride-containing particles were produced in the same manner as the titanium oxynitride-containing particles.
  • N—Nb Niobium oxynitride-containing particles (black pigment) produced by the method described below.
  • niobium powder Niobium powder manufactured by Mitsuwa Chemicals Co., Ltd.
  • a powder feeder TP-99010FDR manufactured by JEOL.
  • Niobium oxynitride-containing particles were produced in the same manner as the titanium oxynitride-containing particles.
  • Acetate (PGMEA) was added to adjust the solid content concentration to 63% by mass and then heated to 75 ° C. under a nitrogen stream.
  • the weight average molecular weight (Mw) of the resin p1 was 11000, the dispersity (Mw / Mn) was 1.8, the acid value was 75 mgKOH / g, and the reduced viscosity was 11 ml / gs.
  • P-2 30% by mass PGMEA solution of resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • Mw 17000
  • dispersity ( Mw / Mn) 4.2
  • acid value 75 mg KOH / g
  • reduced viscosity 12.5 ml / g).
  • P-3 30% by mass PGMEA solution of resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • Mw 7950
  • P-5 PGMEA 30% by mass solution of resin having the following structure (The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • Mw 30000)
  • the photosensitive composition of an Example and a comparative example was each manufactured by mixing the raw material of the following table
  • the raw materials used for the production of the composition are as follows.
  • OX-1 to OX-21, OX-R1 to OX-R4 compounds having the structures described above
  • UV1 UV-503 (Daito Chemical Co., Ltd.)
  • UV2 Compound having the following structure
  • Each photosensitive composition is applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a thickness of 1.0 ⁇ m. It was.
  • an i-line stepper exposure apparatus FPA-3000iS + manufactured by Canon Inc.
  • Were irradiated in 10 mJ / cm 2 increments (exposure process).
  • paddle development was performed at 23 ° C.
  • TMAH tetramethylammonium hydroxide
  • the evaluation of sensitivity is based on the minimum exposure amount (optimum exposure amount) when the film thickness after development in the area exposed to light in the above exposure process is 95% or more with respect to 100% of the film thickness before exposure. ) And measured as sensitivity. It shows that a sensitivity is so high that the value of the above-mentioned minimum exposure amount (optimal exposure amount) is small.
  • Each photosensitive composition is applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a thickness of 1.0 ⁇ m. It was.
  • an i-line stepper exposure apparatus FPA-3000iS + manufactured by Canon Inc.
  • exposure was performed at an exposure amount of 400 mJ / cm 2 through a mask in which a 10 nm line and space pattern was engraved.
  • paddle development was performed at 23 ° C.
  • TMAH tetramethylammonium hydroxide
  • a pattern was formed by the same procedure as the evaluation of developability. The obtained pattern was observed with SEM (Scanning Electron Microscope, magnification: 20000 times), and the presence or absence of a pattern defect was observed from the SEM photograph to evaluate the adhesion.
  • the evaluation criteria are as follows. -Evaluation criteria- A: No pattern defect was observed. B: Almost no pattern defect was observed, but only a part of the defect was observed. There was no problem in practical use. C: Remarkably many pattern defects were observed.
  • ⁇ Pattern cross-sectional shape 1 (pattern shape before post-baking)> A pattern was formed by the same procedure as the evaluation of developability.
  • the cross-sectional shape of the obtained pattern was observed with a SEM (Scanning Electron Microscope, magnification: 20000 times), five patterns were extracted from the SEM photograph, and the average inclination of the cross-section of the five patterns was obtained and the following criteria were obtained.
  • the pattern cross-sectional shape 1 was evaluated. Note that the inclination of the cross section of the pattern is the inclination in the thickness direction of the pattern on the silicon wafer at the portion where the pattern is formed. Specifically, the angle of the part constituted by the surface of the silicon wafer and the side in the thickness direction of the pattern was measured.
  • the case where the inclination of the pattern is less than 90 degrees with respect to the surface of the silicon wafer means that the pattern is tapered (forward tapered) from the silicon wafer side toward the surface side of the pattern.
  • C The average inclination of the five patterns is less than 80 degrees with respect to the silicon wafer.
  • ⁇ Pattern cross-sectional shape 2 (pattern shape after post-baking)> A pattern was formed by the same procedure as the evaluation of developability. The obtained pattern was heated (post-baked) at 200 ° C. for 5 minutes using a hot plate. The pattern cross-sectional shape 2 was evaluated in the same procedure as the pattern cross-sectional shape 1 for the post-baked pattern.
  • the photosensitive compositions of the examples had higher sensitivity than the photosensitive compositions of the comparative examples. Furthermore, there was little coloring after post-baking, and a pattern with good rectangularity could be formed.
  • Red composition 1 Preparation of composition for color filter> (Red composition 1) The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 ⁇ m to prepare Red composition 1.
  • Red pigment dispersion 51.7 parts by mass 40 mass% PGMEA solution of resin 1 0.6 mass parts
  • Green composition 1 The raw materials shown below were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare Green composition 1.
  • Green pigment dispersion 73.7 parts by mass 40 mass% PGMEA solution of Resin 1 0.3 parts by mass Polymerizable compound 2 1.2 mass parts
  • Photopolymerization initiator compound OX-1
  • Surfactant 1 0.2% by mass PGMEA solution ...
  • UV absorber 1 0.5 mass parts PGMEA ... 19.5 parts by mass
  • Blue composition 1 The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 ⁇ m to prepare Blue composition 1.
  • Blue pigment dispersion ... 44.9 parts by mass 40 mass% PGMEA solution of resin 1 2.1 parts by mass Polymerizable compound 1 ... 1.5 parts by mass Polymerizable compound 3 ... 0.7 parts by mass Photopolymerization initiator (compound OX-1) ... 0.8 parts by mass Surfactant 1 0.2% by mass PGMEA solution ... 4.2 parts by mass PGMEA ... 45.8 parts by mass
  • the raw materials used for the color filter composition are as follows. Red pigment dispersion C. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment A mixed solution composed of 4.3 parts by weight of Yellow 139, 6.8 parts by weight of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by weight of PGMEA was added to a bead mill (zirconia beads 0.3 mm). And mixed and dispersed for 3 hours.
  • the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.
  • Green pigment dispersion C I. 6.4 parts by mass of Pigment Green 36; I. Pigment Yellow 150, 5.3 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA were mixed with a bead mill (zirconia beads 0. 3 mm diameter) and mixed and dispersed for 3 hours. After that, the high-pressure disperser NANO-3000-10 with a decompression mechanism (Nippon BEE) The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.
  • Blue pigment dispersion C I. 9.7 parts by mass of Pigment Blue 15: 6; I. A mixture of 2.4 parts by weight of Pigment Violet 23, 5.5 parts by weight of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 82.4 parts by weight of PGMEA was added to a bead mill (Zirconia beads 0. 3 mm diameter) and mixed and dispersed for 3 hours. After that, the high-pressure disperser NANO-3000-10 with a decompression mechanism (Nippon BEE) The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 . This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.
  • Polymerizable compound 1 Compound having the following structure
  • Polymerizable compound 2 polymerizable compound D5 described above
  • Polymerizable compound 3 the above-described polymerizable compound D3
  • Resin 1 Resin E1 described above
  • Surfactant 1 Surfactant F1 described above
  • UV absorber 1 UV absorber UV1 described above
  • Green composition 1 was applied by spin coating so that the film thickness after post-baking was 1.0 ⁇ m. Subsequently, it heated (prebaked) for 2 minutes at 100 degreeC using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a 1.0 ⁇ m square Bayer pattern at an exposure amount of 400 mJ / cm 2 . Then tetramethylammonium hydroxide (TMAH) Using a 0.3 mass% aqueous solution, paddle development was performed at 23 ° C for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water.
  • TMAH tetramethylammonium hydroxide

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Abstract

Provided are a photosensitive composition having an excellent sensitivity, a cured film, a method for manufacturing a color filter, a color filter, a solid-state imaging element, and an image display device. The photosensitive composition contains: a cyclic oxime compound having an electron withdrawing group in which the value of the Taft σ* constant is at least 3.5, and a cyclic oxime site having a cyclic structure formed so as to include an oxime group; and a polymerizable compound.

Description

感光性組成物、硬化膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置Photosensitive composition, cured film, method for producing color filter, color filter, solid-state imaging device, and image display device

　本発明は、感光性組成物に関する。より詳しくは、環状オキシム化合物と重合性化合物とを含む感光性組成物に関する。また、本発明は、前述の感光性組成物を用いて得られる硬化膜に関する。また、本発明は、前述の感光性組成物を用いたカラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置に関する。
The present invention relates to a photosensitive composition. More specifically, the present invention relates to a photosensitive composition containing a cyclic oxime compound and a polymerizable compound. Moreover, this invention relates to the cured film obtained using the above-mentioned photosensitive composition. The present invention also relates to a method for producing a color filter using the above-described photosensitive composition, a color filter, a solid-state imaging device, and an image display device.

　重合性化合物と光重合開始剤とを含む感光性組成物を用いて、カラーフィルタなどに用いられる硬化膜を形成することが行なわれている。光重合開始剤としては、例えば、特許文献１～３に記載のオキシム化合物が知られている。
A cured film used for a color filter or the like is formed using a photosensitive composition containing a polymerizable compound and a photopolymerization initiator. As photopolymerization initiators, for example, oxime compounds described in Patent Documents 1 to 3 are known.

国際公開ＷＯ２００８／０７８６７８号公報International Publication WO2008 / 078678 特開２０１０－３２９８５号公報JP 2010-32985 A 国際公開ＷＯ２００２／１００９０３号公報International Publication WO2002 / 100903

　感光性組成物に求められる特性の一つとして、露光時に高感度であることが挙げられる。近年において、感光性組成物の感度についてのさらなる向上が望まれている。
One of the characteristics required for the photosensitive composition is high sensitivity during exposure. In recent years, further improvement in the sensitivity of the photosensitive composition has been desired.

　よって、本発明の目的は、感度に優れた感光性組成物、硬化膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置を提供することにある。
Therefore, the objective of this invention is providing the photosensitive composition excellent in the sensitivity, a cured film, the manufacturing method of a color filter, a color filter, a solid-state image sensor, and an image display apparatus.

　本発明者の検討によれば、光重合開始剤として、後述する所定の環状オキシム化合物を用いることにより上記の目的を達成できることを見出し、本発明を完成するに至った。本発明は以下を提供する。

　＜１＞　オキシム基を含んで形成される環状構造の環状オキシム部位、および、Ｔａｆｔのσ*定数の値が３．５以上の電子求引性基をそれぞれ有する環状オキシム化合物と、重合性化合物と、を含む感光性組成物。

　＜２＞　環状オキシム化合物は、Ｔａｆｔのσ*定数の値が４以上の電子求引性基を有する、＜１＞に記載の感光性組成物。

　＜３＞　電子求引性基が、ニトロ基、アルキルスルホニル基、アリールスルホニル基およびオニウム基から選ばれる少なくとも１つである、＜１＞または＜２＞に記載の感光性組成物。

　＜４＞　環状オキシム化合物が有する環状オキシム部位は、下記式（ａ－１）で表される、＜１＞～＜３＞のいずれかに記載の感光性組成物；

Figure JPOXMLDOC01-appb-C000005
　式中、Ｒ1は置換基を表し、Ａは、オキシム基を含んで形成される環を表し、ｎは０または１を表す。

　＜５＞　環状オキシム化合物は、環状オキシム部位に、芳香族炭化水素環および複素環から選ばれる少なくとも１つの環が結合した構造を有する、＜１＞～＜４＞のいずれかに記載の感光性組成物。

　＜６＞　環状オキシム化合物は、環状オキシム部位に、カルバゾール環またはジベンゾチオフェン環を含む縮合環が結合した構造を有する、＜１＞～＜５＞のいずれかに記載の感光性組成物。

　＜７＞　環状オキシム化合物は、下記式（１）で表わされる化合物である、＜１＞～＜６＞のいずれかに記載の感光性組成物；

Figure JPOXMLDOC01-appb-C000006
　式（１）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2、Ｒ3、またはＢで表される環と結合して環を形成していてもよく、Ｒ1～Ｒ3はそれぞれ独立して置換基を表し、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｂは芳香族炭化水素環および複素環から選ばれる少なくとも１つを含む環を表し、Ｚ1はＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、ｎは０または１を表し、ｍは０または１を表し、ｑは１以上の整数を表し、ｏ、ｐはそれぞれ独立して０以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏが２以上の場合、ｏ個のＲ3は同一であってもよく、異なっていてもよく、２個のＲ3同士が結合して環を形成していてもよく、ｑが２以上の場合、ｑ個のＺ1は同一であってもよく、異なっていてもよい。

　＜８＞　環状オキシム化合物は、下記式（２）で表わされる化合物である、＜１＞～＜６＞のいずれかに記載の感光性組成物；

Figure JPOXMLDOC01-appb-C000007
　式（２）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2またはＲ3aと結合して環を形成していてもよく、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｒ1、Ｒ2、Ｒ3aおよびＲ3bはそれぞれ独立して置換基を表し、Ｚ1aおよびＺ1bはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、Ｙ1は、－ＣＲY1ＲY2－、－ＮＲY3－または－Ｓ－を表し、ＲY1～ＲY3はそれぞれ独立して水素原子または置換基を表し、ｎは０または１を表し、ｍは０または１を表し、ｏ１、ｏ２、ｐ、ｑ１およびｑ２はそれぞれ独立して０以上の整数を表し、ｑ１およびｑ２の少なくとも一方は１以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏ１が２以上の場合、ｏ１個のＲ3aは同一であってもよく、異なっていてもよく、２個のＲ3a同士が結合して環を形成していてもよく、ｏ２が２以上の場合、ｏ２個のＲ3bは同一であってもよく、異なっていてもよく、２個のＲ3b同士が結合して環を形成していてもよく、ｑ１が２以上の場合、ｑ１個のＺ1aは同一であってもよく、異なっていてもよく、ｑ２が２以上の場合、ｑ２個のＺ1bは同一であってもよく、異なっていてもよい。

　＜９＞　環状オキシム化合物は、下記式（３ａ）または式（３ｂ）で表わされる化合物である、＜１＞～＜６＞のいずれかに記載の感光性組成物；

Figure JPOXMLDOC01-appb-C000008
　式（３ａ）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2またはＲ3cと結合して環を形成していてもよく、Ｙ2は、－ＣＲY21ＲY22－、－ＮＲY23－または－Ｓ－を表し、ＲY21～ＲY23はそれぞれ独立して水素原子または置換基を表す；

　式（３ｂ）中、Ｘ2は、＞ＣＲX10－または＞Ｎ－を表し、Ｒx10は水素原子または置換基を表す；

　式（３ａ）および式（３ｂ）中、Ｒ1、Ｒ2、Ｒ3cおよびＲ3dはそれぞれ独立して置換基を表し、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｚ1cおよびＺ1dはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、ｎは０または１を表し、ｍは０または１を表し、ｏ３、ｏ４、ｐ、ｑ３およびｑ４はそれぞれ独立して０以上の整数を表し、ｑ３およびｑ４の少なくとも一方は１以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏ３が２以上の場合、ｏ３個のＲ3cは同一であってもよく、異なっていてもよく、２個のＲ3c同士が結合して環を形成していてもよく、ｏ４が２以上の場合、ｏ４個のＲ3dは同一であってもよく、異なっていてもよく、２個のＲ3d同士が結合して環を形成していてもよく、ｑ３が２以上の場合、ｑ３個のＺ1cは同一であってもよく、異なっていてもよく、ｑ４が２以上の場合、ｑ４個のＺ1dは同一であってもよく、異なっていてもよい。

　＜１０＞　更に、樹脂を含有する、＜１＞～＜９＞のいずれかに記載の感光性組成物。

　＜１１＞　更に、色材を含有する、＜１＞～＜１０＞のいずれかに記載の感光性組成物。

　＜１２＞　色材が顔料を含む、＜１１＞に記載の感光性組成物。

　＜１３＞　色材が有彩色着色剤、白色着色剤、黒色着色剤および近赤外線吸収色素から選ばれる少なくとも１つを含む、＜１１＞又は＜１２＞に記載の感光性組成物。

　＜１４＞　カラーフィルタの画素形成用の組成物である、＜１＞～＜１３＞のいずれかに記載の感光性組成物。

　＜１５＞　＜１＞～＜１４＞のいずれかに記載の感光性組成物を用いて得られる硬化膜。

　＜１６＞　支持体上に＜１＞～＜１４＞のいずれかに記載の感光性組成物を適用して感光性組成物層を形成する工程と、感光性組成物層をパターン状に露光する工程と、露光後の感光性組成物層を現像してパターンを形成する工程と、を含む、カラーフィルタの製造方法。

　＜１７＞　＜１５＞に記載の硬化膜を有するカラーフィルタ。

　＜１８＞　＜１５＞に記載の硬化膜を有する固体撮像素子。

　＜１９＞　＜１５＞に記載の硬化膜を有する画像表示装置。
According to the study of the present inventors, it has been found that the above object can be achieved by using a predetermined cyclic oxime compound described later as a photopolymerization initiator, and the present invention has been completed. The present invention provides the following.

<1> a cyclic oxime moiety having a cyclic structure formed including an oxime group, a cyclic oxime compound each having an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, a polymerizable compound, A photosensitive composition comprising:

<2> The photosensitive composition according to <1>, wherein the cyclic oxime compound has an electron-withdrawing group having a Taft σ * constant value of 4 or more.

<3> The photosensitive composition according to <1> or <2>, wherein the electron withdrawing group is at least one selected from a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group.

<4> The photosensitive composition according to any one of <1> to <3>, wherein the cyclic oxime moiety of the cyclic oxime compound is represented by the following formula (a-1):

Figure JPOXMLDOC01-appb-C000005
In the formula, R 1 represents a substituent, A represents a ring formed including an oxime group, and n represents 0 or 1.

<5> The photosensitivity according to any one of <1> to <4>, wherein the cyclic oxime compound has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the cyclic oxime moiety. Composition.

<6> The photosensitive composition according to any one of <1> to <5>, wherein the cyclic oxime compound has a structure in which a condensed ring including a carbazole ring or a dibenzothiophene ring is bonded to the cyclic oxime moiety.

<7> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (1):

Figure JPOXMLDOC01-appb-C000006
In the formula (1), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may be bonded to a ring represented by R 2 , R 3 , or B to form a ring; R 1 to R 3 Each independently represents a substituent, L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent, and B Represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring, Z 1 represents an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, and n is 0 or 1 M represents 0 or 1, q represents an integer of 1 or more, o and p each independently represents an integer of 0 or more, and p is 2 or more , P R 2 may be the same or different, and two R 2 may be bonded to each other to form a ring. When o is 2 or more, o R 2 3 may be the same or different, and two R 3 may be bonded to each other to form a ring. When q is 2 or more, q Z 1 are the same. It may be different.

<8> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (2):

Figure JPOXMLDOC01-appb-C000007
In the formula (2), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3a to form a ring, and L is an alkylene group having 1 to 3 carbon atoms or —CR L 1 = CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent, R 1 , R 2 , R 3a and R 3b each independently represent a substituent, Z 1a and Z 1b independently represents an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, Y 1 represents —CR Y1 R Y2 —, —NR Y3 —, or —S—, R Y1 ~ R Y3 each independently represents a hydrogen atom or a substituent, n represents 0 or 1, m is 0 or 1, o1, o2, p, q1 Preliminary q2 independently represents an integer of 0 or more, at least one of q1 and q2 is an integer of 1 or more, when p is 2 or more, p number of R 2 may be the same, or different Two R 2 may be bonded to each other to form a ring. When o1 is 2 or more, o1 R 3a may be the same or different, and 2 R 3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R 3b may be the same or different, and two R 3b may be May be bonded to form a ring, and when q1 is 2 or more, q1 Z 1a may be the same or different, and when q2 is 2 or more, q2 Z 1a 1b may be the same or different.

<9> The photosensitive composition according to any one of <1> to <6>, wherein the cyclic oxime compound is a compound represented by the following formula (3a) or formula (3b);

Figure JPOXMLDOC01-appb-C000008
In the formula (3a), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3c to form a ring, and Y 2 represents —CR Y21 R Y22 —, —NR Y23— or —S—, wherein R Y21 to R Y23 each independently represents a hydrogen atom or a substituent;

In the formula (3b), X 2 represents> CR X10 -or> N-, and R x10 represents a hydrogen atom or a substituent;

In the formulas (3a) and (3b), R 1 , R 2 , R 3c and R 3d each independently represent a substituent, and L is an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 — R L1 and R L2 each independently represent a hydrogen atom or a substituent, and Z 1c and Z 1d each independently represents an electron withdrawing group having a Taft σ * constant value of 3.5 or more. N represents 0 or 1, m represents 0 or 1, o3, o4, p, q3 and q4 each independently represents an integer of 0 or more, and at least one of q3 and q4 is an integer of 1 or more In the case where p is 2 or more, p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring. In the case of 2 or more, the o3 R 3c s may be the same or different, and the two R 3c s May be bonded to form a ring, and when o4 is 2 or more, o4 R 3d may be the same or different, and two R 3d may be bonded to each other to form a ring. When q3 is 2 or more, q3 Z 1c may be the same or different, and when q4 is 2 or more, q4 Z 1d is the same It may be different.

<10> The photosensitive composition according to any one of <1> to <9>, further comprising a resin.

<11> The photosensitive composition according to any one of <1> to <10>, further containing a coloring material.

<12> The photosensitive composition according to <11>, wherein the color material contains a pigment.

<13> The photosensitive composition according to <11> or <12>, wherein the color material includes at least one selected from a chromatic colorant, a white colorant, a black colorant, and a near-infrared absorbing dye.

<14> The photosensitive composition according to any one of <1> to <13>, which is a composition for forming a pixel of a color filter.

<15> A cured film obtained using the photosensitive composition according to any one of <1> to <14>.

<16> A step of forming a photosensitive composition layer by applying the photosensitive composition according to any one of <1> to <14> on a support, and exposing the photosensitive composition layer in a pattern The manufacturing method of a color filter including the process and the process of developing the photosensitive composition layer after exposure, and forming a pattern.

<17> A color filter having the cured film according to <15>.

<18> A solid-state imaging device having the cured film according to <15>.

<19> An image display device having the cured film according to <15>.

　本発明によれば、感度に優れた感光性組成物、硬化膜、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子および画像表示装置を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition excellent in the sensitivity, a cured film, the manufacturing method of a color filter, a color filter, a solid-state image sensor, and an image display apparatus can be provided.

　以下において、本発明の内容について詳細に説明する。

　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。

　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。

　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。

　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。

　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。

　本明細書において、近赤外線とは、波長７００～２５００ｎｍの光をいう。

　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。

　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
Hereinafter, the contents of the present invention will be described in detail.

In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes group (atomic group) which has a substituent with the group (atomic group) which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, a weight average molecular weight and a number average molecular weight are the polystyrene conversion values measured by GPC (gel permeation chromatography) method.

In the present specification, near infrared light refers to light having a wavelength of 700 to 2500 nm.

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

＜感光性組成物＞

　本発明の感光性組成物は、オキシム基を含んで形成される環状構造の環状オキシム部位、および、Ｔａｆｔのσ*定数の値が３．５以上の電子求引性基を有する環状オキシム化合物と、重合性化合物と、を含むことを特徴とする。
<Photosensitive composition>

The photosensitive composition of the present invention comprises a cyclic oxime compound having a cyclic oxime moiety formed containing an oxime group, and an electron-withdrawing group having a Taft σ * constant value of 3.5 or more; And a polymerizable compound.

　本発明の感光性組成物は、露光時における感度に優れている。このような効果が得られる理由については、以下によるものであると推測される。

　本発明の感光性組成物に含まれる環状オキシム化合物は、オキシム基を含んで形成される環状構造の環状オキシム部位を有している。すなわち、この環状オキシム化合物は、オキシム基が環構造に組み込まれた構造を有している。オキシム基が環構造に組み込まれていることにより、オキシム基周りの構造が剛直化し、それによって環状オキシム化合物の吸収スペクトルがシャープになり、吸光度をより高めることができたと推測される。また、環状オキシム化合物がこのような環状オキシム部位を含むことにより、オキシム化合物の励起状態の失活パスを抑制することもできると推測され、光照射による分解効率を高めることができると推測される。また、この環状オキシム化合物は、上述した環状オキシム部位のほかに、更にＴａｆｔのσ*定数の値が３．５以上の電子求引性基を有することにより、環状オキシム化合物の極大吸収波長をより長波長側にシフトさせて、露光時に光源から照射される光の波長にマッチングさせやすくなったものと推測される。このため、この環状オキシム化合物は、露光時にラジカルを効率よく発生させることができると推測される。

　また、環状オキシム化合物が上述した所定の電子求引性基を有することにより、膜中において、環状オキシム化合物と重合性化合物などの成分とが相互作用しやすくなると推測され、環状オキシム化合物が重合性化合物などの成分のより近傍に存在して、これらの成分のより近傍でラジカルを発生させることができると推測される。

　このため、本発明の感光性組成物に光を照射して露光することで、環状オキシム化合物を効率よく分解してラジカルを発生させ、更には、重合性化合物などの成分の近傍でラジカルを効率よく発生させることができると推測され、その結果、優れた感度を得ることができたと推測される。
The photosensitive composition of this invention is excellent in the sensitivity at the time of exposure. The reason why such an effect is obtained is presumed to be as follows.

The cyclic oxime compound contained in the photosensitive composition of the present invention has a cyclic oxime moiety having a cyclic structure formed by containing an oxime group. That is, this cyclic oxime compound has a structure in which an oxime group is incorporated into a ring structure. By incorporating the oxime group into the ring structure, it is presumed that the structure around the oxime group became rigid, thereby sharpening the absorption spectrum of the cyclic oxime compound and increasing the absorbance. Further, it is presumed that the cyclic oxime compound contains such a cyclic oxime moiety, so that it is possible to suppress the deactivation path in the excited state of the oxime compound, and it is presumed that the decomposition efficiency by light irradiation can be increased. . In addition to the above-mentioned cyclic oxime moiety, this cyclic oxime compound further has an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, thereby increasing the maximum absorption wavelength of the cyclic oxime compound. It is presumed that shifting to the long wavelength side facilitates matching with the wavelength of light emitted from the light source during exposure. For this reason, it is estimated that this cyclic oxime compound can generate a radical efficiently at the time of exposure.

In addition, it is presumed that the cyclic oxime compound has the above-described predetermined electron-withdrawing group, so that the cyclic oxime compound and a component such as a polymerizable compound easily interact in the film, and the cyclic oxime compound is polymerizable. It is presumed that radicals can be generated in the vicinity of components such as compounds and in the vicinity of these components.

Therefore, by exposing the photosensitive composition of the present invention to light, the cyclic oxime compound is efficiently decomposed to generate radicals, and further, radicals are efficiently produced in the vicinity of components such as polymerizable compounds. It is presumed that it can be generated well, and as a result, it is presumed that excellent sensitivity could be obtained.

　また、本発明の感光性組成物によれば、得られる硬化膜の硬化性をより高めることもでき、例えば、耐溶剤性などの特性に優れた硬化膜を得ることもできる。また、この感光性組成物は、感度に優れるので、密着性、矩形性、直線性などに優れたパターンを形成することもできる。特に、密着性に優れた微細なパターンを形成することもできる。
Moreover, according to the photosensitive composition of this invention, the sclerosis | hardenability of the cured film obtained can also be improved, for example, the cured film excellent in characteristics, such as solvent resistance, can also be obtained. Moreover, since this photosensitive composition is excellent in sensitivity, it is also possible to form a pattern excellent in adhesion, rectangularity, linearity, and the like. In particular, a fine pattern with excellent adhesion can be formed.

　また、本発明の感光性組成物は、優れた感度を有しつつ、保存安定性にも優れる。このような効果が得られる理由としては、オキシム構造が剛直な構造になったことで、オキシム化合物の加水分解などの経時分解を抑制することができたためであると推測される。なお、感光性組成物の感度が高いと、一般的に保存安定性は低下しやすい傾向にあるが、本発明の感光性組成物は、上述した所定の環状オキシム化合物を用いることにより感度と保存安定性を従来よりも高いレベルで両立させることができる。
In addition, the photosensitive composition of the present invention has excellent sensitivity and storage stability. The reason why such an effect can be obtained is presumed that the decomposition of the oxime compound with time, such as hydrolysis, could be suppressed by the rigid structure of the oxime. In addition, when the sensitivity of the photosensitive composition is high, the storage stability generally tends to decrease. However, the photosensitive composition of the present invention is sensitive and preserved by using the above-mentioned predetermined cyclic oxime compound. Stability can be achieved at a higher level than before.

　また、一般的に、感光性組成物中に色材が含まれる場合、感度が低下し易い傾向にあるが、感光性組成物中に、本発明に係る上記の所定の環状オキシム化合物を含有させることにより、感光性組成物が更に色材を含む場合であっても優れた感度を維持できる。なかでも、有彩色着色剤や黒色着色剤などの可視領域に吸収を有する色材を用いた場合、一般的には感度が低下し易い傾向にあるが、このような色材を含む場合であっても優れた感度を維持できるので、本発明の感光性組成物がこれらの色材を含む場合において特に効果的である。例えば、本発明の感光性組成物は、カラーフィルタの画素形成用の組成物や、ブラックマトリックス等の遮光膜形成用の組成物として好ましく用いることができる。
In general, when a colorant is contained in the photosensitive composition, the sensitivity tends to decrease, but the photosensitive composition contains the predetermined cyclic oxime compound according to the present invention. Thus, excellent sensitivity can be maintained even when the photosensitive composition further contains a coloring material. In particular, when a color material having absorption in the visible region such as a chromatic colorant or a black colorant is used, the sensitivity generally tends to decrease, but this is the case when such a color material is included. However, it is particularly effective when the photosensitive composition of the present invention contains these coloring materials. For example, the photosensitive composition of the present invention can be preferably used as a composition for forming a pixel of a color filter or a composition for forming a light shielding film such as a black matrix.

　また、感光性組成物について、光透過性が低い場合、上記と同様の理由により感度が低下し易い傾向にあるが、感光性組成物中に本発明に係る上記の所定の環状オキシム化合物を含有させることにより、光透過性が低い感光性組成物であっても優れた感度を維持できる。

　このような光透過性が低い感光性組成物の一実施形態としては、例えば、感光性組成物を用いて乾燥後の膜厚が２．０μｍの膜を製膜した際に、前述の膜の波長３６５ｎｍの光に対する光学濃度が１．５以上（好ましくは１．８以上、より好ましくは２．１以上）となる分光特性を有する感光性組成物が挙げられる。光学濃度の上限は、特に限定はないが、５．０以下とすることができる。なお、光学濃度（ＯＤ）とは、光の吸収度合を対数で表示した値であって、下記の式で定義される値である。

　ＯＤ（λ）＝Ｌｏｇ10［Ｔ（λ）／Ｉ（λ）］

　λは、波長を表し、Ｔ（λ）は、波長λにおける透過光量を表し、Ｉ（λ）は波長λにおける入射光量を表す。
Further, when the light transmittance of the photosensitive composition is low, the sensitivity tends to decrease for the same reason as described above, but the photosensitive composition contains the predetermined cyclic oxime compound according to the present invention. As a result, excellent sensitivity can be maintained even with a photosensitive composition having low light transmittance.

As one embodiment of such a light-transmitting photosensitive composition, for example, when a film having a thickness of 2.0 μm after drying is formed using the photosensitive composition, Examples thereof include a photosensitive composition having spectral characteristics such that an optical density with respect to light having a wavelength of 365 nm is 1.5 or more (preferably 1.8 or more, more preferably 2.1 or more). The upper limit of the optical density is not particularly limited, but can be 5.0 or less. The optical density (OD) is a value expressed by the logarithm of the degree of light absorption, and is a value defined by the following equation.

OD (λ) = Log 10 [T (λ) / I (λ)]

λ represents a wavelength, T (λ) represents a transmitted light amount at the wavelength λ, and I (λ) represents an incident light amount at the wavelength λ.

　また、光透過性が低い感光性組成物の他の実施形態としては、感光性組成物を用いて乾燥後の膜厚が４．０μｍの膜を製膜した際において、前述の膜の波長３６０～７００ｎｍの範囲の透過率の最大値が４０％未満（好ましくは３０％未満、より好ましくは２０％未満、更に好ましくは１０％未満）である分光特性を有する感光性組成物が挙げられる。
Further, as another embodiment of the photosensitive composition having low light transmittance, when a film having a film thickness after drying of 4.0 μm is formed using the photosensitive composition, the wavelength 360 of the film described above is used. And a photosensitive composition having a spectral characteristic in which the maximum value of transmittance in the range of ˜700 nm is less than 40% (preferably less than 30%, more preferably less than 20%, and still more preferably less than 10%).

　本発明の感光性組成物は、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタ、ブラックマトリクス、遮光膜、屈折率調整膜、平版印刷版原版の感光層、保護フィルム、紫外線硬化性インキ、各種フォトレジスト、各種ディスプレイ材料、コーティング材料、歯科材料、ワニス、粉末コーティング、接着剤、歯科用組成物、ゲルコート、電気部品、磁気記録材料、微小機械部品、導波管、光学スイッチ、メッキ用マスキング、カラー校正システム、ガラス繊維ケーブルコーティング、スクリーン印刷用ステンシル、ステレオリソグラフィーによる三次元物体、ホログラフィック記録用画像記録材料、マイクロエレクトロニクス回路、ヘルスケア材料などに用いることができる。
The photosensitive composition of the present invention includes a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light shielding film, a refractive index adjustment film, a photosensitive layer of a lithographic printing plate precursor, a protective film, an ultraviolet curable ink, various types Photoresists, various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coats, electrical components, magnetic recording materials, micromechanical components, waveguides, optical switches, masking for plating, It can be used in color proofing systems, glass fiber cable coatings, stencils for screen printing, three-dimensional objects by stereolithography, image recording materials for holographic recording, microelectronic circuits, healthcare materials and the like.

　カラーフィルタとしては、特定の波長の光を透過させる着色画素を有するフィルタが挙げられ、赤色画素、青色画素、緑色画素、黄色画素、シアン色画素およびマゼンタ色画素から選ばれる少なくとも１種の着色画素を有するフィルタであることが好ましい。カラーフィルタは、有彩色着色剤を含む感光性組成物を用いて形成することができる。
Examples of the color filter include a filter having a colored pixel that transmits light of a specific wavelength, and at least one colored pixel selected from a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel. It is preferable that the filter has The color filter can be formed using a photosensitive composition containing a chromatic colorant.

　近赤外線カットフィルタとしては、極大吸収波長を波長７００～１８００ｎｍの範囲に有するフィルタが挙げられる。近赤外線カットフィルタは、極大吸収波長を波長７００～１３００ｎｍの範囲に有するフィルタであることが好ましく、波長７００～１０００ｎｍの範囲に有するフィルタであることがより好ましい。また、近赤外線カットフィルタの波長４００～６５０ｎｍの全範囲での透過率は７０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましい。また、波長７００～１８００ｎｍの範囲の少なくとも１点での透過率は２０％以下であることが好ましい。

また、近赤外線カットフィルタの極大吸収波長における吸光度Ａｍａｘと、波長５５０ｎｍにおける吸光度Ａ５５０との比である吸光度Ａｍａｘ／吸光度Ａ５５０は、２０～５００であることが好ましく、５０～５００であることがより好ましく、７０～４５０であることが更に好ましく、１００～４００であることが特に好ましい。近赤外線カットフィルタは、近赤外線吸収色素を含む感光性組成物を用いて形成することができる。
Examples of the near-infrared cut filter include a filter having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm. The near-infrared cut filter is preferably a filter having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and more preferably a filter having a wavelength range of 700 to 1000 nm. Further, the transmittance of the near infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.

The absorbance Amax / absorbance A550, which is the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, more preferably 50 to 500. 70 to 450 is more preferable, and 100 to 400 is particularly preferable. The near-infrared cut filter can be formed using a photosensitive composition containing a near-infrared absorbing dye.

　近赤外線透過フィルタは、近赤外線の少なくとも一部を透過させるフィルタである。近赤外線透過フィルタは、可視光と近赤外線のいずれも透過させるフィルタ（透明膜）であってもよく、可視光の少なくとも一部を遮光し、近赤外線の少なくとも一部を透過させるフィルタであってもよい。近赤外線透過フィルタとしては、波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１３００ｎｍの範囲における透過率の最小値が７０％以上

（好ましくは７５％以上、より好ましくは８０％以上）である分光特性を満たしているフィルタなどが好ましく挙げられる。近赤外線透過フィルタは、以下の（１）～（４）のいずれかの分光特性を満たしているフィルタであることが好ましい。

　（１）：波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長８００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。

　（２）：波長４００～７５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長９００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。

　（３）：波長４００～８３０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。

　（４）：波長４００～９５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
The near-infrared transmission filter is a filter that transmits at least part of the near-infrared ray. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that blocks at least part of visible light and transmits at least part of near-infrared light. Also good. As the near-infrared transmission filter, the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm is Minimum value is 70% or more

A filter that satisfies the spectral characteristics (preferably 75% or more, more preferably 80% or more) is preferable. The near-infrared transmission filter is preferably a filter satisfying any of the following spectral characteristics (1) to (4).

(1): The maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).

(2): The maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).

(3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).

(4): The maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1300 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).

　本発明の感光性組成物を近赤外線透過フィルタ用の組成物として用いる場合、本発明の感光性組成物は、波長４００～６４０ｎｍの範囲における吸光度の最小値Ａｍｉｎと、波長１１００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘとの比であるＡｍｉｎ／Ｂｍａｘが５以上である分光特性を満たしていることが好ましい。Ａｍｉｎ／Ｂｍａｘは、７．５以上であることがより好ましく、１５以上であることが更に好ましく、３０以上であることが特に好ましい。
When the photosensitive composition of the present invention is used as a composition for a near infrared transmission filter, the photosensitive composition of the present invention has a minimum absorbance Amin in a wavelength range of 400 to 640 nm and a wavelength in a range of 1100 to 1300 nm. It is preferable that Amin / Bmax, which is a ratio with the maximum absorbance Bmax, satisfies a spectral characteristic of 5 or more. Amin / Bmax is more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more.

　ある波長λにおける吸光度Ａλは、以下の式（１）により定義される。

Ａλ＝－ｌｏｇ（Ｔλ／１００）　　　・・・（１）

Ａλは、波長λにおける吸光度であり、Ｔλは、波長λにおける透過率（％）である。

　本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、感光性組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように感光性組成物を塗布し、ホットプレートを用いて１００℃、１２０秒間乾燥して調製した膜を用いて測定することが好ましい。
The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).

Aλ = −log (Tλ / 100) (1)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.

In the present invention, the absorbance value may be a value measured in a solution state or may be a value in a film formed using a photosensitive composition. When measuring the absorbance in a film state, the photosensitive composition is applied on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a film prepared by drying at 100 ° C. for 120 seconds.

　本発明の感光性組成物を近赤外線透過フィルタ用の組成物として用いる場合、本発明の感光性組成物は、以下の（１１）～（１４）のいずれかの分光特性を満たしていることがより好ましい。

　（１１）：波長４００～６４０ｎｍの範囲における吸光度の最小値Ａｍｉｎ１と、波長８００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ１との比であるＡｍｉｎ１／Ｂｍａｘ１が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～６４０ｎｍの範囲の光を遮光して、波長７２０ｎｍ以上の光を透過可能な膜を形成することができる。

　（１２）：波長４００～７５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ２と、波長９００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ２との比であるＡｍｉｎ２／Ｂｍａｘ２が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～７５０ｎｍの範囲の光を遮光して、波長８５０ｎｍ以上の光を透過可能な膜を形成することができる。

　（１３）：波長４００～８５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ３と、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ３との比であるＡｍｉｎ３／Ｂｍａｘ３が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～８５０ｎｍの範囲の光を遮光して、波長９４０ｎｍ以上の光を透過可能な膜を形成することができる。

　（１４）：波長４００～９５０ｎｍの範囲における吸光度の最小値Ａｍｉｎ４と、波長１１００～１３００ｎｍの範囲における吸光度の最大値Ｂｍａｘ４との比であるＡｍｉｎ４／Ｂｍａｘ４が５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～９５０ｎｍの範囲の光を遮光して、波長１０４０ｎｍ以上の光を透過可能な膜を形成することができる。
When the photosensitive composition of the present invention is used as a composition for a near-infrared transmission filter, the photosensitive composition of the present invention must satisfy any of the following spectral characteristics (11) to (14). More preferred.

(11): Amin1 / Bmax1 which is a ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm and the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 640 nm and transmitting light having a wavelength of 720 nm or more.

(12): Amin2 / Bmax2, which is a ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm and the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 750 nm and transmitting light having a wavelength of 850 nm or more.

(13): Amin3 / Bmax3, which is a ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm and the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 850 nm and transmitting light having a wavelength of 940 nm or more.

(14): Amin4 / Bmax4, which is a ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm and the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 950 nm and transmitting light having a wavelength of 1040 nm or more.

　本発明の感光性組成物は、感度に優れ、微細なパターンを形成することもできるため、カラーフィルタ用の感光性組成物として好ましく用いることができる。具体的には、カラーフィルタの画素形成用の感光性組成物として好ましく用いることができ、固体撮像素子に用いられるカラーフィルタの画素形成用の感光性組成物としてより好ましく用いることができる。
Since the photosensitive composition of the present invention is excellent in sensitivity and can form a fine pattern, it can be preferably used as a photosensitive composition for a color filter. Specifically, it can be preferably used as a photosensitive composition for forming a pixel of a color filter, and can be more preferably used as a photosensitive composition for forming a pixel of a color filter used in a solid-state imaging device.

　以下、本発明の感光性組成物に用いられる各成分について説明する。
Hereinafter, each component used for the photosensitive composition of this invention is demonstrated.

＜＜環状オキシム化合物Ａ＞＞

　本発明の感光性組成物は、オキシム基を含んで形成される環状構造の環状オキシム部位、および、Ｔａｆｔのσ*定数の値が３．５以上の電子求引性基をそれぞれ有する環状オキシム化合物（以下、この環状オキシム化合物を環状オキシム化合物Ａともいう）を含有する。すなわち、環状オキシム化合物Ａは、同一分子中に、環状オキシム部位と上記電子求引性基をそれぞれ有する化合物である。
<< cyclic oxime compound A >>

The photosensitive composition of the present invention includes a cyclic oxime compound having a cyclic oxime moiety having an oxime group and an electron withdrawing group having a Taft σ * constant value of 3.5 or more. (Hereinafter, this cyclic oxime compound is also referred to as cyclic oxime compound A). That is, the cyclic oxime compound A is a compound having a cyclic oxime moiety and the electron withdrawing group in the same molecule.

　まず、環状オキシム化合物Ａが有するＴａｆｔのσ*定数の値が３．５以上の電子求引性基（以下、電子求引性基Ａともいう）について説明する。
First, an electron-withdrawing group (hereinafter also referred to as electron-withdrawing group A) having a Taft σ * constant value of 3.5 or more in the cyclic oxime compound A will be described.

　環状オキシム化合物Ａが有する上記電子求引性基ＡのＴａｆｔのσ*定数の値は、感光性組成物に含まれる重合性化合物などと相互作用して環状オキシム化合物Ａが重合性化合物により近接し易いという理由から、４以上であることが好ましく、４．２以上が更に好ましい。上限は、化合物の安定性の観点から１０以下であることが好ましい。なお、Ｔａｆｔのσ*定数とは、置換基の極性を表わすパラメーターのことである。本明細書において、Ｔａｆｔのσ*定数の値は、「Ｄ．Ｄ．Ｐｅｒｒｉｎ，Ｂ．Ｄｅｍｐｓｅｔ，Ｅ．Ｐ．Ｓｅｒｊｅａｎｔ，”ｐｋａ　Ｐｒｅｄｉｃｔｉｏｎ　ｆｏｒ　ｏｒｇａｎｉｃ　Ａｃｉｄｓ　Ａｎｄ　Ｂａｓｅｓ”　Ｓｐｒｉｎｇｅｒ　（１９８１）　Ｐ１０９－１２６のTable  A.1」に記載されているσ*の値が用いられる。上記の文献のTable  A.1に記載されていない場合は、Ｊｏｕｒｎａｌ　ｏｆ　ｔｈｅ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ（Ｔａｆｔ，　Ｒ．　Ｗ、　１９５２，　７４，　２７２９）、Ｊｏｕｒｎａｌ　ｏｆ　ｔｈｅ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ（Ｔａｆｔ，　Ｒ．　Ｗ、　１９５２，　７４，　３１２０）またはＪｏｕｒｎａｌ　ｏｆ　ｔｈｅ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ（Ｔａｆｔ，　Ｒ．　Ｗ、　１９５３，　７５，　４５３８）に記載の方法で求めることができる。
The value of Taft σ * constant of the electron-withdrawing group A of the cyclic oxime compound A interacts with the polymerizable compound and the like contained in the photosensitive composition so that the cyclic oxime compound A is closer to the polymerizable compound. For ease of use, it is preferably 4 or more, more preferably 4.2 or more. The upper limit is preferably 10 or less from the viewpoint of the stability of the compound. The Taft σ * constant is a parameter representing the polarity of a substituent. In the present specification, the value of Taft's σ * constant is given in Table A of “DD Perrin, B. Dempset, EP Sergent,“ pka Prediction for Organic Acids and Bases ”Springer (1981) P109-126. The value of σ * described in “.1” is used. If not listed in Table A.1 of the above literature, Journal of the American Chemical Society (Taft, RW, 1952, 74, 2729), Journal of the American Chemical, 52. , 74, 3120) or Journal of the American Chemical Society (Taft, RW, 1953, 75, 4538).

　上記電子求引性基Ａとしては、感光性組成物に含まれる重合性化合物などと環状オキシム化合物Ａとがより相互作用し易いという理由から、ニトロ基、アルキルスルホニル基、アリールスルホニル基およびオニウム基であることが好ましく、ニトロ基、アルキルスルホニル基およびアリールスルホニル基がより好ましく、ニトロ基が特に好ましい。
As the electron withdrawing group A, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group are preferable because the polymerizable compound and the like contained in the photosensitive composition and the cyclic oxime compound A are more likely to interact with each other. Nitro group, alkylsulfonyl group and arylsulfonyl group are more preferable, and nitro group is particularly preferable.

　上記アルキルスルホニル基としては、炭素数１～２０のアルキルスルホニル基が好ましい。具体例としては、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、シクロヘキシルスルホニル基、オクチルスルホニル基、２－エチルヘキシルスルホニル基、デカノイルスルホニル基、ドデカノイルスルホニル基、オクタデカノイルスルホニル基、シアノメチルスルホニル基、メトキシメチルスルホニル基、パーフルオロアルキルスルホニル基等が挙げられる。
The alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoyl group. Examples include a sulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, a methoxymethylsulfonyl group, a perfluoroalkylsulfonyl group, and the like.

　上記アリールスルホニル基としては、炭素数６～３０のアリールスルホニル基が好ましい。具体例としては、フェニルスルホニル基、１－ナフチルスルホニル基、２－ナフチルスルホニル基、２－クロロフェニルスルホニル基、２－メチルフェニルスルホニル基、２－メトキシフェニルスルホニル基、２－ブトキシフェニルスルホニル基、３－クロロフェニルスルホニル基、３－トリフルオロメチルフェニルスルホニル基、３－シアノフェニルスルホニル基、３－ニトロフェニルスルホニル基、４－フルオロフェニルスルホニル基、４－シアノフェニルスルホニル基、４－メトキシフェニルスルホニル基、４－メチルスルファニルフェニルスルホニル基、４－フェニルスルファニルフェニルスルホニル基、４－ジメチルアミノフェニルスルホニル基等が挙げられる。
The arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples include phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3- Chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4- Examples thereof include a methylsulfanylphenylsulfonyl group, a 4-phenylsulfanylphenylsulfonyl group, and a 4-dimethylaminophenylsulfonyl group.

　上記オニウム基としては、アンモニウム基、スルホニウム基、ホスホニウム基などが挙げられ、アンモニウム基であることが好ましい。アンモニウム基としては、－Ｎ+（Ｒｏ1）（Ｒｏ2）（Ｒｏ3）で表される基が挙げられる。Ｒｏ1～Ｒｏ3はそれぞれ独立して、水素原子、アルキル基およびアリール基を表し、アルキル基およびアリール基が好ましく、アルキル基がより好ましい。アルキル基の炭素数は、１～２０が好ましく、１～１０がより好ましく、１～５が更に好ましい。アルキル基は、直鎖、分岐または環状のいずれであってもよいが、直鎖または分岐のアルキル基であることが好ましく、直鎖のアルキル基であることが更に好ましい。
Examples of the onium group include an ammonium group, a sulfonium group, and a phosphonium group, and an ammonium group is preferable. Examples of the ammonium group include a group represented by -N + (Ro 1 ) (Ro 2 ) (Ro 3 ). Ro 1 to Ro 3 each independently represents a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group or an aryl group, and more preferably an alkyl group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

　上記電子求引性基がオニウム基である場合、環状オキシム化合物は、対アニオンを有することが好ましい。対アニオンとしては、ハロゲンイオン（Ｃｌ-、Ｂｒ-、Ｉ-）、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ＰＦ6 -、ＢＦ4 -、ＣｌＯ4 -、トリス（ハロゲノアルキルスルホニル）メチドアニオン（例えば、（ＣＦ3ＳＯ2）3Ｃ-）、ジ（ハロゲノアルキルスルホニル）イミドアニオン（例えば（ＣＦ3ＳＯ2）2Ｎ-）、テトラアリールボレートアニオン、テトラシアノボレートアニオンなどが挙げられる。
When the electron withdrawing group is an onium group, the cyclic oxime compound preferably has a counter anion. Counter anions include halogen ions (Cl − , Br − , I − ), sulfonate anions, carboxylate anions, sulfonylimide anions, PF 6 − , BF 4 − , ClO 4 − , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF 3 SO 2 ) 3 C − ), di (halogenoalkylsulfonyl) imide anion (for example (CF 3 SO 2 ) 2 N − ), tetraaryl borate anion, tetracyanoborate anion and the like can be mentioned.

　環状オキシム化合物Ａは、上記電子求引性基Ａを１個のみ有していてもよく、２個以上（好ましくは、２～５個、より好ましくは２～３個）有していてもよい。上記電子求引性基Ａを１個のみ有する場合は、溶剤溶解性をより高め易い。また、上記電子求引性基Ａを２個以上有する場合は、ラジカル発生効率をより高め易い。上記電子求引性基Ａを２個以上有する場合、複数個の電子求引性基Ａは同一であってもよく、異なっていてもよい。合成の簡便さの観点から複数個の電子求引性基Ａは同一であることが好ましい。
The cyclic oxime compound A may have only one electron withdrawing group A, or may have two or more (preferably 2 to 5, more preferably 2 to 3). . When it has only one electron withdrawing group A, it is easy to improve solvent solubility. Moreover, when it has two or more said electron withdrawing groups A, it is easy to raise radical generating efficiency more. When two or more electron withdrawing groups A are present, the plurality of electron withdrawing groups A may be the same or different. From the viewpoint of ease of synthesis, the plurality of electron withdrawing groups A are preferably the same.

　次に、環状オキシム化合物Ａが有する環状オキシム部位について説明する。

　環状オキシム化合物Ａは、オキシム基を含んで形成される環状構造の環状オキシム部位を含む。より具体的には、環状オキシム化合物Ａは、オキシム基の窒素原子に直結している炭素原子を含んで形成される環状構造の環状オキシム部位を含む。すなわち、環状オキシム化合物Ａは、オキシム基が環構造に組み込まれた構造を有している。
Next, the cyclic oxime moiety of the cyclic oxime compound A will be described.

The cyclic oxime compound A includes a cyclic oxime moiety having a cyclic structure formed including an oxime group. More specifically, the cyclic oxime compound A includes a cyclic oxime moiety having a cyclic structure formed by including a carbon atom directly connected to a nitrogen atom of the oxime group. That is, the cyclic oxime compound A has a structure in which an oxime group is incorporated into a ring structure.

　環状オキシム部位は、５～８員環の環状構造であることが好ましく、５～７員環の環状構造であることがより好ましく、化合物の安定性という理由から５または６員環の環状構造であることが更に好ましい。また、環状オキシム部位は、環を構成する原子としてヘテロ原子を含んでいてよい。ヘテロ原子としては、酸素原子、窒素原子および硫黄原子が挙げられる。
The cyclic oxime moiety is preferably a 5- to 8-membered cyclic structure, more preferably a 5- to 7-membered cyclic structure, and a 5- or 6-membered cyclic structure for reasons of stability of the compound. More preferably it is. The cyclic oxime moiety may include a hetero atom as an atom constituting the ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

　環状オキシム部位はオキシム基の炭素原子に直結したカルボニル基を有し、このオキシム基とカルボニル基とが環構造に組み込まれていてもよい。このような環構造としては、後述の式（ａ－１）において、ｎが１である構造が挙げられる。この態様によれば、より優れた光ブリーチ性が得られ易い。また、環状オキシム部位が上述のカルボニル基を含まない場合（すなわち、後述の式（ａ－１）において、ｎが０である場合）においては、より高感度化が期待できる。
The cyclic oxime moiety has a carbonyl group directly connected to the carbon atom of the oxime group, and the oxime group and the carbonyl group may be incorporated into the ring structure. Examples of such a ring structure include a structure in which n is 1 in formula (a-1) described later. According to this aspect, more excellent optical bleaching properties are easily obtained. Further, when the cyclic oxime moiety does not contain the above-mentioned carbonyl group (that is, when n is 0 in formula (a-1) described later), higher sensitivity can be expected.

　環状オキシム部位はオキシム基を２個以上含んでいてもよい。環状オキシム部位がオキシム基を２個以上含む場合においては、ラジカル発生効率をより高め易い。また、環状オキシム部位がオキシム基を１個のみ含む場合においては、溶剤溶解性をより高め易い。
The cyclic oxime moiety may contain two or more oxime groups. In the case where the cyclic oxime moiety contains two or more oxime groups, it is easier to increase the radical generation efficiency. Further, when the cyclic oxime moiety contains only one oxime group, it is easier to improve the solvent solubility.

　上記環状オキシム部位は、下記式（ａ－１）で表される構造であることが好ましい。

Figure JPOXMLDOC01-appb-C000009
The cyclic oxime moiety preferably has a structure represented by the following formula (a-1).

Figure JPOXMLDOC01-appb-C000009

　式（ａ－１）中、Ａは、オキシム基を含んで形成される環を表す。Ａが表す環は、５～８員環が好ましく、５～７員環がより好ましく、化合物の安定性の観点から５または６員環であることが更に好ましい。Ａが表す環は、環を構成する原子としてヘテロ原子を含んでいてよい。ヘテロ原子としては、酸素原子、窒素原子および硫黄原子が挙げられる。Ａが表す環は、オキシム基を２個以上含んでいてもよい。
In formula (a-1), A represents a ring formed including an oxime group. The ring represented by A is preferably a 5- to 8-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring from the viewpoint of the stability of the compound. The ring represented by A may contain a hetero atom as an atom constituting the ring. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. The ring represented by A may contain two or more oxime groups.

　式（ａ－１）中、ｎは０または１を表す。高感度化の観点からはｎは０であることが好ましい。また、光ブリーチ性の観点からはｎは１であることが好ましい。
In the formula (a-1), n represents 0 or 1. From the viewpoint of increasing sensitivity, n is preferably 0. Further, n is preferably 1 from the viewpoint of optical bleaching property.

　式（ａ－１）中、Ｒ1は置換基を表す。Ｒ1が表す置換基としては、アルキル基、アリール基、アルケニル基、アルキニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスフィノイル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基、ジアルキルアミノカルボニル基、ジアルキルアミノチオカルボニル基等が挙げられる。これらの基は更に置換基を有していてもよい。さらなる置換基としては、ハロゲン基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ヒドロキシ基、カルボキシル基、ホルミル基、メルカプト基、スルホ基、アミノ基、シアノ基等が挙げられる。
In formula (a-1), R 1 represents a substituent. Examples of the substituent represented by R 1 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and phosphinoyl. Group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. These groups may further have a substituent. Additional substituents include halogen groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, acyloxy groups, acyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylamino groups, dialkylamino groups, arylamino groups. Group, hydroxy group, carboxyl group, formyl group, mercapto group, sulfo group, amino group, cyano group and the like.

　置換基を有してもよいアルキル基としては、炭素数１～３０のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、オクタデシル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、１－エチルペンチル基、シクロペンチル基、シクロヘキシル基、トリフルオロメチル基、２－エチルヘキシル基、フェナシル基、１－ナフトイルメチル基、２－ナフトイルメチル基、４－メチルスルファニルフェナシル基、４－フェニルスルファニルフェナシル基、４－ジメチルアミノフェナシル基、４－シアノフェナシル基、４－メチルフェナシル基、２－メチルフェナシル基、３－フルオロフェナシル基、３－トリフルオロメチルフェナシル基、３－ニトロフェナシル基等が挙げられる。
As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

　置換基を有してもよいアリール基としては、炭素数６～３０のアリール基が好ましく、例えば、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基、９－アンスリル基、９－フェナントリル基、１－ピレニル基、５－ナフタセニル基、１－インデニル基、２－アズレニル基、９－フルオレニル基、ターフェニル基、クオーターフェニル基、ｏ－、ｍ－、及びｐ－トリル基、キシリル基、ｏ－、ｍ－、及びｐ－クメニル基、メシチル基、ペンタレニル基、ビナフタレニル基、ターナフタレニル基、クオーターナフタレニル基、ヘプタレニル基、ビフェニレニル基、インダセニル基、フルオランテニル基、アセナフチレニル基、アセアントリレニル基、フェナレニル基、フルオレニル基、アントリル基、ビアントラセニル基、ターアントラセニル基、クオーターアントラセニル基、アントラキノリル基、フェナントリル基、トリフェニレニル基、ピレニル基、クリセニル基、ナフタセニル基、プレイアデニル基、ピセニル基、ペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基、トリナフチレニル基、ヘプタフェニル基、ヘプタセニル基、ピラントレニル基、オバレニル基、トルイル基等が挙げられる。
The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, or a 9-phenanthryl group. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, an overalenyl group, and a toluyl group.

　置換基を有してもよいアルケニル基としては、炭素数２～１０のアルケニル基が好ましく、例えば、ビニル基、アリル基、スチリル基等が挙げられる。
The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

　置換基を有してもよいアルキニル基としては、炭素数２～１０のアルキニル基が好ましく、例えば、エチニル基、プロピニル基、プロパルギル基等が挙げられる。
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

　置換基を有してもよいアルキルスルフィニル基としては、炭素数１～２０のアルキルスルフィニル基が好ましく、例えば、メチルスルフィニル基、エチルスルフィニル基、プロピルスルフィニル基、イソプロピルスルフィニル基、ブチルスルフィニル基、ヘキシルスルフィニル基、シクロヘキシルスルフィニル基、オクチルスルフィニル基、２－エチルヘキシルスルフィニル基、デカノイルスルフィニル基、ドデカノイルスルフィニル基、オクタデカノイルスルフィニル基、シアノメチルスルフィニル基、メトキシメチルスルフィニル基等が挙げられる。
The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

　置換基を有してもよいアリールスルフィニル基としては、炭素数６～３０のアリールスルフィニル基が好ましく、例えば、フェニルスルフィニル基、１－ナフチルスルフィニル基、２－ナフチルスルフィニル基、２－クロロフェニルスルフィニル基、２－メチルフェニルスルフィニル基、２－メトキシフェニルスルフィニル基、２－ブトキシフェニルスルフィニル基、３－クロロフェニルスルフィニル基、３－トリフルオロメチルフェニルスルフィニル基、３－シアノフェニルスルフィニル基、３－ニトロフェニルスルフィニル基、４－フルオロフェニルスルフィニル基、４－シアノフェニルスルフィニル基、４－メトキシフェニルスルフィニル基、４－メチルスルファニルフェニルスルフィニル基、４－フェニルスルファニルフェニルスルフィニル基、４－ジメチルアミノフェニルスルフィニル基等が挙げられる。
The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms. For example, a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

　置換基を有してもよいアルキルスルホニル基としては、炭素数１～２０のアルキルスルホニル基が好ましく、例えば、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、シクロヘキシルスルホニル基、オクチルスルホニル基、２－エチルヘキシルスルホニル基、デカノイルスルホニル基、ドデカノイルスルホニル基、オクタデカノイルスルホニル基、シアノメチルスルホニル基、メトキシメチルスルホニル基、パーフルオロアルキルスルホニル基等が挙げられる。
The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. It is done.

　置換基を有してもよいアリールスルホニル基としては、炭素数６～３０のアリールスルホニル基が好ましく、例えば、フェニルスルホニル基、１－ナフチルスルホニル基、２－ナフチルスルホニル基、２－クロロフェニルスルホニル基、２－メチルフェニルスルホニル基、２－メトキシフェニルスルホニル基、２－ブトキシフェニルスルホニル基、３－クロロフェニルスルホニル基、３－トリフルオロメチルフェニルスルホニル基、３－シアノフェニルスルホニル基、３－ニトロフェニルスルホニル基、４－フルオロフェニルスルホニル基、４－シアノフェニルスルホニル基、４－メトキシフェニルスルホニル基、４－メチルスルファニルフェニルスルホニル基、４－フェニルスルファニルフェニルスルホニル基、４－ジメチルアミノフェニルスルホニル基等が挙げられる。
The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

　置換基を有してもよいアシル基としては、炭素数２～２０のアシル基が好ましく、例えば、アセチル基、プロパノイル基、ブタノイル基、トリフルオロメチルカルボニル基、ペンタノイル基、ベンゾイル基、１－ナフトイル基、２－ナフトイル基、４－メチルスルファニルベンゾイル基、４－フェニルスルファニルベンゾイル基、４－ジメチルアミノベンゾイル基、４－ジエチルアミノベンゾイル基、２－クロロベンゾイル基、２－メチルベンゾイル基、２－メトキシベンゾイル基、２－ブトキシベンゾイル基、３－クロロベンゾイル基、３－トリフルオロメチルベンゾイル基、３－シアノベンゾイル基、３－ニトロベンゾイル基、４－フルオロベンゾイル基、４－シアノベンゾイル基、４－メトキシベンゾイル基、プロピオニル基等が挙げられる。
The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups, propionyl groups, etc. It is.

　置換基を有してもよいアルコキシカルボニル基としては、炭素数２～２０のアルコキシカルボニル基が好ましく、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、ヘキシルオキシカルボニル基、オクチルオキシカルボニル基、デシルオキシカルボニル基、オクタデシルオキシカルボニル基、トリフルオロメチルオキシカルボニル基等が挙げられる。
The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyl group. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

　置換基を有してもよいアリールオキシカルボニル基としては、フェノキシカルボニル基、１－ナフチルオキシカルボニル基、２－ナフチルオキシカルボニル基、４－メチルスルファニルフェニルオキシカルボニル基、４－フェニルスルファニルフェニルオキシカルボニル基、４－ジメチルアミノフェニルオキシカルボニル基、４－ジエチルアミノフェニルオキシカルボニル基、２－クロロフェニルオキシカルボニル基、２－メチルフェニルオキシカルボニル基、２－メトキシフェニルオキシカルボニル基、２－ブトキシフェニルオキシカルボニル基、３－クロロフェニルオキシカルボニル基、３－トリフルオロメチルフェニルオキシカルボニル基、３－シアノフェニルオキシカルボニル基、３－ニトロフェニルオキシカルボニル基、４－フルオロフェニルオキシカルボニル基、４－シアノフェニルオキシカルボニル基、４－メトキシフェニルオキシカルボニル基等が挙げられる。
The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

　置換基を有してもよいホスフィノイル基としては、総炭素数２～５０のホスフィノイル基が好ましく、例えば、ジメチルホスフィノイル基、ジエチルホスフィノイル基、ジプロピルホスフィノイル基、ジフェニルホスフィノイル基、ジメトキシホスフィノイル基、ジエトキシホスフィノイル基、ジベンゾイルホスフィノイル基、ビス（２，４，６－トリメチルフェニル）ホスフィノイル基等が挙げられる。
The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

　置換基を有してもよい複素環基としては、窒素原子、酸素原子、硫黄原子、リン原子を含む、芳香族或いは脂肪族の複素環基が好ましい。例えば、チエニル基、ベンゾ［ｂ］チエニル基、ナフト［２，３－ｂ］チエニル基、チアントレニル基、フリル基、ピラニル基、イソベンゾフラニル基、クロメニル基、キサンテニル基、フェノキサチイニル基、２Ｈ－ピロリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリジニル基、イソインドリル基、３Ｈ－インドリル基、インドリル基、１Ｈ－インダゾリル基、プリニル基、４Ｈ－キノリジニル基、イソキノリル基、キノリル基、フタラジニル基、ナフチリジニル基、キノキサニリル基、キナゾリニル基、シンノリニル基、プテリジニル基、４ａＨ－カルバゾリル基、カルバゾリル基、β－カルボリニル基、フェナントリジニル基、アクリジニル基、ペリミジニル基、フェナントロリニル基、フェナジニル基、フェナルサジニル基、イソチアゾリル基、フェノチアジニル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、イソクロマニル基、クロマニル基、ピロリジニル基、ピロリニル基、イミダゾリジニル基、イミダゾリニル基、ピラゾリジニル基、ピラゾリニル基、ピペリジル基、ピペラジニル基、インドリニル基、イソインドリニル基、キヌクリジニル基、モルホリニル基、チオキサントニル基等が挙げられる。
The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthonyl group and the like.

　置換基を有してもよいアルキルチオカルボニル基としては、例えば、メチルチオカルボニル基、プロピルチオカルボニル基、ブチルチオカルボニル基、ヘキシルチオカルボニル基、オクチルチオカルボニル基、デシルチオカルボニル基、オクタデシルチオカルボニル基、トリフルオロメチルチオカルボニル基等が挙げられる。
Examples of the alkylthiocarbonyl group which may have a substituent include, for example, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

　置換基を有してもよいアリールチオカルボニル基としては、１－ナフチルチオカルボニル基、２－ナフチルチオカルボニル基、４－メチルスルファニルフェニルチオカルボニル基、４－フェニルスルファニルフェニルチオカルボニル基、４－ジメチルアミノフェニルチオカルボニル基、４－ジエチルアミノフェニルチオカルボニル基、２－クロロフェニルチオカルボニル基、２－メチルフェニルチオカルボニル基、２－メトキシフェニルチオカルボニル基、２－ブトキシフェニルチオカルボニル基、３－クロロフェニルチオカルボニル基、３－トリフルオロメチルフェニルチオカルボニル基、３－シアノフェニルチオカルボニル基、３－ニトロフェニルチオカルボニル基、４－フルオロフェニルチオカルボニル基、４－シアノフェニルチオカルボニル基、４－メトキシフェニルチオカルボニル基等が挙げられる。
The arylthiocarbonyl group which may have a substituent includes 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

　置換基を有してもよいジアルキルアミノカルボニル基としては、ジメチルアミノカルボニル基、ジメエルアミノカルボニル基、ジプロピルアミノカルボニル基、ジブチルアミノカルボニル基等が挙げられる。
Examples of the dialkylaminocarbonyl group which may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

　置換基を有してもよいジアルキルアミノチオカルボニル基としては、ジメチルアミノチオカルボニル基、ジプロピルアミノチオカルボニル基、ジブチルアミノチオカルボニル基等が挙げられる。
Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

　式（ａ－１）のＲ1は、高感度化の点から置換基を有してもよいアシル基であることが好ましく、アセチル基、プロピオニル基、ベンゾイル基、トルイル基がより好ましい。
R 1 in formula (a-1) is preferably an acyl group which may have a substituent from the viewpoint of increasing sensitivity, and more preferably an acetyl group, a propionyl group, a benzoyl group, or a toluyl group.

　環状オキシム化合物Ａは、上述した環状オキシム部位に芳香族炭化水素環および複素環から選ばれる少なくとも１種の環が結合した構造を有することが好ましい。より具体的には、上述した環状オキシム部位に芳香族炭化水素環および複素環から選ばれる少なくとも１種の環が縮環して形成された、環状オキシム部位を含む縮合環を有することが好ましい。このような構造を有する環状オキシム化合物Ａを用いることで、より高感度化を達成することができる。また、上記電子求引性基Ａは、上記芳香族炭化水素環または複素環に結合していることが好ましい。
The cyclic oxime compound A preferably has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the above-described cyclic oxime moiety. More specifically, it is preferable to have a condensed ring containing a cyclic oxime moiety formed by condensing at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring at the cyclic oxime moiety described above. By using the cyclic oxime compound A having such a structure, higher sensitivity can be achieved. The electron withdrawing group A is preferably bonded to the aromatic hydrocarbon ring or heterocyclic ring.

　芳香族炭化水素環は、単環であってもよく、縮合環であってもよい。芳香族炭化水素環の具体例としては、ベンゼン環、ビフェニレン環、ナフタレン環、アントラセン環、フェナントラセン環、アズレン環、フルオレン環等が挙げられる。
The aromatic hydrocarbon ring may be a single ring or a condensed ring. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthracene ring, an azulene ring, and a fluorene ring.

　複素環は、単環であってもよく、縮合環であってもよい。複素環は、窒素原子、酸素原子または硫黄原子を含む芳香族或いは脂肪族の複素環であることが好ましく、より好ましくは、窒素原子または酸素原子を含む芳香族或いは脂肪族の複素環であり、更に好ましくは、窒素原子を含む芳香族或いは脂肪族の複素環である。複素環の具体例としては、ピロール環、フラン環、チオフェン環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、ピペラジン環、ピラン環、クロマン環、イミダゾール環、チアゾール環、ピラゾール環、モルホリン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環およびこれらの環を含む縮合環が挙げられ、ピロール環、フラン環、チオフェン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環が好ましく、チオフェン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環がより好ましく、カルバゾール環およびジベンゾチオフェン環が更に好ましい。
The heterocyclic ring may be a single ring or a condensed ring. The heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, More preferably, it is an aromatic or aliphatic heterocyclic ring containing a nitrogen atom. Specific examples of the heterocyclic ring include pyrrole ring, furan ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, piperazine ring, pyran ring, chroman ring, imidazole ring, thiazole ring, pyrazole ring, morpholine ring, Examples thereof include carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring and condensed rings containing these rings, pyrrole ring, furan ring, thiophene ring, carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring are preferable, A thiophene ring, a carbazole ring, a thianthrene ring, a dihydrophenazine ring, and a dibenzothiophene ring are more preferable, and a carbazole ring and a dibenzothiophene ring are still more preferable.

　環状オキシム化合物Ａは、より高感度化を達成しやすいという理由から、上述した環状オキシム部位にカルバゾール環またはジベンゾチオフェン環を含む縮合環が結合した構造を有することが好ましい。
The cyclic oxime compound A preferably has a structure in which a condensed ring containing a carbazole ring or a dibenzothiophene ring is bonded to the above-mentioned cyclic oxime moiety because it is easy to achieve higher sensitivity.

　本発明で用いられる環状オキシム化合物Ａは、下記式（１）で表わされる化合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000010
　式（１）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2、Ｒ3、またはＢで表される環と結合して環を形成していてもよく、Ｒ1～Ｒ3はそれぞれ独立して置換基を表し、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｂは芳香族炭化水素環および複素環から選ばれる少なくとも１種を含む環を表し、Ｚ1はＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、ｎは０または１を表し、ｍは０または１を表し、ｑは１以上の整数を表し、ｏ、ｐはそれぞれ独立して０以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏが２以上の場合、ｏ個のＲ3は同一であってもよく、異なっていてもよく、２個のＲ3同士が結合して環を形成していてもよく、ｑが２以上の場合、ｑ個のＺ1は同一であってもよく、異なっていてもよい。
The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (1).

Figure JPOXMLDOC01-appb-C000010
In the formula (1), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may be bonded to a ring represented by R 2 , R 3 , or B to form a ring; R 1 to R 3 Each independently represents a substituent, L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent, and B Represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring, Z 1 represents an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, and n is 0 or 1 M represents 0 or 1, q represents an integer of 1 or more, o and p each independently represents an integer of 0 or more, and p is 2 or more , P R 2 may be the same or different, and two R 2 may be bonded to each other to form a ring. When o is 2 or more, o R 2 3 may be the same or different, and two R 3 may be bonded to each other to form a ring. When q is 2 or more, q Z 1 are the same. It may be different.

　式（１）のＺ1が表わすＴａｆｔのσ*定数の値が３．５以上の電子求引性基は、上述した電子求引性基Ａと同義であり、好ましい範囲も同様である。
The electron-withdrawing group having a Taft σ * constant value of 3.5 or more represented by Z 1 in the formula (1) has the same meaning as the above-described electron-withdrawing group A, and the preferred range is also the same.

　式（１）のＸ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表す。

　Ｘ1は、光分解効率をより高め易いという理由から－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－が好ましい。

　Ｒx1～Ｒx3が表わす置換基としては、アルキル基、アリール基、アルケニル基、アルキニル基および複素環基が挙げられる。これらの基の詳細については、式（ａ－１）のＲ1で説明した範囲と同義である。

　Ｒx4が表わす置換基としては、アルキル基、アリール基、アルケニル基、アルキニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスフィノイル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基、ジアルキルアミノカルボニル基、ジアルキルアミノチオカルボニル基等が挙げられ、高感度の観点からアシル基が好ましい。これらの基の詳細については、式（ａ－１）のＲ1で説明した範囲と同義である。

　Ｒx1およびＲx3は、Ｒ2、Ｒ3、またはＢで表される環と結合して環を形成していてもよい。形成される環は、脂肪族環であってもよく、芳香族環であってもよい。
X 1 in the formula (1) represents —O—, —CR x1 R x2 —, —S—, —NR x3 —, or> C═N—O—R x4 , where R x1 to R x4 represent Independently represents a hydrogen atom or a substituent.

X 1 is preferably —O—, —CR x1 R X2 —, or —S— because it is easier to increase the photolysis efficiency.

Examples of the substituent represented by R x1 to R x3 include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. Details of these groups are the same as those described for R 1 in formula (a-1).

Examples of the substituent represented by R x4 include an alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl. Group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like, and an acyl group is preferred from the viewpoint of high sensitivity. Details of these groups are the same as those described for R 1 in formula (a-1).

R x1 and R x3 may combine with the ring represented by R 2 , R 3 , or B to form a ring. The ring formed may be an aliphatic ring or an aromatic ring.

　式（１）のＲ1～Ｒ3はそれぞれ独立して置換基を表す。Ｒ1が表わす置換基は、式（ａ－１）のＲ1で説明した範囲と同義である。Ｒ2およびＲ3が表わす置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基および複素環基等が挙げられる。これらの基の詳細については、式（ａ－１）のＲ1で説明した範囲と同義である。
R 1 to R 3 in the formula (1) each independently represent a substituent. The substituent represented by R 1 has the same meaning as the range described for R 1 in formula (a-1). Examples of the substituent represented by R 2 and R 3 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Details of these groups are the same as those described for R 1 in formula (a-1).

　式（１）のＬは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表す。Ｌが表わすアルキレンは、炭素数１または２のアルキレン基が好ましく、炭素数１のアルキレン基がより好ましい。また、Ｌが表わすアルキレン基は、置換基を有していてもよい。

　Ｌが表わすアルキレン基が有してもよい置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基およびアルキリデン基が挙げられる。ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。アルキリデン基としては、炭素数１～１０のアルキリデン基が好ましく、例えば、メチリデン基、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基などが挙げられる。アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基については、式（ａ－１）のＲ1で説明した基が挙げられる。

　ＲL1およびＲL2が表わす置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基および複素環基が挙げられる。ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基については、式（ａ－１）のＲ1で説明した基が挙げられる。
L in Formula (1) represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, and R L1 and R L2 each independently represent a hydrogen atom or a substituent. The alkylene represented by L is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 1 carbon atom. The alkylene group represented by L may have a substituent.

Examples of the substituent that the alkylene group represented by L may have include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, a heterocyclic group, and an alkylidene group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. The alkylidene group is preferably an alkylidene group having 1 to 10 carbon atoms, and examples thereof include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, and a butylidene group. Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).

Examples of the substituent represented by R L1 and R L2 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).

　式（１）のＢは芳香族炭化水素環および複素環から選ばれる少なくとも１種を含む環を表す。芳香族炭化水素環は、単環であってもよく、縮合環であってもよい。芳香族炭化水素環の具体例としては、ベンゼン環、ビフェニレン環、ナフタレン環、アントラセン環、フェナントラセン環、アズレン環、フルオレン環等が挙げられる。複素環は、単環であってもよく、縮合環であってもよい。複素環は、窒素原子、酸素原子または硫黄原子を含む芳香族或いは脂肪族の複素環であることが好ましく、より好ましくは、窒素原子または酸素原子を含む芳香族或いは脂肪族の複素環であり、更に好ましくは、窒素原子を含む芳香族或いは脂肪族の複素環である。複素環の具体例としては、ピロール環、フラン環、チオフェン環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、ピペラジン環、ピラン環、クロマン環、イミダゾール環、チアゾール環、ピラゾール環、モルホリン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環およびこれらの環を含む縮合環が挙げられ、ピロール環、フラン環、チオフェン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環が好ましく、チオフェン環、カルバゾール環、チアンスレン環、ジヒドロフェナジン環、ジベンゾチオフェン環がより好ましく、カルバゾール環およびジベンゾチオフェン環が更に好ましい。
B in the formula (1) represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring. The aromatic hydrocarbon ring may be a single ring or a condensed ring. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a phenanthracene ring, an azulene ring, and a fluorene ring. The heterocyclic ring may be a single ring or a condensed ring. The heterocyclic ring is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom, more preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom or an oxygen atom, More preferably, it is an aromatic or aliphatic heterocyclic ring containing a nitrogen atom. Specific examples of the heterocyclic ring include pyrrole ring, furan ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, piperazine ring, pyran ring, chroman ring, imidazole ring, thiazole ring, pyrazole ring, morpholine ring, Examples thereof include carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring and condensed rings containing these rings, pyrrole ring, furan ring, thiophene ring, carbazole ring, thianthrene ring, dihydrophenazine ring, dibenzothiophene ring are preferable, A thiophene ring, a carbazole ring, a thianthrene ring, a dihydrophenazine ring, and a dibenzothiophene ring are more preferable, and a carbazole ring and a dibenzothiophene ring are still more preferable.

　式（１）のｎは０または１を表す。高感度化の観点からｎは０であることが好ましい。

式（１）のｍは０または１を表す。式（１）のｑは１以上の整数を表し、１または２が好ましい。式（１）のｏ、ｐはそれぞれ独立して０以上の整数を表し、０～２が好ましく、０～１がより好ましい。ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよい。また、ｏが２以上の場合、ｏ個のＲ3は同一であってもよく、異なっていてもよく、２個のＲ3同士が結合して環を形成していてもよい。これらの基同士が結合して形成される環は、脂肪族環であってもよく、芳香族環であってもよい。
N in the formula (1) represents 0 or 1. From the viewpoint of increasing sensitivity, n is preferably 0.

M in the formula (1) represents 0 or 1. Q in the formula (1) represents an integer of 1 or more, and 1 or 2 is preferable. In the formula (1), o and p each independently represent an integer of 0 or more, preferably 0 to 2, more preferably 0 to 1. When p is 2 or more, p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring. When o is 2 or more, o R 3 s may be the same or different, and two R 3 may be bonded to each other to form a ring. The ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.

　本発明で用いられる環状オキシム化合物Ａは、下記式（２）で表わされる化合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000011
　式（２）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2またはＲ3aと結合して環を形成していてもよく、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｒ1、Ｒ2、Ｒ3aおよびＲ3bはそれぞれ独立して置換基を表し、Ｚ1aおよびＺ1bはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、Ｙ1は、－ＣＲY1ＲY2－、－ＮＲY3－または－Ｓ－を表し、ＲY1～ＲY3はそれぞれ独立して水素原子または置換基を表し、ｎは０または１を表し、ｍは０または１を表し、ｏ１、ｏ２、ｐ、ｑ１およびｑ２はそれぞれ独立して０以上の整数を表し、ｑ１およびｑ２の少なくとも一方は１以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏ１が２以上の場合、ｏ１個のＲ3aは同一であってもよく、異なっていてもよく、２個のＲ3a同士が結合して環を形成していてもよく、ｏ２が２以上の場合、ｏ２個のＲ3bは同一であってもよく、異なっていてもよく、２個のＲ3b同士が結合して環を形成していてもよく、ｑ１が２以上の場合、ｑ１個のＺ1aは同一であってもよく、異なっていてもよく、ｑ２が２以上の場合、ｑ２個のＺ1bは同一であってもよく、異なっていてもよい。
The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (2).

Figure JPOXMLDOC01-appb-C000011
In the formula (2), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3a to form a ring, and L is an alkylene group having 1 to 3 carbon atoms or —CR L 1 = CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent, R 1 , R 2 , R 3a and R 3b each independently represent a substituent, Z 1a and Z 1b independently represents an electron-withdrawing group having a Taft σ * constant value of 3.5 or more, Y 1 represents —CR Y1 R Y2 —, —NR Y3 —, or —S—, R Y1 ~ R Y3 each independently represents a hydrogen atom or a substituent, n represents 0 or 1, m is 0 or 1, o1, o2, p, q1 Preliminary q2 independently represents an integer of 0 or more, at least one of q1 and q2 is an integer of 1 or more, when p is 2 or more, p number of R 2 may be the same, or different Two R 2 may be bonded to each other to form a ring. When o1 is 2 or more, o1 R 3a may be the same or different, and 2 R 3a may be bonded to each other to form a ring. When o2 is 2 or more, o2 R 3b may be the same or different, and two R 3b may be May be bonded to form a ring, and when q1 is 2 or more, q1 Z 1a may be the same or different, and when q2 is 2 or more, q2 Z 1a 1b may be the same or different.

　式（２）のＸ1、Ｌ、Ｒ1、Ｒ2、ｍおよびｎは、式（１）のＸ1、Ｌ、Ｒ1、Ｒ2、ｍおよびｎと同義であり、好ましい範囲も同様である。式（２）のＲ3aおよびＲ3bは、式（１）のＲ3と同義であり、好ましい範囲も同様である。式（２）のｏ１およびｏ２は、式（１）のｏと同義であり、好ましい範囲も同様である。式（２）において、ｏ１が２以上の場合、ｏ１個のＲ3aは同一であってもよく、異なっていてもよく、２個のＲ3a同士が結合して環を形成していてもよく、ｏ２が２以上の場合、ｏ２個のＲ3bは同一であってもよく、異なっていてもよく、２個のＲ3b同士が結合して環を形成していてもよい。これらの基同士が結合して形成される環は、脂肪族環であってもよく、芳香族環であってもよい。
X 1, L, R 1, R 2, m and n of formula (2) has the same meaning as X 1, L, R 1, R 2, m and n of formula (1), the preferred range is also the same is there. R 3a and R 3b in the formula (2) have the same meaning as R 3 in the formula (1), and preferred ranges thereof are also the same. O1 and o2 in the formula (2) have the same meaning as o in the formula (1), and the preferred range is also the same. In the formula (2), if the o1 is 2 or more, o1 amino R 3a may be the same or different, they may form a ring together two R 3a is bonded to when the o2 is 2 or more, o2 one R 3b may be the same or different, two R 3b may be bonded to each other to form a ring. The ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.

　式（２）のＺ1aおよびＺ1bが表わすＴａｆｔのσ*定数の値が３．５以上の電子求引性基は、上述した電子求引性基Ａと同義であり、好ましい範囲も同様である。式（２）において、ｑ１およびｑ２はそれぞれ独立して０以上の整数を表し、ｑ１およびｑ２の少なくとも一方は１以上の整数を表す。ｑ１およびｑ２はそれぞれ独立して０～２が好ましく、０または１がより好ましい。式（２）において、ｑ１が２以上の場合、ｑ１個のＺ1aは同一であってもよく、異なっていてもよく、ｑ２が２以上の場合、ｑ２個のＺ1bは同一であってもよく、異なっていてもよい。
The electron-withdrawing group having a Taft σ * constant value of 3.5 or more represented by Z 1a and Z 1b in the formula (2) is synonymous with the above-described electron-withdrawing group A, and the preferred range is also the same. is there. In Formula (2), q1 and q2 each independently represent an integer of 0 or more, and at least one of q1 and q2 represents an integer of 1 or more. q1 and q2 are each independently preferably 0 to 2, more preferably 0 or 1. In the formula (2), when q1 is 2 or more, q1 Z 1a may be the same or different, and when q2 is 2 or more, q2 Z 1b may be the same Well, it can be different.

　式（２）のＹ1は、－ＣＲY1ＲY2－、－ＮＲY3－または－Ｓ－を表し、ＲY1～ＲY3はそれぞれ独立して水素原子または置換基を表す。ＲY1～ＲY3が表す置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基および複素環基が挙げられる。ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基については、式（ａ－１）のＲ1で説明した基が挙げられる。
Y 1 in the formula (2) represents —CR Y1 R Y2 —, —NR Y3 — or —S—, and R Y1 to R Y3 each independently represents a hydrogen atom or a substituent. Examples of the substituent represented by R Y1 to R Y3 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).

　本発明で用いられる環状オキシム化合物Ａは、下記式（３ａ）または式（３ｂ）で表わされる化合物であることが好ましい。これらの化合物は、より優れた感度を有しており特に好ましく用いられる。

Figure JPOXMLDOC01-appb-C000012
　式（３ａ）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2またはＲ3cと結合して環を形成していてもよく、Ｙ2は、－ＣＲY21ＲY22－、－ＮＲY23－または－Ｓ－を表し、ＲY21～ＲY23はそれぞれ独立して水素原子または置換基を表す；式（３ｂ）中、Ｘ2は、＞ＣＲX10－または＞Ｎ－を表し、Ｒx10は水素原子または置換基を表す；

　式（３ａ）および式（３ｂ）中、Ｒ1、Ｒ2、Ｒ3cおよびＲ3dはそれぞれ独立して置換基

を表し、Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、Ｚ1cおよびＺ1dはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、ｎは０または１を表し、ｍは０または１を表し、ｏ３、ｏ４、ｐ、ｑ３およびｑ４はそれぞれ独立して０以上の整数を表し、ｑ３およびｑ４の少なくとも一方は１以上の整数を表し、ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、ｏ３が２以上の場合、ｏ３個のＲ3cは同一であってもよく、異なっていてもよく、２個のＲ3c同士が結合して環を形成していてもよく、ｏ４が２以上の場合、ｏ４個のＲ3dは同一であってもよく、異なっていてもよく、２個のＲ3d同士が結合して環を形成していてもよく、ｑ３が２以上の場合、ｑ３個のＺ1cは同一であってもよく、異なっていてもよく、ｑ４が２以上の場合、ｑ４個のＺ1dは同一であってもよく、異なっていてもよい。
The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (3a) or (3b). These compounds have more excellent sensitivity and are particularly preferably used.

Figure JPOXMLDOC01-appb-C000012
In the formula (3a), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3c to form a ring, and Y 2 represents —CR Y21 R Y22 —, —NR Y 23 — or —S—, R Y21 to R Y23 each independently represents a hydrogen atom or a substituent; in Formula (3b), X 2 represents> CR X10 — or> N—, and R x10 Represents a hydrogen atom or a substituent;

In formula (3a) and formula (3b), R 1 , R 2 , R 3c and R 3d are each independently a substituent.

L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represents a hydrogen atom or a substituent, and Z 1c and Z 1d are each independently Represents an electron-attracting group having a Taft σ * constant value of 3.5 or more, n represents 0 or 1, m represents 0 or 1, and o3, o4, p, q3 and q4 represent Each independently represents an integer of 0 or more, at least one of q3 and q4 represents an integer of 1 or more, and when p is 2 or more, p R 2 s may be the same or different, may have two R 2 are bonded to each other to form a ring, for o3 is 2 or more, o3 one R 3c may be the same or different, two R 3c They may be bonded to each other to form a ring. When o4 is 2 or more, o4 R 3d are the same, Or two R 3d's may be bonded to each other to form a ring. When q3 is 2 or more, q3 Z 1c's may be the same or different. In the case where q4 is 2 or more, q4 Z 1d may be the same or different.

　式（３ａ）のＸ1、Ｌ、Ｒ1、Ｒ2、ｍおよびｎは、式（１）のＸ1、Ｌ、Ｒ1、Ｒ2、ｍおよびｎと同義であり、好ましい範囲も同様である。
X 1, L, R 1, R 2, m and n of formula (3a) have the same meanings as X 1, L, R 1, R 2, m and n of formula (1), the preferred range is also the same is there.

　式（３ａ）のＹ2は、－ＣＲY21ＲY22－、－ＮＲY23－または－Ｓ－を表し、ＲY21～ＲY23はそれぞれ独立して水素原子または置換基を表す。ＲY21～ＲY23が表す置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基および複素環基が挙げられる。ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基については、式（ａ－１）のＲ1で説明した基が挙げられる。
Y 2 in the formula (3a) represents —CR Y21 R Y22 —, —NR Y23 — or —S—, and R Y21 to R Y23 each independently represents a hydrogen atom or a substituent. Examples of the substituent represented by R Y21 to R Y23 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).

　式（３ｂ）のＬ、Ｒ1、Ｒ2、ｍおよびｎは、式（１）のＬ、Ｒ1、Ｒ2、ｍおよびｎと同義であり、好ましい範囲も同様である。
L of formula (3b), R 1, R 2, m and n are as defined for L, R 1, R 2, m and n Equation (1), and preferred ranges are also the same.

　式（３ｂ）のＸ2は、＞ＣＲX10－または＞Ｎ－を表し、Ｒx10は水素原子または置換基を表す。Ｒx10が表す置換基としては、ハロゲン原子、アルキル基、アリール基、アルケニル基、アルキニル基、アシル基および複素環基が挙げられる。ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。アルキル基、アリール基、アルケニル基、アルキニル基、アシル基、複素環基については、式（ａ－１）のＲ1で説明した基が挙げられる。
X 2 in the formula (3b) represents> CR X10 — or> N—, and R x10 represents a hydrogen atom or a substituent. Examples of the substituent represented by R x10 include a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an acyl group, and a heterocyclic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the alkyl group, aryl group, alkenyl group, alkynyl group, acyl group, and heterocyclic group include the groups described for R 1 in the formula (a-1).

　式（３ａ）および式（３ｂ）のＲ3cおよびＲ3dは、式（１）のＲ3と同義であり、好ましい範囲も同様である。式（３ａ）および式（３ｂ）のｏ３およびｏ４は、式（１）のｏと同義であり、好ましい範囲も同様である。式（３ａ）および式（３ｂ）において、ｏ３が２以上の場合、ｏ３個のＲ3cは同一であってもよく、異なっていてもよく、２個のＲ3c同士が結合して環を形成していてもよく、ｏ４が２以上の場合、ｏ４個のＲ3dは同一であってもよく、異なっていてもよく、２個のＲ3d同士が結合して環を形成していてもよい。

これらの基同士が結合して形成される環は、脂肪族環であってもよく、芳香族環であってもよい。
R 3c and R 3d in formula (3a) and formula (3b) have the same meaning as R 3 in formula (1), and the preferred ranges are also the same. In the formula (3a) and the formula (3b), o3 and o4 have the same meaning as o in the formula (1), and preferred ranges thereof are also the same. In the formula (3a) and formula (3b), when the o3 is 2 or more, o3 one R 3c may be the same or different, form two R 3c are bonded to each other ring And when o4 is 2 or more, o4 R 3d s may be the same or different, and two R 3d may be bonded to each other to form a ring. .

The ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.

　式（３ａ）および式（３ｂ）のＺ1cおよびＺ1dが表わすＴａｆｔのσ*定数の値が３．５以上の電子求引性基は、上述した電子求引性基Ａと同義であり、好ましい範囲も同様である。式（３ａ）および式（３ｂ）において、ｑ３およびｑ４はそれぞれ独立して０以上の整数を表し、ｑ３およびｑ４の少なくとも一方は１以上の整数を表す。ｑ３およびｑ４はそれぞれ独立して０～２が好ましく、０または１がより好ましい。式（３ａ）および式

（３ｂ）において、ｑ３が２以上の場合、ｑ３個のＺ1cは同一であってもよく、異なっていてもよく、ｑ４が２以上の場合、ｑ４個のＺ1dは同一であってもよく、異なっていてもよい。
The electron-withdrawing group having a Taft σ * constant value of 3.5 or more represented by Z 1c and Z 1d in the formulas (3a) and (3b) has the same meaning as the electron-withdrawing group A described above, The preferable range is also the same. In Formula (3a) and Formula (3b), q3 and q4 each independently represent an integer of 0 or more, and at least one of q3 and q4 represents an integer of 1 or more. q3 and q4 are each independently preferably 0 to 2, more preferably 0 or 1. Formula (3a) and Formula

In (3b), when q3 is 2 or more, q3 Z 1c may be the same or different, and when q4 is 2 or more, q4 Z 1d may be the same , May be different.

　本発明で用いられる環状オキシム化合物Ａは、下記式（４ａ）または式（４ｂ）で表わされる化合物であることが好ましい。これらの化合物を用いた場合においては、感光性組成物の経時安定性をより向上させ易い。

Figure JPOXMLDOC01-appb-C000013
The cyclic oxime compound A used in the present invention is preferably a compound represented by the following formula (4a) or formula (4b). When these compounds are used, it is easier to improve the temporal stability of the photosensitive composition.

Figure JPOXMLDOC01-appb-C000013

　式（４ａ）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、Ｒx1およびＲx3は、Ｒ2またはＲ3aと結合して環を形成していてもよい；

式（４ａ）および式（４ｂ）中、Ｒ1、Ｒ3eおよびＲ3fはそれぞれ独立して置換基を表し、Ｚ1eおよびＺ1fはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、ｏ５、ｏ６、ｑ５およびｑ６はそれぞれ独立して０以上の整数を表し、ｑ５およびｑ６の少なくとも一方は１以上の整数を表し、ｏ５が２以上の場合、ｏ５個のＲ3eは同一であってもよく、異なっていてもよく、２個のＲ3e同士が結合して環を形成していてもよく、ｏ６が２以上の場合、ｏ６個のＲ3fは同一であってもよく、異なっていてもよく、２個のＲ3f同士が結合して環を形成していてもよく、ｑ５が２以上の場合、ｑ５個のＺ1eは同一であってもよく、異なっていてもよく、ｑ６が２以上の場合、ｑ６個のＺ1fは同一であってもよく、異なっていてもよい。
In the formula (4a), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4 , and R x1 to R x4 represent Each independently represents a hydrogen atom or a substituent, and R x1 and R x3 may combine with R 2 or R 3a to form a ring;

In Formula (4a) and Formula (4b), R 1 , R 3e and R 3f each independently represent a substituent, and Z 1e and Z 1f each independently represent Taft's σ * constant value of 3.5 When the above-mentioned electron withdrawing group is represented, o5, o6, q5 and q6 each independently represents an integer of 0 or more, at least one of q5 and q6 represents an integer of 1 or more, and o5 is 2 or more, o5 amino R 3e may be the same or different, may form two R 3e are bonded to each other ring in the case of o6 is 2 or more, o6 amino R 3f May be the same or different, and two R 3f may be bonded to each other to form a ring. When q5 is 2 or more, q5 Z 1e are the same. May be different, and when q6 is 2 or more, q6 Z 1f may be the same or different. May be.

　式（４ａ）のＸ1およびＲ1は、式（１）のＸ1およびＲ1と同義であり、好ましい範囲も同様である。
X 1 and R 1 of formula (4a) has the same meaning as X 1 and R 1 of formula (1), and preferred ranges are also the same.

　式（４ｂ）のＲ1は、式（１）のＲ1と同義であり、好ましい範囲も同様である。
R 1 in formula (4b) has the same meaning as R 1 in formula (1), and the preferred range is also the same.

　式（４ａ）および式（４ｂ）のＲ3eおよびＲ3fは、式（１）のＲ3と同義であり、好ましい範囲も同様である。式（４ａ）および式（４ｂ）のｏ５およびｏ６は、式（１）のｏと同義であり、好ましい範囲も同様である。式（４ａ）および式（４ｂ）において、ｏ５が２以上の場合、ｏ５個のＲ3eは同一であってもよく、異なっていてもよく、２個のＲ3e同士が結合して環を形成していてもよく、ｏ６が２以上の場合、ｏ６個のＲ3fは同一であってもよく、異なっていてもよく、２個のＲ3f同士が結合して環を形成していてもよい。

これらの基同士が結合して形成される環は、脂肪族環であってもよく、芳香族環であってもよい。
R 3e and R 3f in formula (4a) and formula (4b) have the same meaning as R 3 in formula (1), and the preferred ranges are also the same. In formula (4a) and formula (4b), o5 and o6 have the same meaning as o in formula (1), and the preferred range is also the same. In Formula (4a) and Formula (4b), when o5 is 2 or more, o5 R 3e s may be the same or different, and two R 3e may be bonded to each other to form a ring. When o6 is 2 or more, o6 R 3f may be the same or different, and two R 3f may be bonded to each other to form a ring. .

The ring formed by bonding these groups may be an aliphatic ring or an aromatic ring.

　式（４ａ）および式（４ｂ）のＺ1eおよびＺ1fが表わすＴａｆｔのσ*定数の値が３．５以上の電子求引性基は、上述した電子求引性基Ａと同義であり、好ましい範囲も同様である。式（４ａ）および式（４ｂ）において、ｑ５およびｑ６はそれぞれ独立して０以上の整数を表し、ｑ５およびｑ６の少なくとも一方は１以上の整数を表す。ｑ５およびｑ６はそれぞれ独立して０～２が好ましく、０または１がより好ましい。式（４ａ）および式

（４ｂ）において、ｑ５が２以上の場合、ｑ５個のＺ1eは同一であってもよく、異なっていてもよく、ｑ６が２以上の場合、ｑ６個のＺ1fは同一であってもよく、異なっていてもよい。
The electron-withdrawing group having a Taft σ * constant value of 3.5 or more represented by Z 1e and Z 1f in the formulas (4a) and (4b) has the same meaning as the electron-withdrawing group A described above, The preferable range is also the same. In Formula (4a) and Formula (4b), q5 and q6 each independently represent an integer of 0 or more, and at least one of q5 and q6 represents an integer of 1 or more. q5 and q6 are each independently preferably 0 to 2, more preferably 0 or 1. Formula (4a) and Formula

In (4b), when q5 is 2 or more, q5 Z 1e may be the same or different, and when q6 is 2 or more, q6 Z 1f may be the same , May be different.

　環状オキシム化合物Ａの具体例としては、下記構造の化合物が挙げられる。

Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Specific examples of the cyclic oxime compound A include compounds having the following structure.

Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022

　環状オキシム化合物Ａは、波長３５０～５００ｎｍの範囲に極大吸収波長を有することが好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有することがより好ましい。また、環状オキシム化合物Ａの波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、１００００～３０００００であることが好ましく、１５０００～３０００００であることがより好ましく、２００００～２０００００であることが更に好ましい。環状オキシム化合物Ａのモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。
The cyclic oxime compound A preferably has a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 360 to 480 nm. The molar extinction coefficient of the cyclic oxime compound A at a wavelength of 365 nm or a wavelength of 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, and still more preferably 20,000 to 200,000. The molar extinction coefficient of the cyclic oxime compound A can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

　環状オキシム化合物Ａの含有量は、感光性着色組成物の全固形分中、０．１～３０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましく、２質量％以上がより好ましい。上限は、２５質量％以下がより好ましく、２０質量％以下が更に好ましく、１５質量％以下が特に好ましい。環状オキシム化合物Ａは１種単独で用いてもよいし、２種以上を併用してもよい。環状オキシム化合物Ａを２種以上併用する場合は、それらの合計量が上記範囲となることが好ましい。
The content of the cyclic oxime compound A is preferably 0.1 to 30% by mass in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less. The cyclic oxime compound A may be used alone or in combination of two or more. When using 2 or more types of cyclic oxime compounds A together, it is preferable that those total amounts become the said range.

＜＜重合性化合物＞＞

　本発明の感光性組成物は、重合性化合物を含有する。重合性化合物としては、例えば、エチレン性不飽和基を有する化合物などが挙げられる。エチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。重合性化合物はラジカルにより重合可能な化合物（ラジカル重合性化合物）であることが好ましい。
<< polymerizable compound >>

The photosensitive composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound is preferably a compound that can be polymerized by a radical (radical polymerizable compound).

　重合性化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～３０００が好ましい。上限は、２０００以下がより好ましく、１５００以下が更に好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。
The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.

　重合性化合物は、エチレン性不飽和基を３個以上含む化合物であることが好ましく、エチレン性不飽和基を３～１５個含む化合物であることがより好ましく、エチレン性不飽和基を３～６個含む化合物であることが更に好ましい。また、重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。
The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. More preferably, it is a compound containing one. The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.

　重合性モノマーについては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７の記載を参酌することができ、これらの内容は本明細書に組み込まれる。重合性化合物としては、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）

が好ましい。これらのオリゴマータイプも使用できる。また、重合性化合物としては、ＮＫエステルＡ－ＴＭＭＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＲＰ－１０４０、ＤＰＣＡ－２０（日本化薬（株）製）を使用することもできる。また、重合性化合物としては、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることも好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。
Regarding the polymerizable monomer, refer to the descriptions in paragraph Nos. 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph numbers 0254 to 0257 of JP-A-2008-292970. The contents of which are incorporated herein. As the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and (meth) acryloyl groups bonded via ethylene glycol and / or propylene glycol residues Compound (for example, commercially available from Sartomer) , SR454, SR499)

Is preferred. These oligomer types can also be used. As the polymerizable compound, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy modified tri (meth). It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.

　重合性化合物は、酸基を有していてもよい。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有するラジカル重合性化合物の市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。
The polymerizable compound may have an acid group. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable. Examples of commercially available radical polymerizable compounds having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.

　酸基を有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。
A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling.

　重合性化合物は、カプロラクトン構造を有する化合物であることも好ましい。カプロラクトン構造を有する重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。
The polymerizable compound is also preferably a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

　重合性化合物は、アルキレンオキシ基を有する化合物であることも好ましい。アルキレンオキシ基を有する重合性化合物は、エチレンオキシ基および／またはプロピレンオキシ基を有する化合物であることが好ましく、エチレンオキシ基を有する化合物であることがより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物であることがさらに好ましい。アルキレンオキシ基を有する重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。
The polymerizable compound is also preferably a compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. A tri- to hexa-functional (meth) acrylate compound is more preferable. Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 which is an acrylate.

　重合性化合物としては、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載されたエチレンオキサイド系骨格を有するウレタン化合物も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載された分子内にアミノ構造やスルフィド構造を有する重合性化合物を用いることも好ましい。市販品としては、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）などが挙げられる。

　また、重合性化合物としては、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。

　また、重合性化合物としては、特開２０１７－４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物を用いることもできる。
Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Commercially available products include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- 600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

As the polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.

As the polymerizable compound, compounds described in JP-A-2017-48367, JP-A-6057891, and JP-A-6031807 can also be used.

　重合性化合物の含有量は、感光性着色組成物の全固形分中、０．１～５０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましく、５質量％以上がより好ましい。上限は、４５質量％以下がより好ましく、４０質量％以下が更に好ましく、３０質量％以下が特に好ましい。重合性化合物は１種単独で用いてもよいし、２種以上を併用してもよい。重合性化合物を２種以上併用する場合は、それらの合計量が上記範囲となることが好ましい。
The content of the polymerizable compound is preferably from 0.1 to 50% by mass in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 5% by mass or more. The upper limit is more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less. A polymeric compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that those total amount becomes the said range.

＜＜色材＞＞

　本発明の感光性組成物は、色材を含むことが好ましい。色材としては、有彩色着色剤、白色着色剤、黒色着色剤および近赤外線吸収色素が挙げられる。色材の種類は、感光性組成物の用途に応じて適宜選択することができる。色材は、顔料であってもよく、染料であってもよいが、より耐光性に優れた膜が得られやすいという理由から顔料であることが好ましい。
<< Color material >>

The photosensitive composition of the present invention preferably contains a color material. Examples of the color material include chromatic colorants, white colorants, black colorants, and near infrared absorbing dyes. The kind of color material can be appropriately selected according to the use of the photosensitive composition. The colorant may be a pigment or a dye, but is preferably a pigment because it is easy to obtain a film with more excellent light resistance.

（有彩色着色剤）

　有彩色着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などが挙げられる。有彩色着色剤は、顔料であってもよく、染料であってもよい。好ましくは顔料である。顔料の平均粒径（ｒ）は、２０ｎｍ≦ｒ≦３００ｎｍであることが好ましく、２５ｎｍ≦ｒ≦２５０ｎｍであることがより好ましく、３０ｎｍ≦ｒ≦２００ｎｍであることが更に好ましい。ここでいう「平均粒径」とは、顔料の一次粒子が集合した二次粒子についての平均粒径を意味する。また、使用しうる顔料の二次粒子の粒径分布（以下、単に「粒径分布」ともいう。）は、平均粒径±１００ｎｍの範囲に含まれる二次粒子が全体の７０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。
(Chromatic colorant)

Examples of the chromatic colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. The chromatic colorant may be a pigment or a dye. A pigment is preferable. The average particle diameter (r) of the pigment is preferably 20 nm ≦ r ≦ 300 nm, more preferably 25 nm ≦ r ≦ 250 nm, and still more preferably 30 nm ≦ r ≦ 200 nm. The “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated. The particle size distribution of secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles contained in the range of the average particle size ± 100 nm are 70% by mass or more of the total. It is preferable that it is 80% by mass or more.

　顔料は、有機顔料であることが好ましい。有機顔料としては以下のものが挙げられる。

　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等（以上、黄色顔料）、

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等（以上、赤色顔料）、

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９，６２，６３等（以上、緑色顔料）、

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２等

（以上、紫色顔料）、

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等（以上、青色顔料）。

　これら有機顔料は、単独で若しくは種々組合せて用いることができる。
The pigment is preferably an organic pigment. The following are mentioned as an organic pigment.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)

C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc.

(Purple pigment),

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment).

These organic pigments can be used alone or in various combinations.

　また、黄色顔料として、下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料を用いることもできる。

Figure JPOXMLDOC01-appb-C000023
　式中、Ｒ1およびＲ2はそれぞれ独立して、－ＯＨまたは－ＮＲ5Ｒ6であり、Ｒ3およびＲ4はそれぞれ独立して、＝Ｏまたは＝ＮＲ7であり、Ｒ5～Ｒ7はそれぞれ独立して、水素原子またはアルキル基である。Ｒ5～Ｒ7が表すアルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基は、ハロゲン原子、ヒドロキシ基、アルコキシ基、シアノ基およびアミノ基が好ましい。
Further, as a yellow pigment, a metal comprising at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomer structure thereof, two or more metal ions, and a melamine compound Azo pigments can also be used.

Figure JPOXMLDOC01-appb-C000023
In the formula, R 1 and R 2 are each independently —OH or —NR 5 R 6 , R 3 and R 4 are each independently ═O or ═NR 7 , and R 5 to R 7 Each independently represents a hydrogen atom or an alkyl group. The alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an amino group.

　式（Ｉ）において、Ｒ1およびＲ2は－ＯＨであることが好ましい。また、Ｒ3およびＲ4は＝Ｏであることが好ましい。
In the formula (I), R 1 and R 2 are preferably —OH. R 3 and R 4 are preferably ═O.

　金属アゾ顔料におけるメラミン化合物は、下記式（ＩＩ）で表される化合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000024
　式中Ｒ11～Ｒ13は、それぞれ独立して水素原子またはアルキル基である。アルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基はヒドロキシ基が好ましい。Ｒ11～Ｒ13の少なくとも一つは水素原子であることが好ましく、Ｒ11～Ｒ13の全てが水素原子であることがより好ましい。
The melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).

Figure JPOXMLDOC01-appb-C000024
In the formula, R 11 to R 13 each independently represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. The substituent is preferably a hydroxy group. Preferably, at least one of R 11 ~ R 13 is a hydrogen atom, more preferably all of R 11 ~ R 13 is a hydrogen atom.

　上記の金属アゾ顔料は、上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、Ｚｎ2+およびＣｕ2+を少なくとも含む金属イオンと、メラミン化合物とを含む態様の金属アゾ顔料であることが好ましい。この態様においては、金属アゾ顔料の全金属イオンの１モルを基準として、Ｚｎ2+およびＣｕ2+を合計で９５～１００モル％含有することが好ましく、９８～１００モル％含有することがより好ましく、９９．９～１００モル％含有することが更に好ましく、１００モル％であることが特に好ましい。また、金属アゾ顔料中のＺｎ2+とＣｕ2+とのモル比は、Ｚｎ2+：Ｃｕ2+＝１９９：１～１：１５であることが好ましく、１９：１～１：１であることがより好ましく、９：１～２：１であることが更に好ましい。また、この態様において、金属アゾ顔料は、更にＺｎ2+およびＣｕ2+以外の二価もしくは三価の金属イオン

（以下、金属イオンＭｅ１ともいう）を含んでいてもよい。金属イオンＭｅ１としては、Ｎｉ2+、Ａｌ3+、Ｆｅ2+、Ｆｅ3+、Ｃｏ2+、Ｃｏ3+、Ｌａ3+、Ｃｅ3+、Ｐｒ3+、Ｎｄ2+、Ｎｄ3+、Ｓｍ2+、Ｓｍ3+、Ｅｕ2+、Ｅｕ3+、Ｇｄ3+、Ｔｂ3+、Ｄｙ3+、Ｈｏ3+、Ｙｂ2+、Ｙｂ3+、Ｅｒ3+、Ｔｍ3+、Ｍｇ2+、Ｃａ2+、Ｓｒ2+、Ｍｎ2+、Ｙ3+、Ｓｃ3+、Ｔｉ2+、Ｔｉ3+、Ｎｂ3+、Ｍｏ2+、Ｍｏ3+、Ｖ2+、Ｖ3+、Ｚｒ2+、Ｚｒ3+、Ｃｄ2+、Ｃｒ3+、Ｐｂ2+、Ｂａ2+が挙げられ、Ａｌ3+、Ｆｅ2+、Ｆｅ3+、Ｃｏ2+、Ｃｏ3+、Ｌａ3+、Ｃｅ3+、Ｐｒ3+、Ｎｄ3+、Ｓｍ3+、Ｅｕ3+、Ｇｄ3+、Ｔｂ3+、Ｄｙ3+、Ｈｏ3+、Ｙｂ3+、Ｅｒ3+、Ｔｍ3+、Ｍｇ2+、Ｃａ2+、Ｓｒ2+、Ｍｎ2+およびＹ3+から選ばれる少なくとも１種であることが好ましく、Ａｌ3+、Ｆｅ2+、Ｆｅ3+、Ｃｏ2+、Ｃｏ3+、Ｌａ3+、Ｃｅ3+、Ｐｒ3+、Ｎｄ3+、Ｓｍ3+、Ｔｂ3+、Ｈｏ3+およびＳｒ2+から選ばれる少なくとも１種であることが更に好ましく、Ａｌ3+、Ｆｅ2+、Ｆｅ3+、Ｃｏ2+およびＣｏ3+から選ばれる少なくとも１種であることが特に好ましい。金属イオンＭｅ１の含有量は、金属アゾ顔料の全金属イオンの１モルを基準として、５モル％以下であることが好ましく、２モル％以下であることがより好ましく、０．１モル％以下であることが更に好ましい。
The metal azo pigment includes a metal ion containing at least one anion selected from the azo compound represented by the formula (I) and an azo compound having a tautomer structure thereof, and at least Zn 2+ and Cu 2+ And a metal azo pigment comprising an melamine compound. In this embodiment, the total amount of Zn 2+ and Cu 2+ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. The content is preferably 99.9 to 100 mol%, more preferably 100 mol%. The molar ratio of Zn 2+ to Cu 2+ in the metal azo pigment is preferably Zn 2+ : Cu 2+ = 199: 1 to 1:15, preferably 19: 1 to 1: 1. More preferably, it is 9: 1 to 2: 1. In this embodiment, the metal azo pigment further contains a divalent or trivalent metal ion other than Zn 2+ and Cu 2+.

(Hereinafter also referred to as metal ion Me1). As metal ions Me1, Ni 2+ , Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Yb 2+ , Yb 3+ , Er 3+ , Tm 3+ , Mg 2 + , Ca 2+ , Sr 2+ , Mn 2+ , Y 3+ , Sc 3+ , Ti 2+ , Ti 3+ , Nb 3+ , Mo 2+ , Mo 3+ , V 2+ , V 3+ , Zr <2+> , Zr <3+> , Cd <2+> , Cr <3+> , Pb <2+> , Ba <2+> are mentioned, Al <3+> , Fe <2+> , Fe <3+> , Co <2+> , Co <3+> , La <3+> , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Yb 3+ , Er 3+ , Tm 3+ , Mg 2+, Ca 2+, Sr 2+, is preferably at least one selected from Mn 2+ and Y 3+, Al 3+, Fe 2+ , Fe 3+, o 2+, Co 3+, La 3+ , Ce 3+, Pr 3+, Nd 3+, Sm 3+, Tb 3+, further be at least one selected from Ho 3+ and Sr 2+ Particularly preferred is at least one selected from Al 3+ , Fe 2+ , Fe 3+ , Co 2+ and Co 3+ . The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment. More preferably it is.

　上記の金属アゾ顔料については、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。
Regarding the above metal azo pigments, paragraph numbers 0011 to 0062 and 0137 to 0276 in JP-A-2017-171912, paragraph numbers 0010 to 0062 and 0138 to 0295 in JP-A-2017-171913, and JP-A-2017-171914. The descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the publication and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.

　また、赤色顔料として、芳香族環に酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。このような化合物としては、式（ＤＰＰ１）で表される化合物であることが好ましく、式（ＤＰＰ２）で表される化合物であることがより好ましい。

Figure JPOXMLDOC01-appb-C000025
Further, as the red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. Such a compound is preferably a compound represented by the formula (DPP1), and more preferably a compound represented by the formula (DPP2).

Figure JPOXMLDOC01-appb-C000025

　上記式中、Ｒ11およびＲ13はそれぞれ独立して置換基を表し、Ｒ12およびＲ14はそれぞれ独立して水素原子、アルキル基、アリール基またはヘテロアリール基を表し、ｎ１１およびｎ１３はそれぞれ独立して０～４の整数を表し、Ｘ12およびＸ14はそれぞれ独立して酸素原子、硫黄原子または窒素原子を表し、Ｘ12が酸素原子または硫黄原子の場合は、ｍ１２は１を表し、Ｘ12が窒素原子の場合は、ｍ１２は２を表し、Ｘ14が酸素原子または硫黄原子の場合は、ｍ１４は１を表し、Ｘ14が窒素原子の場合は、ｍ１４は２を表す。Ｒ11およびＲ13が表す置換基としては、アルキル基、アリール基、ハロゲン原子、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロアリールオキシカルボニル基、アミド基、シアノ基、ニトロ基、トリフルオロメチル基、スルホキシド基、スルホ基などが好ましい具体例として挙げられる。
In the above formula, R 11 and R 13 each independently represent a substituent, R 12 and R 14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n11 and n13 each independently And X 12 and X 14 each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, and when X 12 is an oxygen atom or a sulfur atom, m12 represents 1, If 12 is a nitrogen atom, m12 represents 2, if X 14 is an oxygen atom or a sulfur atom, m14 represents 1, if X 14 is a nitrogen atom, m14 represents 2. Examples of the substituent represented by R 11 and R 13 include alkyl group, aryl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, amide group, cyano group, nitro group, trifluoro group. A methyl group, a sulfoxide group, a sulfo group and the like are preferable examples.

　また、緑色顔料として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子が平均８～１２個であり、塩素原子が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開ＷＯ２０１５／１１８７２０号公報に記載の化合物が挙げられる。
Further, as the green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 is used. You can also. Specific examples include the compounds described in International Publication No. WO2015 / 118720.

　また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落００２２～００３０、特開２０１１－１５７４７８号公報の段落００４７に記載の化合物などが挙げられる。
Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraphs 0022 to 0030 of JP2012-247491A and paragraph 0047 of JP2011-157478A.

　染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。また、これらの染料の多量体を用いてもよい。また、特開２０１５－０２８１４４号公報、特開２０１５－３４９６６号公報に記載の染料を用いることもできる。
There is no restriction | limiting in particular as dye, A well-known dye can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dyes. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

（白色着色剤）

　本発明において、白色着色剤とは、純白色のみならず、白に近い明るい灰色（例えば灰白色、薄灰色など）の着色剤などを含む。白色着色剤は、顔料であってもよく、染料であってもよい。白色顔料としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などが挙げられる。白色着色剤は、チタン原子を有する粒子であることが好ましく、酸化チタンがより好ましい。
(White colorant)

In the present invention, the white colorant includes not only pure white but also a light gray (for example, grayish white or light gray) colorant close to white. The white colorant may be a pigment or a dye. White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow Examples include resin particles and zinc sulfide. The white colorant is preferably a particle having a titanium atom, and more preferably titanium oxide.

　酸化チタンは、二酸化チタン（ＴｉＯ2）の含有量（純度）が７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、８５質量％以上であることが更に好ましい。酸化チタンは、ＴｉnＯ2n-1（ｎは２～４の数を表す。）で表される低次酸化チタン、酸窒化チタン等の含有量が３０質量％以下であることが好ましく、２０質量％以下であることがより好ましく、１５質量％以下であることが更に好ましい。
Titanium oxide preferably has a titanium dioxide (TiO 2 ) content (purity) of 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more. The titanium oxide preferably has a content of low-order titanium oxide, titanium oxynitride or the like represented by Ti n O 2n-1 (where n represents a number of 2 to 4) of 30% by mass or less, The content is more preferably no more than mass%, and even more preferably no more than 15 mass%.

　酸化チタンの形状には特に制限はない。例えば、等方性形状（例えば、球状、多面体状等）、異方性形状（例えば、針状、棒状、板状等）、不定形状等の形状が挙げられる。酸化チタンの硬度（モース硬度）は、５～８であることが好ましく、７～７．５であることがより好ましい。酸化チタンの真比重（密度）は、１．０～６．０ｇ／ｃｍ3であることが好ましく、３．９～４．５ｇ／ｃｍ3であることがより好ましい。酸化チタンの嵩比重は０．１ｇ／ｃｍ3～１．０ｇ／ｃｍ3であることが好ましく、０．２ｇ／ｃｍ3～０．４ｇ／ｃｍ3であることがより好ましい。
There is no restriction | limiting in particular in the shape of a titanium oxide. For example, isotropic shapes (for example, spherical shape, polyhedral shape, etc.), anisotropic shapes (for example, needle shape, rod shape, plate shape, etc.), irregular shapes, and the like can be mentioned. The hardness (Mohs' hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5. The true specific gravity (density) of titanium oxide is preferably 1.0 to 6.0 g / cm 3 , and more preferably 3.9 to 4.5 g / cm 3 . The bulk specific gravity of titanium oxide is preferably 0.1 g / cm 3 to 1.0 g / cm 3 , and more preferably 0.2 g / cm 3 to 0.4 g / cm 3 .

　白色着色剤は、市販されているものを用いることができる。市販品はそのまま使用してもよく、分級処理して用いてもよい。酸化チタンの市販品としては、例えば、石原産業（株）製の商品名タイペークＲ－５５０、Ｒ－５８０、Ｒ－６３０、Ｒ－６７０、Ｒ－６８０、Ｒ－７８０、Ｒ－７８０－２、Ｒ－８２０、Ｒ－８３０、Ｒ－８５０、Ｒ－８５５、Ｒ－９３０、Ｒ－９８０、ＣＲ－５０、ＣＲ－５０－２、ＣＲ－５７、ＣＲ－５８、ＣＲ－５８－２、ＣＲ－６０、ＣＲ－６０－２、ＣＲ－６３、ＣＲ－６７、ＣＲ－Ｓｕｐｅｒ７０、ＣＲ－８０、ＣＲ－８５、ＣＲ－９０、ＣＲ－９０－２、ＣＲ－９３、ＣＲ－９５、ＣＲ－９５３、ＣＲ－９７、ＰＦ－７３６、ＰＦ－７３７、ＰＦ－７４２、ＰＦ－６９０、ＰＦ－６９１、ＰＦ－７１１、ＰＦ－７３９、ＰＦ－７４０、ＰＣ－３、Ｓ－３０５、ＣＲ－ＥＬ、ＰＴ－３０１、ＰＴ－４０１Ｍ、ＰＴ－４０１Ｌ、ＰＴ－５０１Ａ、ＰＴ－５０１Ｒ、ＵＴ７７１、ＴＴＯ－５１Ｃ、ＴＴＯ－８０Ａ、ＴＴＯ－Ｓ－２、Ａ－２２０、ＭＰＴ－１３６、ＭＰＴ－１４０、ＭＰＴ－１４１；堺化学工業（株）製の商品名Ｒ－３Ｌ、Ｒ－５Ｎ、Ｒ－７Ｅ、Ｒ－１１Ｐ、Ｒ－２１、Ｒ－２５、Ｒ－３２、Ｒ－４２、Ｒ－４４、Ｒ－４５Ｍ、Ｒ－６２Ｎ、Ｒ－３１０、Ｒ－６５０、ＳＲ－１、Ｄ－９１８、ＧＴＲ－１００、ＦＴＲ－７００、ＴＣＲ－５２、Ａ－１１０、Ａ－１９０、ＳＡ－１、ＳＡ－１Ｌ、ＳＴＲ－１００Ａ－ＬＰ、ＳＴＲ－１００Ｃ－ＬＰ、ＴＣＡ－１２３Ｅ；テイカ（株）製の商品名ＪＲ、ＪＲＮＣ、ＪＲ－３０１、ＪＲ－４０３、ＪＲ－４０５、ＪＲ－６００Ａ、ＪＲ－６００Ｅ、ＪＲ－６０３、ＪＲ－６０５、ＪＲ－７０１、ＪＲ－８００、ＪＲ－８０５、ＪＲ－８０６、ＪＲ－１０００、ＭＴ－０１、ＭＴ－０５、ＭＴ－１０ＥＸ、ＭＴ－１００Ｓ、ＭＴ－１００ＴＶ、ＭＴ－１００Ｚ、ＭＴ－１００ＡＱ、ＭＴ－１００ＷＰ、ＭＴ－１００ＳＡ、ＭＴ－１００ＨＤ、ＭＴ－１５０ＥＸ、ＭＴ－１５０Ｗ、ＭＴ－３００ＨＤ、ＭＴ－５００Ｂ、ＭＴ－５００ＳＡ、ＭＴ－５００ＨＤ、ＭＴ－６００Ｂ、ＭＴ－６００ＳＡ、ＭＴ－７００Ｂ、ＭＴ－７００ＢＳ、ＭＴ－７００ＨＤ、ＭＴ－７００Ｚ；チタン工業（株）製の商品名ＫＲ－３１０、ＫＲ－３８０、ＫＲ－３８０Ｎ、ＳＴ－４８５ＳＡ１５；富士チタン工業（株）製の商品名ＴＲ－６００、ＴＲ－７００、ＴＲ－７５０、ＴＲ－８４０、ＴＲ－９００；白石カルシウム（株）製の商品名Ｂｒｉｌｌｉａｎｔ１５００等が挙げられる。また、特開２０１５－６７７９４号公報の段落番号００２５～００２７に記載の酸化チタンを用いることもできる。チタン酸ストロンチウムの市販品としては、ＳＷ－１００（チタン工業（株）製）などが挙げられる。硫酸バリウムの市販品としては、ＢＦ－１Ｌ（堺化学工業（株）製）などが挙げられる。酸化亜鉛の市販品としては、Ｚｉｎｃｏｘ　Ｓｕｐｅｒ　Ｆ－１（ハクスイテック（株）製）などが挙げられる。酸化ジルコニウムの市販品としては、Ｚ－ＮＸ（太陽鉱工（株）製）などが挙げられる。また、白色着色剤は「酸化チタン　物性と応用技術　清野学著　１３～４５ページ　１９９１年６月２５日発行、技報堂出版発行」に記載の酸化チタンを用いることもできる。
A commercially available white colorant can be used. Commercial products may be used as they are or may be used after classification. Commercially available products of titanium oxide include, for example, trade names of Taipei R-550, R-580, R-630, R-670, R-680, R-780, R-780-2 manufactured by Ishihara Sangyo Co., Ltd. R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2, CR- 60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR-953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3, S-305, CR-EL, PT- 301, PT-401M, PT-401L, T-501A, PT-501R, UT771, TTO-51C, TTO-80A, TTO-S-2, A-220, MPT-136, MPT-140, MPT-141; trade names of Sakai Chemical Industry Co., Ltd. R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, R-45M, R-62N, R-310, R- 650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A-190, SA-1, SA-1L, STR-100A-LP, STR-100C-LP, TCA-123E; trade names of JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR- 800, R-805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT- 100HD, MT-150EX, MT-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700BS, MT-700HD, MT-700Z; Trade names KR-310, KR-380, KR-380N, ST-485SA15 manufactured by Titanium Industry Co., Ltd .; Trade names TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd. TR-900; trade name Brilliant 1500 manufactured by Shiraishi Calcium Co., Ltd. It is done. Further, titanium oxides described in paragraph numbers 0025 to 0027 of JP-A-2015-67794 can also be used. Examples of commercially available strontium titanate include SW-100 (manufactured by Titanium Industry Co., Ltd.). Examples of commercially available barium sulfate include BF-1L (manufactured by Sakai Chemical Industry Co., Ltd.). Examples of commercially available products of zinc oxide include Zincox Super F-1 (manufactured by Hakutech Co., Ltd.). Examples of commercially available zirconium oxide include Z-NX (manufactured by Taiyo Mining Co., Ltd.). Further, as the white colorant, titanium oxide described in “Titanium oxide physical properties and applied technology, Kiyono Manabu, pages 13 to 45, published on June 25, 1991, published by Gihodo Publishing” can also be used.

　白色着色剤は、単一の無機物からなるものだけでなく、他の素材と複合させた粒子を用いてもよい。例えば、内部に空孔や他の素材を有する粒子、コア粒子に無機粒子を多数付着させた粒子、ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子を用いることが好ましい。上記ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子としては、例えば、特開２０１５－４７５２０号公報の段落番号００１２～００４２の記載を参酌することができ、この内容は本明細書に組み込まれる。
The white colorant may be not only a single inorganic material but also particles combined with other materials. For example, particles having pores or other materials inside, particles having a large number of inorganic particles attached to the core particles, cores composed of polymer particles and shell layers composed of inorganic nanoparticles are used, and shell composite particles. It is preferable. Examples of the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles can refer to, for example, the descriptions in paragraph numbers 0012 to 0042 of JP-A-2015-47520, This content is incorporated herein.

　白色着色剤は、中空無機粒子を用いることもできる。中空無機粒子とは、内部に空洞を有する構造の無機粒子であり、外殻に包囲された空洞を有する無機粒子のことを言う。中空無機粒子としては、特開２０１１－７５７８６号公報、国際公開ＷＯ２０１３－６１６２１号公報、特開２０１５－１６４８８１号公報などに記載された中空無機粒子が挙げられ、これらの内容は本明細書に組み込まれる。
As the white colorant, hollow inorganic particles can be used. The hollow inorganic particle is an inorganic particle having a structure having a cavity inside, and means an inorganic particle having a cavity surrounded by an outer shell. Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Laid-Open No. 2011-75786, International Publication WO2013-61621, Japanese Patent Application Laid-Open No. 2015-164881, and the like, the contents of which are incorporated herein. It is.

（黒色着色剤）

　黒色着色剤としては、カーボンブラック、チタンブラック、酸窒化ジルコニウム、酸窒化バナジウム、酸窒化ニオブなどの無機黒色着色剤（無機黒色顔料）や、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などの有機黒色着色剤が挙げられる。
(Black colorant)

Black colorants include inorganic black colorants (inorganic black pigments) such as carbon black, titanium black, zirconium oxynitride, vanadium oxynitride, niobium oxynitride, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. Organic black colorant.

　無機黒色着色剤としては、チタンブラックであることが好ましい。チタンブラックは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンであることが好ましい。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいことが好ましい。具体的には、平均一次粒子径が１０～４５ｎｍであることが好ましい。
The inorganic black colorant is preferably titanium black. Titanium black is a black particle containing a titanium atom, and is preferably low-order titanium oxide or titanium oxynitride. The surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water repellent material as disclosed in JP-A-2007-302836 is also possible. Titanium black preferably has a small primary particle size and average primary particle size for each particle. Specifically, the average primary particle diameter is preferably 10 to 45 nm.

　チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のＳｉ原子とＴｉ原子との含有比が０．２０～０．５０の範囲に調整した分散物などが挙げられる。上記分散物については、特開２０１２－１６９５５６号公報の段落００２０～０１０５の記載を参酌でき、この内容は本明細書に組み込まれる。チタンブラックの市販品としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名：三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名：赤穂化成（株）製）などが挙げられる。また、特開２０１３－２４９４７１号公報の段落０１４９に記載されたカーボンブラックを用いることもできる。
Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to be in the range of 0.20 to 0.50, and the like. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification. Commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D (trade name) : Ako Kasei Co., Ltd.). Also, carbon black described in paragraph 0149 of JP2013-249471A can be used.

　有機黒色着色剤は、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。

アゾメチン化合物としては、特開平１－１７０６０１号公報、特開平２－３４６６４号公報などに記載のものが挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。ビスベンゾフラノン化合物は、下記式のいずれかで表される化合物またはこれらの混合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000026
The organic black colorant is preferably a bisbenzofuranone compound or a perylene compound. Examples of the bisbenzofuranone compounds include compounds described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available. Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.

Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd. The bisbenzofuranone compound is preferably a compound represented by any of the following formulas or a mixture thereof.

Figure JPOXMLDOC01-appb-C000026

　式中、Ｒ1およびＲ2はそれぞれ独立して水素原子又は置換基を表し、Ｒ3およびＲ4はそれぞれ独立して置換基を表し、ａおよびｂはそれぞれ独立して０～４の整数を表し、ａが２以上の場合、複数のＲ3は、同一であってもよく、異なってもよく、複数のＲ3は結合して環を形成していてもよく、ｂが２以上の場合、複数のＲ4は、同一であってもよく、異なってもよく、複数のＲ4は結合して環を形成していてもよい。
In the formula, R 1 and R 2 each independently represent a hydrogen atom or a substituent, R 3 and R 4 each independently represent a substituent, and a and b each independently represent an integer of 0 to 4 And when a is 2 or more, the plurality of R 3 may be the same or different, the plurality of R 3 may be bonded to form a ring, and b is 2 or more. The plurality of R 4 may be the same or different, and the plurality of R 4 may be bonded to form a ring.

　Ｒ1～Ｒ4が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、－ＯＲ301、－ＣＯＲ302、－ＣＯＯＲ303、－ＯＣＯＲ304、－ＮＲ305Ｒ306、－ＮＨＣＯＲ307、－ＣＯＮＲ308Ｒ309、－ＮＨＣＯＮＲ310Ｒ311、－ＮＨＣＯＯＲ312、－ＳＲ313、－ＳＯ2Ｒ314、－ＳＯ2ＯＲ315、－ＮＨＳＯ2Ｒ316または－ＳＯ2ＮＲ317Ｒ318を表し、Ｒ301～Ｒ318は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表す。
The substituents represented by R 1 to R 4 are a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, —OR 301 , —COR 302 , —COOR 303 , —OCOR 304 , —NR 305 R 306 , —NHCOR 307 , —CONR 308 R 309 , —NHCONR 310 R 311 , —NHCOOR 312 , —SR 313 , —SO 2 R 314 , —SO 2 OR 315 , —NHSO 2 R 316 or —SO 2 NR 317 R 318 , each of R 301 to R 318 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

　ビスベンゾフラノン化合物の詳細については、特表２０１０－５３４７２６号公報の段落番号００１４～００３７の記載を参酌でき、この内容は本明細書に組み込まれる。
For details of the bisbenzofuranone compound, the description in paragraphs 0014 to 0037 of JP-T-2010-534726 can be referred to, and the contents thereof are incorporated herein.

（近赤外線吸収色素）

　近赤外線吸収色素としては、波長７００～１８００ｎｍの範囲に極大吸収波長を有する化合物であることが好ましく、波長７００～１３００ｎｍの範囲に極大吸収波長を有する化合物であることがより好ましく、波長７００～１０００ｎｍの範囲に極大吸収波長を有する化合物であることが更に好ましい。また、近赤外線吸収剤は、波長５００ｎｍにおける吸光度Ａ1と極大吸収波長における吸光度Ａ2との比率Ａ1／Ａ2が、０．０８以下であることが好ましく、０．０４以下であることがより好ましい。
(Near-infrared absorbing dye)

The near infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and a wavelength of 700 to 1000 nm. It is more preferable that the compound has a maximum absorption wavelength in the range. Also, near infrared absorber, that the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength in the wavelength 500nm is preferably 0.08 or less, 0.04 or less More preferred.

　近赤外線吸収色素としては、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、イミニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物及びジベンゾフラノン化合物などが挙げられ、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、クロコニウム化合物、フタロシアニン化合物、ナフタロシアニン化合物およびイミニウム化合物から選ばれる少なくとも１種が好ましく、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、クロコニウム化合物、およびイミニウム化合物から選ばれる少なくとも１種がより好ましく、ピロロピロール化合物が特に好ましい。フタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物、特開２００６－３４３６３１号公報に記載のオキシチタニウムフタロシアニン、特開２０１３－１９５４８０号公報の段落番号００１３～００２９に記載の化合物、特許第６０８１７７１号公報に記載のバナジウムフタロシアニンが挙げられ、これらの内容は本明細書に組み込まれる。ナフタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。また、近赤外線吸収色素は、特開２０１６－１４６６１９号公報に記載された化合物を用いることもできる。
As the near-infrared absorbing dye, pyrrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, iminium compound, dithiol compound, triarylmethane compound, pyromethene compound, An azomethine compound, an anthraquinone compound, a dibenzofuranone compound and the like are mentioned, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a croconium compound, a phthalocyanine compound, a naphthalocyanine compound and an iminium compound is preferable, and a pyrrolopyrrole compound, cyanine Selected from compounds, squarylium compounds, croconium compounds, and iminium compounds More preferably at least one that, pyrrolo-pyrrole compounds are particularly preferred. Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, oxytitanium phthalocyanine described in JP2006-343631, paragraph Nos. 0013 to 0029 of JP2013-195480A. And the vanadium phthalocyanine described in Japanese Patent No. 6081771, the contents of which are incorporated herein. Examples of the naphthalocyanine compound include compounds described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated herein. As the near-infrared absorbing dye, the compounds described in JP-A-2016-146619 can also be used.

　ピロロピロール化合物としては、式（ＰＰ）で表される化合物が挙げられる。

Figure JPOXMLDOC01-appb-C000027
　式中、Ｒ1aおよびＲ1bは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ2およびＲ3は、各々独立に水素原子または置換基を表し、Ｒ2およびＲ3は、互いに結合して環を形成してもよく、Ｒ4は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲ4AＲ4B、または金属原子を表し、Ｒ4は、Ｒ1a、Ｒ1bおよびＲ3から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ4AおよびＲ4Bは、各々独立に置換基を表す。Ｒ4AおよびＲ4Bは互いに結合して環を形成していてもよい。式（ＰＰ）の詳細については、特開２００９－２６３６１４号公報の段落番号００１７～００４７、特開２０１１－６８７３１号公報の段落番号００１１～００３６、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。
Examples of the pyrrolopyrrole compound include a compound represented by the formula (PP).

Figure JPOXMLDOC01-appb-C000027
In the formula, R 1a and R 1b each independently represents an alkyl group, an aryl group or a heteroaryl group, R 2 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 and R 3 are They may combine with each other to form a ring, and each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR 4A R 4B , or a metal atom, and R 4 represents R At least one selected from 1a , R 1b and R 3 may be covalently or coordinately bonded, and R 4A and R 4B each independently represent a substituent. R 4A and R 4B may be bonded to each other to form a ring. For details of the formula (PP), paragraph numbers 0017 to 0047 of JP2009-263614A, paragraph numbers 0011 to 0036 of JP2011-68731A, paragraph numbers 0010 to 0024 of WO2015 / 166873. The contents of which are incorporated herein by reference.

　式（ＰＰ）において、Ｒ1aおよびＲ1bは、各々独立に、アリール基またはヘテロアリール基が好ましく、アリール基がより好ましい。また、Ｒ1aおよびＲ1bが表すアルキル基、アリール基およびヘテロアリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、特開２００９－２６３６１４号公報の段落番号００２０～００２２に記載された置換基や、以下の置換基Ｔが挙げられる。
In formula (PP), R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in paragraph numbers 0020 to 0022 of JP-A-2009-263614 and the following substituent T.

（置換基Ｔ）

　アルキル基（好ましくは炭素数１～３０のアルキル基）、アルケニル基（好ましくは炭素数２～３０のアルケニル基）、アルキニル基（好ましくは炭素数２～３０のアルキニル基）、アリール基（好ましくは炭素数６～３０のアリール基）、アミノ基（好ましくは炭素数０～３０のアミノ基）、アルコキシ基（好ましくは炭素数１～３０のアルコキシ基）

、アリールオキシ基（好ましくは炭素数６～３０のアリールオキシ基）、ヘテロアリールオキシ基、アシル基（好ましくは炭素数１～３０のアシル基）、アルコキシカルボニル基

（好ましくは炭素数２～３０のアルコキシカルボニル基）、アリールオキシカルボニル基

（好ましくは炭素数７～３０のアリールオキシカルボニル基）、アシルオキシ基（好ましくは炭素数２～３０のアシルオキシ基）、アシルアミノ基（好ましくは炭素数２～３０のアシルアミノ基）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０のアルコキシカルボニルアミノ基）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０のアリールオキシカルボニルアミノ基）、スルファモイル基（好ましくは炭素数０～３０のスルファモイル基）、カルバモイル基（好ましくは炭素数１～３０のカルバモイル基）、アルキルチオ基（好ましくは炭素数１～３０のアルキルチオ基）、アリールチオ基

（好ましくは炭素数６～３０のアリールチオ基）、ヘテロアリールチオ基（好ましくは炭素数１～３０）、アルキルスルホニル基（好ましくは炭素数１～３０）、アリールスルホニル基（好ましくは炭素数６～３０）、ヘテロアリールスルホニル基（好ましくは炭素数１～３０）、アルキルスルフィニル基（好ましくは炭素数１～３０）、アリールスルフィニル基（好ましくは炭素数６～３０）、ヘテロアリールスルフィニル基（好ましくは炭素数１～３０）、ウレイド基（好ましくは炭素数１～３０）、ヒドロキシ基、カルボキシル基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基、メルカプト基、ハロゲン原子、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基（好ましくは炭素数１～３０）。これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。置換基としては、上述した置換基Ｔで説明した基が挙げられる。
(Substituent T)

An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably Aryl group having 6 to 30 carbon atoms), amino group (preferably amino group having 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 30 carbon atoms)

An aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, an acyl group (preferably an acyl group having 1 to 30 carbon atoms), an alkoxycarbonyl group

(Preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group

(Preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group ( Preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), A carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group

(Preferably an arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably having 1 to 30 carbon atoms), alkylsulfonyl group (preferably having 1 to 30 carbon atoms), arylsulfonyl group (preferably having 6 to 30 carbon atoms) 30), heteroarylsulfonyl group (preferably having 1 to 30 carbon atoms), alkylsulfinyl group (preferably having 1 to 30 carbon atoms), arylsulfinyl group (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1-30 carbon atoms, ureido group (preferably 1-30 carbon atoms), hydroxy group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imido acid group, mercapto group, halogen Atoms, cyano groups, alkylsulfino groups, arylsulfino groups, hydrazino groups, imino groups, hete Aryl group (preferably having 1 to 30 carbon atoms). When these groups are further substitutable groups, they may further have a substituent. Examples of the substituent include the groups described above for the substituent T.

　Ｒ1a、Ｒ1bで表される基の具体例としては、アルコキシ基を置換基として有するアリール基、ヒドロキシ基を置換基として有するアリール基、アシルオキシ基を置換基として有するアリール基などが挙げられる。
Specific examples of the group represented by R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxy group as a substituent, and an aryl group having an acyloxy group as a substituent.

　式（ＰＰ）において、Ｒ2およびＲ3は、各々独立に水素原子または置換基を表す。置換基としては上述した置換基Ｔが挙げられる。Ｒ2およびＲ3の少なくとも一方は電子求引性基が好ましい。電子求引性基としては、シアノ基、カルボキシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルカルボニル基、アリールカルボニル基、アルキルスルホニル基、アリールスルホニル基などが挙げられ、シアノ基が好ましい。
In the formula (PP), R 2 and R 3 each independently represents a hydrogen atom or a substituent. Examples of the substituent include the above-described substituent T. At least one of R 2 and R 3 is preferably an electron withdrawing group. Examples of the electron withdrawing group include a cyano group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group, and a cyano group is preferable. .

　式（ＰＰ）において、Ｒ2は電子求引性基（好ましくはシアノ基）を表し、Ｒ3はヘテロアリール基を表すことが好ましい。ヘテロアリール基は、５員環または６員環が好ましい。また、ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が２～８の縮合環がより好ましく、単環または縮合数が２～４の縮合環が更に好ましい。ヘテロアリール基を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。ヘテロ原子としては、例えば、窒素原子、酸素原子、硫黄原子が例示される。ヘテロアリール基は、窒素原子を１個以上有することが好ましい。式（ＰＰ）における２個のＲ2同士は同一であってもよく、異なっていてもよい。また、式（ＰＰ）における２個のＲ3同士は同一であってもよく、異なっていてもよい。
In the formula (PP), R 2 represents an electron withdrawing group (preferably a cyano group), and R 3 preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and even more preferably a single ring or a condensed ring having 2 to 4 condensations. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. Two R 2 in the formula (PP) may be the same or different. Moreover, two R < 3 > in Formula (PP) may be the same, and may differ.

　式（ＰＰ）において、Ｒ4は、水素原子、アルキル基、アリール基、ヘテロアリール基または－ＢＲ4AＲ4Bで表される基であることが好ましく、水素原子、アルキル基、アリール基または－ＢＲ4AＲ4Bで表される基であることがより好ましく、－ＢＲ4AＲ4Bで表される基であることが更に好ましい。Ｒ4AおよびＲ4Bが表す置換基としては、ハロゲン原子、アルキル基、アルコキシ基、アリール基、または、ヘテロアリール基が好ましく、アルキル基、アリール基、または、ヘテロアリール基がより好ましく、アリール基が特に好ましい。これらの基はさらに置換基を有していてもよい。式（ＰＰ）における２個のＲ4同士は同一であってもよく、異なっていてもよい。Ｒ4AおよびＲ4Bは互いに結合して環を形成していてもよい。
In the formula (PP), R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR 4A R 4B , and preferably a hydrogen atom, an alkyl group, an aryl group or —BR A group represented by 4A R 4B is more preferred, and a group represented by —BR 4A R 4B is more preferred. The substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Particularly preferred. These groups may further have a substituent. Two R 4 s in the formula (PP) may be the same or different. R 4A and R 4B may be bonded to each other to form a ring.

　ピロロピロール化合物の具体例としては、後述する実施例に記載の化合物が挙げられる。また、ピロロピロール化合物としては、特開２００９－２６３６１４号公報の段落番号００１６～００５８に記載の化合物、特開２０１１－６８７３１号公報の段落番号００３７～００５２に記載の化合物、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００３３に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Specific examples of the pyrrolopyrrole compound include compounds described in Examples described later. Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph Nos. 0037 to 0052 of JP-A-2011-68731, and international publication WO2015 / 166873. Examples include compounds described in paragraph numbers 0010 to 0033 of the publication, and the contents thereof are incorporated in the present specification.

　スクアリリウム化合物は、下記式（ＳＱ１）で表される化合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000028
　式中、Ａｓ1およびＡｓ2は、それぞれ独立してアリール基、複素環基または式（Ａｓ－１）で表される基を表す；

Figure JPOXMLDOC01-appb-C000029
　式中、＊は結合手を表し、Ｒｓ1～Ｒｓ3は、それぞれ独立して水素原子またはアルキル基を表し、Ａｓ3は複素環基を表し、ｎs1は、０以上の整数を表し、Ｒｓ1とＲｓ2は、互いに結合して環を形成してもよく、Ｒｓ1とＡｓ3は、互いに結合して環を形成してもよく、Ｒｓ2とＲｓ3は、互いに結合して環を形成してもよく、ｎs1が２以上の場合、複数のＲｓ2およびＲｓ3はそれぞれ同一であってもよく、異なっていてもよい。
The squarylium compound is preferably a compound represented by the following formula (SQ1).

Figure JPOXMLDOC01-appb-C000028
In the formula, As 1 and As 2 each independently represent an aryl group, a heterocyclic group or a group represented by the formula (As-1);

Figure JPOXMLDOC01-appb-C000029
In the formula, * represents a bond, Rs 1 to Rs 3 each independently represents a hydrogen atom or an alkyl group, As 3 represents a heterocyclic group, n s1 represents an integer of 0 or more, Rs 1 and Rs 2 may be bonded to each other to form a ring, Rs 1 and As 3 may be bonded to each other to form a ring, and Rs 2 and Rs 3 may be bonded to each other to form a ring. When n s1 is 2 or more, a plurality of Rs 2 and Rs 3 may be the same or different.

　Ａｓ1およびＡｓ2が表わすアリール基の炭素数は、６～４８が好ましく、６～２２がより好ましく、６～１２が特に好ましい。
The number of carbon atoms of the aryl group represented by As 1 and As 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

　Ａｓ1、Ａｓ2およびＡｓ3が表わす複素環基は、５員環または６員環の複素環基が好ましい。また、複素環基は、単環の複素環基または縮合数が２～８の縮合環の複素環基が好ましく、単環の複素環基または縮合数が２～４の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２または３の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２の縮合環の複素環基が特に好ましい。複素環基の環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子が例示され、窒素原子、硫黄原子が好ましい。複素環基の環を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。
The heterocyclic group represented by As 1 , As 2 and As 3 is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4. Are more preferable, a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable. Examples of the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.

　式（Ａｓ－１）におけるＲｓ1～Ｒｓ3は、それぞれ独立して水素原子またはアルキル基を表す。Ｒｓ1～Ｒｓ3が表わすアルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。Ｒｓ1～Ｒｓ3は水素原子であることが好ましい。
Rs 1 to Rs 3 in the formula (As-1) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by Rs 1 to Rs 3 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. Rs 1 to Rs 3 are preferably hydrogen atoms.

　式（Ａｓ－１）におけるｎs1は、０以上の整数を表す。ｎs1は０～２の整数が好ましく、０または１がより好ましく、０が更に好ましい。
In the formula (As-1), n s1 represents an integer of 0 or more. n s1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

　式（Ａｓ－１）において、Ｒｓ1とＲｓ2は、互いに結合して環を形成してもよく、Ｒｓ1とＡｓ3は、互いに結合して環を形成してもよく、Ｒｓ2とＲｓ3は、互いに結合して環を形成してもよい。上記の環を形成する場合の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、炭素数１～１０のアルキレン基およびそれらの組み合わせからなる群より選ばれる２価の連結基が好ましい。連結基としてのアルキレン基は無置換であってもよく、置換基を有していてもよい。置換基としては上述した置換基Ｔが挙げられる。
In the formula (As-1), Rs 1 and Rs 2 may be bonded to each other to form a ring, and Rs 1 and As 3 may be bonded to each other to form a ring, and Rs 2 and Rs 2 3 may be bonded to each other to form a ring. The linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. . The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.

　式（ＳＱ１）において、Ａｓ1およびＡｓ2が表わす基は置換基を有することが好ましい。置換基としては上述した置換基Ｔが挙げられる。
In the formula (SQ1), the group represented by As 1 and As 2 preferably has a substituent. Examples of the substituent include the above-described substituent T.

　式（ＳＱ１）において、Ａｓ1およびＡｓ2がそれぞれ独立してアリール基または複素環基であるか、あるいは、Ａｓ1およびＡｓ2がそれぞれ独立して式（Ａｓ－１）で表される基であることが好ましい。
In the formula (SQ1), As 1 and As 2 are each independently an aryl group or a heterocyclic group, or As 1 and As 2 are each independently a group represented by the formula (As-1) Preferably there is.

　なお、式（ＳＱ１）においてカチオンは、以下のように非局在化して存在している。

Figure JPOXMLDOC01-appb-C000030
In the formula (SQ1), cations are delocalized as follows.

Figure JPOXMLDOC01-appb-C000030

　スクアリリウム化合物の具体例としては、特開２０１１－２０８１０１号公報の段落番号００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落番号００６０～００６１に記載の化合物、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００４０に記載の化合物、国際公開ＷＯ２０１３／１３３０９９号公報に記載の化合物、国際公開ＷＯ２０１４／０８８０６３号公報に記載の化合物、特開２０１４－１２６６４２号公報に記載の化合物、特開２０１６－１４６６１９号公報に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、特開２０１７－２５３１１号公報に記載の化合物、国際公開ＷＯ２０１６／１５４７８２号公報に記載の化合物、特許５８８４９５３号公報に記載の化合物、特許６０３６６８９号公報に記載の化合物、特許５８１０６０４号公報に記載の化合物、特開２０１７－０６８１２０号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Specific examples of the squarylium compound include compounds described in JP-A-2011-208101, paragraphs 0044 to 0049, compounds described in JP-A-6065169, paragraphs 0060 to 0061, and international publication WO2016 / 181987. The compound described in Paragraph No. 0040, the compound described in International Publication WO2013 / 133099, the compound described in International Publication WO2014 / 088063, the compound described in JP2014-126642A, JP2016-146619A Compounds described in Japanese Laid-Open Patent Publication No. 2015-176046, compounds described in Japanese Patent Laid-Open No. 2017-25311, compounds described in International Publication No. WO2016 / 154787, compounds described in Japanese Patent No. 5884953 , Patent 603 A compound according to 689 JP-compound described in Japanese Patent No. 5810604, can be mentioned compounds described in JP-A-2017-068120, the contents of which are incorporated herein.

　シアニン化合物は、式（Ｃｙ１）で表される化合物が好ましい。

Figure JPOXMLDOC01-appb-C000031
The cyanine compound is preferably a compound represented by the formula (Cy1).

Figure JPOXMLDOC01-appb-C000031

　Ｒｃｙ1～Ｒｃｙ5は、それぞれ独立に、水素原子または置換基を表し、Ｒｃｙ1～Ｒｃｙ5のうち、２つが結合して環を形成していてもよい。ｎcy1は０～２の整数を表し、ｎcy1が２の場合、複数のＲｃｙ4およびＲｃｙ5は同一であってもよく、異なっていてもよい。Ａｃｙ1およびＡｃｙ2は、それぞれ独立にアリール基または複素環基を表す。式中のＣｙで表される部位がカチオン部である場合、Ｙは対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｙは対カチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。
Rcy 1 to Rcy 5 each independently represents a hydrogen atom or a substituent, and two of Rcy 1 to Rcy 5 may combine to form a ring. n cy1 represents an integer of 0 to 2, and when n cy1 is 2, a plurality of Rcy 4 and Rcy 5 may be the same or different. Acy 1 and Acy 2 each independently represents an aryl group or a heterocyclic group. When the site represented by Cy in the formula is a cation moiety, Y represents a counter anion, c represents a number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. , Y represents a counter cation, c represents a number necessary to balance the charge, and when the charge of the site represented by Cy in the formula is neutralized in the molecule, c is 0.

　Ｒｃｙ1～Ｒｃｙ5は、それぞれ独立に、水素原子または置換基を表す。置換基としては上述した置換基Ｔが挙げられる。式（Ｃｙ１）において、Ｒｃｙ1～Ｒｃｙ5のうち、２つが結合して環を形成していてもよい。上記の環を形成する場合の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、炭素数１～１０のアルキレン基およびそれらの組み合わせからなる群より選ばれる２価の連結基が好ましい。連結基としてのアルキレン基は無置換であってもよく、置換基を有していてもよい。置換基としては上述した置換基Ｔが挙げられる。
Rcy 1 to Rcy 5 each independently represents a hydrogen atom or a substituent. Examples of the substituent include the above-described substituent T. In the formula (Cy1), two members out of Rcy 1 to Rcy 5 may be bonded to form a ring. The linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. . The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.

　ｎcy1は０～２の整数を表し、０または１が好ましい。ｎcy1が２の場合、複数のＲｃｙ4およびＲｃｙ5は同一であってもよく、異なっていてもよい。
n cy1 represents an integer of 0 to 2, preferably 0 or 1. When n cy1 is 2, the plurality of Rcy 4 and Rcy 5 may be the same or different.

　Ａｃｙ1およびＡｃｙ2が表わすアリール基の炭素数は、６～４８が好ましく、６～２２がより好ましく、６～１２が特に好ましい。Ａｃｙ1およびＡｃｙ2が表わす複素環基は、５員環または６員環の複素環基が好ましい。また、複素環基は、単環の複素環基または縮合数が２～８の縮合環の複素環基が好ましく、単環の複素環基または縮合数が２～４の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２または３の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２の縮合環の複素環基が特に好ましい。複素環基の環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子が挙げられ、酸素原子、硫黄原子が好ましい。複素環基の環を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。Ａｃｙ1およびＡｃｙ2が表わす基は置換基を有していてもよい。置換基としては上述した置換基Ｔが挙げられる。
The number of carbon atoms of the aryl group represented by Acy 1 and Acy 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12. The heterocyclic group represented by Acy 1 and Acy 2 is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4. Are more preferable, a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable. Examples of the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom, and an oxygen atom and a sulfur atom are preferable. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2. The groups represented by Acy 1 and Acy 2 may have a substituent. Examples of the substituent include the above-described substituent T.

　式（Ｃｙ１）において、式中のＣｙで表される部位がカチオン部である場合、Ｙは対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表す。対アニオンとしては、ハロゲンイオン（Ｃｌ-、Ｂｒ-、Ｉ-）、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ＰＦ6 -、ＢＦ4 -、ＣｌＯ4 -、トリス（ハロゲノアルキルスルホニル）メチドアニオン（例えば、（ＣＦ3ＳＯ2）3Ｃ-）、ジ（ハロゲノアルキルスルホニル）イミドアニオン（例えば（ＣＦ3ＳＯ2）2Ｎ-）、テトラアリールボレートアニオン、テトラシアノボレートアニオンなどが挙げられる。

　式（Ｃｙ１）において、式中のＣｙで表される部位がアニオン部である場合、Ｙは対カチオンを表し、ｃは電荷のバランスを取るために必要な数を表す。対カチオンとしては、アルカリ金属イオン（Ｌｉ+、Ｎａ+、Ｋ+など）、アルカリ土類金属イオン（Ｍｇ2+、Ｃａ2+、Ｂａ2+、Ｓｒ2+など）、遷移金属イオン（Ａｇ+、Ｆｅ2+、Ｃｏ2+、Ｎｉ2+、Ｃｕ2+、Ｚｎ2+など）、その他の金属イオン（Ａｌ3+など）、アンモニウムイオン、トリエチルアンモニウムイオン、トリブチルアンモニウムイオン、ピリジニウムイオン、テトラブチルアンモニウムイオン、グアニジニウムイオン、テトラメチルグアニジニウムイオン、ジアザビシクロウンデセニウムイオンなどが挙げられる。

　式（Ｃｙ１）において、式中のＣｙで表される部位の電荷が分子内で中和されている場合、Ｙは存在しない。すなわち、ｃは０である。
In the formula (Cy1), when the site represented by Cy in the formula is a cation moiety, Y represents a counter anion, and c represents a number necessary for balancing electric charges. Counter anions include halogen ions (Cl − , Br − , I − ), sulfonate anions, carboxylate anions, sulfonylimide anions, PF 6 − , BF 4 − , ClO 4 − , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF 3 SO 2 ) 3 C − ), di (halogenoalkylsulfonyl) imide anion (for example (CF 3 SO 2 ) 2 N − ), tetraaryl borate anion, tetracyanoborate anion and the like can be mentioned.

In the formula (Cy1), when the site represented by Cy in the formula is an anion moiety, Y represents a counter cation, and c represents a number necessary for balancing the charge. As counter cations, alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ etc.), transition metal ions (Ag + Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+, etc.), other metal ions (such as Al 3+ ), ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion, tetrabutyl Ammonium ions, guanidinium ions, tetramethylguanidinium ions, diazabicycloundecenium ions and the like can be mentioned.

In the formula (Cy1), Y is not present when the charge at the site represented by Cy in the formula is neutralized in the molecule. That is, c is 0.

　シアニン化合物の具体例としては、特開２００９－１０８２６７号公報の段落番号００４４～００４５に記載の化合物、特開２００２－１９４０４０号公報の段落番号００２６～００３０に記載の化合物、特開２０１５－１７２００４号公報に記載の化合物、特開２０１５－１７２１０２号公報に記載の化合物、特開２００８－８８４２６号公報に記載の化合物、特開２０１７－０３１３９４号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Specific examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040, and JP-A No. 2015-172004. Compounds described in JP-A-2015-172102, compounds described in JP-A-2008-88426, compounds described in JP-A-2017-031394, and the like. Incorporated herein.

（クロコニウム化合物）

　クロコニウム化合物は、下記式（Ｃｒ１）で表される化合物であることが好ましい。

Figure JPOXMLDOC01-appb-C000032
　式中、Ａｃ1およびＡｃ2は、それぞれ独立してアリール基、複素環基または式（Ａｃ－１）で表される基を表す；


　式中、＊は結合手を表し、Ｒｃ1～Ｒｃ3は、それぞれ独立して水素原子またはアルキル基を表し、Ａｃ3は複素環基を表し、ｎc1は、０以上の整数を表し、Ｒｃ1とＲｃ2は、互いに結合して環を形成してもよく、Ｒｃ1とＡｃ3は、互いに結合して環を形成してもよく、Ｒｃ2とＲｃ3は、互いに結合して環を形成してもよく、ｎc1が２以上の場合、複数のＲｃ2およびＲｃ3はそれぞれ同一であってもよく、異なっていてもよい。
(Croconium compound)

The croconium compound is preferably a compound represented by the following formula (Cr1).

Figure JPOXMLDOC01-appb-C000032
In the formula, Ac 1 and Ac 2 each independently represent an aryl group, a heterocyclic group or a group represented by the formula (Ac-1);


In the formula, * represents a bond, Rc 1 to Rc 3 each independently represents a hydrogen atom or an alkyl group, Ac 3 represents a heterocyclic group, n c1 represents an integer of 0 or more, Rc 1 and Rc 2 may be bonded to each other to form a ring, Rc 1 and Ac 3 may be bonded to each other to form a ring, and Rc 2 and Rc 3 may be bonded to each other to form a ring. When n c1 is 2 or more, the plurality of Rc 2 and Rc 3 may be the same or different.

　Ａｃ1およびＡｃ2が表わすアリール基の炭素数は、６～４８が好ましく、６～２２がより好ましく、６～１２が特に好ましい。
The number of carbon atoms of the aryl group represented by Ac 1 and Ac 2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

　Ａｃ1、Ａｃ2およびＡｃ3が表わす複素環基は、５員環または６員環の複素環基が好ましい。また、複素環基は、単環の複素環基または縮合数が２～８の縮合環の複素環基が好ましく、単環の複素環基または縮合数が２～４の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２または３の縮合環の複素環基がより好ましく、単環の複素環基または縮合数が２の縮合環の複素環基が特に好ましい。複素環基の環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子が例示され、窒素原子、硫黄原子が好ましい。複素環基の環を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。
The heterocyclic group represented by Ac 1 , Ac 2 and Ac 3 is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group is preferably a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 8, and a monocyclic heterocyclic group or a condensed heterocyclic group having a condensed number of 2 to 4. Are more preferable, a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 or 3 is more preferable, and a monocyclic heterocyclic group or a heterocyclic group having a condensed number of 2 is particularly preferable. Examples of the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 to 2.

　式（Ａｃ－１）におけるＲｃ1～Ｒｃ3は、それぞれ独立して水素原子またはアルキル基

を表す。Ｒｃ1～Ｒｃ3が表わすアルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。Ｒｃ1～Ｒｃ3は水素原子であることが好ましい。
Rc 1 to Rc 3 in formula (Ac-1) are each independently a hydrogen atom or an alkyl group

Represents. The alkyl group represented by Rc 1 to Rc 3 preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. Rc 1 to Rc 3 are preferably hydrogen atoms.

　式（Ａｃ－１）におけるｎc1は、０以上の整数を表す。ｎc1は０～２の整数が好ましく、０または１がより好ましく、１が更に好ましい。
N c1 in formula (Ac-1) represents an integer of 0 or more. n c1 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.

　式（Ａｃ－１）において、Ｒｃ1とＲｃ2は、互いに結合して環を形成してもよく、Ｒｃ1とＡｃ3は、互いに結合して環を形成してもよく、Ｒｃ2とＲｃ3は、互いに結合して環を形成してもよい。上記の環を形成する場合の連結基としては、－ＣＯ－、－Ｏ－、－ＮＨ－、炭素数１～１０のアルキレン基およびそれらの組み合わせからなる群より選ばれる２価の連結基が好ましい。連結基としてのアルキレン基は無置換であってもよく、置換基を有していてもよい。置換基としては上述した置換基Ｔが挙げられる。
In the formula (Ac-1), Rc 1 and Rc 2 may combine with each other to form a ring, Rc 1 and Ac 3 may combine with each other to form a ring, and Rc 2 and Rc 2 3 may be bonded to each other to form a ring. The linking group for forming the ring is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. . The alkylene group as the linking group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T.

　式（Ｃｒ１）において、Ａｃ1およびＡｃ2が表わす基は置換基を有することが好ましい。置換基としては上述した置換基Ｔが挙げられる。
In the formula (Cr1), the groups represented by Ac 1 and Ac 2 preferably have a substituent. Examples of the substituent include the above-described substituent T.

　式（Ｃｒ１）において、Ａｃ1およびＡｃ2がそれぞれ独立してアリール基または複素環基であるか、あるいは、Ａｃ1およびＡｃ2がそれぞれ独立して式（Ａｃ－１）で表される基であることが好ましい。
In Formula (Cr1), Ac 1 and Ac 2 are each independently an aryl group or a heterocyclic group, or Ac 1 and Ac 2 are each independently a group represented by Formula (Ac-1) Preferably there is.

　なお、式（Ｃｒ１）においてカチオンは、以下のように非局在化して存在している。

Figure JPOXMLDOC01-appb-C000034
In the formula (Cr1), cations are delocalized as follows.

Figure JPOXMLDOC01-appb-C000034

　クロコニウム化合物の具体例としては、特開平５－１５５１４５号公報に記載された化合物、特開２００７－３１６４４号公報に記載された化合物も挙げられ、これらの内容は本明細書に組み込まれる。
Specific examples of the croconium compound include the compounds described in JP-A-5-155145 and the compounds described in JP-A-2007-31644, the contents of which are incorporated herein.

　イミニウム化合物は、下記式（Ｉｍ）で表される化合物が好ましい。
The iminium compound is preferably a compound represented by the following formula (Im).

　式（Ｉｍ）

Figure JPOXMLDOC01-appb-C000035
　式中、Ｒ11～Ｒ18は、それぞれ独立に、アルキル基またはアリール基を表し、Ｖ11～Ｖ15は、それぞれ独立に、アルキル基、アリール基、ハロゲン原子、アルコキシ基またはシアノ基を表し、Ｘは対アニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、ｎ１～ｎ５は、それぞれ独立に、０～４である。
Formula (Im)

Figure JPOXMLDOC01-appb-C000035
In the formula, each of R 11 to R 18 independently represents an alkyl group or an aryl group, and each of V 11 to V 15 independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a cyano group, X represents a counter anion, c represents a number necessary for balancing the charge, and n1 to n5 are each independently 0 to 4.

　Ｒ11～Ｒ18は、それぞれ独立に、アルキル基またはアリール基を表す。アルキル基の炭素数は、１～２０が好ましく、１～１２がより好ましく、１～８が特に好ましい。アルキル基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アリール基の炭素数は、６～２５が好ましく、６～１５がさらに好ましく、６～１２がより好ましい。

アルキル基およびアリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基Ｔで説明した基が挙げられる。
R 11 to R 18 each independently represents an alkyl group or an aryl group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms.

The alkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above for the substituent T.

　Ｖ11～Ｖ15は、それぞれ独立に、アルキル基、アリール基、ハロゲン原子、アルコキシ基またはシアノ基を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。アルキル基の炭素数は、１～２０が好ましく、１～１２がより好ましく、１～８が特に好ましい。アルキル基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖が特に好ましい。アリール基の炭素数は、６～２５が好ましく、６～１５がさらに好ましく、６～１２がより好ましい。アルコキシ基の炭素数は、１～２０が好ましく、１～１２がより好ましく、１～８が特に好ましい。アルコキシ基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖が特に好ましい。
V 11 to V 15 each independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group or a cyano group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.

　ｎ１～ｎ５は、それぞれ独立に、０～４である。ｎ１～ｎ４は、０～２が好ましく、０または１がより好ましい。ｎ５は、０～３が好ましく０～２がより好ましい。
n1 to n5 are each independently 0 to 4. n1 to n4 are preferably 0 to 2, and more preferably 0 or 1. n5 is preferably 0 to 3, and more preferably 0 to 2.

　Ｘは対アニオンを表す。対アニオンとしては、ハロゲンイオン（Ｃｌ-、Ｂｒ-、Ｉ-）

、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ＰＦ6 -、ＢＦ4 -、ＣｌＯ4 -、トリス（ハロゲノアルキルスルホニル）メチドアニオン（例えば、（ＣＦ3ＳＯ2）3Ｃ-）、ジ（ハロゲノアルキルスルホニル）イミドアニオン（例えば（ＣＦ3ＳＯ2）2Ｎ-）、テトラアリールボレートアニオン、テトラシアノボレートアニオンなどが挙げられる。
X represents a counter anion. Counter anions include halogen ions (Cl − , Br − , I − ).

, Sulfonate anion, carboxylate anion, sulfonylimide anion, PF 6 − , BF 4 − , ClO 4 − , tris (halogenoalkylsulfonyl) methide anion (eg, (CF 3 SO 2 ) 3 C − ), di (halogenoalkyl) (Sulfonyl) imide anion (for example, (CF 3 SO 2 ) 2 N − ), tetraarylborate anion, tetracyanoborate anion and the like.

　ｃは電荷のバランスを取るために必要な数を表し、例えば、２であることが好ましい。
c represents a number necessary for balancing the electric charge, and is preferably 2, for example.

　イミニウム化合物の具体例としては、特表２００８－５２８７０６号公報に記載の化合物、特開２０１２－０１２３９９号公報に記載の化合物および特開２００７－９２０６０号公報に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
Specific examples of the iminium compound include a compound described in JP-T-2008-528706, a compound described in JP-A-2012-012399, and a compound described in JP-A-2007-92060. Are incorporated herein.

　近赤外線吸収色素は市販品を用いることもできる。近赤外線吸収色素の市販品としては、ＳＤＯ－Ｃ３３（有本化学工業（株）製）、イーエクスカラーＩＲ－１４、イーエクスカラーＩＲ－１０Ａ、イーエクスカラーＴＸ－ＥＸ－８０１Ｂ、イーエクスカラーＴＸ－ＥＸ－８０５Ｋ（（株）日本触媒製）、ＳｈｉｇｅｎｏｘＮＩＡ－８０４１、ＳｈｉｇｅｎｏｘＮＩＡ－８０４２、ＳｈｉｇｅｎｏｘＮＩＡ－８１４、ＳｈｉｇｅｎｏｘＮＩＡ－８２０、ＳｈｉｇｅｎｏｘＮＩＡ－８３９（ハッコーケミカル社製）、ＥｐｏｌｉｔｅＶ－６３、Ｅｐｏｌｉｇｈｔ３８０１、Ｅｐｏｌｉｇｈｔ３０３６（ＥＰＯＬＩＮ社製）、ＰＲＯ－ＪＥＴ８２５ＬＤＩ（富士フイルム（株）製）、ＮＫ－３０２７、ＮＫ－５０６０（（株）林原製）、ＹＫＲ－３０７０（三井化学（株）製）などが挙げられる。
A commercial item can also be used for the near-infrared absorbing dye. Commercially available near-infrared absorbing dyes include SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), e-ex color IR-14, e-ex color IR-10A, e-ex color TX-EX-801B, e-ex color TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 And PRO-JET825LDI (manufactured by FUJIFILM Corporation), NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.) and the like.

　感光性組成物の全固形分中における色材の含有量は、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることが更に好ましく、４０質量％以上であることがより一層好ましく、５０質量％以上であることが更に一層好ましい。上限は、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。特に、感光性組成物中の色材の含有量が増加するに伴い、感度が低下し易い傾向にあるが、本発明の感光性組成物によれば、感光性組成物中の色材の含有量が高くても、優れた感度を維持することができる。このため、感光性組成物の全固形分中における色材の含有量が高い場合において本発明の効果がより顕著である。
The content of the coloring material in the total solid content of the photosensitive composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. The content is more preferably at least 50% by mass, even more preferably at least 40% by mass, and even more preferably at least 50% by mass. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. In particular, as the content of the color material in the photosensitive composition increases, the sensitivity tends to decrease, but according to the photosensitive composition of the present invention, the content of the color material in the photosensitive composition. Even if the amount is high, excellent sensitivity can be maintained. For this reason, when the content of the coloring material in the total solid content of the photosensitive composition is high, the effect of the present invention is more remarkable.

　本発明の感光性組成物に用いられる色材は、有彩色着色剤、黒色着色剤および白色着色剤から選ばれる少なくとも１種を含むことが好ましく、有彩色着色剤および黒色着色剤から選ばれる少なくとも１種を含むことがより好ましく、有彩色着色剤を含むことが更に好ましい。また、色材の全質量中における有彩色着色剤および黒色着色剤の含有量は、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。上限は、１００質量％とすることができ、９０質量％以下とすることもできる。
The color material used in the photosensitive composition of the present invention preferably contains at least one selected from a chromatic colorant, a black colorant, and a white colorant, and at least selected from a chromatic colorant and a black colorant. It is more preferable to include one type, and it is more preferable to include a chromatic colorant. Further, the content of the chromatic colorant and the black colorant in the total mass of the colorant is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass or more. Is more preferable. The upper limit can be 100% by mass, or 90% by mass or less.

　本発明の感光性組成物をカラーフィルタ用の組成物（より具体的にはカラーフィルタの着色画素形成用の組成物）として用いる場合においては、感光性組成物の全固形分中における有彩色着色剤の含有量は３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。上限は、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。また、色材の全質量中における有彩色着色剤の含有量は、２５質量％以上であることが好ましく、４５質量％以上であることがより好ましく、６５質量％以上であることが更に好ましい。上限は、１００質量％とすることができ、７５質量％以下とすることもできる。
When the photosensitive composition of the present invention is used as a composition for a color filter (more specifically, a composition for forming a colored pixel of a color filter), chromatic coloring in the total solid content of the photosensitive composition. The content of the agent is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. Further, the content of the chromatic colorant in the total mass of the coloring material is preferably 25% by mass or more, more preferably 45% by mass or more, and further preferably 65% by mass or more. The upper limit can be 100% by mass, or 75% by mass or less.

　本発明の感光性組成物を光散乱層形成用の組成物や、カラーフィルタの白色画素形成用の組成物などとして用いる場合においては、感光性組成物の全固形分中における白色着色剤の含有量は３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。上限は、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。また、色材の全質量中における白色着色剤の含有量は、２５質量％以上であることが好ましく、４５質量％以上であることがより好ましく、６５質量％以上であることが更に好ましい。上限は、１００質量％とすることができ、７５質量％以下とすることもできる。
In the case where the photosensitive composition of the present invention is used as a composition for forming a light scattering layer or a composition for forming a white pixel of a color filter, the white colorant is contained in the total solid content of the photosensitive composition. The amount is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. Further, the content of the white colorant in the total mass of the coloring material is preferably 25% by mass or more, more preferably 45% by mass or more, and further preferably 65% by mass or more. The upper limit can be 100% by mass, or 75% by mass or less.

　本発明の感光性組成物を遮光膜形成用の組成物やブラックマトリックス形成用の組成物として用いる場合においては、感光性組成物の全固形分中における黒色着色剤（好ましくは無機黒色着色剤）の含有量は３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。上限は、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。また、色材の全質量中における黒色着色剤の含有量は、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。上限は、１００質量％とすることができ、９０質量％以下とすることもできる。
When the photosensitive composition of the present invention is used as a composition for forming a light-shielding film or a composition for forming a black matrix, a black colorant (preferably an inorganic black colorant) in the total solid content of the photosensitive composition. The content of is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. Further, the content of the black colorant in the total mass of the coloring material is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. The upper limit can be 100% by mass, or 90% by mass or less.

　本発明の感光性組成物を近赤外線透過フィルタ用の組成物として用いる場合、本発明で用いられる色材は、以下の（１）～（３）の少なくとも一つの要件を満たすことが好ましい。
When the photosensitive composition of the present invention is used as a composition for a near-infrared transmission filter, the color material used in the present invention preferably satisfies at least one of the following requirements (1) to (3).

（１）：２種類以上の有彩色着色剤を含み、２種以上の有彩色着色剤の組み合わせで黒色を形成している。赤色着色剤、青色着色剤、黄色着色剤、紫色着色剤および緑色着色剤から選ばれる２種類以上の着色剤の組み合わせで黒色を形成していることが好ましい。

（２）：有機黒色着色剤を含む。

（３）：上記（１）または（２）において、更に近赤外線吸収色素を含む。
(1): Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants. It is preferable that black is formed by a combination of two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant and a green colorant.

(2): Contains an organic black colorant.

(3): In the above (1) or (2), a near infrared absorbing dye is further contained.

　上記（１）の態様の好ましい組み合わせとしては、例えば以下が挙げられる。

（１－１）赤色着色剤と青色着色剤とを含有する態様。

（１－２）赤色着色剤と青色着色剤と黄色着色剤とを含有する態様。

（１－３）赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤とを含有する態様。

（１－４）赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤とを含有する態様。

（１－５）赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤とを含有する態様。

（１－６）赤色着色剤と青色着色剤と緑色着色剤とを含有する態様。

（１－７）黄色着色剤と紫色着色剤とを含有する態様。
Examples of the preferred combination of the above aspect (1) include the following.

(1-1) An embodiment containing a red colorant and a blue colorant.

(1-2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant.

(1-3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(1-4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(1-5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(1-6) An embodiment containing a red colorant, a blue colorant, and a green colorant.

(1-7) An embodiment containing a yellow colorant and a purple colorant.

　上記の（２）の態様においては、更に有彩色着色剤を含有することも好ましい。有機黒色着色剤と有彩色着色剤とを併用することで、優れた分光特性が得られ易い。有機黒色着色剤と組み合わせて用いる有彩色着色剤としては、例えば、赤色着色剤、青色着色剤、紫色着色剤などが挙げられ、赤色着色剤および青色着色剤が好ましい。これらは単独で使用してもよく、２種以上を併用してもよい。また、有彩色着色剤と有機黒色着色剤との混合割合は、有機黒色着色剤１００質量部に対して、有彩色着色剤が１０～２００質量部が好ましく、１５～１５０質量部がより好ましい。
In the above aspect (2), it is preferable to further contain a chromatic colorant. By using the organic black colorant and the chromatic colorant in combination, excellent spectral characteristics can be easily obtained. Examples of the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more. The mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass with respect to 100 parts by mass of the organic black colorant.

　上記の（３）の態様においては、色材の全質量中における近赤外線吸収色素の含有量は、５～４０質量％であることが好ましい。上限は、３０質量％以下が好ましく、２５質量％以下がより好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。
In the above aspect (3), the content of the near-infrared absorbing dye in the total mass of the coloring material is preferably 5 to 40% by mass. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

＜＜樹脂＞＞

　本発明の感光性組成物は、樹脂を含有することができる。なお、本発明において樹脂とは、色材以外の有機化合物であって、分子量が３０００以上の有機化合物のことを言う。

樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。
<< Resin >>

The photosensitive composition of the present invention can contain a resin. In the present invention, the resin refers to an organic compound other than a color material and having a molecular weight of 3000 or more.

Resin is mix | blended by the use which disperse | distributes particles, such as a pigment, in a composition, and the use of a binder, for example. Note that a resin mainly used for dispersing particles such as pigment is also referred to as a dispersant. However, such use of the resin is an example, and it can be used for purposes other than such use.

　樹脂の重量平均分子量（Ｍｗ）は、３０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、４０００以上が好ましく、５０００以上がより好ましい。
The weight average molecular weight (Mw) of the resin is preferably 3000-2 million. The upper limit is preferably 1000000 or less, and more preferably 500000 or less. The lower limit is preferably 4000 or more, and more preferably 5000 or more.

　樹脂としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。
Resins include (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.

　本発明において、樹脂として酸基を有する樹脂を用いることが好ましい。この態様によれば、感光性組成物の現像性を向上させることができ、矩形性に優れた画素を形成しやすい。酸基としては、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。酸基を有する樹脂は、例えば、アルカリ可溶性樹脂として用いることができる。
In the present invention, it is preferable to use a resin having an acid group as the resin. According to this aspect, the developability of the photosensitive composition can be improved, and a pixel having excellent rectangularity can be easily formed. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxyl group is preferable. The resin having an acid group can be used as an alkali-soluble resin, for example.

　酸基を有する樹脂は、側鎖に酸基を有する繰り返し単位を含むことが好ましく、酸基を側鎖に有する繰り返し単位を樹脂の全繰り返し単位中５～７０モル％含むことがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の上限は、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の下限は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましい。
The resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of a repeating unit having an acid group in the side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

　酸基を有する樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分に由来する繰り返し単位を含むことも好ましい。
The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a repeating unit derived from the component.

Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036

　式（ＥＤ１）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。

Figure JPOXMLDOC01-appb-C000037
　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の詳細については、特開２０１０－１６８５３９号公報の記載を参酌でき、この内容は本明細書に組み込まれる。
In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Figure JPOXMLDOC01-appb-C000037
In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. The details of the formula (ED2) can be referred to the description of JP 2010-168539 A, the content of which is incorporated herein.

　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。
As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

　本発明で用いられる樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含むことも好ましい。

Figure JPOXMLDOC01-appb-C000038
　式（Ｘ）中、Ｒ1は、水素原子またはメチル基を表し、Ｒ2は炭素数２～１０のアルキレン基を表し、Ｒ3は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。
It is also preferable that the resin used in the present invention contains a repeating unit derived from a compound represented by the following formula (X).

Figure JPOXMLDOC01-appb-C000038
In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。
Regarding the resin having an acid group, description in paragraph Nos. 0558 to 0571 of JP2012-208494A (paragraph No. 0685 to 0700 in corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408A, The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the resin which has an acid group can also use a commercial item.

　酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下が好ましく、３００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下が更に好ましい。酸基を有する樹脂の重量平均分子量（Ｍｗ）は、５０００～１０００００が好ましい。また、酸基を有する樹脂の数平均分子量（Ｍｎ）は、１０００～２００００が好ましい。
The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100,000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.

　酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。

Figure JPOXMLDOC01-appb-C000039
Examples of the resin having an acid group include a resin having the following structure.

Figure JPOXMLDOC01-appb-C000039

　本発明の感光性組成物は、分散剤としての樹脂を含むこともできる。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。

酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。
The photosensitive composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred.

The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g. The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

　分散剤として用いる樹脂は、酸基を有する繰り返し単位を含むことが好ましい。分散剤として用いる樹脂が酸基を有する繰り返し単位を含むことにより、フォトリソグラフィ法によりパターン形成する際、現像残渣の発生をより抑制できる。
The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, the generation of a development residue can be further suppressed when a pattern is formed by a photolithography method.

　分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細は、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。グラフト樹脂の具体例としては、下記構造の樹脂が挙げられる。

Figure JPOXMLDOC01-appb-C000040
The resin used as the dispersant is also preferably a graft resin. Details of the graft resin can be referred to the descriptions in paragraph numbers 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Specific examples of the graft resin include resins having the following structure.

Figure JPOXMLDOC01-appb-C000040

　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造を有する主鎖と、原子数４０～１０，０００の側鎖を含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子とは、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。ポリイミン系分散剤の具体例としては、下記構造の樹脂が挙げられる。

Figure JPOXMLDOC01-appb-C000041
The resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa 14 or less, and a side chain containing a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain A resin having a basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the polyimine-based dispersant, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. Specific examples of the polyimine dispersant include resins having the following structure.

Figure JPOXMLDOC01-appb-C000041

　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えばデンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１、および、下記構造の化合物が挙げられる。

Figure JPOXMLDOC01-appb-C000042
The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Examples of such a resin include dendrimers (including star polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP2013-043662A and compounds having the following structures.

Figure JPOXMLDOC01-appb-C000042

　また、上述した酸基を有する樹脂（アルカリ可溶性樹脂）を分散剤として用いることもできる。
Further, the above-described resin having an acid group (alkali-soluble resin) can be used as a dispersant.

　また、分散剤として用いる樹脂は、エチレン性不飽和結合基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。
Moreover, it is also preferable that resin used as a dispersing agent is resin containing the repeating unit which has an ethylenically unsaturated bond group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol% in all repeating units of the resin. % Is more preferable.

　分散剤は、市販品としても入手可能であり、そのような具体例としては、ＢＹＫＣｈｅｍｉｅ社製のＤＩＳＰＥＲＢＹＫシリーズ（例えば、ＤＩＳＰＥＲＢＹＫ－１１１、１６１など）、日本ルーブリゾール（株）製のソルスパースシリーズ（例えば、ソルスパース７６５００など）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。なお、上記分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。
Dispersants are also available as commercial products, and specific examples thereof include BYPER Chemie's DISPERBYK series (for example, DISPERBYK-111, 161, etc.), Nippon Lubrizol Corporation Solsperse series ( For example, Solsperse 76500). In addition, pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein. The resin described as the dispersant can be used for purposes other than the dispersant. For example, it can be used as a binder.

　本発明の感光性組成物が樹脂を含む場合、感光性組成物の全固形分中における樹脂の含有量は、５～５０質量％が好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下が更に好ましい。また、感光性組成物の全固形分中における酸基を有する樹脂の含有量は、５～５０質量％が好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。上限は、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下が更に好ましい。また、樹脂全量中における酸基を有する樹脂の含有量は、優れた現像性が得られやすいという理由から３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上が更に好ましく、８０質量％以上が特に好ましい。上限は、１００質量％とすることができ、９５質量％とすることもでき、９０質量％以下とすることもできる。
When the photosensitive composition of the present invention contains a resin, the content of the resin in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. The content of the resin having an acid group in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. Further, the content of the resin having an acid group in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, because excellent developability is easily obtained. 80 mass% or more is particularly preferable. The upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.

　また、感光性組成物の全固形分中における重合性化合物と樹脂との合計の含有量は、硬化性、現像性および被膜性の観点から１５～６５質量％が好ましい。下限は、２０質量％以上が好ましく、２５質量％以上がより好ましく、３０質量％以上が更に好ましい。上限は、６０質量％以下が好ましく、５０質量％以下がより好ましく、４０質量％以下が更に好ましい。また、重合性化合物の１００質量部に対して、樹脂を３０～３００質量部含有することが好ましい。下限は５０質量部以上が好ましく、８０質量部以上がより好ましい。上限は２５０質量部以下が好ましく、２００質量部以下がより好ましい。
Further, the total content of the polymerizable compound and the resin in the total solid content of the photosensitive composition is preferably 15 to 65% by mass from the viewpoints of curability, developability and film property. The lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less. The resin is preferably contained in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the polymerizable compound. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

＜＜環状エーテル基を有する化合物＞＞

　本発明の感光性組成物は、環状エーテル基を有する化合物を含有することができる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。環状エーテル基を有する化合物は、エポキシ基を有する化合物であることが好ましい。エポキシ基を有する化合物としては、１分子内にエポキシ基を１つ以上有する化合物が挙げられ、エポキシ基を２つ以上有する化合物が好ましい。エポキシ基は、１分子内に１～１００個有することが好ましい。エポキシ基の上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。エポキシ基の下限は、２個以上が好ましい。エポキシ基を有する化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。
<< Compound having a cyclic ether group >>

The photosensitive composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably 2 or more. Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The described compounds and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.

　エポキシ基を有する化合物は、低分子化合物（例えば、分子量２０００未満、さらには、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。
The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

　エポキシ基を有する化合物としては、エポキシ樹脂を好ましく用いることができる。エポキシ樹脂としては、例えばフェノール化合物のグリシジルエーテル化物であるエポキシ樹脂、各種ノボラック樹脂のグリシジルエーテル化物であるエポキシ樹脂、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂、複素環式エポキシ樹脂、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ハロゲン化フェノール類をグリシジル化したエポキシ樹脂、エポキシ基をもつケイ素化合物とそれ以外のケイ素化合物との縮合物、エポキシ基を持つ重合性不飽和化合物とそれ以外の他の重合性不飽和化合物との共重合体等が挙げられる。エポキシ樹脂のエポキシ当量は、３１０～３３００ｇ／ｅｑであることが好ましく、３１０～１７００ｇ／ｅｑであることがより好ましく、３１０～１０００ｇ／ｅｑであることが更に好ましい。
As the compound having an epoxy group, an epoxy resin can be preferably used. Examples of the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type. Epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group and other Examples thereof include copolymers with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.

　環状エーテル基を有する化合物の市販品としては、例えば、ＥＨＰＥ３１５０（（株）ダイセル製）、ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（以上、日油（株）製、エポキシ基含有ポリマー）等が挙げられる。
Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corp.), EPICLON N-695 (manufactured by DIC Corp.), Marproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, manufactured by NOF Corporation, epoxy group-containing polymer).

　本発明の感光性組成物が環状エーテル基を有する化合物を含有する場合、感光性組成物の全固形分中における環状エーテル基を有する化合物の含有量は、０．１～２０質量％が好ましい。下限は、例えば０．５質量％以上が好ましく、１質量％以上がより好ましい。

上限は、例えば、１５質量％以下が好ましく、１０質量％以下が更に好ましい。環状エーテル基を有する化合物は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。
When the photosensitive composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably from 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.

For example, the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one type or two or more types. In the case of two or more types, the total amount thereof is preferably in the above range.

＜＜他の光重合開始剤＞＞

　本発明の感光性組成物は、上述した環状オキシム化合物以外の他の光重合開始剤（以下、他の光重合開始剤ともいう）を含有してもよい。他の光重合開始剤としては、例えば、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物、クマリン化合物などが挙げられ、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物が好ましく、オキシム化合物、α－アミノケトン化合物がより好ましい。他の光重合開始剤としてのオキシム化合物は、上述した環状オキシム部位を有さないオキシム化合物や、上述した電子求引性基を有さないオキシム化合物が挙げられる。他の光重合開始剤の詳細については、特開２０１７－１２６０４４号公報の段落番号００１３～００３１を参酌でき、この内容は本明細書に組み込まれる。
<< Other photopolymerization initiators >>

The photosensitive composition of this invention may contain other photoinitiators (henceforth other photoinitiators) other than the cyclic oxime compound mentioned above. Other photopolymerization initiators include, for example, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazole dimers. Onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, coumarin compounds, etc., oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, Acylphosphine compounds are preferable, and oxime compounds and α-aminoketone compounds are more preferable. Examples of the oxime compound as another photopolymerization initiator include the oxime compound having no cyclic oxime moiety described above and the oxime compound having no electron withdrawing group described above. For details of other photopolymerization initiators, paragraphs 0013 to 0031 of JP-A No. 2017-126044 can be referred to, the contents of which are incorporated herein.

　α－ヒドロキシケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９、及び、ＩＲＧＡＣＵＲＥ－３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－８１９、ＤＡＲＯＣＵＲ－ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。
Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF). Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819, DAROCUR-TPO (manufactured by BASF).

　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１６－２１０１２号公報に記載の化合物などを用いることができる。本発明において好適に用いることができるオキシム化合物としては、例えば、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）、特開２０００－６６３８５号公報、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報に記載の化合物等も挙げられる。オキシム化合物の市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光重合開始剤２）、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。
Examples of oxime compounds include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. These compounds can be used. Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2- Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979, pp. 1653-1660), J. MoI. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP 2000-66385 A, JP 2000-80068 A, Special Table 2004 Examples thereof include compounds described in JP-A-534797 and JP-A-2006-342166. Commercial products of oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP 2012-14052 A), Adeka Arcles NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation) Etc.

　他の光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。この内容は本明細書に組み込まれる。
As another photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

　他の光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。この内容は本明細書に組み込まれる。
As another photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Compound (C-3). This content is incorporated herein.

　他の光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。

ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。
As another photopolymerization initiator, an oxime compound having a nitro group can be used.

The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

　本発明は、光重合開始剤として、２官能あるいは３官能以上の光重合開始剤を用いてもよい。このような光重合開始剤を用いることにより、光重合開始剤の１分子から２つ以上のラジカル等の活性種が発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、組成物の経時安定性を向上させることができる。そのような光重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開ＷＯ２０１５／００４５６５号公報、特表２０１６－５３２６７５号公報の段落番号０４１７～０４１２、国際公開ＷＯ２０１７／０３３６８０号公報の段落番号００３９～００５５に記載されているオキシム化合物の２量体や、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開ＷＯ２０１６／０３４９６３号公報に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）などが挙げられる。
In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator. By using such a photopolymerization initiator, active species such as two or more radicals are generated from one molecule of the photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in a solvent or the like is improved, the precipitation with time is less likely to occur, and the temporal stability of the composition can be improved. Specific examples of such a photopolymerization initiator include paragraphs 0417 to 0412 in JP2010-527339A, JP2011-524436A, International Publication WO2015 / 004565, and JP2016-532675A. A dimer of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. WO2017 / 033680, Compound (E) and Compound (G) described in JP2013-522445A, International Cmpd 1 to 7 described in published WO2016 / 034963, oxime ester photoinitiator described in paragraph No. 0007 of JP-T-2017-523465, paragraph No. 0020 to JP-A No. 2017-167399 Photoinitiators described in 0033, JP 2017 Photopolymerization initiators described in paragraphs 0017 to 0026 of JP-151342 (A), and the like.

　本発明の感光性組成物が他の光重合開始剤を含有する場合、他の光重合開始剤の含有量は、上述した環状オキシム化合物Ａの１００質量部に対して１０～９０質量部が好ましい。下限は、１５質量部以上が好ましく、２０質量部％以上がより好ましい。上限は、８０質量部以下が好ましく、７０質量部以下が更に好ましい。環状オキシム化合物Ａと他の光重合開始剤の割合が上記範囲であれば、深部まで十分に硬化した膜が得られやすい。
When the photosensitive composition of the present invention contains another photopolymerization initiator, the content of the other photopolymerization initiator is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the cyclic oxime compound A described above. . The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less. When the ratio between the cyclic oxime compound A and the other photopolymerization initiator is within the above range, a film that is sufficiently cured to a deep portion is easily obtained.

　本発明の感光性組成物は、他の光重合開始剤を実質的に含有しないことも好ましい。この態様によれば、得られる膜についての硬化の度合いのばらつきをより抑制し易い。発明の感光性組成物は、他の光重合開始剤を実質的に含有しない場合とは、感光性組成物の全固形分中における他の光重合開始剤の含有量が、０．１以下であることを意味し、０．０５質量％以下であることが好ましく、０．０１質量％以下であることが更に好ましく、他の光重合開始剤を含有しないことが特に好ましい。
It is also preferable that the photosensitive composition of the present invention contains substantially no other photopolymerization initiator. According to this aspect, it is easier to suppress variation in the degree of curing of the obtained film. When the photosensitive composition of the invention contains substantially no other photopolymerization initiator, the content of the other photopolymerization initiator in the total solid content of the photosensitive composition is 0.1 or less. In other words, it is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably no other photopolymerization initiator.

＜＜増感剤＞＞

　本発明の感光性組成物は、上述した環状オキシム化合物Ａのラジカル発生効率の向上や、感光波長の長波長化の目的で、増感剤をさらに含有していてもよい。増感剤としては、多核芳香族化合物（例えば、フェナントレン、アントラセン、ピレン、ペリレン、トリフェニレン、９，１０－ジアルコキシアントラセン）、キサンテン化合物（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、チオキサントン化合物（例えば、イソプロピルチオキサントン、ジエチルチオキサントン、クロロチオキサントン）、シアニン化合物（例えば、チアカルボシアニン、オキサカルボシアニン）

、メロシアニン化合物（例えば、メロシアニン、カルボメロシアニン）、フタロシアニン化合物、チアジン化合物（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン化合物（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アントラキノン化合物（例えば、アントラキノン）、スクアリリウム化合物（例えば、スクアリリウム）、クマリン化合物（例えば、７－ジエチルアミノ－４－メチルクマリン）、ケトクマリン化合物、フェノチアジン化合物、フェナジン化合物、スチリルベンゼン化合物、アゾ化合物、ジフェニルメタン化合物、トリフェニルメタン化合物、ジスチリルベンゼン化合物、カルバゾール化合物、ポルフィリン化合物、スピロ化合物、キナクリドン化合物、インジゴ化合物、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体、アセトフェノン化合物、ベンゾフェノン化合物、チオキサントン化合物、ミヒラーズケトン化合物などが挙げられる。増感剤は、波長３００～４５０ｎｍの範囲に極大吸収波長を有する化合物であることが好ましい。増感剤の具体例としては、後述の実施例に記載の化合物や、特開２０１３－２４９４７１号公報の段落番号０１７２～０２２２に記載された化合物が挙げられる。
<< Sensitizer >>

The photosensitive composition of the present invention may further contain a sensitizer for the purpose of improving the radical generation efficiency of the cyclic oxime compound A and increasing the photosensitive wavelength. Sensitizers include polynuclear aromatic compounds (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthene compounds (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal) ), Thioxanthone compounds (eg, isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanine compounds (eg, thiacarbocyanine, oxacarbocyanine)

, Merocyanine compounds (eg merocyanine, carbomerocyanine), phthalocyanine compounds, thiazine compounds (eg thionine, methylene blue, toluidine blue), acridine compounds (eg acridine orange, chloroflavin, acriflavine), anthraquinone compounds (eg anthraquinone) , Squarylium compounds (eg squarylium), coumarin compounds (eg 7-diethylamino-4-methylcoumarin), ketocoumarin compounds, phenothiazine compounds, phenazine compounds, styrylbenzene compounds, azo compounds, diphenylmethane compounds, triphenylmethane compounds, distyryl Benzene compounds, carbazole compounds, porphyrin compounds, spiro compounds, quinacridone compounds, indigo compounds, pyrites Um compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone compounds, benzophenone compounds, thioxanthone compounds, and Michler's ketone compound. The sensitizer is preferably a compound having a maximum absorption wavelength in the wavelength range of 300 to 450 nm. Specific examples of the sensitizer include compounds described in Examples described later and compounds described in paragraph numbers 0172 to 0222 of JP2013-249471A.

　本発明の感光性組成物が増感剤を含有する場合、感光性組成物の全固形分中における増感剤の含有量は、０．１～２０質量％が好ましい。下限は、例えば０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、例えば、１５質量％以下が好ましく、１０質量％以下が更に好ましい。増感剤は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。
When the photosensitive composition of the present invention contains a sensitizer, the content of the sensitizer in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. For example, the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one sensitizer or two or more sensitizers may be used. In the case of two or more types, the total amount thereof is preferably in the above range.

＜＜シランカップリング剤＞＞

　本発明の感光性組成物は、シランカップリング剤を含有することができる。この態様によれば、得られる硬化膜の支持体との密着性をより向上させることができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
<< Silane coupling agent >>

The photosensitive composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesiveness with the support body of the cured film obtained can be improved more. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth) allyl groups, (meth) acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. And a phenyl group, and an amino group, a (meth) acryloyl group and an epoxy group are preferable. Specific examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph Nos. 0056 to 0066 of JP-A-2009-242604. Is incorporated herein by reference.

　感光性組成物の全固形分中におけるシランカップリング剤の含有量は、０．１～５質量％が好ましい。上限は、３質量％以下が好ましく、２質量％以下がより好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。シランカップリング剤は、１種のみでもよく、２種以上でもよい。２種以上の場合は、合計量が上記範囲となることが好ましい。
The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

＜＜顔料誘導体＞＞

　本発明の感光性組成物が顔料を含む場合、更に顔料誘導体を含有することが好ましい。

顔料誘導体としては、発色団の一部分を、酸基、塩基性基またはフタルイミドメチル基で置換した構造を有する化合物が挙げられる。
<< Pigment derivative >>

When the photosensitive composition of this invention contains a pigment, it is preferable to contain a pigment derivative further.

Examples of the pigment derivative include a compound having a structure in which a part of the chromophore is substituted with an acid group, a basic group or a phthalimidomethyl group.

　顔料誘導体を構成する発色団としては、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、フタロシアニン系骨格、アントラキノン系骨格、キナクリドン系骨格、ジオキサジン系骨格、ペリノン系骨格、ペリレン系骨格、チオインジゴ系骨格、イソインドリン系骨格、イソインドリノン系骨格、キノフタロン系骨格、スレン系骨格、金属錯体系骨格等が挙げられ、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、キノフタロン系骨格、イソインドリン系骨格およびフタロシアニン系骨格が好ましく、アゾ系骨格およびベンゾイミダゾロン系骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。顔料誘導体の具体例としては、例えば、特開２０１１－２５２０６５号公報の段落番号０１６２～０１８３の記載を参酌でき、この内容は本明細書に組み込まれる。
The chromophores constituting the pigment derivatives include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone skeleton. Perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, selenium skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone skeleton, diketopyrrolo A pyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acid group which a pigment derivative has, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable. As specific examples of the pigment derivative, for example, the description of paragraph numbers 0162 to 0183 in JP 2011-252065 A can be referred to, the contents of which are incorporated herein.

　本発明の感光性組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料１００質量部に対し、１～３０質量部が好ましく、３～２０質量部がさらに好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。本発明の感光性組成物は、顔料誘導体を１種のみ含んでいてもよいし、２種以上含んでいてもよい。顔料誘導体を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
When the photosensitive composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. The photosensitive composition of this invention may contain only 1 type of pigment derivatives, and may contain 2 or more types. When two or more kinds of pigment derivatives are contained, the total amount thereof is preferably within the above range.

＜＜溶剤＞＞

　本発明の感光性組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤の例としては、例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類などが挙げられる。これらの詳細については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテートなどが挙げられる。本発明において有機溶剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。また、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドも溶解性向上の観点から好ましい。ただし溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。
<< Solvent >>

The photosensitive composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Regarding these details, paragraph number 0223 of International Publication No. WO2015 / 166779 can be referred to, the contents of which are incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like. In this invention, the organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Also, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are preferable from the viewpoint of improving solubility. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons or the like (for example, 50 ppm by weight per part of organic solvent). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).

　本発明においては、金属含有量の少ない溶剤を用いることが好ましく、溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。
In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a solvent having a mass ppt (parts per trill) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフルオロエチレン、ポリエチレンまたはナイロンが好ましい。
Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

　溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。
The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

　本発明において、有機溶剤は、過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。
In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

　感光性組成物中における溶剤の含有量は、１０～９５質量％であることが好ましい。下限は２０質量％以上が好ましく、３０質量％以上がより好ましく、４０質量％以上であることが更に好ましく、５０質量％以上であることがより一層好ましく、５５質量％以上であることが更に一層好ましく、６０質量％以上であることが特に好ましい。上限は、９０質量％であることが好ましい。
The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more. It is preferably 60% by mass or more. The upper limit is preferably 90% by mass.

　また、本発明の感光性組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、感光性組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、本発明の感光性組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として感光性組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した組成物の段階いずれの段階でも可能である。
Moreover, it is preferable that the photosensitive composition of this invention does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation. In the present invention, “substantially containing no environmentally regulated substance” means that the content of the environmentally regulated substance in the photosensitive composition is 50 mass ppm or less, and is 30 mass ppm or less. Preferably, it is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as REACH (Registration Evaluation Authorization and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) regulations, VOC (Volatile Organic Registered) The method is strictly regulated. These compounds may be used as a solvent when producing each component used in the photosensitive composition of the present invention, and may be mixed into the photosensitive composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and consideration for the environment. As a method for reducing the environmentally regulated substances, there is a method of heating and depressurizing the system so as to make it equal to or higher than the boiling point of the environmentally regulated substances to distill off the environmentally regulated substances from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and the solvent is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding during the vacuum distillation and causing cross-linking between molecules. May be. These distillation methods can be performed either at the raw material stage, the product obtained by reacting the raw material (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a composition stage prepared by mixing these compounds. It is also possible in stages.

＜＜重合禁止剤＞＞

　本発明の感光性組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。感光性組成物の全固形分中における重合禁止剤の含有量は、０．００１～５質量％が好ましい。
<< Polymerization inhibitor >>

The photosensitive composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.001 to 5% by mass.

＜＜界面活性剤＞＞

　本発明の感光性組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。
<< Surfactant >>

The photosensitive composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. As for the surfactant, paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.

　本発明において、界面活性剤はフッ素系界面活性剤であることが好ましい。感光性組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。
In the present invention, the surfactant is preferably a fluorosurfactant. By including a fluorosurfactant in the photosensitive composition, liquid properties (particularly, fluidity) can be further improved, and liquid-saving properties can be further improved. In addition, a film with small thickness unevenness can be formed.

　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。
The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

　フッ素系界面活性剤としては、特開２０１４－４１３１８号公報の段落番号００６０～００６４（対応する国際公開２０１４／１７６６９号公報の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。
Examples of the fluorosurfactant include surfactants described in paragraph Nos. 0060 to 0064 of JP-A No. 2014-41318 (paragraph Nos. 0060 to 0064 of the corresponding International Publication No. 2014/17669) and JP-A No. 2011-2011. The surfactants described in paragraph Nos. 0117 to 0132 of No. 132503 are listed, the contents of which are incorporated herein. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) .

　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられる。
In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heat is applied. It can be used suitably. Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21.

　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。
The fluorine-based surfactant is also preferably a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such a fluorosurfactant can be referred to the description in JP-A-2016-216602, the contents of which are incorporated herein.

　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。

Figure JPOXMLDOC01-appb-C000043
　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。
As the fluorosurfactant, a block polymer can be used. Examples thereof include compounds described in JP2011-89090A. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention.

Figure JPOXMLDOC01-appb-C000043
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.

　また、フッ素系界面活性剤は、エチレン性不飽和結合基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。
In addition, as the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated bond group in the side chain can also be used. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）

製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）

、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）

製）などが挙げられる。
Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BASF) Etsu Chemical Co., Ltd.), SOLSPERSE 20000 (manufactured by Lubrizol Japan (Ltd.)), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.

Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.)

Olfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.)

Manufactured).

　シリコン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越シリコーン株式会社製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。
Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

　感光性組成物の全固形分中における界面活性剤の含有量は、０．００１質量％～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。界面活性剤は、１種のみでもよく、２種以上でもよい。２種以上の場合は、合計量が上記範囲となることが好ましい。
The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. In the case of two or more types, the total amount is preferably within the above range.

＜＜紫外線吸収剤＞＞

　本発明の感光性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の具体例としては、下記構造の化合物などが挙げられる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。

Figure JPOXMLDOC01-appb-C000044
<< UV absorber >>

The photosensitive composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, aminodiene compound, salicylate compound, benzophenone compound, benzotriazole compound, acrylonitrile compound, hydroxyphenyltriazine compound, indole compound, triazine compound, or the like can be used. Details of these are described in paragraph numbers 0052 to 0072 in JP2012-208374A, paragraph numbers 0317 to 0334 in JP2013-68814A, and paragraph numbers 0061 to 0080 in JP2016-162946A. Which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structure. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). Moreover, as a benzotriazole compound, the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat is mentioned.

Figure JPOXMLDOC01-appb-C000044

　感光性組成物の全固形分中における紫外線吸収剤の含有量は、０．０１～１０質量％が好ましく、０．０１～５質量％がより好ましい。本発明において、紫外線吸収剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。
The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. In this invention, only 1 type may be used for an ultraviolet absorber and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

＜＜酸化防止剤＞＞

　本発明の感光性組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ）などが挙げられる。
<< Antioxidant >>

The photosensitive composition of the present invention can contain an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferred. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, phosphorus antioxidant can also be used suitably for antioxidant. As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO-80. Adeka Stub AO-330 (above, ADEKA Co., Ltd.) and the like.

　感光性組成物の全固形分中における酸化防止剤の含有量は、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。
The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

＜＜その他成分＞＞

　本発明の感光性組成物は、必要に応じて、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、本発明の感光性組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開ＷＯ２０１４／０２１０２３号公報、国際公開ＷＯ２０１７／０３０００５号公報、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。
<< Other ingredients >>

The photosensitive composition of the present invention may be a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, etc.) as necessary. Leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, and the like). Properties such as film properties can be adjusted by appropriately containing these components. These components are described in, for example, paragraph No. 0183 of JP2012-003225A or later (paragraph No. 0237 of US Patent Application Publication No. 2013/0034812), paragraph of JP2008-250074, for example. Descriptions of numbers 0101 to 0104, 0107 to 0109, and the like can be referred to, and the contents thereof are incorporated in this specification. Moreover, the photosensitive composition of this invention may contain a latent antioxidant as needed. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound that functions as an antioxidant due to elimination of the protecting group can be mentioned. Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Unexamined Patent Publication No. 2017-008219. Examples of commercially available products include ADEKA ARKLES GPA-5001 (manufactured by ADEKA Corporation).

　本発明の感光性組成物の粘度（２３℃）は、例えば、塗布により膜を形成する場合、１～１００ｍＰａ・ｓであることが好ましい。下限は、２ｍＰａ・ｓ以上がより好ましく、３ｍＰａ・ｓ以上が更に好ましい。上限は、５０ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下が更に好ましく、１５ｍＰａ・ｓ以下が特に好ましい。
The viscosity (23 ° C.) of the photosensitive composition of the present invention is preferably 1 to 100 mPa · s, for example, when a film is formed by coating. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.

＜収容容器＞

　本発明の感光性組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。
<Container>

There is no limitation in particular as a storage container of the photosensitive composition of this invention, A well-known storage container can be used. Moreover, as a container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin, and a bottle having six types of resin and a seven layer structure are used. It is also preferable to use it. Examples of such a container include a container described in JP-A-2015-123351.

　本発明の感光性組成物を液晶表示装置用途のカラーフィルタ形成用の組成物として用いる場合、本発明の感光性組成物により形成されたカラーフィルタを備えた液晶表示素子の電圧保持率は、７０％以上であることが好ましく、９０％以上であることがより好ましい。高い電圧保持率を得るための公知の手段を適宜組み込むことができ、典型的な手段としては純度の高い素材の使用（例えばイオン性不純物の低減）や、組成物中の酸性官能基量の制御が挙げられる。電圧保持率は、例えば特開２０１１－００８００４号公報の段落０２４３、特開２０１２－２２４８４７号公報の段落０１２３～０１２９に記載の方法等で測定することができる。
When the photosensitive composition of the present invention is used as a composition for forming a color filter for use in a liquid crystal display device, the voltage holding ratio of the liquid crystal display element provided with the color filter formed of the photosensitive composition of the present invention is 70. % Or more is preferable, and 90% or more is more preferable. Known means for obtaining a high voltage holding ratio can be appropriately incorporated. Typical examples include the use of high-purity materials (for example, reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. Is mentioned. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP2011-008004A and paragraphs 0123 to 0129 of JP2012-224847A.

＜感光性組成物の調製方法＞

　本発明の感光性組成物は、前述の成分を混合して調製できる。感光性組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して感光性組成物を調製してもよいし、必要に応じては、各成分を適宜配合した２つ以上の溶液または分散液をあらかじめ調製し、使用時（塗布時）にこれらを混合して感光性組成物として調製してもよい。
<Method for preparing photosensitive composition>

The photosensitive composition of the present invention can be prepared by mixing the aforementioned components. In preparing the photosensitive composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the photosensitive composition. If necessary, two or more solutions in which each component is appropriately blended or A dispersion liquid may be prepared in advance, and these may be mixed at the time of use (at the time of application) to prepare a photosensitive composition.

　また、本発明の感光性組成物が顔料などの粒子を含む場合は、粒子を分散させるプロセスを含むことが好ましい。粒子を分散させるプロセスにおいて、粒子の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における粒子の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、粒子を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。また粒子を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。
Moreover, when the photosensitive composition of this invention contains particle | grains, such as a pigment, it is preferable to include the process of disperse | distributing particle | grains. In the process of dispersing the particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the pulverization efficiency by increasing the filling rate of beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, the process and disperser for dispersing particles are described in “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)”. The process and disperser described in Paragraph No. 0022 of Japanese Unexamined Patent Publication No. 2015-157893 can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling process. For the materials, equipment, processing conditions, etc. used in the salt milling process, for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.

　本発明の感光性組成物の調製にあたり、異物の除去や欠陥の低減などの目的で感光性組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。フィルタの孔径は、０．０１～７．０μｍ程度が適しており、好ましくは０．０１～３．０μｍ程度であり、更に好ましくは０．０５～０．５μｍ程度である。フィルタの孔径が上記範囲であれば、微細な異物を確実に除去できる。また、ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。具体的には、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）のフィルタカートリッジが挙げられる。フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。
In preparing the photosensitive composition of the present invention, it is preferable to filter the photosensitive composition with a filter for the purpose of removing foreign substances or reducing defects. As a filter, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable. The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the hole diameter of a filter is the said range, a fine foreign material can be removed reliably. It is also preferable to use a fiber-shaped filter medium. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Specifically, filter cartridges of SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno Co., Ltd. may be mentioned. When using a filter, you may combine a different filter (For example, a 1st filter, a 2nd filter, etc.). In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. Further, filtration with the first filter may be performed only on the dispersion, and after mixing other components, filtration may be performed with the second filter.

＜硬化膜＞

　本発明の硬化膜は、上述した本発明の感光性組成物から得られる硬化膜である。本発明の硬化膜は、カラーフィルタ、近赤外線透過フィルタ、近赤外線カットフィルタ、ブラックマトリクス、遮光膜、屈折率調整膜、平版印刷版原版の感光層、保護フィルム、UV硬化性インキ、各種フォトレジスト、各種ディスプレイ材料、コーティング材料、歯科材料、ワニス、粉末コーティング、接着剤、歯科用組成物、ゲルコート、電気部品、磁気記録材料、微小機械部品、導波管、光学スイッチ、メッキ用マスキング、カラー校正システム、ガラス繊維ケーブルコーティング、スクリーン印刷ステンシル、ステレオリソグラフィーによる三次元物体、ホログラフィック記録用画像記録材料、マイクロエレクトロニクス回路、ヘルスケア材料などに用いることができる。膜厚は、目的に応じて適宜調整できる。

例えば、膜厚は２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。
<Curing film>

The cured film of the present invention is a cured film obtained from the above-described photosensitive composition of the present invention. The cured film of the present invention includes a color filter, a near infrared transmission filter, a near infrared cut filter, a black matrix, a light shielding film, a refractive index adjusting film, a photosensitive layer of a lithographic printing plate precursor, a protective film, a UV curable ink, and various photoresists. Various display materials, coating materials, dental materials, varnishes, powder coatings, adhesives, dental compositions, gel coats, electrical components, magnetic recording materials, micromechanical components, waveguides, optical switches, masking for plating, color calibration It can be used in systems, glass fiber cable coatings, screen printing stencils, stereolithographic three-dimensional objects, image recording materials for holographic recording, microelectronic circuits, healthcare materials and the like. The film thickness can be appropriately adjusted according to the purpose.

For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

＜カラーフィルタの製造方法＞

　本発明のカラーフィルタの製造方法は、支持体上に上述した本発明の感光性組成物を適用して感光性組成物層を形成する工程と、感光性組成物層をパターン状に露光する工程と、露光後の感光性組成物層を現像してパターンを形成する工程と、を含む。以下、各工程について説明する。
<Color filter manufacturing method>

The method for producing a color filter of the present invention includes a step of forming a photosensitive composition layer by applying the above-described photosensitive composition of the present invention on a support, and a step of exposing the photosensitive composition layer in a pattern. And a step of developing the photosensitive composition layer after exposure to form a pattern. Hereinafter, each step will be described.

　まず、支持体上に本発明の感光性組成物を適用して感光性組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層が設けられていてもよい。
First, the photosensitive composition of the present invention is applied on a support to form a photosensitive composition layer. There is no limitation in particular as a support body, According to a use, it can select suitably. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, a black matrix for isolating each pixel is formed on the silicon substrate. In addition, the silicon substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the substrate surface.

　感光性組成物の適用方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、組成物の塗布方法については、国際公開ＷＯ２０１７／０３０１７４号公報、国際公開ＷＯ２０１７／０１８４１９号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。
As a method for applying the photosensitive composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A). Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. There are no particular limitations on the application method in the ink jet, and for example, the method described in “Expanding and usable ink jet-unlimited possibilities seen in patents, published in February 2005, Sumibe Techno Research” (particularly from page 115) 133), JP-A 2003-262716, JP-A 2003-185831, JP-A 2003-261827, JP-A 2012-126830, JP-A 2006-169325, and the like. Can be mentioned. Moreover, about the coating method of a composition, the description of international publication WO2017 / 030174 and international publication WO2017 / 018419 can be referred to, These content is integrated in this specification.

　支持体上に形成した感光性組成物層は、乾燥（プリベーク）してもよい。低温プロセスによりカラーフィルタを製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０～３０００秒が好ましく、４０～２５００秒がより好ましく、８０～２２００秒がさらに好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。
The photosensitive composition layer formed on the support may be dried (prebaked). When producing a color filter by a low temperature process, it is not necessary to perform prebaking. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The pre-bake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 2200 seconds. Pre-baking can be performed with a hot plate, an oven, or the like.

　次に、感光性組成物層をパターン状に露光する（露光工程）。例えば、支持体上に形成した感光性組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部の感光性組成物層を硬化させることができる。
Next, the photosensitive composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the photosensitive composition layer formed on the support through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the photosensitive composition layer of an exposure part can be hardened.

　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。

また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。各種LEDやLD光源も利用できる。またEBやEUVなど放射線領域の光源も利用できる。
Examples of radiation (light) that can be used for exposure include g-line and i-line.

Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can be used. Examples of the light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. A long wave light source of 300 nm or more can also be used. Various LED and LD light sources can also be used. In addition, radiation sources such as EB and EUV can be used.

　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光

（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。パルス露光の場合、パルス幅は、１００ナノ秒（ｎｓ）以下であることが好ましく、５０ナノ秒以下であることがより好ましく、３０ナノ秒以下であることが更に好ましい。パルス幅の下限は、特に限定はないが、１フェノム秒（ｆｓ）以上とすることができ、１０フェノム秒以上とすることもできる。周波数は、１ｋＨｚ以上であることが好ましく、２ｋＨｚ以上であることがより好ましく、４ｋＨｚ以上であることが更に好ましい。周波数の上限は５０ｋＨｚ以下であることが好ましく、２０ｋＨｚ以下であることがより好ましく、１０ｋＨｚ以下であることが更に好ましい。最大瞬間照度は、５０００００００Ｗ／ｍ2以上であることが好ましく、１００００００００Ｗ／ｍ2以上であることがより好ましく、２００００００００Ｗ／ｍ2以上であることが更に好ましい。また、最大瞬間照度の上限は、１０００００００００Ｗ／ｍ2以下であることが好ましく、８００００００００Ｗ／ｍ2以下であることがより好ましく、５００００００００Ｗ／ｍ2以下であることが更に好ましい。なお、パルス幅とは、パルス周期における光が照射されている時間のことである。また、周波数とは、１秒あたりのパルス周期の回数のことである。また、最大瞬間照度とは、パルス周期における光が照射されている時間内での平均照度のことである。また、パルス周期とは、パルス露光における光の照射と休止を１サイクルとする周期のことである。
In addition, during exposure, exposure may be performed by continuously irradiating light, or by irradiating in pulses.

(Pulse exposure) may be performed. Note that the pulse exposure is an exposure method in which exposure is performed by repeatedly irradiating and pausing light in a short cycle (for example, a millisecond level or less). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 phenomsecond (fs) or more, and may be 10 phenomseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less. Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more. The upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less. The pulse width is the time during which light is irradiated in the pulse period. The frequency is the number of pulse periods per second. The maximum instantaneous illuminance is the average illuminance within the time during which light is irradiated in the pulse period. The pulse period is a period in which light irradiation and pause in pulse exposure are one cycle.

　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ2が好ましく、０．０５～１．０Ｊ／ｃｍ2がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ2～１０００００Ｗ／ｍ2（例えば、５０００Ｗ／ｍ2、１５０００Ｗ／ｍ2、または、３５０００Ｗ／ｍ2）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ2、酸素濃度３５体積％で照度２００００Ｗ／ｍ2などとすることができる。
Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2. The oxygen concentration at the time of exposure can be selected as appropriate. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially It may be exposed in an oxygen-free manner, or may be exposed in a high oxygen atmosphere (for example, 22%, 30%, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure illuminance can be appropriately set, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). Can do. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.

　次に、露光後の感光性組成物層を現像してパターンを形成する（現像工程）。より具体的には、未露光部の感光性組成物層を現像除去してパターンを形成する。未露光部の感光性組成物層の現像除去は、現像液を用いて行うことができる。これにより、未露光部の感光性組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。現像液の温度は、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。
Next, the photosensitive composition layer after exposure is developed to form a pattern (development process). More specifically, a pattern is formed by developing and removing the photosensitive composition layer in the unexposed area. The development removal of the photosensitive composition layer of an unexposed part can be performed using a developing solution. Thereby, the photosensitive composition layer of an unexposed part elutes in a developing solution, and only the photocured part remains on a support body. The temperature of the developer is preferably 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

　現像液は、アルカリ剤を純水で希釈したアルカリ性水溶液（アルカリ現像液）であることが好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の感光性着色組成物層が形成された支持体を回転させつつ、現像後の感光性着色組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルの支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。
The developer is preferably an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Organic compounds such as ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. As surfactant, the surfactant mentioned above is mentioned, A nonionic surfactant is preferable. The developer may be once manufactured as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of convenience of transportation and storage. The dilution factor is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to rinse (rinse) with pure water after development. The rinsing is preferably performed by supplying a rinsing liquid to the photosensitive coloring composition layer after development while rotating the support on which the photosensitive coloring composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the periphery of the support. At this time, when moving from the central part of the support body of the nozzle to the peripheral part, the nozzle may be moved while gradually decreasing the moving speed of the nozzle. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

　現像後、乾燥を施した後に加熱処理（ポストベーク）を行うことが好ましい。ポストベークは、硬化を完全なものとするための現像後の加熱処理であり、加熱温度は、例えば１００～２４０℃が好ましく、２００～２４０℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。
It is preferable to perform heat treatment (post-bake) after development and drying. The post-baking is a heat treatment after development for complete curing, and the heating temperature is preferably, for example, 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .

　上記の工程を経て、パターン（画素）を形成することができる。２色以上の画素を有するカラーフィルタを製造する場合は、上記の各工程を所望の色相数だけ繰り返すことにより、複数色の画素を有するカラーフィルタを製造することができる。
A pattern (pixel) can be formed through the above steps. When a color filter having two or more color pixels is manufactured, a color filter having a plurality of color pixels can be manufactured by repeating the above steps for the desired number of hues.

　ここで、本発明のカラーフィルタの製造方法として、カラーフィルタの画素を形成する際に本発明の感光性組成物を用いる態様を中心に説明したが、本発明はこの態様に限定されるものではない。例えば、本発明の感光性組成物は、カラーフィルタを構成する各色の画素を隔離するブラックマトリックスの形成にも適用することができる。すなわち、上記の各工程を行うことにより、支持体上にブラックマトリクス（黒色パターン）を形成することができる。
Here, as a method for producing the color filter of the present invention, the embodiment using the photosensitive composition of the present invention when forming the pixel of the color filter has been mainly described. However, the present invention is not limited to this embodiment. Absent. For example, the photosensitive composition of the present invention can also be applied to the formation of a black matrix that isolates pixels of each color constituting a color filter. That is, a black matrix (black pattern) can be formed on the support by performing the above steps.

＜カラーフィルタ＞

　次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の硬化膜を有する。本発明の硬化膜をカラーフィルタに用いる場合においては、本発明の硬化膜は、有彩色着色剤を含むことが好ましい。すなわち、本発明の硬化膜は、有彩色着色剤を含む感光性組成物を用いて形成されたものであることが好ましい。本発明のカラーフィルタにおいて本発明の硬化膜の膜厚は、目的に応じて適宜調整できる。膜厚は、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上が更に好ましい。本発明のカラーフィルタは、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や画像表示装置などに用いることができる。
<Color filter>

Next, the color filter of the present invention will be described. The color filter of the present invention has the above-described cured film of the present invention. When using the cured film of this invention for a color filter, it is preferable that the cured film of this invention contains a chromatic colorant. That is, the cured film of the present invention is preferably formed using a photosensitive composition containing a chromatic colorant. In the color filter of the present invention, the thickness of the cured film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.

＜固体撮像素子＞

　本発明の固体撮像素子は、上述した本発明の硬化膜を有する。本発明の固体撮像素子の構成としては、本発明の硬化膜を備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
<Solid-state imaging device>

The solid-state imaging device of the present invention has the above-described cured film of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口した遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、カラーフィルタを有する構成である。更に、デバイス保護膜上であってカラーフィルタの下（基板に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。

また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各着色画素が埋め込まれた構造を有していてもよい。この場合の隔壁は各着色画素に対して低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。本発明の固体撮像素子を備えた撮像装置は、デジタルカメラや、撮像機能を有する電子機器（携帯電話等）の他、車載カメラや監視カメラ用としても用いることができる。
The substrate has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.)). And a device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to cover only the entire surface of the light shielding film and the photodiode light receiving portion. And having a color filter on the device protective film. Further, the device has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the color filter (on the side close to the substrate) on the device protective film, or a constitution having the condensing means on the color filter. There may be.

In addition, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a lattice shape. In this case, the partition walls preferably have a low refractive index for each colored pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A. The image pickup apparatus including the solid-state image pickup device of the present invention can be used for an in-vehicle camera and a monitoring camera in addition to a digital camera and an electronic apparatus (such as a mobile phone) having an image pickup function.

＜画像表示装置＞

　本発明の画像表示装置は、上述した本発明の硬化膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
<Image display device>

The image display device of the present invention has the above-described cured film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and details of each image display device, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junaki Ibuki, Industrial Book ( (Issued in 1989)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。また、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In the structural formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

　以下の各試験例で使用した光重合開始剤は下記構造の化合物である。以下の化合物のうち、ＯＸ－１～ＯＸ－２１は、本発明に係る環状オキシム化合物（環状オキシム化合物Ａ）である。また、ＯＸ－Ｒ１～ＯＸ－Ｒ４は、比較化合物である。
The photopolymerization initiator used in each of the following test examples is a compound having the following structure. Of the following compounds, OX-1 to OX-21 are cyclic oxime compounds (cyclic oxime compound A) according to the present invention. OX-R1 to OX-R4 are comparative compounds.

　（本発明に係る環状オキシム化合物）

Figure JPOXMLDOC01-appb-C000045
(Cyclic oxime compound according to the present invention)

Figure JPOXMLDOC01-appb-C000045

　（比較化合物）

Figure JPOXMLDOC01-appb-C000046
(Comparative compound)

Figure JPOXMLDOC01-appb-C000046

［試験例１］

（実施例１－１）

　光重合開始剤として化合物ＯＸ－１を０．０８ｍｍｏｌと、重合性化合物としてペンタエリスリトールテトラアクリレートを１ｇと、バインダー樹脂としてポリメチルメタクリレート（Ａｌｄｒｉｃｈ社製、重量平均分子量＝９９６０００）を１ｇと、溶剤としてシクロヘキサノンを１６ｇとを混合して実施例１－１の感光性組成物を調製した。得られた感光性組成物をガラス基板上にスピンコータにて塗布し、４０℃で１０分間乾燥して、１．５μｍの膜厚の塗膜を形成した。この塗膜上にステップタブレット２１段（コダック社製）のグレイスケールフィルムを置き、露光機（ウシオ電機株式会社製、「ＵＶＣ－２５３４／１ＭＮＬＣ３－ＡＡ０８」、１２０Ｗ／ｃｍ2メタルハライドランプ１灯）を用いて積算光量３００ｍＪ／ｃｍ2の紫外線を照射した後、トルエン中に６０秒間含浸させて現像処理を行った。ステップタブレットに対応した完全に硬化して不溶化した段数を感度として評価したところ、感度は６段であった。なお、感度は数字が大きいほど感度が高いことを示す。
[Test Example 1]

Example 1-1

0.08 mmol of compound OX-1 as a photopolymerization initiator, 1 g of pentaerythritol tetraacrylate as a polymerizable compound, 1 g of polymethyl methacrylate (manufactured by Aldrich, weight average molecular weight = 996000) as a binder resin, and as a solvent A photosensitive composition of Example 1-1 was prepared by mixing 16 g of cyclohexanone. The obtained photosensitive composition was applied onto a glass substrate with a spin coater and dried at 40 ° C. for 10 minutes to form a coating film having a thickness of 1.5 μm. A 21-step gray scale film (made by Kodak) was placed on this coating film, and an exposure machine (USHIO Inc., “UVC-2534 / 1MNLC3-AA08”, one 120 W / cm 2 metal halide lamp) was placed. The sample was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm 2 and then impregnated in toluene for 60 seconds for development. When the number of steps completely cured and insolubilized corresponding to the step tablet was evaluated as sensitivity, the sensitivity was 6 steps. In addition, a sensitivity shows that a sensitivity is so high that a number is large.

（実施例１－２～１－２１、比較例１－１～１－４）

　実施例１－１において、光重合開始剤として化合物ＯＸ－１の０．０８ｍｍｏｌを、それぞれ下記表に記載の化合物の０．０８ｍｍｏｌに置き替えた他は、実施例１－１と全く同一の操作で実施例１－２～１－２１、比較例１－１～１－４の感光性組成物を調製し、実施例１－１と同様にして感度段数を評価した。実施例１－２～１－２１、及び比較例１－１～１－４の評価結果を実施例１－１の評価結果と合わせて下記表に示す。

Figure JPOXMLDOC01-appb-T000047
(Examples 1-2 to 1-21, Comparative Examples 1-1 to 1-4)

In Example 1-1, the procedure was exactly the same as Example 1-1, except that 0.08 mmol of compound OX-1 as a photopolymerization initiator was replaced with 0.08 mmol of the compounds shown in the following table, respectively. Then, photosensitive compositions of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 were prepared, and the number of sensitivity steps was evaluated in the same manner as Example 1-1. The evaluation results of Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-4 are shown in the following table together with the evaluation results of Example 1-1.

Figure JPOXMLDOC01-appb-T000047

　上記表に示されるように、実施例の感光性組成物は比較例の感光性組成物よりも感度が高かった。
As shown in the above table, the photosensitive compositions of the examples had higher sensitivity than the photosensitive compositions of the comparative examples.

［試験例２］

（分散液の調製）

　下記表に記載の原料を、それぞれ下記の表に記載の質量部で混合し、更に直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ビーズミル（減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製））にて３時間混合および分散して各分散液を調製した。
[Test Example 2]

(Preparation of dispersion)

The raw materials listed in the following table were mixed in the respective parts by mass described in the following table, and further 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, and a bead mill (high pressure disperser with pressure reducing mechanism NANO-3000-10 ( Each dispersion was prepared by mixing and dispersing for 3 hours using Nippon BEE Co., Ltd.).

Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048

　各分散液の製造に用いた原料は以下の通りである。
The raw materials used for the production of each dispersion are as follows.

（色材）

　ＰＲ２５４　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２５４（赤色顔料）

　ＰＲ２６４　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２６４（赤色顔料）

　ＰＹ１３９　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１３９（黄色顔料）

　ＰＹ１５０　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１５０（黄色顔料）

　ＰＹ１８５　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１８５（黄色顔料）

　ＰＧ３６　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ３６（緑色顔料）

　ＰＧ５８　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ５８（緑色顔料）

　ＰＢ１５：６　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６（青色顔料）

　ＰＶ２３　：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ２３（紫色顔料）
(Color material)

PR254: C.I. I. Pigment Red254 (red pigment)

PR264: C.I. I. Pigment Red 264 (red pigment)

PY139: C.I. I. Pigment Yellow 139 (yellow pigment)

PY150: C.I. I. Pigment Yellow 150 (yellow pigment)

PY185: C.I. I. Pigment Yellow 185 (yellow pigment)

PG36: C.I. I. Pigment Green 36 (green pigment)

PG58: C.I. I. Pigment Green 58 (green pigment)

PB15: 6: C.I. I. Pigment Blue 15: 6 (blue pigment)

PV23: C.I. I. Pigment Violet 23 (purple pigment)

　Ｐｃ１：　以下の方法で製造したハロゲン化亜鉛フタロシアニン顔料（緑色顔料）

　塩化スルフリル（４５．５質量部）、無水塩化アルミニウム（５４．５質量部）、塩化ナトリウム（７質量部）を４０℃で混合し、亜鉛フタロシアニン顔料（１５質量部）を加えた。これに臭素（３５質量部）を滴下して加え、１９．５時間かけて１３０℃まで昇温し１時間保持した。その後反応混合物を水に取り出し、ハロゲン化亜鉛フタロシアニン粗顔料を析出させた。この水性スラリーを濾過し、６０℃の湯洗浄、１％硫酸水素ナトリウム水洗浄、６０℃の湯洗浄を行い、９０℃で乾燥させ、２．７質量部の精製されたハロゲン化亜鉛フタロシアニン粗顔料Ａを得た。精製したハロゲン化亜鉛フタロシアニン粗顔料Ａ（１質量部）、粉砕した塩化ナトリウム（１０質量部）、ジエチレングリコール（１質量部）を双腕型ニーダーに仕込み、１００℃で８時間混練した。混練後８０℃の水（１００質量部）に取り出し、１時間攪拌後、濾過、湯洗、乾燥、粉砕しハロゲン化亜鉛フタロシアニン顔料を得た。得られたハロゲン化亜鉛フタロシアニン顔料は、質量分析とフラスコ燃焼イオンクロマトグラフによるハロゲン含有量分析から、平均組成ＺｎＰｃＢｒ9.8Ｃｌ3.1Ｈ3.1であった。なお、Ｐｃはフタロシアニンの略語である。
Pc1: zinc halide phthalocyanine pigment (green pigment) produced by the following method

Sulfuryl chloride (45.5 parts by mass), anhydrous aluminum chloride (54.5 parts by mass) and sodium chloride (7 parts by mass) were mixed at 40 ° C., and zinc phthalocyanine pigment (15 parts by mass) was added. Bromine (35 parts by mass) was added dropwise thereto, and the temperature was raised to 130 ° C. over 19.5 hours and held for 1 hour. Thereafter, the reaction mixture was taken out into water, and a halogenated zinc phthalocyanine crude pigment was precipitated. This aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% aqueous sodium hydrogen sulfate, washed with hot water at 60 ° C., dried at 90 ° C., and 2.7 parts by weight of a purified zinc halide phthalocyanine crude pigment A was obtained. Purified zinc halide phthalocyanine crude pigment A (1 part by mass), crushed sodium chloride (10 parts by mass) and diethylene glycol (1 part by mass) were charged into a double-arm kneader and kneaded at 100 ° C. for 8 hours. After kneading, the mixture was taken out into water (100 parts by mass) at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a zinc halide phthalocyanine pigment. The obtained zinc halide phthalocyanine pigment had an average composition of ZnPcBr 9.8 Cl 3.1 H 3.1 from mass analysis and halogen content analysis by flask combustion ion chromatography. Pc is an abbreviation for phthalocyanine.

　ＰＰ１、ＰＰ２：下記構造の化合物（近赤外線吸収色素）

Figure JPOXMLDOC01-appb-C000049
PP1, PP2: Compounds having the following structure (near infrared absorbing dyes)

Figure JPOXMLDOC01-appb-C000049

　ＩＢｋ　：　Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ（ＢＡＳＦ社製、黒色着色剤）

　ＰＢｋ３２　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３２（黒色着色剤）

　ＴＴＯ－８０Ａ：酸化チタン（ＴＴＯ－８０Ａ、石原産業（株）製、白色顔料）
IBk: Irgaphor Black (manufactured by BASF, black colorant)

PBk32: C.I. I. Pigment Black 32 (black colorant)

TTO-80A: Titanium oxide (TTO-80A, manufactured by Ishihara Sangyo Co., Ltd., white pigment)

　Ｎ－Ｔｉ：以下に示す方法で作製した酸窒化チタン含有粒子（黒色顔料）。

　酸窒化チタン含有粒子の作製には、特開２００５－３４３７８４号公報の００４２段落、及び、図１に記載された装置を用いた。具体的には、上記公報の図１における、放電容器１をステンレス製の真空チャンバ（福伸工業株式会社製）とした装置（以下、「ナノ粒子製造装置」という。）を用いて酸窒化チタン含有粒子を作製した。まず、排気ポンプにより真空チャンバ内の空気を排気した。次に、真空チャンバに、ヘリウム（Ｈｅ）ガス（純度９９．９９％）、及び、アルゴンガスの混合ガス（標準状態での混合比５０／５０体積％）を６００Ｔｏｒｒ（７９．９９ｋＰａ）の圧力となるまで供給した。ナノ粒子製造装置の放電電極としては、タングステンを長さ５００ｍｍ、直径１２ｍｍ、及び、中空口径６ｍｍの中空構造の棒状に成形加工したものを使用した。放電電極の配置は、特開２００５－３４３７８４号公報の図１と同様にした。具体的には、１２個の放電電極を６個ずつ２段に配置した。なお、上段と下段との間の距離は約１６０ｍｍとした。中空構造の放電電極は、原材料供給装置と接続されており、放電電極の中空部分から原料ガスを真空チャンバ内へと供給できるようにした。放電は、各放電電極に位相差のある交流（電圧２０～４０Ｖ、電流７０～１００Ａ）を印加しながら、各放電電極の先端を接触させた状態で開始する。アーク放電が発生した後各放電電極の先端を離間させるように外方に向かって移動させ、隣接する放電電極の先端の間の距離が５～１０ｍｍとなる位置にセットしてアーク放電を続行した。アーク放電を１５分行った後、原材料供給装置の供給タンクを加温して、原料ガスを真空チャンバ内へと導入した。まず、ＮＨ3ガス（液化アンモニウムＥＣＯＡＮ、昭和電工社製）を０．５気圧、Ｈ2ガス（水素ガス、昭和電工ガスプロダクツ）を０．１気圧、Ａｒガス（アルゴンガス、大陽日酸）を０．４気圧で導入した。続いて、供給タンクを２１０℃に加温し、ＴｉＣｌ4ガス（ＴＬＴ－１、東邦チタニウム社製）

を、放電電極から６００気圧で導入した。ＴｉＣｌ4ガスの導入と同時に、粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）を用いて硫黄微粉末（微粉硫黄３２５ｍｅｓｈ、鶴見化学工業製）を窒素ガスにより供給した。供給量は、得られる酸窒化チタン含有粒子中における、Ｘ線光電子分光分析により検出される硫黄原子の質量基準の含有量をＴE（質量％）とし、蛍光Ｘ線分析により検出される硫黄原子の質量基準の含有量をＴX（質量％）とした両者の比（ＴE／ＴX）が１．１未満となるように調整した。真空チャンバ内にＴｉＣｌ4ガス、及び、硫黄微粉末を混合した窒素ガスの導入を１時間行った後、交流電源からの電圧印加を停止し、上記ガスの供給を停止した。次に、真空チャンバの内壁に付着した粒子を回収した。次に、得られた粒子を、Ｏ2含有量、及び、水分含有量をそれぞれ１００ｐｐｍ以下に制御した窒素（Ｎ2）ガスを導入した密閉容器内に入れ、２４時間静置した。上記で得られた粒子を、減圧オーブンＶＡＣ－１０１Ｐ（エスペック製）を用いて２００℃で加熱して、酸窒化チタン含有粒子を得た。なお、加熱中の減圧オーブンの内圧は１．０×１０3Ｐａとした。
N—Ti: Titanium oxynitride-containing particles (black pigment) produced by the method described below.

For the production of titanium oxynitride-containing particles, the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used. Specifically, titanium oxynitride using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge vessel 1 in FIG. 1 of the above publication is a stainless steel vacuum chamber (Fukushin Kogyo Co., Ltd.) is used. Containing particles were produced. First, the air in the vacuum chamber was exhausted by an exhaust pump. Next, helium (He) gas (purity 99.99%) and argon gas mixed gas (mixing ratio 50/50% by volume in a standard state) are set in a vacuum chamber at a pressure of 600 Torr (79.99 kPa). Supplied until As the discharge electrode of the nanoparticle production apparatus, a tungsten electrode formed into a hollow rod having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm was used. The arrangement of the discharge electrodes was the same as that shown in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in two stages of 6 each. The distance between the upper stage and the lower stage was about 160 mm. The discharge electrode having a hollow structure is connected to a raw material supply device so that the source gas can be supplied from the hollow portion of the discharge electrode into the vacuum chamber. The discharge is started in a state where the tips of the discharge electrodes are in contact with each other while applying alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to the discharge electrodes. After arc discharge occurred, the tip of each discharge electrode was moved outward so as to be separated, and the arc discharge was continued by setting the distance between the tips of adjacent discharge electrodes to be 5 to 10 mm. . After performing arc discharge for 15 minutes, the supply tank of the raw material supply apparatus was heated, and the source gas was introduced into the vacuum chamber. First, NH 3 gas (liquefied ammonium ECOAN, Showa Denko KK) 0.5 atm, H 2 gas (hydrogen gas, Showa Denko Gas Products) 0.1 atm, Ar gas (argon gas, Taiyo Nippon Sanso) Was introduced at 0.4 atm. Subsequently, the supply tank is heated to 210 ° C., and TiCl 4 gas (TLT-1, manufactured by Toho Titanium Co., Ltd.)

Was introduced from the discharge electrode at 600 atm. Simultaneously with the introduction of TiCl 4 gas, a fine sulfur powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Co., Ltd.) was supplied with nitrogen gas using a powder supply device TP-99010 FDR (manufactured by JEOL Ltd.). The supply amount is the sulfur atom detected by fluorescent X-ray analysis, where T E (mass%) is the sulfur-based mass reference content detected by X-ray photoelectron spectroscopy in the obtained titanium oxynitride-containing particles. The ratio (T E / T X ) between the two based on the mass-based content of T x (mass%) was adjusted to be less than 1.1. After introduction of nitrogen gas mixed with TiCl 4 gas and sulfur fine powder into the vacuum chamber for 1 hour, voltage application from the AC power supply was stopped and supply of the gas was stopped. Next, the particles adhering to the inner wall of the vacuum chamber were collected. Next, the obtained particles were placed in an airtight container into which nitrogen (N 2 ) gas whose O 2 content and water content were controlled to 100 ppm or less, respectively, and allowed to stand for 24 hours. The particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain titanium oxynitride-containing particles. The internal pressure of the vacuum oven during heating was 1.0 × 10 3 Pa.

　Ｎ－Ｚｒ：以下に示す方法で作製した酸窒化ジルコニウム含有粒子（黒色顔料）

　上記酸窒化チタン含有粒子の製造において、ＴｉＣｌ4ガスの導入に換えて、ジルコニウム粉末（和光純薬工業製ジルコニウム粉末）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の酸窒化チタン含有粒子と同様の方法で酸窒化ジルコニウム含有粒子を製造した。
N-Zr: Zirconium oxynitride-containing particles (black pigment) prepared by the following method

In the production of the titanium oxynitride-containing particles, instead of introducing TiCl 4 gas, the above-mentioned acid was used except that zirconium powder (zirconium powder manufactured by Wako Pure Chemical Industries, Ltd.) was introduced with a powder supply device TP-99010 FDR (manufactured by JEOL Ltd.). Zirconium oxynitride-containing particles were produced in the same manner as the titanium nitride-containing particles.

　Ｎ－Ｖ：以下に示す方法で作製した酸窒化バナジウム含有粒子（黒色顔料）

　上記酸窒化チタン含有粒子の製造において、ＴｉＣｌ4ガスの導入に換えて、バナジウム粉末（太陽鉱工製金属バナジウム粉末ＶＨＯ）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の酸窒化チタン含有粒子と同様の方法で酸窒化バナジウム含有粒子を製造した。
NV: Vanadium oxynitride-containing particles (black pigment) prepared by the following method

In the production of the titanium oxynitride-containing particles, instead of introducing TiCl 4 gas, vanadium powder (metal vanadium powder VHO manufactured by Taiyo Mining Co., Ltd.) was introduced using a powder feeder TP-99010 FDR (manufactured by JEOL). Vanadium oxynitride-containing particles were produced in the same manner as the titanium oxynitride-containing particles.

　Ｎ－Ｎｂ：以下に示す方法で作製した酸窒化ニオブ含有粒子（黒色顔料）。

　上記酸窒化チタン含有粒子の製造において、ＴｉＣｌ4ガスの導入に換えて、ニオブ粉末（三津和化学薬品製ニオブ（粉末）を粉末供給装置ＴＰ－９９０１０ＦＤＲ（日本電子製）で導入した以外は上述の酸窒化チタン含有粒子と同様の方法で酸窒化ニオブ含有粒子を製造した。
N—Nb: Niobium oxynitride-containing particles (black pigment) produced by the method described below.

In the production of the titanium oxynitride-containing particles, instead of introducing TiCl 4 gas, niobium powder (Nitsu powder manufactured by Mitsuwa Chemicals Co., Ltd.) was introduced using a powder feeder TP-99010FDR (manufactured by JEOL). Niobium oxynitride-containing particles were produced in the same manner as the titanium oxynitride-containing particles.

（顔料誘導体）

　Ｓｙｎ１～４：下記構造の化合物

Figure JPOXMLDOC01-appb-C000050
(Pigment derivative)

Syn1 to 4: Compounds having the following structure

Figure JPOXMLDOC01-appb-C000050

（有機溶剤）

　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
(Organic solvent)

PGMEA: Propylene glycol monomethyl ether acetate

（分散剤）

　Ｐ－１：以下の方法で合成した樹脂ｐ１の３０質量％ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）溶液

　多官能チオール化合物（下記構造の化合物Ｓ－１）の９．０５質量部、及びマクロモノマー（下記構造の化合物ＭＭ－１、Ｍｗ＝３０００）の９０．９５質量部の混合溶液にプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を加えて固形分濃度を６３質量％に調整した後、窒素気流下、７５℃に加熱した。次いで、この混合溶液に、２，２’－アゾビス（イソ酪酸）ジメチル（Ｖ－６０１、和光純薬工業（株）製）の０．４質量部を加えて２時間加熱後、再度２，２’－アゾビス（イソ酪酸）ジメチルの０．４質量部を加えて、窒素気流下、９０℃で２時間反応させた。その後、室温（２５℃、以下同様）まで冷却した。次いで、得られた反応物の７６．９３質量部と、エチレン性不飽和結合基を有するモノマー（下記構造の化合物ｍ－１）の２３．０６質量部との混合溶液を、窒素気流下、７５℃に加熱した。ついで、この混合溶液に、２，２’－アゾビス（イソ酪酸）ジメチルの０．４質量部を加えて２時間加熱後、再度２，２’－アゾビス（イソ酪酸）ジメチルの０．４質量部を加えて、窒素気流下、９０℃で２時間反応させた。その後、室温まで冷却させた後、混合溶液にＰＧＭＥＡを加えて固形分濃度を３０質量％に調整して、樹脂ｐ１の３０質量％ＰＧＭＥＡ溶液を得た。樹脂ｐ１の重量平均分子量（Ｍｗ）は１１０００であり、分散度（Ｍｗ／Ｍｎ）は１．８であり、酸価は７５ｍｇＫＯＨ／ｇであり、還元粘度は１１ｍｌ／ｇｓであった。

Figure JPOXMLDOC01-appb-C000051
(Dispersant)

P-1: 30 mass% PGMEA (propylene glycol monomethyl ether acetate) solution of resin p1 synthesized by the following method

Propylene glycol monomethyl ether in a mixed solution of 9.05 parts by mass of a polyfunctional thiol compound (compound S-1 having the following structure) and 90.95 parts by mass of a macromonomer (compound MM-1, having the following structure, Mw = 3000). Acetate (PGMEA) was added to adjust the solid content concentration to 63% by mass and then heated to 75 ° C. under a nitrogen stream. Next, 0.4 parts by mass of 2,2′-azobis (isobutyric acid) dimethyl (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added to this mixed solution, heated for 2 hours, and then again 2,2 0.4 parts by mass of '-azobis (isobutyric acid) dimethyl was added and reacted at 90 ° C. for 2 hours under a nitrogen stream. Then, it cooled to room temperature (25 degreeC, the following similarly). Next, a mixed solution of 76.93 parts by mass of the obtained reaction product and 23.06 parts by mass of a monomer having an ethylenically unsaturated bond group (compound m-1 having the following structure) was added under a nitrogen stream to 75 Heated to ° C. Next, 0.4 parts by mass of 2,2′-azobis (isobutyric acid) dimethyl was added to this mixed solution, heated for 2 hours, and then again 0.4 parts by mass of 2,2′-azobis (isobutyric acid) dimethyl. And reacted at 90 ° C. for 2 hours under a nitrogen stream. Then, after making it cool to room temperature, PGMEA was added to the mixed solution, solid content concentration was adjusted to 30 mass%, and the 30 mass% PGMEA solution of resin p1 was obtained. The weight average molecular weight (Mw) of the resin p1 was 11000, the dispersity (Mw / Mn) was 1.8, the acid value was 75 mgKOH / g, and the reduced viscosity was 11 ml / gs.

Figure JPOXMLDOC01-appb-C000051

　Ｐ－２：下記構造の樹脂の３０質量％ＰＧＭＥＡ溶液（主鎖に付記された数値はモル比であり、側鎖に付記された数値は繰り返し単位の数である。Ｍｗ＝１７０００、分散度（Ｍｗ／Ｍｎ）＝４．２、酸価＝７５ｍｇＫＯＨ／ｇ、還元粘度＝１２．５ｍｌ／ｇ）。

Figure JPOXMLDOC01-appb-C000052
P-2: 30% by mass PGMEA solution of resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 17000, dispersity ( Mw / Mn) = 4.2, acid value = 75 mg KOH / g, reduced viscosity = 12.5 ml / g).

Figure JPOXMLDOC01-appb-C000052

　Ｐ－３：下記構造の樹脂の３０質量％ＰＧＭＥＡ溶液（主鎖に付記された数値はモル比であり、側鎖に付記された数値は繰り返し単位の数である。Ｍｗ＝７９５０）

Figure JPOXMLDOC01-appb-C000053
　Ｐ－４：下記構造の樹脂の３０質量％ＰＧＭＥＡ溶液（主鎖に付記された数値はモル比である。Ｍｗ＝１２０００）

Figure JPOXMLDOC01-appb-C000054
　Ｐ－５：下記構造の樹脂のＰＧＭＥＡ３０質量％溶液（主鎖に付記された数値はモル比であり、側鎖に付記された数値は繰り返し単位の数である。Ｍｗ＝３００００）

Figure JPOXMLDOC01-appb-C000055
P-3: 30% by mass PGMEA solution of resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 7950)

Figure JPOXMLDOC01-appb-C000053
P-4: 30% by mass PGMEA solution of a resin having the following structure (the numerical values attached to the main chain are molar ratios, Mw = 12000)

Figure JPOXMLDOC01-appb-C000054
P-5: PGMEA 30% by mass solution of resin having the following structure (The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 30000)

Figure JPOXMLDOC01-appb-C000055

＜感光性組成物の製造＞

　下記表に記載の原料を混合して実施例および比較例の感光性組成物をそれぞれ製造した。

Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000057
<Production of photosensitive composition>

The photosensitive composition of an Example and a comparative example was each manufactured by mixing the raw material of the following table | surface.

Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000057

　組成物の製造に用いた原料は以下の通りである。
The raw materials used for the production of the composition are as follows.

（樹脂）

　Ｅ１：下記構造の樹脂。（主鎖に付記した数値はモル比である。Ｍｗ＝１０，０００、酸価＝７０ｍｇＫＯＨ／ｇ）

　Ｅ２：下記構造の樹脂。（主鎖に付記した数値はモル比である。Ｍｗ＝１０，０００、酸価＝７０ｍｇＫＯＨ／ｇ）

　Ｅ３：下記構造の樹脂。（主鎖に付記した数値はモル比である。Ｍｗ＝４０，０００、酸価＝１００ｍｇＫＯＨ／ｇ）

Figure JPOXMLDOC01-appb-C000058
(resin)

E1: Resin having the following structure. (Values added to the main chain are molar ratios. Mw = 10,000, acid value = 70 mgKOH / g)

E2: Resin having the following structure. (Values added to the main chain are molar ratios. Mw = 10,000, acid value = 70 mgKOH / g)

E3: Resin having the following structure. (Numerical values attached to the main chain are molar ratios. Mw = 40,000, acid value = 100 mgKOH / g)

Figure JPOXMLDOC01-appb-C000058

（重合性化合物）

　Ｄ１：ＫＡＹＡＲＡＤ　ＲＰ－１０４０（日本化薬（株）製、ラジカル重合性化合物）

　Ｄ２：アロニックス　ＴＯ－２３４９（東亞合成（株）製、ラジカル重合性化合物）

　Ｄ３：アロニックス　Ｍ－３０５（東亞合成（株）製、ラジカル重合性化合物）

　Ｄ４：ＮＫエステル　Ａ－ＴＭＭＴ（新中村化学工業（株）製、ラジカル重合性化合物）

　Ｄ５：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（株）製、ラジカル重合性化合物）
(Polymerizable compound)

D1: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., radical polymerizable compound)

D2: Aronix TO-2349 (produced by Toagosei Co., Ltd., radical polymerizable compound)

D3: Aronix M-305 (manufactured by Toagosei Co., Ltd., radical polymerizable compound)

D4: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., radical polymerizable compound)

D5: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., radical polymerizable compound)

（光重合開始剤）

　ＯＸ－１～ＯＸ－２１、ＯＸ－Ｒ１～ＯＸ－Ｒ４：上述した構造の化合物

　Ｉ－１：ＩＲＧＡＣＵＲＥ－３６９（ＢＡＳＦ社製、α－アミノアルキルフェノン化合物）
(Photopolymerization initiator)

OX-1 to OX-21, OX-R1 to OX-R4: compounds having the structures described above

I-1: IRGACURE-369 (manufactured by BASF, α-aminoalkylphenone compound)

（有機溶剤）

　Ｊ１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）

　Ｊ２：シクロヘキサノン

　Ｊ３：プロピレングリコールモノメチルエーテル（ＰＧＭＥ）

　Ｊ４：酢酸ブチル

　Ｊ５：乳酸エチル
(Organic solvent)

J1: Propylene glycol monomethyl ether acetate (PGMEA)

J2: Cyclohexanone

J3: Propylene glycol monomethyl ether (PGME)

J4: Butyl acetate

J5: Ethyl lactate

（その他添加剤）

［紫外線吸収剤］

　ＵＶ１：ＵＶ－５０３（大東化学（株）製）

　ＵＶ２：下記構造の化合物

Figure JPOXMLDOC01-appb-C000059
(Other additives)

[Ultraviolet absorber]

UV1: UV-503 (Daito Chemical Co., Ltd.)

UV2: Compound having the following structure

Figure JPOXMLDOC01-appb-C000059

［界面活性剤］

　Ｆ１：下記混合物（Ｍｗ＝１４０００、フッ素系界面活性剤）。下記の式中、繰り返し単位の割合を示す％は質量％である。

Figure JPOXMLDOC01-appb-C000060
[Surfactant]

F1: The following mixture (Mw = 14000, fluorosurfactant). In the following formula,% indicating the ratio of repeating units is mass%.

Figure JPOXMLDOC01-appb-C000060

［重合禁止剤］

　Ｇ１：ｐ－メトキシフェノール

［酸化防止剤］

　ＡＯ１：アデカスタブ　ＡＯ－８０（（株）ＡＤＥＫＡ製）
[Polymerization inhibitor]

G1: p-methoxyphenol

[Antioxidant]

AO1: ADK STAB AO-80 (manufactured by ADEKA Corporation)

［増感剤］

　Ｚ１～Ｚ３：下記構造の化合物

Figure JPOXMLDOC01-appb-C000061
[Sensitizer]

Z1 to Z3: Compounds having the following structures

Figure JPOXMLDOC01-appb-C000061

［近赤外線吸収色素］

　Ａ５、Ａ８、Ａ１２：下記構造の化合物

Figure JPOXMLDOC01-appb-C000062
[Near-infrared absorbing dye]

A5, A8, A12: Compounds having the following structure

Figure JPOXMLDOC01-appb-C000062

＜評価＞

　上記のようにして得られた各感光性組成物を用いて、以下の評価を行った。
<Evaluation>

The following evaluation was performed using each photosensitive composition obtained as described above.

（保存安定性（経時安定性）の評価）

　上記で得られた各感光性組成物を、ガラス容器に入れて密封し、５０℃１ヶ月保存した後、室温に戻し、下記の感度評価の経時変動の度合いを評価し、下記判定基準に従って保存安定性を評価した。

－判定基準－

　Ａ：１０ｍＪ／ｃｍ2未満の感度変動。

　Ｂ：１０ｍＪ／ｃｍ2以上５０ｍＪ／ｃｍ2未満の感度変動。

　Ｃ：５０ｍＪ／ｃｍ2以上の感度変動。
(Evaluation of storage stability (aging stability))

Each photosensitive composition obtained above is sealed in a glass container, stored at 50 ° C. for 1 month, returned to room temperature, evaluated for the degree of temporal change in sensitivity evaluation below, and stored according to the following criteria. Stability was evaluated.

-Criteria-

A: Sensitivity fluctuation less than 10 mJ / cm 2 .

B: Sensitivity fluctuation of 10 mJ / cm 2 or more and less than 50 mJ / cm 2 .

C: Sensitivity fluctuation of 50 mJ / cm 2 or more.

（感度の評価）

　シリコンウエハ上に、各感光性組成物をスピンコータを用いて塗布し、次いで、ホットプレートを用いて、１００℃、１２０秒間の加熱（プリベーク）を行い、膜厚が１．０μｍの塗膜を得た。

　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉＳ＋（Ｃａｎｏｎ（株）製）を使用して、１０ｎｍのラインアンドスペースのパターンが刻まれているマスクを介して、５０～１０００ｍＪ／ｃｍ2の範囲の露光量を、１０ｍＪ／ｃｍ2の刻みで変化させて照射した（露光工程）。次いで、テトラメチルアンモニウムハイドロオキサイド（ＴＭＡＨ）０．３％水溶液を用いて、２３℃にて６０秒間パドル現像を行い、その後、純水を用いて２０秒スピンシャワーにて、リンスを行い、更に純水にて水洗を行った。その後、パターン表面に付着した水滴をエアーで除去し、パターンを自然乾燥させて、パターンを得た。

　感度の評価は、上記の露光工程において光が照射された領域の現像後の膜厚が、露光前の膜厚１００％に対して９５％以上であった時の最少の露光量（最適露光量）を測定し、これを感度として評価した。上述の最少の露光量（最適露光量）の値が小さいほど感度が高いことを示す。
(Evaluation of sensitivity)

Each photosensitive composition is applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a thickness of 1.0 μm. It was.

Next, using an i-line stepper exposure apparatus FPA-3000iS + (manufactured by Canon Inc.), an exposure dose in the range of 50 to 1000 mJ / cm 2 through a mask in which a 10 nm line and space pattern is engraved. Were irradiated in 10 mJ / cm 2 increments (exposure process). Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinsed with pure water for 20 seconds in a spin shower, and further purified. Washed with water. Thereafter, water droplets adhering to the pattern surface were removed with air, and the pattern was naturally dried to obtain a pattern.

The evaluation of sensitivity is based on the minimum exposure amount (optimum exposure amount) when the film thickness after development in the area exposed to light in the above exposure process is 95% or more with respect to 100% of the film thickness before exposure. ) And measured as sensitivity. It shows that a sensitivity is so high that the value of the above-mentioned minimum exposure amount (optimal exposure amount) is small.

（現像性の評価）

　シリコンウエハ上に、各感光性組成物をスピンコータを用いて塗布し、次いで、ホットプレートを用いて、１００℃、１２０秒間の加熱（プリベーク）を行い、膜厚が１．０μｍの塗膜を得た。

　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉＳ＋（Ｃａｎｏｎ（株）製）を使用して、１０ｎｍのラインアンドスペースのパターンが刻まれているマスクを介して、４００ｍＪ／ｃｍ2の露光量で露光した。次いで、テトラメチルアンモニウムハイドロオキサイド（ＴＭＡＨ）０．３％水溶液を用いて、２３℃にて６０秒間パドル現像を行い、その後、純水を用いて２０秒スピンシャワーにて、リンスを行い、更に純水にて水洗を行った。その後、パターン表面に付着した水滴をエアーで除去し、パターンを自然乾燥させて、パターンを得た。

　パターンが形成されたシリコンウエハをＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ、倍率：２００００倍）にて観察し、ＳＥＭ写真から光が照射されなかった領域（未露光部）での残渣の有無を観察して、現像性を評価した。評価基準は以下の通りである。

－評価基準－

　Ａ：未露光部には、残渣がまったく確認されなかった。

　Ｂ：未露光部に、残渣がわずかに確認されたが、実用上問題のない程度であった。

　Ｃ：未露光部に、残渣が著しく確認された。
(Evaluation of developability)

Each photosensitive composition is applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate to obtain a coating film having a thickness of 1.0 μm. It was.

Next, using an i-line stepper exposure apparatus FPA-3000iS + (manufactured by Canon Inc.), exposure was performed at an exposure amount of 400 mJ / cm 2 through a mask in which a 10 nm line and space pattern was engraved. Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinsed with pure water for 20 seconds in a spin shower, and further purified. Washed with water. Thereafter, water droplets adhering to the pattern surface were removed with air, and the pattern was naturally dried to obtain a pattern.

The silicon wafer on which the pattern was formed was observed with an SEM (Scanning Electron Microscope, magnification: 20000 times), and from the SEM photograph, the presence or absence of a residue was observed in an area not irradiated with light (unexposed portion), and developed. Sex was evaluated. The evaluation criteria are as follows.

-Evaluation criteria-

A: No residue was confirmed at all in the unexposed area.

B: A slight residue was confirmed in the unexposed area, but there was no practical problem.

C: The residue was remarkably confirmed in the unexposed part.

（密着性の評価）

　現像性の評価と同様の手順でパターンを形成した。得られたパターンをＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ、倍率：２００００倍）にて観察し、ＳＥＭ写真からパターン欠損の有無を観察して、密着性を評価した。評価基準は以下の通りである。

－評価基準－

　Ａ：パターン欠損がまったく観察されなかった。

　Ｂ：パターン欠損がほとんど観察されなかったが、一部分のみ欠損が観察された。実用上問題のない程度であった。

　Ｃ：パターン欠損が著しく多く観察された。
(Evaluation of adhesion)

A pattern was formed by the same procedure as the evaluation of developability. The obtained pattern was observed with SEM (Scanning Electron Microscope, magnification: 20000 times), and the presence or absence of a pattern defect was observed from the SEM photograph to evaluate the adhesion. The evaluation criteria are as follows.

-Evaluation criteria-

A: No pattern defect was observed.

B: Almost no pattern defect was observed, but only a part of the defect was observed. There was no problem in practical use.

C: Remarkably many pattern defects were observed.

＜ポストベーク後の着色の評価＞

　現像性の評価と同様の手順でパターンを形成した。得られたパターンをホットプレートで２００℃、１時間加熱し、下記基準に基づいてポストベーク前後の色差ΔＥａｂ＊を、大塚電子（株）製ＭＣＰＤ－３０００で評価した。

－評価基準－

　Ａ：ΔＥａｂ＊≦５

　Ｂ：５＜ΔＥａｂ＊＜８

　Ｃ：ΔＥａｂ＊≧８
<Evaluation of coloring after post-baking>

A pattern was formed by the same procedure as the evaluation of developability. The obtained pattern was heated on a hot plate at 200 ° C. for 1 hour, and the color difference ΔEab * before and after post-baking was evaluated with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. based on the following criteria.

-Evaluation criteria-

A: ΔEab * ≦ 5

B: 5 <ΔEab * <8

C: ΔEab * ≧ 8

＜パターン断面形状１（ポストベーク前のパターン形状）＞

　現像性の評価と同様の手順でパターンを形成した。得られたパターンの断面形状をＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ、倍率：２００００倍）にて観察し、ＳＥＭ写真から５個のパターンを抽出し、５個のパターンの断面の平均傾きを求めて以下の基準でパターン断面形状１を評価した。なお、パターンの断面の傾きは、パターンを形成した部分におけるシリコンウエハ上のパターンの厚み方向における傾きのことである。具体的には、シリコンウエハの表面とパターンの厚み方向の辺とで構成される部分の角度を測定した。パターンの傾きがシリコンウエハの表面に対して９０度未満である場合とは、パターンは、シリコンウエハ側からパターンの表面側に向かって先細（順テーパ状）であることを意味する。

－評価基準－

　Ａ：５個のパターンの平均傾きがシリコンウエハに対して８０度以上１００度未満である。

　Ｂ：５個のパターンの平均傾きがシリコンウエハに対して１００度を超える。

　Ｃ：５個のパターンの平均傾きがシリコンウエハに対して８０度未満である。
<Pattern cross-sectional shape 1 (pattern shape before post-baking)>

A pattern was formed by the same procedure as the evaluation of developability. The cross-sectional shape of the obtained pattern was observed with a SEM (Scanning Electron Microscope, magnification: 20000 times), five patterns were extracted from the SEM photograph, and the average inclination of the cross-section of the five patterns was obtained and the following criteria were obtained. The pattern cross-sectional shape 1 was evaluated. Note that the inclination of the cross section of the pattern is the inclination in the thickness direction of the pattern on the silicon wafer at the portion where the pattern is formed. Specifically, the angle of the part constituted by the surface of the silicon wafer and the side in the thickness direction of the pattern was measured. The case where the inclination of the pattern is less than 90 degrees with respect to the surface of the silicon wafer means that the pattern is tapered (forward tapered) from the silicon wafer side toward the surface side of the pattern.

-Evaluation criteria-

A: The average inclination of the five patterns is not less than 80 degrees and less than 100 degrees with respect to the silicon wafer.

B: The average inclination of the five patterns exceeds 100 degrees with respect to the silicon wafer.

C: The average inclination of the five patterns is less than 80 degrees with respect to the silicon wafer.

＜パターン断面形状２（ポストベーク後のパターン形状）＞

　現像性の評価と同様の手順でパターンを形成した。得られたパターンをホットプレートを用いて、２００℃で５分間加熱（ポストベーク）した。ポストベーク後のパターンについて、上記パターン断面形状１と同様の手順でパターン断面形状２を評価した。

－評価基準－

　Ａ：５個のパターンの平均傾きがシリコンウエハに対して８０度以上１００度未満である。

　Ｂ：５個のパターンの平均傾きがシリコンウエハに対して１００度を超える。

　Ｃ：５個のパターンの平均傾きがシリコンウエハに対して８０度未満である。
<Pattern cross-sectional shape 2 (pattern shape after post-baking)>

A pattern was formed by the same procedure as the evaluation of developability. The obtained pattern was heated (post-baked) at 200 ° C. for 5 minutes using a hot plate. The pattern cross-sectional shape 2 was evaluated in the same procedure as the pattern cross-sectional shape 1 for the post-baked pattern.

-Evaluation criteria-

A: The average inclination of the five patterns is not less than 80 degrees and less than 100 degrees with respect to the silicon wafer.

B: The average inclination of the five patterns exceeds 100 degrees with respect to the silicon wafer.

C: The average inclination of the five patterns is less than 80 degrees with respect to the silicon wafer.

Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063

　上記表に示されるように、実施例の感光性組成物は比較例の感光性組成物よりも感度が高かった。更には、ポストベーク後の着色も少なく、矩形性の良いパターンを形成することができた。
As shown in the above table, the photosensitive compositions of the examples had higher sensitivity than the photosensitive compositions of the comparative examples. Furthermore, there was little coloring after post-baking, and a pattern with good rectangularity could be formed.

［試験例３］

＜カラーフィルタ用組成物の調製＞

（Ｒｅｄ組成物１）

　以下に示す原料を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｒｅｄ組成物１を調製した。

　Ｒｅｄ顔料分散液・・・５１．７質量部

　樹脂１の４０質量％ＰＧＭＥＡ溶液・・・０．６質量部

　重合性化合物１・・・０．６質量部

　光重合開始剤（化合物ＯＸ－１）・・・０．３質量部

　界面活性剤１の０．２質量％ＰＧＭＥＡ溶液・・・４．２質量部

　ＰＧＭＥＡ・・・４２．６質量部
[Test Example 3]

<Preparation of composition for color filter>

(Red composition 1)

The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 μm to prepare Red composition 1.

Red pigment dispersion: 51.7 parts by mass

40 mass% PGMEA solution of resin 1 0.6 mass parts

Polymerizable compound 1 ... 0.6 parts by mass

Photopolymerization initiator (compound OX-1): 0.3 part by mass

Surfactant 1 0.2% by mass PGMEA solution ... 4.2 parts by mass

PGMEA ... 42.6 parts by mass

（Ｇｒｅｅｎ組成物１）

　以下に示す原料を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｇｒｅｅｎ組成物１を調製した。

　Ｇｒｅｅｎ顔料分散液・・・７３．７質量部

　樹脂１の４０質量％ＰＧＭＥＡ溶液・・・０．３質量部

　重合性化合物２・・・１．２質量部

　光重合開始剤（化合物ＯＸ－１）・・・０．６質量部

　界面活性剤１の０．２質量％ＰＧＭＥＡ溶液・・・４．２質量部

　紫外線吸収剤１・・・０．５質量部

　ＰＧＭＥＡ・・・１９．５質量部
(Green composition 1)

The raw materials shown below were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare Green composition 1.

Green pigment dispersion: 73.7 parts by mass

40 mass% PGMEA solution of Resin 1 0.3 parts by mass

Polymerizable compound 2 1.2 mass parts

Photopolymerization initiator (compound OX-1) 0.6 mass parts

Surfactant 1 0.2% by mass PGMEA solution ... 4.2 parts by mass

UV absorber 1 0.5 mass parts

PGMEA ... 19.5 parts by mass

（Ｂｌｕｅ組成物１）

　以下に示す原料を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｂｌｕｅ組成物１を調製した。

　Ｂｌｕｅ顔料分散液・・・４４．９質量部

　樹脂１の４０質量％ＰＧＭＥＡ溶液・・・２．１質量部

　重合性化合物１・・・１．５質量部

　重合性化合物３・・・０．７質量部

　光重合開始剤（化合物ＯＸ－１）・・・・０．８質量部

　界面活性剤１の０．２質量％ＰＧＭＥＡ溶液・・・４．２質量部

　ＰＧＭＥＡ・・・４５．８質量部
(Blue composition 1)

The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.45 μm to prepare Blue composition 1.

Blue pigment dispersion ... 44.9 parts by mass

40 mass% PGMEA solution of resin 1 2.1 parts by mass

Polymerizable compound 1 ... 1.5 parts by mass

Polymerizable compound 3 ... 0.7 parts by mass

Photopolymerization initiator (compound OX-1) ... 0.8 parts by mass

Surfactant 1 0.2% by mass PGMEA solution ... 4.2 parts by mass

PGMEA ... 45.8 parts by mass

　カラーフィルタ用組成物に用いた原料は以下である。

　Ｒｅｄ顔料分散液

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４の９．６質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ

　Ｙｅｌｌｏｗ　１３９の４．３質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の６．８質量部と、ＰＧＭＥＡの７９．３質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）を用いて３時間混合および分散した。

その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ3の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｒｅｄ顔料分散液を得た。
The raw materials used for the color filter composition are as follows.

Red pigment dispersion

C. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment

A mixed solution composed of 4.3 parts by weight of Yellow 139, 6.8 parts by weight of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by weight of PGMEA was added to a bead mill (zirconia beads 0.3 mm). And mixed and dispersed for 3 hours.

Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

　Ｇｒｅｅｎ顔料分散液

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　３６の６．４質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０の５．３質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の５．２質量部と、ＰＧＭＥＡの８３．１質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）を用いて３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー

（株）製）を用いて、２０００ｋｇ／ｃｍ3の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｇｒｅｅｎ顔料分散液を得た。
Green pigment dispersion

C. I. 6.4 parts by mass of Pigment Green 36; I. Pigment Yellow 150, 5.3 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA were mixed with a bead mill (zirconia beads 0. 3 mm diameter) and mixed and dispersed for 3 hours. After that, the high-pressure disperser NANO-3000-10 with a decompression mechanism (Nippon BEE)

The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

　Ｂｌｕｅ顔料分散液

　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６の９．７質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３の２．４質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の５．５質量部と、ＰＧＭＥＡの８２．４質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）を用いて３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー

（株）製）を用いて、２０００ｋｇ／ｃｍ3の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｂｌｕｅ顔料分散液を得た。
Blue pigment dispersion

C. I. 9.7 parts by mass of Pigment Blue 15: 6; I. A mixture of 2.4 parts by weight of Pigment Violet 23, 5.5 parts by weight of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 82.4 parts by weight of PGMEA was added to a bead mill (Zirconia beads 0. 3 mm diameter) and mixed and dispersed for 3 hours. After that, the high-pressure disperser NANO-3000-10 with a decompression mechanism (Nippon BEE)

The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 . This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.

　重合性化合物１：下記構造の化合物

Figure JPOXMLDOC01-appb-C000064
　重合性化合物２：上述した重合性化合物Ｄ５

　重合性化合物３：上述した重合性化合物Ｄ３
Polymerizable compound 1: Compound having the following structure

Figure JPOXMLDOC01-appb-C000064
Polymerizable compound 2: polymerizable compound D5 described above

Polymerizable compound 3: the above-described polymerizable compound D3

　樹脂１：上述した樹脂Ｅ１

　界面活性剤１：上述した界面活性剤Ｆ１

　紫外線吸収剤１：上述した紫外線吸収剤ＵＶ１
Resin 1: Resin E1 described above

Surfactant 1: Surfactant F1 described above

UV absorber 1: UV absorber UV1 described above

（カラーフィルタの作製）

　シリコンウエハ上に、Ｇｒｅｅｎ組成物１をポストベーク後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用い、１００℃で２分間加熱（プレベーク）した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、４００ｍＪ／ｃｍ2の露光量にて、１．０μｍ四方のＢａｙｅｒパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム

（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用い、２００℃で５分間加熱（ポストベーク）して、１．０μｍ四方のベイヤーパターンの緑色画素（緑色パターン）を形成した。Ｒｅｄ組成物１、Ｂｌｕｅ組成物１についてもＧｒｅｅｎ組成物１の場合と同様の手順で順次パターニングして、シリコンウエハ上の緑色画素の抜け部に、１．０μｍ四方のアイランドパターンの赤色画素（赤色パターン）

および１．０μｍ四方のアイランドパターンの青色画素（青色パターン）をそれぞれ形成し、カラーフィルタを製造した。このカラーフィルタを固体撮像素子に組み込んだところ、この固体撮像素子は、高解像度で、色分離性に優れることが確認された。
(Production of color filter)

On the silicon wafer, Green composition 1 was applied by spin coating so that the film thickness after post-baking was 1.0 μm. Subsequently, it heated (prebaked) for 2 minutes at 100 degreeC using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a 1.0 μm square Bayer pattern at an exposure amount of 400 mJ / cm 2 . Then tetramethylammonium hydroxide

(TMAH) Using a 0.3 mass% aqueous solution, paddle development was performed at 23 ° C for 60 seconds. Then, it rinsed with the spin shower and further washed with pure water. Next, using a hot plate, heating was performed at 200 ° C. for 5 minutes (post-baking) to form a 1.0 μm square Bayer pattern green pixel (green pattern). The red composition 1 and the blue composition 1 are also sequentially patterned in the same procedure as in the case of the green composition 1, and a red pixel (red color of an island pattern of 1.0 μm square is formed on the green pixel on the silicon wafer. pattern)

A blue pixel (blue pattern) having an island pattern of 1.0 μm square was formed, and a color filter was manufactured. When this color filter was incorporated into a solid-state imaging device, it was confirmed that the solid-state imaging device has high resolution and excellent color separation.

Claims (19)


  1. 　オキシム基を含んで形成される環状構造の環状オキシム部位、および、Ｔａｆｔのσ*定数の値が３．５以上の電子求引性基をそれぞれ有する環状オキシム化合物と、

    　重合性化合物と、

    　を含む感光性組成物。
    A cyclic oxime moiety having a cyclic structure formed including an oxime group, and a cyclic oxime compound each having an electron-withdrawing group having a Taft σ * constant value of 3.5 or more;

    A polymerizable compound;

    A photosensitive composition comprising:

  2. 　前記環状オキシム化合物は、Ｔａｆｔのσ*定数の値が４以上の電子求引性基を有する、請求項１に記載の感光性組成物。
    The photosensitive composition according to claim 1, wherein the cyclic oxime compound has an electron-attracting group having a Taft σ * constant value of 4 or more.

  3. 　前記電子求引性基が、ニトロ基、アルキルスルホニル基、アリールスルホニル基およびオニウム基から選ばれる少なくとも１つである、請求項１または２に記載の感光性組成物。
    3. The photosensitive composition according to claim 1, wherein the electron withdrawing group is at least one selected from a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and an onium group.

  4. 　前記環状オキシム化合物が有する前記環状オキシム部位は、下記式（ａ－１）で表される、請求項１～３のいずれか１項に記載の感光性組成物；

    Figure JPOXMLDOC01-appb-C000001
    　式中、Ｒ1は置換基を表し、Ａは、オキシム基を含んで形成される環を表し、ｎは０または１を表す。
    The photosensitive composition according to any one of claims 1 to 3, wherein the cyclic oxime moiety of the cyclic oxime compound is represented by the following formula (a-1);

    Figure JPOXMLDOC01-appb-C000001
    In the formula, R 1 represents a substituent, A represents a ring formed including an oxime group, and n represents 0 or 1.

  5. 　前記環状オキシム化合物は、前記環状オキシム部位に、芳香族炭化水素環および複素環から選ばれる少なくとも１つの環が結合した構造を有する、請求項１～４のいずれか１項に記載の感光性組成物。
    The photosensitive composition according to claim 1, wherein the cyclic oxime compound has a structure in which at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring is bonded to the cyclic oxime moiety. object.

  6. 　前記環状オキシム化合物は、前記環状オキシム部位に、カルバゾール環またはジベンゾチオフェン環を含む縮合環が結合した構造を有する、請求項１～５のいずれか１項に記載の感光性組成物。
    The photosensitive composition according to any one of claims 1 to 5, wherein the cyclic oxime compound has a structure in which a condensed ring including a carbazole ring or a dibenzothiophene ring is bonded to the cyclic oxime moiety.

  7. 　前記環状オキシム化合物は、下記式（１）で表わされる化合物である、請求項１～６のいずれか１項に記載の感光性組成物；

    Figure JPOXMLDOC01-appb-C000002
    　式（１）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、

    　Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、

    　Ｒx1およびＲx3は、Ｒ2、Ｒ3、またはＢで表される環と結合して環を形成していてもよく、

    　Ｒ1～Ｒ3はそれぞれ独立して置換基を表し、

    　Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、

    　Ｂは芳香族炭化水素環および複素環から選ばれる少なくとも１つを含む環を表し、

    　Ｚ1はＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、

    　ｎは０または１を表し、

    　ｍは０または１を表し、

    　ｑは１以上の整数を表し、

    　ｏ、ｐはそれぞれ独立して０以上の整数を表し、

    　ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、

    　ｏが２以上の場合、ｏ個のＲ3は同一であってもよく、異なっていてもよく、２個のＲ3同士が結合して環を形成していてもよく、

    　ｑが２以上の場合、ｑ個のＺ1は同一であってもよく、異なっていてもよい。
    The photosensitive composition according to any one of claims 1 to 6, wherein the cyclic oxime compound is a compound represented by the following formula (1):

    Figure JPOXMLDOC01-appb-C000002
    In the formula (1), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4

    R x1 to R x4 each independently represents a hydrogen atom or a substituent,

    R x1 and R x3 may be bonded to a ring represented by R 2 , R 3 , or B to form a ring;

    R 1 to R 3 each independently represents a substituent,

    L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent,

    B represents a ring containing at least one selected from an aromatic hydrocarbon ring and a heterocyclic ring;

    Z 1 represents an electron-attracting group having a Taft σ * constant value of 3.5 or more,

    n represents 0 or 1,

    m represents 0 or 1;

    q represents an integer of 1 or more,

    o and p each independently represent an integer of 0 or more,

    When p is 2 or more, p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring,

    When o is 2 or more, o R 3 s may be the same or different, and two R 3 may be bonded to each other to form a ring,

    When q is 2 or more, q Z 1 s may be the same or different.

  8. 　前記環状オキシム化合物は、下記式（２）で表わされる化合物である、請求項１～６のいずれか１項に記載の感光性組成物；

    Figure JPOXMLDOC01-appb-C000003
    　式（２）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、

    　Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、

    　Ｒx1およびＲx3は、Ｒ2またはＲ3aと結合して環を形成していてもよく、

    　Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、

    　Ｒ1、Ｒ2、Ｒ3aおよびＲ3bはそれぞれ独立して置換基を表し、

    　Ｚ1aおよびＺ1bはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、

    　Ｙ1は、－ＣＲY1ＲY2－、－ＮＲY3－または－Ｓ－を表し、ＲY1～ＲY3はそれぞれ独立して水素原子または置換基を表し、

    　ｎは０または１を表し、

    　ｍは０または１を表し、

    　ｏ１、ｏ２、ｐ、ｑ１およびｑ２はそれぞれ独立して０以上の整数を表し、ｑ１および

    ｑ２の少なくとも一方は１以上の整数を表し、

    　ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、

    　ｏ１が２以上の場合、ｏ１個のＲ3aは同一であってもよく、異なっていてもよく、２個のＲ3a同士が結合して環を形成していてもよく、

    　ｏ２が２以上の場合、ｏ２個のＲ3bは同一であってもよく、異なっていてもよく、２個のＲ3b同士が結合して環を形成していてもよく、

    　ｑ１が２以上の場合、ｑ１個のＺ1aは同一であってもよく、異なっていてもよく、

    　ｑ２が２以上の場合、ｑ２個のＺ1bは同一であってもよく、異なっていてもよい。
    The photosensitive composition according to any one of claims 1 to 6, wherein the cyclic oxime compound is a compound represented by the following formula (2):

    Figure JPOXMLDOC01-appb-C000003
    In the formula (2), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4

    R x1 to R x4 each independently represents a hydrogen atom or a substituent,

    R x1 and R x3 may combine with R 2 or R 3a to form a ring,

    L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent,

    R 1 , R 2 , R 3a and R 3b each independently represent a substituent;

    Z 1a and Z 1b each independently represent an electron-withdrawing group having a Taft σ * constant value of 3.5 or more,

    Y 1 represents —CR Y1 R Y2 —, —NR Y3 — or —S—, wherein R Y1 to R Y3 each independently represents a hydrogen atom or a substituent,

    n represents 0 or 1,

    m represents 0 or 1;

    o1, o2, p, q1 and q2 each independently represents an integer of 0 or more, q1 and

    at least one of q2 represents an integer of 1 or more;

    When p is 2 or more, p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring,

    If o1 is 2 or more, o1 amino R 3a may be the same or different, may form a ring two R 3a are bonded to each other,

    If o2 is 2 or more, o2 one R 3b may be the same or different, may form a ring two R 3b are bonded to each other,

    When q1 is 2 or more, q1 Z 1a may be the same or different,

    When q2 is 2 or more, q2 Z 1b s may be the same or different.

  9. 　前記環状オキシム化合物は、下記式（３ａ）または式（３ｂ）で表わされる化合物である、請求項１～６のいずれか１項に記載の感光性組成物；

    Figure JPOXMLDOC01-appb-C000004
    　式（３ａ）中、Ｘ1は、－Ｏ－、－ＣＲx1ＲX2－、－Ｓ－、－ＮＲx3－、または、＞Ｃ＝Ｎ－Ｏ－Ｒx4を表し、

    　Ｒx1～Ｒx4はそれぞれ独立して水素原子または置換基を表し、

    　Ｒx1およびＲx3は、Ｒ2またはＲ3cと結合して環を形成していてもよく、

    　Ｙ2は、－ＣＲY21ＲY22－、－ＮＲY23－または－Ｓ－を表し、ＲY21～ＲY23はそれぞれ独立して水素原子または置換基を表す；

    　式（３ｂ）中、Ｘ2は、＞ＣＲX10－または＞Ｎ－を表し、Ｒx10は水素原子または置換基を表す；

    　式（３ａ）および式（３ｂ）中、Ｒ1、Ｒ2、Ｒ3cおよびＲ3dはそれぞれ独立して置換基を表し、

    　Ｌは炭素数１～３のアルキレン基または－ＣＲL1＝ＣＲL2－を表し、ＲL1およびＲL2はそれぞれ独立して水素原子または置換基を表し、

    　Ｚ1cおよびＺ1dはそれぞれ独立してＴａｆｔのσ*定数の値が３．５以上の電子求引性基を表し、

    　ｎは０または１を表し、

    　ｍは０または１を表し、

    　ｏ３、ｏ４、ｐ、ｑ３およびｑ４はそれぞれ独立して０以上の整数を表し、ｑ３およびｑ４の少なくとも一方は１以上の整数を表し、

    　ｐが２以上の場合、ｐ個のＲ2は同一であってもよく、異なっていてもよく、２個のＲ2同士が結合して環を形成していてもよく、

    　ｏ３が２以上の場合、ｏ３個のＲ3cは同一であってもよく、異なっていてもよく、２個のＲ3c同士が結合して環を形成していてもよく、

    　ｏ４が２以上の場合、ｏ４個のＲ3dは同一であってもよく、異なっていてもよく、２個のＲ3d同士が結合して環を形成していてもよく、

    　ｑ３が２以上の場合、ｑ３個のＺ1cは同一であってもよく、異なっていてもよく、

    　ｑ４が２以上の場合、ｑ４個のＺ1dは同一であってもよく、異なっていてもよい。
    The photosensitive composition according to any one of claims 1 to 6, wherein the cyclic oxime compound is a compound represented by the following formula (3a) or (3b):

    Figure JPOXMLDOC01-appb-C000004
    In the formula (3a), X 1 represents —O—, —CR x1 R X2 —, —S—, —NR x3 —, or> C═N—O—R x4

    R x1 to R x4 each independently represents a hydrogen atom or a substituent,

    R x1 and R x3 may combine with R 2 or R 3c to form a ring,

    Y 2 represents —CR Y21 R Y22 —, —NR Y23 — or —S—, wherein R Y21 to R Y23 each independently represents a hydrogen atom or a substituent;

    In the formula (3b), X 2 represents> CR X10 -or> N-, and R x10 represents a hydrogen atom or a substituent;

    In formula (3a) and formula (3b), R 1 , R 2 , R 3c and R 3d each independently represent a substituent,

    L represents an alkylene group having 1 to 3 carbon atoms or —CR L1 ═CR L2 —, R L1 and R L2 each independently represent a hydrogen atom or a substituent,

    Z 1c and Z 1d each independently represents an electron-withdrawing group having a Taft σ * constant value of 3.5 or more,

    n represents 0 or 1,

    m represents 0 or 1;

    o3, o4, p, q3 and q4 each independently represent an integer of 0 or more, at least one of q3 and q4 represents an integer of 1 or more,

    When p is 2 or more, p R 2 s may be the same or different, and two R 2 may be bonded to each other to form a ring,

    If o3 is 2 or more, o3 one R 3c may be the same or different, may form a ring two R 3c are bonded to each other,

    If o4 is 2 or more, o4 one R 3d may be the same or different, may form a ring two R 3d are bonded to each other,

    When q3 is 2 or more, q3 Z 1c s may be the same or different,

    When q4 is 2 or more, q4 Z 1d s may be the same or different.

  10. 　更に、樹脂を含有する、請求項１～９のいずれか１項に記載の感光性組成物。
    The photosensitive composition according to any one of claims 1 to 9, further comprising a resin.

  11. 　更に、色材を含有する、請求項１～１０のいずれか１項に記載の感光性組成物。
    The photosensitive composition according to any one of claims 1 to 10, further comprising a coloring material.

  12. 　前記色材が顔料を含む、請求項１１に記載の感光性組成物。
    The photosensitive composition of Claim 11 in which the said coloring material contains a pigment.

  13. 　前記色材が有彩色着色剤、白色着色剤、黒色着色剤および近赤外線吸収色素から選ばれる少なくとも１つを含む、請求項１１又は１２に記載の感光性組成物。
    The photosensitive composition of Claim 11 or 12 in which the said coloring material contains at least 1 chosen from a chromatic colorant, a white colorant, a black colorant, and a near-infrared absorption pigment | dye.

  14. 　カラーフィルタの画素形成用の組成物である、請求項１～１３のいずれか１項に記載の感光性組成物。
    The photosensitive composition according to any one of claims 1 to 13, which is a composition for forming a pixel of a color filter.

  15. 　請求項１～１４のいずれか１項に記載の感光性組成物を用いて得られる硬化膜。
    A cured film obtained using the photosensitive composition according to any one of claims 1 to 14.

  16. 　支持体上に請求項１～１４のいずれか１項に記載の感光性組成物を適用して感光性組成物層を形成する工程と、

    　前記感光性組成物層をパターン状に露光する工程と、

    　露光後の前記感光性組成物層を現像してパターンを形成する工程と、

    　を含む、カラーフィルタの製造方法。
    Applying the photosensitive composition according to any one of claims 1 to 14 on a support to form a photosensitive composition layer;

    Exposing the photosensitive composition layer in a pattern;

    Developing the photosensitive composition layer after exposure to form a pattern;

    A method for producing a color filter, comprising:

  17. 　請求項１５に記載の硬化膜を有するカラーフィルタ。
    A color filter having the cured film according to claim 15.

  18. 　請求項１５に記載の硬化膜を有する固体撮像素子。
    A solid-state imaging device having the cured film according to claim 15.

  19. 　請求項１５に記載の硬化膜を有する画像表示装置。
    An image display device comprising the cured film according to claim 15.
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WO2021166860A1 (en) * 2020-02-20 2021-08-26 富士フイルム株式会社 Photosensitive composition, film, optical filter, solid-state imaging element and image display device
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