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WO2015182277A1 - Coloring composition, film, color filter, pattern formation method, method for producing color filter, solid-state imaging element, and infrared ray sensor - Google Patents

Coloring composition, film, color filter, pattern formation method, method for producing color filter, solid-state imaging element, and infrared ray sensor Download PDF

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Publication number
WO2015182277A1
WO2015182277A1 PCT/JP2015/061804 JP2015061804W WO2015182277A1 WO 2015182277 A1 WO2015182277 A1 WO 2015182277A1 JP 2015061804 W JP2015061804 W JP 2015061804W WO 2015182277 A1 WO2015182277 A1 WO 2015182277A1
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WIPO (PCT)
Prior art keywords
colorant
group
polymerizable compound
color filter
colored composition
Prior art date
Application number
PCT/JP2015/061804
Other languages
French (fr)
Japanese (ja)
Inventor
大貴 瀧下
上村　哲也
江副　利秀
嶋田　和人
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020167032230A priority Critical patent/KR101925813B1/en
Priority to JP2016523375A priority patent/JP6325097B2/en
Publication of WO2015182277A1 publication Critical patent/WO2015182277A1/en

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    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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

Definitions

  • the present invention relates to a coloring composition.
  • the coloring composition preferably used for formation of a color filter.
  • the present invention also relates to a pattern forming method using a colored composition and a method for producing a color filter.
  • Color filters are indispensable components for solid-state image sensors and liquid crystal displays.
  • color filters for solid-state imaging devices are required to improve color separation and color reproducibility.
  • Such a color filter is formed with a plurality of colored regions. For example, it is formed with red, green, and blue colored regions (hereinafter also referred to as “colored patterns” or “colored pixels”).
  • a coloring pattern first, in the first hue, a coloring composition having a colorant of red, green, or blue is applied, and is colored by performing exposure, development, and heat treatment as necessary. After the pattern is formed, the same coating, exposure, development, and heat treatment processes as necessary are repeated in the second hue and the third hue.
  • Patent Document 1 discloses a resin black matrix having a maximum light transmittance of 1% or less in a wavelength range of 400 to 700 nm and an average light transmittance of 60 or more in a wavelength range of 850 to 3000 nm.
  • Sensing using near infrared rays is utilized in various applications.
  • Near-infrared light has a longer wavelength than visible light, so it is difficult to scatter and can be used for distance measurement and three-dimensional measurement. Utilizing such near-infrared characteristics, it is used in proximity sensors, motion sensors, and the like.
  • near infrared rays are invisible to humans, animals, etc., even if the subject is illuminated with a near infrared light source at night, the subject is not noticed. It can also be used to shoot without.
  • a colored composition capable of forming a film capable of transmitting near-infrared rays with little visible light-derived noise is applied and cured to form a film. It was found that wrinkles are likely to occur on the surface. It was also found that wrinkles are likely to occur on the surface as the film thickness is increased.
  • an object of the present invention is to provide a coloring composition capable of transmitting a near-infrared ray with less visible light-derived noise and capable of forming a film in which wrinkles are suppressed. Moreover, it aims at providing the film
  • the colored composition contains a polymerizable compound having a chain containing two or more alkyleneoxy groups as repeating units (that is, a chain having two or more repeating units of alkyleneoxy groups).
  • a polymerizable compound having a chain containing two or more alkyleneoxy groups as repeating units that is, a chain having two or more repeating units of alkyleneoxy groups.
  • the ratio A / B between the minimum absorbance A in the wavelength range of 400 nm to 580 nm and the minimum absorbance B in the wavelength range of 580 nm to 770 nm is 0.3 to 3, and the wavelength range is 400 nm to 750 nm.
  • a colored composition comprising a colorant and a polymerizable compound, wherein the polymerizable compound contains a polymerizable compound having a chain having two or more alkyleneoxy group repeating units, and the colorant is red
  • the polymerizable compound contains a polymerizable compound having a chain having two or more alkyleneoxy group repeating units, and the colorant is red
  • Colorant A / total colorant in the mass ratio is 0.01 to 0.7
  • yellow colorant / total colorant in the mass ratio of the yellow colorant to the total amount of colorant is 0.05 to 0.5.
  • the colorant contains a red colorant, a purple colorant, a yellow colorant, and a blue colorant, and the red colorant / total colorant is a mass ratio of the red colorant to the total colorant amount is 0.
  • the yellow colorant / total colorant is 0.1 to 0.4, which is the mass ratio of the yellow colorant to the total amount of the colorant, and the mass ratio of the blue colorant to the total amount of the colorant.
  • a certain blue colorant / total colorant is 0.2 to 0.6, and a purple colorant / total colorant, which is a mass ratio of the purple colorant to the total amount of colorant, is 0.01 to 0.3, ⁇
  • ⁇ 4> The colored composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerizable compound contains a polymerizable compound having a chain having an ethyleneoxy group repeating unit number of 2 or more.
  • the polymerizable compound is any one of ⁇ 1> to ⁇ 4>, wherein a value obtained by dividing the molecular weight value of the polymerizable compound by the number of polymerizable groups contained in the polymerizable compound is 100 to 300.
  • the coloring composition as described in. ⁇ 6> The colored composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerizable compound has a cyclic structure.
  • ⁇ 7> The colored composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polymerizable compound has a heterocyclic structure.
  • ⁇ 8> The polymerizable compound according to any one of ⁇ 1> to ⁇ 7>, wherein the polymerizable compound has a partial structure represented by the following general formula (1); is there.
  • ⁇ 9> The colored composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a resin and a photopolymerization initiator.
  • ⁇ 10> The colored composition according to ⁇ 9>, wherein the resin contains a resin having a hydroxyl group.
  • the maximum transmittance in the wavelength range of 400 to 780 nm is 15% or less, and the transmittance at a wavelength of 850 nm is 80% or more.
  • ⁇ 1> to ⁇ 10> The colored composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> The colored composition according to any one of ⁇ 1> to ⁇ 11>, wherein the viscosity at 25 ° C. is 100 to 150 mP ⁇ s.
  • ⁇ 13> A film obtained by curing the colored composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> A color filter having the film according to ⁇ 13>.
  • ⁇ 15> A step of applying the colored composition according to any one of ⁇ 1> to ⁇ 12> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, Forming a colored pattern by developing and removing an unexposed portion.
  • ⁇ 16> A method for producing a color filter, comprising the pattern forming method according to ⁇ 15>.
  • ⁇ 17> A solid-state imaging device having the color filter according to ⁇ 14> or the color filter obtained by the method for producing a color filter according to ⁇ 16>.
  • ⁇ 18> An infrared sensor having a color filter according to ⁇ 14> or a color filter obtained by the method for producing a color filter according to ⁇ 16>.
  • the present invention it is possible to provide a coloring composition capable of transmitting a near infrared ray with less visible light-derived noise and capable of forming a film in which wrinkles are suppressed.
  • membrane using this coloring composition, a color filter, the pattern formation method, the manufacturing method of a color filter, a solid-state image sensor, and an infrared sensor can be provided.
  • the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
  • solid content means solid content in 25 degreeC.
  • the viscosity refers to a viscosity at 25 ° C.
  • 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).
  • radiation means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure means not only exposure with a deep ultraviolet ray, an X-ray, EUV light, etc. represented by a mercury lamp and an excimer laser, but also drawing with a particle beam such as an electron beam or an ion beam unless otherwise specified. Are also included in the exposure.
  • (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.
  • “monomer” and “monomer” are synonymous.
  • “Monomer” is distinguished from “oligomer” and “polymer”, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • 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. It is.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
  • the pigment used in the present invention means an insoluble coloring compound that is difficult to dissolve in a solvent. Typically, it means a dye compound that exists in a dispersed state as particles in the composition.
  • the pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less, for example, for both propylene glycol monomethyl ether acetate and water.
  • a first aspect of the colored composition of the present invention includes a colorant and a polymerizable compound, and the polymerizable compound has a chain containing two or more alkyleneoxy groups as repeating units (that is, the number of repeating units of the alkyleneoxy group is A polymerizable compound having a chain of 2 or more (hereinafter also referred to as an alkyleneoxy chain), and a colored composition having a minimum absorbance A in a wavelength range of 400 nm to less than 580 nm and a wavelength of 580 nm to 770 nm inclusive.
  • the ratio A / B to the minimum absorbance B is 0.3 to 3, and the minimum absorbance C in the wavelength range from 400 nm to 750 nm and the maximum absorbance D in the wavelength range from 850 nm to 1300 nm.
  • the ratio C / D is 5 or more.
  • the absorbance ratio A / B described above is preferably 0.4 to 2.5, and more preferably 0.5 to 2.
  • the above-described absorbance ratio C / D is preferably 10 or more, and more preferably 50 or more.
  • the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
  • a ⁇ ⁇ log (T ⁇ ) (1)
  • a ⁇ is the absorbance at wavelength ⁇
  • T ⁇ is the transmittance at wavelength ⁇ .
  • the absorbance value of the colored composition may be a value measured in the state of a solution, or may be a value of a film formed using the colored composition.
  • a colored composition is applied onto a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and then a hot plate at 100 ° C. for 120 seconds. It is preferable to use a membrane prepared by drying with The film thickness of the film can be measured by using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the substrate having the film.
  • the absorbance can be measured using a conventionally known spectrophotometer.
  • the measurement conditions for absorbance are not particularly limited.
  • the measurement is preferably performed under conditions adjusted so that the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm is 0.1 to 3.0.
  • the measurement error can be further reduced.
  • the method for adjusting the minimum absorbance A in the wavelength range of 400 nm or more and less than 580 nm to be 0.1 to 3.0 For example, when measuring the absorbance in a liquid state, a method of adjusting the optical path length of the sample cell can be mentioned. Moreover, when measuring a light absorbency in the state of a film
  • the second aspect of the colored composition of the present invention includes a colorant and a polymerizable compound, and the polymerizable compound has a chain containing two or more alkyleneoxy groups as repeating units (that is, a repeating unit of an alkyleneoxy group).
  • a polymerizable compound having a chain having a number of 2 or more) and the colorant includes at least one colorant A selected from a red colorant and a purple colorant, a yellow colorant, and a blue colorant.
  • the colorant A / total colorant which is at least a mass ratio of the colorant A selected from the red colorant and the purple colorant to the total amount of the colorant, is 0.01 to 0.7, and the colorant of the yellow colorant
  • the yellow colorant / total colorant which is a mass ratio to the total amount, is 0.05 to 0.5
  • the blue colorant / total colorant which is the mass ratio of the blue colorant to the total amount of colorant, is 0.05 to 0.00.
  • the colorant includes a red colorant, a purple colorant, a yellow colorant, and a blue colorant
  • the red colorant / total colorant is a mass ratio of the red colorant to the total amount of the colorant.
  • the yellow colorant / total colorant is 0.1 to 0.4, and the mass ratio of the yellow colorant to the total amount of the colorant is 0.1 to 0.4, and the mass ratio of the blue colorant to the total amount of the colorant
  • the blue colorant / total colorant is 0.2 to 0.6, and the purple colorant / total colorant, which is the mass ratio of the purple colorant to the total amount of colorant, is 0.01 to 0.3. Is preferred.
  • the color composition of the first aspect in which the absorbance ratio A / B is 0.3 to 3 and the absorbance ratio C / D is 5 or more, and each colorant is contained in the above range.
  • the colored composition according to the second aspect can form a film that can transmit near infrared rays with less visible light-derived noise.
  • the coloring composition of this invention can form the film
  • a colored composition capable of forming a film capable of transmitting near-infrared rays with less visible light-derived noise has a low permeability to i-line and the like, and therefore tends to have a lower curability inside the film than the film surface. It is in. For this reason, since the film
  • the polymerizable compound having an alkyleneoxy chain has flexibility, the influence of shrinkage of the film accompanying the curing of the polymerizable compound can be suppressed, so that it is presumed that a film in which wrinkles are suppressed can be formed.
  • it is useful when forming a film having a film thickness of 1 ⁇ m or more, and further 6 ⁇ m.
  • each component of the coloring composition of the present invention will be described.
  • the coloring composition of the present invention contains a colorant.
  • the colorant may be a pigment or a dye. Preferably, it is a pigment because it has high resistance to heat and light.
  • the colorant preferably has a pigment content of 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more based on the total amount of the colorant. .
  • the pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these.
  • 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.
  • black pigments such as carbon black (CI Pigment Black 7), titanium black, iron, Examples thereof include metal oxides such as cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.
  • the well-known dye currently used for the color filter can be used.
  • the chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.
  • an acid dye and / or a derivative thereof may be suitably used.
  • direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
  • acid alizarin violet N acid black 1, 2, 24, 48, acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1, acid chroma violet K, acid Fuchsin; acid green 1,3,5,9,16,25,27,50, acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95, acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176,
  • azo, xanthene and phthalocyanine acid dyes are also preferred.
  • I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
  • the dye triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo
  • a colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene is preferable. Further, pigments and dyes may be used in combination.
  • bisbenzofuranone pigments examples include those described in JP-A-2012-528448, JP-A-2010-534726, JP-A-2012-515234, and the like.
  • IRGAPHOR BK manufactured by BASF Is available as Examples of the azomethine pigment 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 azo dye is not particularly limited, and preferred examples include compounds represented by the following formula (A-1).
  • the colorant it is preferable to include at least a yellow colorant and a blue colorant, and it is more preferable to include a red colorant, a yellow colorant, a blue colorant, and a purple colorant.
  • the colorant preferably contains a pigment, more preferably contains a yellow pigment and a blue pigment, and more preferably contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment. According to this aspect, it is possible to obtain a colored composition capable of forming a film capable of transmitting near-infrared rays with little visible light-derived noise.
  • red pigments include C.I. I. Pigment Red 254 is preferred.
  • yellow pigments include C.I. I. Pigment Yellow 139 is preferred.
  • the blue pigment include C.I. I. Pigment Blue 15: 6 is preferred.
  • Purple pigments include, for example, C.I. I. Pigment Violet 23 is preferred.
  • the colorant preferably contains at least one selected from bisbenzofuranone pigments, azomethine pigments, perylene pigments, and azo dyes. It is more preferable to contain one or more selected from pigments, azomethine pigments and perylene pigments.
  • the mass ratio of the red colorant to the total amount of the colorant is 0.1 to 0.5
  • the mass ratio of the yellow colorant to the total amount of the colorant The ratio is preferably 0.1 to 0.4
  • the mass ratio of the blue colorant to the total amount of the colorant is preferably 0.2 to 0.6.
  • the mass ratio of the red colorant to the total amount of colorant is 0.3 to 0.5
  • the mass ratio of the yellow colorant to the total amount of colorant is 0.1 to 0.3
  • the blue colorant is based on the total amount of colorant.
  • the mass ratio is more preferably 0.4 to 0.6.
  • the mass ratio of the yellow colorant to the total amount of the colorant is 0.1 to 0.4, and the mass of the blue colorant relative to the total amount of the colorant
  • the ratio is preferably 0.2 to 0.6
  • the mass ratio of the purple colorant to the total amount of the colorant is preferably 0.01 to 0.3.
  • the mass ratio of the yellow colorant to the total amount of colorant is 0.2 to 0.3
  • the mass ratio of the blue colorant to the total amount of colorant is 0.4 to 0.6
  • the purple colorant is based on the total amount of colorant.
  • the mass ratio is more preferably 0.1 to 0.25.
  • the mass ratio of the red colorant to the total amount of the colorant is 0.1 to 0.5, and the yellow colorant is colored.
  • the mass ratio to the total amount of the colorant is 0.1 to 0.4, the mass ratio of the blue colorant to the total amount of the colorant is 0.2 to 0.6, and the mass ratio of the purple colorant to the total amount of the colorant is 0.00. It is preferably 01 to 0.3.
  • the mass ratio of the red colorant to the total amount of colorant is 0.3 to 0.5, the mass ratio of the yellow colorant to the total amount of colorant is 0.1 to 0.3, and the blue colorant is based on the total amount of colorant.
  • the mass ratio is 0.3 to 0.5, and the mass ratio of the purple colorant to the total amount of the colorant is 0.01 to 0.2.
  • the color ratio of the red colorant to the total amount of the colorant is 0.35 to 0.41, the mass ratio of the yellow colorant to the total amount of the colorant is 0.13 to 0.1.9, and the colorant of the blue colorant.
  • the mass ratio with respect to the total amount is preferably 0.34 to 0.40, and the mass ratio of the purple colorant to the total amount of the colorant is particularly preferably 0.06 to 0.12.
  • the ratio A / B between the minimum value A of the absorbance in the wavelength range from 400 nm to less than 580 nm and the minimum value B in the wavelength range from 580 nm to 770 nm is 0.3 to 3
  • a colored composition having a ratio C / D of 5 or more between the minimum absorbance C in the wavelength range of 400 nm to 750 nm and the maximum absorbance D in the wavelength range of 850 nm to 1300 nm can be obtained.
  • the content of the colorant is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and more preferably 3 to 70% by mass of the total solid content of the colored composition. % Is more preferable.
  • Pigment dispersion when a pigment is used as the colorant, it is preferably used in the form of a pigment dispersion in which the pigment is dispersed together with a resin, an organic solvent, a pigment derivative and the like.
  • the composition of the pigment dispersion and the method for preparing the pigment dispersion are described in detail below.
  • the average particle diameter of the pigment is preferably 20 to 300 nm, more preferably 25 to 250 nm, and still more preferably 30 to 200 nm.
  • the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated.
  • the average particle diameter of the pigment is obtained by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value. be able to.
  • the particle size distribution of the secondary particles of the pigment (hereinafter, simply referred to as “particle size distribution”) is 70% by mass or more, preferably 80% by mass, of secondary particles falling into (average particle size ⁇ 100) nm. % Or more is preferable.
  • the particle size distribution is a value measured using a scattering intensity distribution.
  • the pigment having the average particle size and particle size distribution described above is obtained by mixing and dispersing a commercially available pigment, preferably with a resin and an organic solvent, and using a pulverizer such as a bead mill or a roll mill while pulverizing. Can be prepared.
  • the pigment thus obtained is usually in the form of a pigment dispersion.
  • a fine and sized pigment it is preferable to use a fine and sized pigment. Refinement of the pigment is achieved by preparing a high-viscosity liquid composition together with the pigment, the organic solvent, and the water-soluble inorganic salts, and applying a stress and grinding using a wet pulverizer.
  • a water-soluble organic solvent is preferable.
  • the water-soluble organic solvent include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl.
  • examples include ether acetate.
  • the amount of the water-soluble organic solvent used in the miniaturization step is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the pigment.
  • other solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, and undecane.
  • water-soluble inorganic salts used in the pigment refinement process examples include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
  • the amount of the water-soluble inorganic salt used in the miniaturization step is preferably 1 to 50 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the pigment.
  • the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably from 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of a high grinding effect.
  • the operation time is preferably 1 to 8 hours together with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C.
  • the water-soluble inorganic salt as a grinding medium preferably has a grinding particle size of 5 to 50 ⁇ m, a sharp particle size distribution, and a spherical shape.
  • Resins (dispersed resin) that can be used in the preparation of pigment dispersions include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight Unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol Surfactants such as amines can be mentioned.
  • polymer dispersants for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight Unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthal
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
  • the terminal-modified polymer having an anchor site to the pigment surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like.
  • examples thereof include polymers having a sulfonic acid group at the terminal end described in JP-A-273191 and the like, and polymers having a partial skeleton of an organic dye and a heterocyclic ring described in JP-A-9-77994.
  • polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
  • the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like.
  • reaction product of polyester a reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, a macromonomer described in JP-A-10-339949, JP-A-2004-37986 and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc.
  • a known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization.
  • macromonomer AA-6 polymethyl methacrylate whose terminal group is a methacryloyl group
  • AS-6 polystyrene whose terminal group is a methacryloyl group
  • AN-6S terminal group is methacryloyl
  • AB-6 polybutyl acrylate whose terminal group is a methacryloyl group
  • Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd.
  • polyester macromonomer described in JP-A-2-272009 examples include a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion.
  • a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is most preferred.
  • block type polymer having an anchor site to the pigment surface block type polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • a kraft copolymer containing a structural unit represented by any one of the following formulas (1) to (4) can also be used.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom or a methyl group Are more preferable, and a methyl group is particularly preferable.
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, preferably an oxygen atom.
  • R 3 represents a branched or straight chain alkylene group (preferably having 1 to 10 carbon atoms, more preferably 2 or 3), and —CH 2 —CH (CH 3 ) from the viewpoint of dispersion stability.
  • a group represented by — or a group represented by —CH (CH 3 ) —CH 2 — is preferred.
  • Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group.
  • the description of paragraph numbers 0025 to 0069 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
  • Specific examples of the craft copolymer include the following. Further, resins described in JP-A-2012-255128, paragraphs 0072 to 0094 can be used.
  • an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used.
  • the oligoimine resin includes a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain.
  • a resin having a basic nitrogen atom on one side is preferred.
  • the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
  • the oligoimine resin includes, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2a). Examples include resins containing units.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms).
  • a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
  • R 8 and R 9 are the same groups as R 1 .
  • L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms).
  • an imino group preferably having a carbon number of 0 to 6
  • an ether group preferably having a carbon number of 0 to 6
  • a thioether group preferably having a carbonyl group, or a combination group thereof.
  • a single bond or —CR 5 R 6 —NR 7 — is preferable.
  • R 5 R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms).
  • R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • L a is a structural site ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed and is particularly preferably a structural part to form pyrrolidine. This structural part may further have a substituent such as an alkyl group.
  • X represents a group having a functional group of pKa14 or less.
  • Y represents a side chain having 40 to 10,000 atoms.
  • the resin oligoimine-based resin
  • the resin further contains, as a copolymerization component, one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5) You may do it.
  • the resin contains such a repeating unit, the dispersion performance of the pigment can be further improved.
  • R 1 , R 2 , R 8 , R 9 , L, La, a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
  • Ya represents a side chain having an anionic group having 40 to 10,000 atoms.
  • the repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.
  • oligoimine-based resin described above, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the oligoimine resin include the following. Also, resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
  • the resin is also available as a commercial product. Specific examples of such resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group) manufactured by BYK Chemie.
  • Polymer 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”, manufactured by EFKA “EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 ( Fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo pigment derivatives), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fan Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No.
  • DA-705, DA-725 “ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”manufactured by Kao Corporation,“ Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (poly Xylethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, manufactured by Nippon Lubrizol Co., Ltd.
  • 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxy) manufactured by Nikko Chemical Co., Ltd.
  • Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Surfactant, anionic surfactant such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, manufactured by Morishita Sangyo Co., Ltd.
  • Disperse Aid 6 Disperse Aid 8
  • Disperse Aid 15 Disperse Aid 9100 “manufactured by San Nopco Polymer dispersant, manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 And “Ionet S-20” manufactured by Sanyo Chemical Co., Ltd.
  • Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain.
  • the acidic cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable.
  • An alkali-soluble resin containing is also preferred.
  • the content of the resin (dispersion resin) in the pigment dispersion is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the upper limit is preferably 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less.
  • the lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.
  • the amount of pigment means the total amount of pigment contained in the total amount of colorant.
  • the pigment dispersion preferably further contains a pigment derivative.
  • the pigment derivative is a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a phthalimidomethyl group, or the like.
  • the pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
  • pigments for constituting the pigment derivative diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindolinone pigment, isoindolinone pigment, examples include quinophthalone pigments, selenium pigments, and metal complex pigments.
  • a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable.
  • the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
  • a quinoline pigment derivative, a benzimidazolone pigment derivative and an isoindoline pigment derivative are preferable, and a quinoline pigment derivative and a benzimidazolone pigment derivative are particularly preferable.
  • the content of the pigment derivative in the pigment dispersion is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the pigment dispersion preferably contains an organic solvent.
  • the organic solvent is selected depending on the solubility of each component contained in the pigment dispersion and the coating property when the pigment dispersion is applied to the coloring composition.
  • esters, ethers, ketones, and aromatic hydrocarbons are used as the organic solvent.
  • the organic solvent which can be contained in the coloring composition mentioned later.
  • the content of the organic solvent in the pigment dispersion is preferably 50 to 95% by mass, more preferably 70 to 90% by mass.
  • the coloring composition of the present invention contains a polymerizable compound.
  • the polymerizable compound is a compound having a polymerizable group, and a known polymerizable compound that can be polymerized by a radical can be used.
  • a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, methallyl group, acryloyl group, methacryloyl group, allyloxycarbonyl group, and methallyloxycarbonyl group.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof.
  • the polymerizable compound is preferably a compound having one or more polymerizable groups, and more preferably a compound having two or more polymerizable groups.
  • a polyfunctional polymerizable compound having 4 or more functional groups having 4 or more polymerizable groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.
  • the present invention includes a polymerizable compound containing a polymerizable compound having a chain containing two or more alkyleneoxy groups as repeating units (that is, a chain having 2 or more repeating units of alkyleneoxy groups; an alkyleneoxy chain).
  • a polymerizable compound having an alkyleneoxy chain has flexibility, the shrinkage of the film accompanying the curing of the polymerizable compound can be suppressed, and the generation of wrinkles on the film surface can be effectively suppressed.
  • the alkyleneoxy chain preferably has 2 to 30 repeating units of an alkyleneoxy group, more preferably 2 to 20, and still more preferably 5 to 15.
  • the alkyleneoxy group preferably has 2 or more carbon atoms, more preferably 2 to 10, more preferably 2 to 4, and particularly preferably 2.
  • the alkyleneoxy group may be either linear or branched, but is preferably linear.
  • the alkyleneoxy group is preferably unsubstituted. That is, the alkyleneoxy chain is preferably represented by “— ((CH 2 ) a —O) b —”.
  • a is preferably 2 or more, more preferably 2 to 20.
  • b is preferably 2 or more, more preferably 2 to 10.
  • the polymerizable compound having an alkyleneoxy chain is a polymer having a chain containing two or more ethyleneoxy groups as repeating units (that is, a chain having two or more ethyleneoxy group repeating units, also referred to as an ethyleneoxy chain). It is preferable that it is an ionic compound. Since the polymerizable compound having an ethyleneoxy chain is particularly excellent in flexibility, generation of wrinkles on the film surface can be more effectively suppressed.
  • the polymerizable compound having an alkyleneoxy chain preferably has a molecular weight of 100 to 2000, more preferably 1000 to 2000. Further, the value obtained by dividing the molecular weight value of the polymerizable compound by the number of polymerizable groups contained in the polymerizable compound is preferably 100 to 300, more preferably 200 to 300. According to this aspect, since the crosslinking density of the polymerizable compound is moderate, the generation of wrinkles can be more effectively suppressed.
  • the molecular weight value of the polymerizable compound is a theoretical value obtained from the molecular structure when the polymerizable compound is a monomer, and means a weight average molecular weight when the polymerizable compound is an oligomer or a polymer.
  • the polymerizable compound having an alkyleneoxy chain preferably has a cyclic structure. Adhesiveness improves by having a cyclic structure.
  • the cyclic structure include an aromatic ring structure, an alicyclic structure, and a heterocyclic structure.
  • a heterocyclic structure is preferred.
  • the heterocyclic ring is preferably a 5-membered ring or a 6-membered ring.
  • the heterocycle is preferably a monocycle or a condensed ring, and preferably a monocycle. Examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is preferable.
  • the number of heteroatoms is preferably 1 to 3, more preferably 2 to 3, and particularly preferably 3.
  • the polymerizable compound having an alkyleneoxy chain preferably has a partial structure represented by the following general formula (1). * In the formula is a connecting hand.
  • Examples of the polymerizable compound having a cyclic structure include a compound represented by “Ar— (L—X) n ”.
  • Ar represents an aromatic ring structure, an alicyclic structure, or a heterocyclic structure.
  • L represents a single bond or a linking group.
  • X represents a hydrogen atom or a polymerizable group. When n is 1, X represents a polymerizable group. When n is 2 or more, at least one of the plurality of Xs represents a polymerizable group.
  • the polymerizable group one or more selected from a vinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, an allyloxycarbonyl group, and a methallyloxycarbonyl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.
  • Examples of the polymerizable compound having a partial structure represented by the formula (1) include a polymerizable compound represented by the following general formula (1a).
  • X 1 ⁇ X 3 each independently represent a hydrogen atom or a polymerizable group, at least one of X 1 ⁇ X 3 represents a polymerizable group.
  • the polymerizable group one or more selected from a vinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, an allyloxycarbonyl group, and a methallyloxycarbonyl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.
  • the plurality of X 1 to X 3 may be the same or different.
  • L 1 represents a (1 + n1) -valent linking group
  • L 2 represents a (1 + n2) -valent linking group
  • L 3 represents a (1 + n3) -valent linking group
  • L At least one of 1 to L 3 represents a linking group containing — ((CH 2 ) a —O) b —.
  • a represents an integer of 2 or more
  • b represents an integer of 2 or more.
  • linking group represented by L 1 to L 3 for example, in the case of a divalent linking group, — ((CH 2 ) a —O) b —, — (CH 2 ) c —, —CO—, and — Examples thereof include a group formed by combining one or more selected from NH-.
  • a represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 4, and still more preferably 2.
  • b represents an integer of 2 or more, preferably 2 to 30, more preferably 2 to 20, and still more preferably 5 to 15.
  • c represents an integer of 1 or more, preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
  • the linking group represented by L 1 to L 3 is a trivalent or higher linking group, among the groups listed as examples of the divalent linking group described above, a group in which one or more hydrogen atoms have been removed can be used.
  • n1 to n3 each independently represents an integer of 1 or more. 1 or 2 is preferred.
  • polymerizable compound represented by the general formula (1a) include the following compounds.
  • Examples of commercially available polymerizable compounds represented by the general formula (1a) include UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the polymerizable compound having an alkyleneoxy chain for example, at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5) can also be used. .
  • each E independently represents — ((CH 2 ) y CH 2 O). — Or — ((CH 2 ) y CH (CH 3 ) O) —, each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, methacryloyl group, hydrogen atom Or a carboxyl group.
  • the total number of acryloyl groups and methacryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • at least one of m represents an integer of 2 to 10
  • the sum of each m is an integer from 2 to 40.
  • the total number of acryloyl groups and methacryloyl groups is 5 or 6, and each n independently represents an integer of 0 to 10, and at least one of n represents an integer of 2 to 10 And the sum of each n is an integer from 2 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — in general formula (Z-4) or general formula (Z-5) is oxygen A form in which the end on the atom side is bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the compound represented by the general formula (Z-4) or (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or the general formula (Z-5).
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • the polymerizable compound used in the colored composition of the present invention preferably contains 50-100% by mass of the above-mentioned polymerizable compound having an alkyleneoxy chain, based on the total amount of the polymerizable compound, and 80-100% by mass. Is more preferable, and 95 to 100% by mass is still more preferable, and it is particularly preferable that it is composed only of a polymerizable compound having an alkyleneoxy chain.
  • the colored composition of the present invention may contain a polymerizable compound other than the polymerizable compound having an alkyleneoxy chain (hereinafter referred to as “other polymerizable compound”).
  • a polymerizable compound other than the polymerizable compound having an alkyleneoxy chain hereinafter referred to as “other polymerizable compound”.
  • a conventionally well-known polymeric compound can be used.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof, amides, and multimers thereof can be mentioned.
  • an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and a multimer thereof can be used.
  • addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional can also be used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol can also be used.
  • a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be used in the present invention.
  • a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure, which has at least one addition-polymerizable ethylene group can be used.
  • Examples include monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate
  • a polyfunctional alcohol such as glycerin or
  • Urethane (meth) acrylates as described in each publication, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
  • JP 2010-160418 A JP 2010-129825 A, JP 4364216 A, etc., having a fluorene ring and having two or more functional ethylenically unsaturated groups. It can also be used.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group is disclosed in paragraph No. of JP-A-2008-292970.
  • the compounds described in ⁇ 0254> to ⁇ 0257> can also be used.
  • polymerizable compounds represented by the following general formulas (MO-1) to (MO-5) can be used.
  • T is an alkyleneoxy group
  • the terminal on the carbon atom side is bonded to R.
  • n is 0 to 14 and m is 1 to 8.
  • a plurality of R and T present in one molecule may be the same or different.
  • at least one of a plurality of Rs is —OC ( ⁇ O) CH ⁇ CH 2 or —OC ( ⁇ O) C (CH 3 ) ⁇
  • a group represented by CH 2 is represented.
  • the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979 are disclosed in the present invention. Can also be suitably used.
  • 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) Yakuhin 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; manufactured by Nippon Kayaku Co., Ltd.), ethyleneoxy-modified dipentaerythritol hexaacrylate (as a commercial product, A -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryl
  • polymerizable compound 2- (meth) acryloyloxyethyl caproate acid phosphate (PM-20 manufactured by Nippon Kayaku Co., Ltd. as a commercial product), urethane acrylate (Shin Nakamura Chemical Co., Ltd. as a commercial product)
  • Preferable examples include U-6LPA manufactured by U.S.A., pentaerythritol tri- or tetraacrylate (commercially available products such as M-303, M-305, M-306, M-450, and M-452 manufactured by Toagosei Co., Ltd.).
  • polymerizable compounds having a caprolactone structure can be used as other polymerizable compounds.
  • the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, diester.
  • ⁇ -caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone Can be mentioned.
  • polyhydric alcohols such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone
  • Z-1 a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents 1 or 2
  • “*” represents a bond
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond
  • the content of the polymerizable compound is preferably 25 to 65% by mass, more preferably 25 to 60% by mass, and further preferably 25 to 50% by mass based on the total solid content of the colored composition. If content of a polymeric compound is the said range, it will be easy to form a film
  • the film surface and the film of the colored composition applied in the form of a film can be obtained. The inside curability can be made more uniform, and the generation of wrinkles can be more effectively suppressed.
  • the generation of residues during pattern formation can be more effectively suppressed.
  • the ratio P / M between the mass P of the colorant contained in the colored composition and the mass M of the polymerizable compound contained in the colored composition is preferably 0.05 to 0.35. 0.1 to 0.35 is more preferable.
  • the curability of the coloring composition applied in the form of a film can be made substantially uniform on the film surface and inside the film, and the generation of wrinkles can be more effectively suppressed.
  • the generation of residues during pattern formation can be suppressed.
  • the coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (I).
  • n represents an integer of 2 to 4
  • L represents a divalent to tetravalent linking group.
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination.
  • the blending amount of the polyfunctional thiol compound in the colored composition of the present invention is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass based on the total solid content excluding the solvent. .
  • the polyfunctional thiol compound may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
  • Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the colored composition of the present invention preferably contains a resin.
  • the resin does not include the above-described polymerizable compound having an alkyleneoxy chain.
  • the resin preferably has a hydroxyl group. By having a hydroxyl group, adhesion to a support material such as a silicon substrate can be improved.
  • the resin content is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass of the total solid content of the colored composition.
  • the ratio M / B between the mass M of the polymerizable compound contained in the colored composition and the mass B of the mass polymerizable compound of the resin contained in the colored composition is 0.4-3. 0.0 is preferable, 0.4 to 0.9 is more preferable, and 0.4 to 0.8 is still more preferable. According to this aspect, the curability of the coloring composition applied in the form of a film can be made substantially uniform on the film surface and inside the film, and the generation of wrinkles can be more effectively suppressed.
  • the resin include the dispersion resins described above and alkali-soluble resins described below. Hereinafter, the alkali-soluble resin will be described.
  • the coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved.
  • the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably from 5000 to 100,000.
  • the number average molecular weight (Mn) is preferably 1000 to 20,000.
  • the alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
  • the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
  • Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.
  • the alkali-soluble resin a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
  • examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak type resins, acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having hydroxyl groups added with acid anhydrides.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • the alkali-soluble phenol resin can be suitably used when the colored composition of the present invention is a positive composition.
  • the alkali-soluble phenol resin include novolak resins and vinyl polymers.
  • the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst.
  • the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like. Phenols and aldehydes can be used alone or in combination of two or more.
  • Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
  • the molecular weight distribution of the novolak resin may be adjusted using a means such as fractionation.
  • an alkali-soluble resin having a polymerizable group may be used.
  • the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group.
  • an alkali-soluble resin having a polymerizable group an alkali-soluble resin containing a polymerizable group in a side chain is useful.
  • the alkali-soluble resin containing a polymerizable group is prepared by reacting an isocyanate group and a hydroxyl group in advance, leaving one unreacted isocyanate group and containing a polymerizable group such as a (meth) acryloyl group, and a carboxyl group.
  • alkali-soluble resin containing a polymerizable group examples include NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH containing polyurethane acrylic oligomer. 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation) and the like.
  • Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
  • the alkali-soluble resin is a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”).
  • ED general formula
  • ether dimers a compound represented by the following general formula (ED2)
  • 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.
  • ED2 the description in JP 2010-168539 A can be referred to.
  • the hydrocarbon group represented by R 1 and R 2 is preferably a hydrocarbon group having 1 to 25 carbon atoms.
  • the hydrocarbon group may have a substituent.
  • the hydrocarbon group is not particularly limited. For example, straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl, etc.
  • An aryl group such as phenyl; an alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; And alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like.
  • an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon hydrocarbon group which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.
  • ether dimers include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl)
  • dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers may be only one kind or two or more kinds.
  • the content of the ether dimer in the monomer component is not particularly limited, but is preferably 2 to 60% by mass, more preferably 5 to 55% by mass, and still more preferably 5 to 50% by mass.
  • the resin (a) may be a copolymer obtained by copolymerizing other monomers together with the ether dimer.
  • ether dimer dimer examples include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types. With respect to the other monomers described above, for example, the description in JP-A-2004-300204, 0016 to 0022 can be referred to, and these contents are incorporated in this specification.
  • the weight average molecular weight (Mw) of the resin (a) is not particularly limited, but is preferably 5000 to 200000, more preferably from the viewpoint of the viscosity of the colored composition and the heat resistance of the film formed from the colored composition. Is from 5,000 to 100,000, more preferably from 5,000 to 20,000.
  • the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.
  • the resin (a) can be easily obtained by polymerizing a monomer containing an ether dimer. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
  • combination of resin (a) Although conventionally well-known various polymerization methods can be employ
  • the resin (a) can be synthesized according to the synthesis method of the resin (a) described in JP-A-2004-300204.
  • exemplary compounds of the resin (a) are shown. However, the present invention is not limited to these.
  • the composition ratio of the exemplary compounds shown below is mol%.
  • alkali-soluble resin a resin containing a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X) can also be used.
  • 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 a benzene ring which may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
  • the carbon number of the alkyl group of R 3 is preferably 1-10.
  • the alkyl group of R 3 may contain a benzene ring.
  • Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • Specific examples of the resin containing a structural unit derived from the ethylenically unsaturated monomer represented by the above formula (X) include resins described in JP2012-247591A and JP2013-24934A Etc.
  • the acid value of the alkali-soluble resin 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 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
  • the content of the alkali-soluble resin is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass with respect to the total solid content of the coloring composition.
  • the coloring composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be a photopolymerization initiator that generates an active radical by causing some action with a photoexcited sensitizer, and is a photopolymerization initiator that initiates cationic polymerization according to the type of polymerizable compound. May be.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
  • Oxime compounds such as organic peroxides, thio compounds, ketone compounds (eg, benzophenone, 2-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzoin, benzoin methyl ether, acridone, N-methylacridone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone), aromatic onium salts, Ketoxime ether, Mino acetophenone compounds, such as hydroxy acetophenone. Among these, oxime compounds are preferable.
  • halogenated hydrocarbon compounds having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 Examples thereof include compounds described in the specification (for example, compounds having an oxadiazole skeleton).
  • photopolymerization initiators other than those mentioned above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc.
  • polyhalogen compounds for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.
  • N-phenylglycine etc.
  • acylphosphine oxides for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Zinc oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.
  • metallocenes for example, bis ( ⁇ 5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, ⁇ 5-cyclopentadienyl- ⁇ 6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.
  • Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-60
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • the photopolymerization initiator include oxime compounds.
  • the coloring composition contains an oxime compound as a photopolymerization initiator
  • the pattern property dependency on the time from application of the coloring composition to exposure (hereinafter simply referred to as “PCD dependency”). Is also good).
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Examples of the oxime compound suitably used as the photopolymerization initiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane- Examples include 2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
  • IRGACURE OXE-01 manufactured by BASF
  • IRGACURE OXE-02 manufactured by BASF
  • TRONLY TR-PBG-304 TRONLY TR-PBG-309
  • TRONLY TR-PBG-305 Changzhou Power Electronics New Materials Limited
  • a company manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD
  • Adeka Arkles NCI-831 Adeka Arkles NCI-930 (Adeka) are also preferably used.
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following general formula (OX-1).
  • the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
  • oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.
  • the oxime compound has an absorption maximum wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, it is preferable to measure at a concentration of 0.01 g / L using ethyl acetate in an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian).
  • the content of the photopolymerization initiator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass with respect to the total solid content of the coloring composition. Within this range, good sensitivity and pattern formability can be obtained.
  • a photoinitiator may use only 1 type and may use it in combination of 2 or more type. When using 2 or more types in combination, the total content is preferably in the above range.
  • the coloring composition of the present invention can contain an ultraviolet absorber.
  • the ultraviolet absorber is preferably a compound having an extinction coefficient per 1 g at a wavelength of 365 nm of more than 100 and an extinction coefficient per 1 g at a wavelength of 400 nm or more. If the extinction coefficient per gram at a wavelength of 365 nm exceeds 100, an excellent ultraviolet absorption effect can be obtained even with a small amount. In addition, if the extinction coefficient per gram at a wavelength of 400 nm or more is 10 or less, the influence on device spectroscopy in the visible region can be reduced.
  • the extinction coefficient is a value measured with an ultraviolet-visible spectrophotometer (Varian, Carry-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate.
  • the ultraviolet absorber a compound represented by the following general formula (I) which is a conjugated diene compound is preferable.
  • this conjugated diene compound is used, fluctuations in development performance after exposure, especially when low-illuminance exposure is performed, can be suppressed, and exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum can be reduced. It can suppress more effectively.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 May be the same as or different from each other. However, R 1 and R 2 do not represent a hydrogen atom at the same time.
  • R 3 and R 4 represent an electron withdrawing group.
  • the electron-withdrawing group is preferably an electron-withdrawing group having a Hammett's substituent constant ⁇ p value (hereinafter simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less, and the ⁇ p value is 0.30.
  • ⁇ p value Hammett's substituent constant
  • Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
  • Substituent constants obtained by Hammett's rule include a ⁇ p value and a ⁇ m value, and these values are described in many general books.
  • R 3 is preferably a group selected from a cyano group, —COOR 5 , —CONHR 5 , —COR 5 , and —SO 2 R 5 .
  • R 4 is preferably a group selected from a cyano group, —COOR 6 , —CONHR 6 , —COR 6 , and —SO 2 R 6 .
  • R 5 and R 6 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • R 3 and R 4 may combine with each other to form a ring.
  • At least one of R 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Moreover, the copolymer with another monomer may be sufficient.
  • the colored composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.01 to from the total solid content of the colored composition of the present invention. 10% by mass is preferable and 0.01 to 5% by mass is more preferable. If the content of the ultraviolet absorber is in the above range, the sensitivity is good, and furthermore, a fine pattern shape (in particular, a rectangle) can be finely formed. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination. When using 2 or more types in combination, the total content is preferably in the above range.
  • the ratio (D / B) between the mass (D) of the photopolymerization initiator and the mass (B) of the ultraviolet absorber is 0. .25 to 1.25 is preferable, 0.3 to 1.1 is more preferable, and a range of 0.4 to 1.0 is particularly preferable. If the above-mentioned ratio is within the above range, the sensitivity is good, and furthermore, a fine pattern shape (in particular, a rectangle) can be finely formed.
  • the coloring composition of the present invention can contain an organic solvent.
  • the organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but particularly the solubility of an ultraviolet absorber, an alkali-soluble resin, etc., the coating property of the coloring composition, It is preferable to select in consideration of safety.
  • Examples of the organic solvent include the following.
  • Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Alkyl acetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (For example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • 2-oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • diethylene glycol dimethyl ether tetrahydrofuran
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate
  • diethylene glycol monomethyl ether diethylene glycol monoethyl ether, diethylene glycol monobutyl ether
  • propylene glycol monomethyl ether propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.
  • ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons
  • Preferred examples include toluene and xylene.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • organic solvents particularly preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate,
  • a mixed solution composed of two or more selected from heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the amount of the organic solvent contained in the colored composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass with respect to the total amount of the colored composition.
  • the colored composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength.
  • the sensitizer include sensitizers having an absorption wavelength in the wavelength region of 300 nm to 450 nm.
  • the sensitizer is preferably one that sensitizes the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.
  • sensitizer examples include polynuclear aromatics such as phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxyanthracene, xanthene such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal.
  • polynuclear aromatics such as phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxyanthracene
  • xanthene such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal.
  • Thioxanthones cyanines, merocyanines, phthalocyanines, thiazines such as thionine, methylene blue and toluidine blue, acridines, anthraquinones, squariums, coumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds , Diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazo Triazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N- aryl oxazolidinone and the like.
  • the content of the sensitizer in the coloring composition is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency in the deep part and initiation decomposition efficiency, and preferably 0.5 to 15%.
  • the mass% is more preferable.
  • a sensitizer may be used individually by 1 type and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
  • Chain transfer agent Depending on the photopolymerization initiator used, it is preferable to add a chain transfer agent to the colored composition of the present invention.
  • chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds.
  • thiol compounds include 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, and 3-mercaptopropion.
  • An acid etc. can be used individually or in mixture of 2 or more types.
  • the colored composition in the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, p-methoxyphenol is preferred.
  • the addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the mass of the colored composition.
  • the coloring composition of the present invention may contain a substrate adhesion agent for the purpose of improving the substrate adhesion.
  • a substrate adhesion agent it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
  • silane coupling agents include ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, and ⁇ -mercaptopropyl.
  • Examples include trimethoxysilane, ⁇ -aminopropyltriethoxysilane, and phenyltrimethoxysilane.
  • ⁇ -methacryloxypropyltrimethoxysilane is preferable as the substrate adhesive.
  • the content of the substrate adhesion agent is from 0.1 to 30 masses based on the total solid content of the colored composition from the viewpoint of leaving no residue in the unexposed areas when the colored composition is exposed and developed. %, More preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass.
  • the colored composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved. can do. That is, when a film is formed using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is reduced. Is improved, and the coating property to the coated surface is improved. Therefore, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more 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 Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin 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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone 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), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the composition.
  • the coloring composition comprises a thermal polymerization initiator, a thermal polymerization component, an epoxy compound, a plasticizer such as dioctyl phthalate, a developability improver such as a low molecular weight organic carboxylic acid, other fillers, and an antioxidant.
  • a plasticizer such as dioctyl phthalate
  • a developability improver such as a low molecular weight organic carboxylic acid
  • other fillers such as a low molecular weight organic carboxylic acid
  • an antioxidant such as an agent and an anti-aggregation agent can be contained.
  • the coloring composition of this invention can be prepared by mixing each component mentioned above.
  • the components constituting the colored composition may be blended together, or may be sequentially blended after each component is dissolved and dispersed in a solvent.
  • a colored composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (application). May be mixed to prepare a composition.
  • any filter can be used without any particular limitation as long as it is a filter that has been used for filtration.
  • filter materials include: fluorine resins such as polytetrafluoroethylene (PTFE); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
  • the pore size of the filter is not particularly limited, but is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 2.5 ⁇ m, and still more preferably 0.01 to 2.0 ⁇ m.
  • the pore size of the filter can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
  • filter filtration two or more types of filters may be used in combination. For example, filtration can be performed first using a first filter, and then using a second filter having a hole diameter different from that of the first filter. At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or twice or more, respectively.
  • a filter formed of the same material as the first filter described above can be used.
  • the colored composition of the present invention has a viscosity at 25 ° C. of preferably 1 to 200 mPa ⁇ s, more preferably 50 to 200 mPa ⁇ s, and particularly preferably 100 to 150 mPa ⁇ s.
  • the colored composition is preferably 1 to 50 mPa ⁇ s, more preferably 1 to 20 mPa ⁇ s, and more preferably 1 to 15 mPa ⁇ s. Is particularly preferred.
  • the coloring composition is preferably 50 to 200 mPa ⁇ s, more preferably 50 to 150 mPa ⁇ s, and particularly preferably 100 to 150 mPa ⁇ s. preferable.
  • the viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24 measurement range 0.6 to 1200 mPa ⁇ s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
  • the colored composition of the present invention has a light transmittance in the thickness direction of a film when a film having a thickness of 12.0 ⁇ m after drying is formed, and has a maximum transmittance in a wavelength range of 400 to 780 nm.
  • the value is preferably 15% or less
  • the transmittance at a wavelength 850 is preferably 80% or more.
  • the maximum value of transmittance in the wavelength range of 400 to 780 nm is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.
  • the transmittance at a wavelength of 850 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.
  • the minimum transmittance in the wavelength range of 850 to 1300 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.
  • the film of the present invention is formed by curing the above-described colored composition of the present invention.
  • a film is preferably used for a color filter.
  • the maximum value of light transmittance in the film thickness direction is 15% or less in the wavelength range of 400 to 780 nm, and the minimum value in the wavelength range of 850 to 1300 nm is 80% or more. preferable. By having such spectral characteristics, it is possible to obtain a film that can transmit near-infrared rays with less visible light-derived noise.
  • Spectral characteristics of the film of the present invention are as follows: a transmittance in a wavelength range of 300 to 1300 nm using a spectrophotometer (ref. Glass substrate) of an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). Is a measured value.
  • the thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m, and particularly preferably 3 to 15 ⁇ m.
  • the film having the above spectral characteristics tended to generate wrinkles on the film surface as the film thickness increased. However, according to the present invention, the generation of wrinkles can be suppressed even when the film thickness is large. When the value is large, the effect of the present invention is remarkably obtained.
  • the pattern forming method of the present invention includes a step of applying a colored composition on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and developing and removing an unexposed portion. Forming a colored pattern.
  • a pattern forming method is used for manufacturing a colored layer of a color filter. That is, the present invention also discloses a method for manufacturing a color filter including the pattern forming method of the present invention.
  • color filter for solid-state image sensors
  • this invention is not limited to this method.
  • the color filter for the solid-state imaging device may be simply referred to as “color filter”.
  • the colored composition layer is formed by applying the colored composition of the present invention on the support.
  • a substrate for a solid-state imaging device in which an imaging device (light receiving device) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate), a silicon substrate, a non-alkali glass substrate, a soda glass substrate, Examples include a Pyrex (registered trademark) glass substrate, a quartz glass substrate, and those obtained by attaching a transparent conductive film thereto. In some cases, a black matrix for isolating each pixel is formed on these substrates. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.
  • various coating methods such as slit coating, ink jet method, spin coating, spin coating, roll coating, and screen printing are applied. Can do.
  • Drying (pre-baking) of the colored composition layer coated on the support can be performed at a temperature of 50 to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.
  • the thickness of the colored composition layer after drying is preferably 0.5 to 30 ⁇ m, more preferably 0.60 to 25 ⁇ m, still more preferably 0.70 to 20 ⁇ m, and particularly preferably 0.80 ⁇ m to 15 ⁇ m. preferable.
  • Exposure Step the colored composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thereby, a cured film is obtained.
  • Radiation (light) that can be used for exposure is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferably used.
  • Irradiation dose (exposure dose) is preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2, particularly preferably 80 ⁇ 500mJ / cm 2.
  • a development step is performed to elute the uncured portion after exposure into the developer and leave the photocured portion.
  • the development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined with these. Unevenness of development can be prevented by pre-wetting the surface to be developed with water or the like before touching the developer.
  • the developer an organic alkali developer that does not damage the underlying circuit or the like is desirable.
  • the development temperature is preferably 20 to 30 ° C.
  • the development time is preferably 20 to 90 seconds.
  • the developer preferably contains an alkaline agent.
  • the alkaline agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8.
  • -Organic alkaline compounds such as -diazabicyclo- [5,4,0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
  • an alkaline aqueous solution obtained by diluting the above-mentioned alkaline agent with pure water so as to be 0.001 to 10% by mass, preferably 0.01 to 1% by mass is preferably used.
  • a developer composed of such an alkaline aqueous solution it is generally preferable that after development, the excess developer is washed and removed by rinsing with pure water, followed by drying.
  • Post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 270 ° C. is performed.
  • 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. .
  • the irradiation time is preferably 10 to 180 seconds, more preferably 30 to 60 seconds.
  • post-exposure is preferably performed first.
  • a color filter is manufactured by performing each process demonstrated above.
  • the color filter may be configured with only the colored pixels exhibiting the specific spectral characteristics of the present invention, or the colored pixels exhibiting the spectral characteristics described above, and red, green, blue, magenta, yellow, cyan, black, and colorless. You may comprise the color filter which has coloring pixels, such as.
  • the colored pixels exhibiting the specific spectral characteristics of the present invention may be provided first or later.
  • the colored composition in the present invention can be easily washed and removed using a known cleaning liquid even when it adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus.
  • the surfactant described above may be added to the cleaning liquid as a surfactant that the coloring composition may contain.
  • the color filter of the present invention can be suitably mounted on a solid-state imaging device such as a CCD image sensor, a CMOS image sensor, an organic CMOS image sensor, or a CIGS image sensor.
  • a solid-state imaging device such as a CCD image sensor, a CMOS image sensor, an organic CMOS image sensor, or a CIGS image sensor.
  • it is suitable to be mounted on a high-resolution solid-state imaging device exceeding 1 million pixels.
  • the color filter of the present invention can be disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and a microlens for collecting light.
  • the solid-state imaging device of the present invention includes the above-described color filter of the present invention.
  • the configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
  • the support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.).
  • a light-shielding film made of tungsten or the like having an opening only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part.
  • the solid-state image sensor color filter of the present invention is included.
  • a configuration having a light condensing means for example, a microlens, etc., the same applies hereinafter
  • a structure having the light condensing means on the color filter etc. It may be.
  • the infrared sensor of the present invention includes the color filter of the present invention.
  • the configuration of the infrared sensor of the present invention is a configuration provided with the color filter of the present invention and is not particularly limited as long as it is a configuration that functions as an infrared sensor. For example, the following configurations can be given.
  • the substrate there are a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.), a transfer electrode made of polysilicon, etc., and a photodiode on the photodiode and the transfer electrode
  • a light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part.
  • the color filter of the present invention is included.
  • the device protective layer has a condensing means (for example, a microlens etc., the same shall apply hereinafter) on the device protective layer and below the color filter of the present invention (on the side close to the substrate), or condensing on the color filter of the present invention.
  • a condensing means for example, a microlens etc., the same shall apply hereinafter
  • the structure etc. which have a means may be sufficient.
  • the organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and the organic material plays a role of capturing light and converting it into an electric signal.
  • This is a two-layer hybrid structure in which an inorganic material plays a role of taking out a signal to the outside.
  • the aperture ratio can be 100% with respect to incident light.
  • the organic photoelectric conversion film is a structure-free continuous film that can be laid on a CMOS signal reading substrate, and therefore does not require an expensive fine processing process and is suitable for pixel miniaturization.
  • reference numeral 110 is a solid-state image sensor.
  • the imaging region provided on the solid-state imaging device 110 has a near infrared absorption filter 111 and a color filter 112.
  • the near-infrared absorption filter 111 transmits light in the visible light region (for example, light having a wavelength of 300 to 700 nm) and light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1300 nm, More preferably, it is configured to shield light having a wavelength of 1000 to 1300 nm.
  • the color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used. A region 114 where the near infrared absorption filter 111 is not formed is provided between the near infrared transmission filter 113 and the solid-state imaging device 110. In the region 114, a resin layer (for example, a transparent resin layer) that can transmit light having a wavelength that has passed through the infrared transmission filter 113 is disposed.
  • a resin layer for example, a transparent resin layer
  • the near-infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays having a specific wavelength, and is configured by the color filter of the present invention having the above-described spectrum.
  • the near infrared transmission filter 113 preferably blocks light having a wavelength of 400 to 780 nm and transmits light having a wavelength of 850 to 1300 nm.
  • a microlens 115 is disposed on the incident light hv side of the color filter 112 and the near-infrared transmission filter 113.
  • a planarization layer 116 is formed so as to cover the microlens 115. In the embodiment shown in FIG.
  • the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
  • the thickness of the color filter 112 and the thickness of the infrared transmission filter 113 are the same, but the thickness of both may be different.
  • the color filter 112 is provided closer to the incident light h ⁇ than the near-infrared absorption filter 111. However, the order of the near-infrared absorption filter 111 and the color filter 112 is changed.
  • the near-infrared absorption filter 111 may be provided on the incident light h ⁇ side with respect to the color filter 112.
  • the near-infrared absorption filter 111 and the color filter 112 are stacked adjacent to each other.
  • both filters are not necessarily adjacent to each other, and another layer is provided between them. May be.
  • this infrared sensor since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
  • FIG. 2 is a functional block diagram of the imaging apparatus.
  • the imaging device emits infrared light, the lens optical system 1, the solid-state imaging device 10, the signal processing unit 20, the signal switching unit 30, the control unit 40, the signal storage unit 50, the light emission control unit 60, and the like.
  • Infrared LED 70 of the light emitting element and image output units 80 and 81 are provided.
  • the infrared sensor 100 described above can be used as the solid-state imaging device 10.
  • the configuration other than the solid-state imaging device 10 and the lens optical system 1 may be formed entirely or partially on the same semiconductor substrate.
  • paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in the present specification.
  • pigment dispersion B-2 A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-2 was prepared.
  • pigment dispersion B-5 A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-5 was prepared. Yellow pigment (CI Pigment Yellow 139 14.8 parts Dispersion resin 1: BYK manufactured BYK-111 3.0 parts Alkali-soluble resin 2 2.2 parts Organic solvent: Propylene glycol methyl ether acetate (PGMEA ) 80.0 parts
  • pigment dispersion B-6 A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-6 was prepared.
  • Dispersion resin 1 BYK-made BYK-111 3.0 parts Alkali-soluble resin 1 2.2 parts
  • Organic solvent Propylene glycol methyl ether acetate ( PGMEA) 80.0 parts [resin] -Dispersing resin 1: trade name; BYK-111 (manufactured by BYK) Dispersing resin 2: the following structure (Mw: 7950) -Dispersing resin 3: the following structure (Mw: 30000) -Alkali-soluble resin 1: the following structure (ratio in repeating units is molar ratio) Alkali-soluble resin 2: the following structure (ratio in repeating units is molar ratio)
  • Example 1 (Preparation of coloring composition) The following components were mixed to prepare the coloring composition of Example 1.
  • -Pigment dispersion B-1 (see Table 1 below for the mass ratio of each pigment) 11.2 parts-Pigment dispersion B-2 (See Table 1 below for the mass ratio of each pigment) 9.1 parts-below 40 mass% PGMEA solution of alkali-soluble resin 1 54.2 parts ⁇
  • the following polymerizable compound 1 13.6 parts ⁇
  • the following photopolymerization initiator 1 2.0 parts ⁇
  • Surfactant 1 Megafac manufactured by DIC Corporation 0.42 part of 10% by mass PGMEA solution of F-781F
  • the following UV absorber 1 0.41 part
  • polymerization inhibitor 0.01 part of p-methoxyphenol
  • organic solvent 1 PGMEA 9.2 parts
  • Example 2-6 Comparative Examples 1-2
  • the pigment dispersion, alkali-soluble resin, polymerizable compound, photopolymerization initiator, surfactant and organic solvent were changed to those shown in Table 2 below and in amounts (parts by mass).
  • Table 1 for the mass ratio of each pigment in the pigment dispersion. Also, in Table 2, it means that those without numerical values are not used.
  • Examples 2 to 6 and Comparative Examples 1 to 2 A colored composition was prepared.
  • Each pigment ratio in Table 1 is the ratio (in terms of mass) of each pigment in the total pigment.
  • alkali-soluble resin 1 is a value (part by mass) in a 40% by mass PGMEA solution.
  • alkali-soluble resin 2 is a value (mass part) in a 40 mass% PGMEA solution.
  • Surfactant 1 is a value (parts by mass) in a 10% by mass PGMEA solution.
  • Alkali-soluble resin 1 following structure (ratio in repeating unit is molar ratio)
  • Alkali-soluble resin 2 the following structure (ratio in repeating units is molar ratio)
  • Photopolymerization initiator 1 structure shown
  • the colored composition is spin-coated on a glass substrate, applied so that the film thickness after post-baking is 12 ⁇ m, dried on a hot plate at 100 ° C. for 120 seconds, dried, and further heated at 200 ° C. Using this, heat treatment (post-bake) was performed for 300 seconds.
  • a substrate having a colored layer is measured using a UV-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech) (ref. Glass substrate), and a minimum absorbance A in a wavelength range of 400 nm to less than 580 nm, a wavelength of 580 nm or more.
  • the coloring composition was applied onto a silicon wafer using a spin coater so that the film thickness after drying was 12 ⁇ m, and heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), 50 mJ / cm 2 up to 50 ⁇ 750mJ / cm 2 using a photomask having a square pixel pattern of 1.4 ⁇ m angle is formed The optimum exposure amount for resolving the square pixel pattern was determined by increasing each time, and exposure was performed at this optimum exposure amount.
  • the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. to form a colored pattern on the silicon wafer.
  • the silicon wafer on which the colored pattern was formed was rinsed with pure water and then spray-dried.
  • a heat treatment post-bake was performed for 300 seconds using a 200 ° C. hot plate to obtain silicon wafers having colored patterns as color filters of Examples 1 to 6 and Comparative Examples 1 and 2, respectively.
  • the surface of the color filter was measured with an AFM (atomic force microscope), and the surface roughness (Ra) was obtained by calculation.
  • Example 1 to 6 using the colored sensation composition of the present invention, it was possible to form a film capable of transmitting near-infrared rays with less visible light-derived noise and having no wrinkles. .
  • Examples 1 to 6 were excellent in adhesion.
  • Comparative Examples 1 and 2 had many wrinkles on the film surface.
  • lens optical system 10: solid-state imaging device
  • 20 signal processing unit
  • 30 signal switching unit
  • 40 control unit
  • 50 signal storage unit
  • 60 light emission control unit
  • 70 infrared LED
  • 80 81
  • Image output unit 100: Infrared sensor
  • 110 Solid-state imaging device
  • 111 Near-infrared absorption filter
  • 112 Color filter
  • 113 Near-infrared transmission filter
  • 114 Region
  • 115 Micro lens
  • 116 Flattening layer
  • H ⁇ incident light

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Abstract

Provided is a coloring composition capable of forming a film in which wrinkles are suppressed and capable of transmitting near-infrared rays in the state of there being low visible-light-derived noise. Also provided are: a film that uses the coloring composition; a color filter; a pattern formation method; a method for producing a color filter; a solid-state imaging element; and an infrared ray sensor. The coloring composition contains a coloring agent and a polymerizable compound, the polymerizable compound has a chain having at least 2 repeating units of an alkyleneoxy group, the ratio A/B of the coloring composition and that is the minimum value (A) of light absorbance in the wavelength range of at least 400 nm and less than 580 nm with respect to the minimum value (B) of light absorbance in the wavelength range of 580-770 nm inclusive is 0.3-3, and the ratio C/D that is the minimum value (C) of light absorbance in the wavelength range of 400-750 nm inclusive with respect to the maximum value (D) of light absorbance in the wavelength range of 850-1300 nm inclusive is at least 5.

Description

着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサColoring composition, film, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, and infrared sensor
　本発明は、着色組成物に関する。特に、カラーフィルタの形成に好ましく用いられる着色組成物に関する。さらに、着色組成物を用いた膜、カラーフィルタ、固体撮像素子および赤外線センサに関する。また、着色組成物を用いたパターン形成方法およびカラーフィルタの製造方法にも関する。 The present invention relates to a coloring composition. In particular, it is related with the coloring composition preferably used for formation of a color filter. Furthermore, it is related with the film | membrane, color filter, solid-state image sensor, and infrared sensor which used the coloring composition. The present invention also relates to a pattern forming method using a colored composition and a method for producing a color filter.
　カラーフィルタは、固体撮像素子や液晶ディスプレイに不可欠な構成部品である。特に、固体撮像素子用のカラーフィルタでは、色分解性の向上および色再現性の向上が求められている。 Color filters are indispensable components for solid-state image sensors and liquid crystal displays. In particular, color filters for solid-state imaging devices are required to improve color separation and color reproducibility.
　このようなカラーフィルタは、複数の色相の着色領域を備えて形成されている。例えば、赤色、緑色及び青色の着色領域（以下、「着色パターン」または「着色画素」ともいう。）を備えて形成される。着色パターンの形成方法としては、まず、第１の色相において、赤色、緑色、青色の何れかの着色剤を有する着色組成物を塗布し、露光、現像、必要に応じて加熱処理を行って着色パターンを形成した後、第２の色相、第３の色相において同様の塗布、露光、現像、必要に応じた加熱処理のプロセスを繰り返すことになる。 Such a color filter is formed with a plurality of colored regions. For example, it is formed with red, green, and blue colored regions (hereinafter also referred to as “colored patterns” or “colored pixels”). As a method for forming a coloring pattern, first, in the first hue, a coloring composition having a colorant of red, green, or blue is applied, and is colored by performing exposure, development, and heat treatment as necessary. After the pattern is formed, the same coating, exposure, development, and heat treatment processes as necessary are repeated in the second hue and the third hue.
　特許文献１には、波長４００～７００ｎｍの範囲における最高光透過率が１％以下であり、且つ波長８５０～３０００ｎｍの範囲における平均光透過率が６０以上である樹脂ブラックマトリックスが開示されている。 Patent Document 1 discloses a resin black matrix having a maximum light transmittance of 1% or less in a wavelength range of 400 to 700 nm and an average light transmittance of 60 or more in a wavelength range of 850 to 3000 nm.
特開２００９－６９８２２号公報JP 2009-69822 A
　近赤外線を用いたセンシングは、様々な用途で活用されている。
　近赤外線は可視光に比べて波長が長いので散乱しにくく、距離計測や、３次元計測などにも活用可能である。このような近赤外線の特徴を利用して、近接センサや、モーションセンサ等に使用されている。また、近赤外線は人間、動物などの目に見えないので、夜間に被写体を近赤外線光源で照らしても被写体に気付かれることなく、夜行性の野生動物を撮影する用途、防犯用途として相手を刺激せずに撮影することにも使用可能である。
　近年においては、可視光由来のノイズが少ない状態で近赤外線を透過可能なカラーフィルタの開発が望まれている。 Sensing using near infrared rays is utilized in various applications.
Near-infrared light has a longer wavelength than visible light, so it is difficult to scatter and can be used for distance measurement and three-dimensional measurement. Utilizing such near-infrared characteristics, it is used in proximity sensors, motion sensors, and the like. In addition, because near infrared rays are invisible to humans, animals, etc., even if the subject is illuminated with a near infrared light source at night, the subject is not noticed. It can also be used to shoot without.
In recent years, it has been desired to develop a color filter that can transmit near-infrared rays with little noise derived from visible light.
　しかしながら、本発明者らの検討によれば、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成可能な着色組成物を、膜状に適用して硬化して製膜したところ、表面に皺が発生しやすいことが分かった。また、膜厚を大きくするに伴い、表面に皺が発生しやすいことが分かった。 However, according to the study by the present inventors, a colored composition capable of forming a film capable of transmitting near-infrared rays with little visible light-derived noise is applied and cured to form a film. It was found that wrinkles are likely to occur on the surface. It was also found that wrinkles are likely to occur on the surface as the film thickness is increased.
　よって、本発明の目的は、可視光由来のノイズが少ない状態で近赤外線を透過可能で、かつ、皺の抑制された膜を形成可能な着色組成物を提供することを目的とする。また、かかる着色組成物を用いた膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサを提供することを目的とする。 Therefore, an object of the present invention is to provide a coloring composition capable of transmitting a near-infrared ray with less visible light-derived noise and capable of forming a film in which wrinkles are suppressed. Moreover, it aims at providing the film | membrane, color filter, pattern formation method, manufacturing method of a color filter, solid-state image sensor, and infrared sensor which used this coloring composition.
　本発明者らは詳細に検討した結果、着色組成物に、アルキレンオキシ基を繰り返し単位として２以上含む鎖（すなわち、アルキレンオキシ基の繰り返し単位数が２以上の鎖）を有する重合性化合物を含有させることにより、上記目的が達成できることを見出し、本発明を完成するに至った。すなわち、本発明は、以下の通りである。＜１＞　着色剤と重合性化合物とを含む着色組成物であって、重合性化合物は、アルキレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有し、着色組成物の、波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａと、波長５８０ｎｍ以上７７０ｎｍ以下の範囲における吸光度の最小値Ｂとの比率Ａ／Ｂが０．３～３であり、波長４００ｎｍ以上７５０ｎｍ以下の範囲における吸光度の最小値Ｃと、波長８５０ｎｍ以上１３００ｎｍ以下の範囲における吸光度の最大値Ｄとの比率Ｃ／Ｄが５以上である、着色組成物。
＜２＞　着色剤と重合性化合物とを含む着色組成物であって、重合性化合物は、アルキレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有し、着色剤は、赤色着色剤および紫色着色剤から選ばれる１種以上の着色剤Ａと、黄色着色剤と、青色着色剤と、を少なくとも含み、赤色着色剤および紫色着色剤から選ばれる着色剤Ａの着色剤全量に対する質量比である着色剤Ａ／全着色剤が、０．０１～０．７であり、黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．０５～０．５であり、青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．０５～０．６である、着色組成物。
＜３＞　着色剤は、赤色着色剤と、紫色着色剤と、黄色着色剤と、青色着色剤とを含み、赤色着色剤の着色剤全量に対する質量比である赤色着色剤／全着色剤が０．１～０．５であり、黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．１～０．４であり、青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．２～０．６であり、紫色着色剤の着色剤全量に対する質量比である紫色着色剤／全着色剤が０．０１～０．３である、＜２＞に記載の着色組成物。
＜４＞　重合性化合物は、エチレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有する、＜１＞～＜３＞のいずれかに記載の着色組成物。
＜５＞　重合性化合物は、重合性化合物の分子量の値を、重合性化合物中に含まれる重合性基の数で割った値が１００～３００である、＜１＞～＜４＞のいずれかに記載の着色組成物。
＜６＞　重合性化合物は、環状構造を有する、＜１＞～＜５＞のいずれかに記載の着色組成物。
＜７＞　重合性化合物は、ヘテロ環構造を有する、＜１＞～＜６＞のいずれかに記載の着色組成物。
＜８＞　重合性化合物は、下記一般式（１）で表される部分構造を有する、＜１＞～＜７＞のいずれかに記載の着色組成物；ただし、式中の＊は連結手である。
Figure JPOXMLDOC01-appb-C000002
 ＜９＞　更に、樹脂および光重合開始剤を含有する、＜１＞～＜８＞のいずれかに記載の着色組成物。
＜１０＞　樹脂は、ヒドロキシル基を有する樹脂を含有する、＜９＞に記載の着色組成物。
＜１１＞　乾燥後の膜厚が１２．０μｍの膜を形成した際に、波長４００～７８０ｎｍの範囲における透過率の最大値が１５％以下であり、波長８５０ｎｍの透過率が８０％以上である、＜１＞～＜１０＞のいずれかに記載の着色組成物。
＜１２＞　２５℃における粘度が１００～１５０ｍＰ・ｓである、＜１＞～＜１１＞のいずれかに記載の着色組成物。
＜１３＞　＜１＞～＜１２＞のいずれかに記載の着色組成物を硬化してなる膜。
＜１４＞　＜１３＞に記載の膜を有するカラーフィルタ。
＜１５＞　＜１＞～＜１２＞のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含むパターン形成方法。
＜１６＞　＜１５＞に記載のパターン形成方法を含む、カラーフィルタの製造方法。
＜１７＞　＜１４＞に記載のカラーフィルタまたは＜１６＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。
＜１８＞　＜１４＞に記載のカラーフィルタまたは＜１６＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する赤外線センサ。 As a result of detailed studies by the inventors, the colored composition contains a polymerizable compound having a chain containing two or more alkyleneoxy groups as repeating units (that is, a chain having two or more repeating units of alkyleneoxy groups). As a result, the inventors have found that the above object can be achieved, and have completed the present invention. That is, the present invention is as follows. <1> A colored composition containing a colorant and a polymerizable compound, wherein the polymerizable compound contains a polymerizable compound having a chain having 2 or more repeating units of an alkyleneoxy group, The ratio A / B between the minimum absorbance A in the wavelength range of 400 nm to 580 nm and the minimum absorbance B in the wavelength range of 580 nm to 770 nm is 0.3 to 3, and the wavelength range is 400 nm to 750 nm. A colored composition having a ratio C / D of 5 or more between the minimum value C of the absorbance at and the maximum value D of the absorbance in the wavelength range of 850 nm to 1300 nm.
<2> A colored composition comprising a colorant and a polymerizable compound, wherein the polymerizable compound contains a polymerizable compound having a chain having two or more alkyleneoxy group repeating units, and the colorant is red At least one colorant A selected from a colorant and a purple colorant, a yellow colorant, and a blue colorant, and at least the total amount of the colorant A selected from a red colorant and a purple colorant Colorant A / total colorant in the mass ratio is 0.01 to 0.7, and yellow colorant / total colorant in the mass ratio of the yellow colorant to the total amount of colorant is 0.05 to 0.5. A colored composition having a blue colorant / total colorant in a mass ratio of the blue colorant to the total amount of colorant of 0.05 to 0.6.
<3> The colorant contains a red colorant, a purple colorant, a yellow colorant, and a blue colorant, and the red colorant / total colorant is a mass ratio of the red colorant to the total colorant amount is 0. The yellow colorant / total colorant is 0.1 to 0.4, which is the mass ratio of the yellow colorant to the total amount of the colorant, and the mass ratio of the blue colorant to the total amount of the colorant. A certain blue colorant / total colorant is 0.2 to 0.6, and a purple colorant / total colorant, which is a mass ratio of the purple colorant to the total amount of colorant, is 0.01 to 0.3, < The coloring composition as described in 2>.
<4> The colored composition according to any one of <1> to <3>, wherein the polymerizable compound contains a polymerizable compound having a chain having an ethyleneoxy group repeating unit number of 2 or more.
<5> The polymerizable compound is any one of <1> to <4>, wherein a value obtained by dividing the molecular weight value of the polymerizable compound by the number of polymerizable groups contained in the polymerizable compound is 100 to 300. The coloring composition as described in.
<6> The colored composition according to any one of <1> to <5>, wherein the polymerizable compound has a cyclic structure.
<7> The colored composition according to any one of <1> to <6>, wherein the polymerizable compound has a heterocyclic structure.
<8> The polymerizable compound according to any one of <1> to <7>, wherein the polymerizable compound has a partial structure represented by the following general formula (1); is there.
Figure JPOXMLDOC01-appb-C000002
 <9> The colored composition according to any one of <1> to <8>, further comprising a resin and a photopolymerization initiator.
<10> The colored composition according to <9>, wherein the resin contains a resin having a hydroxyl group.
<11> When a film having a dried film thickness of 12.0 μm is formed, the maximum transmittance in the wavelength range of 400 to 780 nm is 15% or less, and the transmittance at a wavelength of 850 nm is 80% or more. <1> to <10> The colored composition according to any one of <1> to <10>.
<12> The colored composition according to any one of <1> to <11>, wherein the viscosity at 25 ° C. is 100 to 150 mP · s.
<13> A film obtained by curing the colored composition according to any one of <1> to <12>.
<14> A color filter having the film according to <13>.
<15> A step of applying the colored composition according to any one of <1> to <12> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, Forming a colored pattern by developing and removing an unexposed portion.
<16> A method for producing a color filter, comprising the pattern forming method according to <15>.
<17> A solid-state imaging device having the color filter according to <14> or the color filter obtained by the method for producing a color filter according to <16>.
<18> An infrared sensor having a color filter according to <14> or a color filter obtained by the method for producing a color filter according to <16>.
　本発明によれば、可視光由来のノイズが少ない状態で近赤外線を透過可能で、かつ、皺の抑制された膜を形成可能な着色組成物を提供できる。また、かかる着色組成物を用いた膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサを提供できる。 According to the present invention, it is possible to provide a coloring composition capable of transmitting a near infrared ray with less visible light-derived noise and capable of forming a film in which wrinkles are suppressed. Moreover, the film | membrane using this coloring composition, a color filter, the pattern formation method, the manufacturing method of a color filter, a solid-state image sensor, and an infrared sensor can be provided.
本発明の赤外線センサの一実施形態の構成を示す概略断面図である。It is a schematic sectional drawing which shows the structure of one Embodiment of the infrared sensor of this invention. 本発明の赤外線センサを適用した撮像装置の機能ブロック図である。It is a functional block diagram of the imaging device to which the infrared sensor of the present invention is applied.
　本明細書において、全固形分とは、着色組成物の全組成から溶剤を除いた成分の総質量をいう。また、固形分とは、２５℃における固形分をいう。
　本明細書において、粘度とは、２５℃における粘度をいう。
　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、置換基を有さないものと共に置換基を有するものをも包含するものである。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）をも包含するものである。
　本明細書において、「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等を意味する。
　本明細書において、「光」とは、活性光線または放射線を意味する。
　本明細書において、「露光」とは、特に断らない限り、水銀灯、エキシマレーザに代表される遠紫外線、Ｘ線、ＥＵＶ光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
　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、「単量体」と「モノマー」とは同義である。また、「単量体」は、「オリゴマー」および「ポリマー」と区別され、重量平均分子量が２，０００以下の化合物をいう。
　本明細書において、重合性化合物とは、重合性官能基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基を言う。
　本明細書において、化学式中のＭｅはメチル基を、Ｅｔはエチル基を、Ｐｒはプロピル基を、Ｂｕはブチル基を、Ｐｈはフェニル基をそれぞれ示す。
　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。
　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、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ×１５．０ｃｍを、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ(Ｎ－メチルピロリジノン)溶液を用いることによって求めることができる。
　本発明に用いられる顔料は、溶剤に溶解しにくい不溶性の色素化合物を意味する。典型的には、組成物中に粒子として分散された状態で存在する色素化合物を意味する。ここで、溶剤とは、任意の溶剤が挙げられ、水、後述する有機溶剤の欄で例示する溶剤が挙げられる。本発明に用いられる顔料は、例えば、プロプレングリコールモノメチルエーテルアセテ－トおよび水のいずれに対しても、２５℃における溶解度が０．１ｇ／１００ｇＳｏｌｖｅｎｔ以下が好ましい。 In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition. Moreover, solid content means solid content in 25 degreeC.
In this specification, the viscosity refers to a viscosity at 25 ° C.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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, “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
In this specification, “light” means actinic rays or radiation.
In this specification, “exposure” means not only exposure with a deep ultraviolet ray, an X-ray, EUV light, etc. represented by a mercury lamp and an excimer laser, but also drawing with a particle beam such as an electron beam or an ion beam unless otherwise specified. Are also included in the exposure.
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, “monomer” and “monomer” are synonymous. “Monomer” is distinguished from “oligomer” and “polymer”, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
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. It is.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
The pigment used in the present invention means an insoluble coloring compound that is difficult to dissolve in a solvent. Typically, it means a dye compound that exists in a dispersed state as particles in the composition. Here, with a solvent, arbitrary solvents are mentioned, The solvent illustrated in the column of water and the organic solvent mentioned later is mentioned. The pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less, for example, for both propylene glycol monomethyl ether acetate and water.
　＜着色組成物＞
　本発明の着色組成物の第一の態様は、着色剤と重合性化合物とを含み、重合性化合物は、アルキレンオキシ基を繰り返し単位として２以上含む鎖（すなわち、アルキレンオキシ基の繰り返し単位数が２以上の鎖。以下、アルキレンオキシ鎖ともいう）を有する重合性化合物を含有し、着色組成物の、波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａと、波長５８０ｎｍ以上７７０ｎｍ以下の範囲における吸光度の最小値Ｂとの比率Ａ／Ｂが０．３～３であり、波長４００ｎｍ以上７５０ｎｍ以下の範囲における吸光度の最小値Ｃと、波長８５０ｎｍ以上１３００ｎｍ以下の範囲における吸光度の最大値Ｄとの比率Ｃ／Ｄが５以上である。
　上述した吸光度の比率Ａ／Ｂは、０．４～２．５が好ましく、０．５～２がより好ましい。また、上述した吸光度の比率Ｃ／Ｄは、１０以上が好ましく、５０以上がより好ましい。着色組成物の吸光度の比率Ａ／Ｂ、Ｃ／Ｄを、それぞれ上記範囲とすることにより、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成しやすい。
　上記吸光度の達成手段は、特に定めるものではないが、各着色剤の種類及び含有量を調整することにより、上記吸光度とすることが好ましい実施形態として挙げられる。また、その他の達成手段として、例えば特定の波長を反射する材料を組み合わせることなどが挙げられる。 <Coloring composition>
A first aspect of the colored composition of the present invention includes a colorant and a polymerizable compound, and the polymerizable compound has a chain containing two or more alkyleneoxy groups as repeating units (that is, the number of repeating units of the alkyleneoxy group is A polymerizable compound having a chain of 2 or more (hereinafter also referred to as an alkyleneoxy chain), and a colored composition having a minimum absorbance A in a wavelength range of 400 nm to less than 580 nm and a wavelength of 580 nm to 770 nm inclusive. The ratio A / B to the minimum absorbance B is 0.3 to 3, and the minimum absorbance C in the wavelength range from 400 nm to 750 nm and the maximum absorbance D in the wavelength range from 850 nm to 1300 nm. The ratio C / D is 5 or more.
The absorbance ratio A / B described above is preferably 0.4 to 2.5, and more preferably 0.5 to 2. Further, the above-described absorbance ratio C / D is preferably 10 or more, and more preferably 50 or more. By setting the absorbance ratios A / B and C / D of the coloring composition within the above ranges, it is easy to form a film capable of transmitting near infrared rays with less visible light-derived noise.
Although the means for achieving the absorbance is not particularly defined, it is preferable to obtain the absorbance by adjusting the type and content of each colorant. Other achievement means include, for example, combining materials that reflect a specific wavelength.
　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）　　　・・・（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。 The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = −log (Tλ) (1)
Aλ is the absorbance at wavelength λ, and Tλ is the transmittance at wavelength λ.
　着色組成物の吸光度の値は、溶液の状態で測定した値であってもよく、着色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、乾燥後の膜厚が所定の膜厚となるように着色組成物を塗布し、１００℃、１２０秒間ホットプレートで乾燥して調製した膜を用いることが好ましい。
　膜の膜厚は、膜を有する基板を、触針式表面形状測定器（ＵＬＶＡＣ社製　ＤＥＫＴＡＫ１５０）を用いて測定することができる。
　吸光度は、従来公知の分光光度計を用いて測定できる。吸光度の測定条件は特に限定はない。例えば、波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａが、０．１～３．０になるように調整した条件で測定することが好ましい。このような条件で吸光度を測定することで、測定誤差をより小さくできる。波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａが、０．１～３．０になるように調整する方法としては、特に限定はない。例えば、液状の状態で吸光度を測定する場合は、試料セルの光路長を調整する方法が挙げられる。また、膜の状態で吸光度を測定する場合は、膜厚を調整する方法などが挙げられる。 The absorbance value of the colored composition may be a value measured in the state of a solution, or may be a value of a film formed using the colored composition. When measuring the absorbance in a film state, a colored composition is applied onto a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and then a hot plate at 100 ° C. for 120 seconds. It is preferable to use a membrane prepared by drying with
The film thickness of the film can be measured by using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) for the substrate having the film.
The absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions for absorbance are not particularly limited. For example, the measurement is preferably performed under conditions adjusted so that the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm is 0.1 to 3.0. By measuring the absorbance under such conditions, the measurement error can be further reduced. There is no particular limitation on the method for adjusting the minimum absorbance A in the wavelength range of 400 nm or more and less than 580 nm to be 0.1 to 3.0. For example, when measuring the absorbance in a liquid state, a method of adjusting the optical path length of the sample cell can be mentioned. Moreover, when measuring a light absorbency in the state of a film | membrane, the method etc. which adjust a film thickness are mentioned.
　また、本発明の着色組成物の第二の態様は、着色剤と重合性化合物とを含み、重合性化合物は、アルキレンオキシ基を繰り返し単位として２以上含む鎖（すなわち、アルキレンオキシ基の繰り返し単位数が２以上の鎖）を有する重合性化合物を含有し、着色剤は、赤色着色剤および紫色着色剤から選ばれる１種以上の着色剤Ａと、黄色着色剤と、青色着色剤と、を少なくとも含み、赤色着色剤および紫色着色剤から選ばれる着色剤Ａの着色剤全量に対する質量比である着色剤Ａ／全着色剤が、０．０１～０．７であり、黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．０５～０．５であり、青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．０５～０．６である。
　この態様において、着色剤は、赤色着色剤と、紫色着色剤と、黄色着色剤と、青色着色剤とを含み、赤色着色剤の着色剤全量に対する質量比である赤色着色剤／全着色剤が０．１～０．５であり、黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．１～０．４であり、青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．２～０．６であり、紫色着色剤の着色剤全量に対する質量比である紫色着色剤／全着色剤が０．０１～０．３であることが好ましい。
　着色剤全量に対する上記着色剤を、上記範囲とすることにより、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成しやすい。 The second aspect of the colored composition of the present invention includes a colorant and a polymerizable compound, and the polymerizable compound has a chain containing two or more alkyleneoxy groups as repeating units (that is, a repeating unit of an alkyleneoxy group). A polymerizable compound having a chain having a number of 2 or more), and the colorant includes at least one colorant A selected from a red colorant and a purple colorant, a yellow colorant, and a blue colorant. The colorant A / total colorant, which is at least a mass ratio of the colorant A selected from the red colorant and the purple colorant to the total amount of the colorant, is 0.01 to 0.7, and the colorant of the yellow colorant The yellow colorant / total colorant, which is a mass ratio to the total amount, is 0.05 to 0.5, and the blue colorant / total colorant, which is the mass ratio of the blue colorant to the total amount of colorant, is 0.05 to 0.00. 6.
In this embodiment, the colorant includes a red colorant, a purple colorant, a yellow colorant, and a blue colorant, and the red colorant / total colorant is a mass ratio of the red colorant to the total amount of the colorant. The yellow colorant / total colorant is 0.1 to 0.4, and the mass ratio of the yellow colorant to the total amount of the colorant is 0.1 to 0.4, and the mass ratio of the blue colorant to the total amount of the colorant The blue colorant / total colorant is 0.2 to 0.6, and the purple colorant / total colorant, which is the mass ratio of the purple colorant to the total amount of colorant, is 0.01 to 0.3. Is preferred.
By setting the colorant relative to the total amount of the colorant within the above range, it is easy to form a film capable of transmitting near infrared rays with little noise derived from visible light.
　上述した吸光度の比率Ａ／Ｂが０．３～３であり、上述した吸光度の比率Ｃ／Ｄが５以上である第一の態様の着色組成物、および、各着色剤を上述した範囲で含有する第二の態様の着色組成物は、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成することができる。
　そして、本発明の着色組成物は、アルキレンオキシ鎖を有する重合性化合物を含有することにより、皺の抑制された膜を形成できる。
　本発明の着色組成物が、アルキレンオキシ鎖を有する重合性化合物を含有することにより、このような効果が得られる理由は、次によるものであると推測される。
　すなわち、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成可能な着色組成物は、ｉ線などの透過性が低いため、膜表面に比べて膜内部の硬化性が低い傾向にある。このため、膜表面が膜内部よりも先に硬化し易いため、従来は、重合性化合物の硬化に伴う収縮によって、膜表面に皺が発生しやすかった。アルキレンオキシ鎖を有する重合性化合物は、柔軟性を有しているため、重合性化合物の硬化に伴う膜の収縮による影響を抑制できたため、皺の抑制された膜を形成できたと推測される。特に、膜厚が１μｍ以上、さらには、６μｍの膜を形成する際に有益である。
　以下、本発明の着色組成物の各成分について、説明する。 The color composition of the first aspect in which the absorbance ratio A / B is 0.3 to 3 and the absorbance ratio C / D is 5 or more, and each colorant is contained in the above range. The colored composition according to the second aspect can form a film that can transmit near infrared rays with less visible light-derived noise.
And the coloring composition of this invention can form the film | membrane by which the wrinkle was suppressed by containing the polymeric compound which has an alkyleneoxy chain | strand.
The reason why such an effect can be obtained when the colored composition of the present invention contains a polymerizable compound having an alkyleneoxy chain is presumed to be as follows.
That is, a colored composition capable of forming a film capable of transmitting near-infrared rays with less visible light-derived noise has a low permeability to i-line and the like, and therefore tends to have a lower curability inside the film than the film surface. It is in. For this reason, since the film | membrane surface is hardened | cured easily before the inside of a film | membrane, conventionally, it was easy to generate | occur | produce wrinkles on the film | membrane surface by the shrinkage | contraction accompanying hardening of a polymeric compound. Since the polymerizable compound having an alkyleneoxy chain has flexibility, the influence of shrinkage of the film accompanying the curing of the polymerizable compound can be suppressed, so that it is presumed that a film in which wrinkles are suppressed can be formed. In particular, it is useful when forming a film having a film thickness of 1 μm or more, and further 6 μm.
Hereinafter, each component of the coloring composition of the present invention will be described.
＜＜着色剤＞＞
　本発明の着色組成物は、着色剤を含有する。
　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、熱や光に対する耐性が高いという理由から顔料である。また、着色剤は、顔料の含有量が、着色剤の全量に対して９５質量％以上であることが好ましく、９７質量％以上であることがより好ましく、９９質量％以上であることが更に好ましい。 << Colorant >>
The coloring composition of the present invention contains a colorant.
The colorant may be a pigment or a dye. Preferably, it is a pigment because it has high resistance to heat and light. The colorant preferably has a pigment content of 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more based on the total amount of the colorant. .
　顔料は、有機顔料であることが好ましく、以下のものを挙げることができる。但し本発明は、これらに限定されるものではない。
　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）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１等（以上、黒色顔料）
　これら有機顔料は、単独若しくは種々組合せて用いることができる。
　無機顔料としては、金属酸化物、金属錯塩等で示される金属化合物を挙げることができ、具体的には、カーボンブラック（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７等）、チタンブラック等の黒色顔料、鉄、コバルト、アルミニウム、カドミウム、鉛、銅、チタン、マグネシウム、クロム、亜鉛、アンチモン等の金属酸化物、および上記金属の複合酸化物を挙げることができる。 The pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these.
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, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 (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, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, 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),
C. I. Pigment Black 1, etc. (above, black pigment)
These organic pigments can be used alone or in various combinations.
Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, black pigments such as carbon black (CI Pigment Black 7), titanium black, iron, Examples thereof include metal oxides such as cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.
　染料としては特に制限はなく、カラーフィルタに使用されている公知の染料が使用できる。
　化学構造としては、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アンスラピリドン系、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使用できる。また、これらの染料の多量体を用いてもよい。
　また、染料としては、酸性染料及び／又はその誘導体が好適に使用できる場合がある。
　その他、直接染料、塩基性染料、媒染染料、酸性媒染染料、アゾイック染料、分散染料、油溶染料、食品染料、及び／又は、これらの誘導体等も有用に使用することができる。 There is no restriction | limiting in particular as dye, The well-known dye currently used for the color filter can be used.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.
Moreover, as a dye, an acid dye and / or a derivative thereof may be suitably used.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
　以下に酸性染料の具体例を挙げるが、これらに限定されるものではない。
　ａｃｉｄ　ａｌｉｚａｒｉｎ　ｖｉｏｌｅｔ　Ｎ、
　ａｃｉｄ　ｂｌａｃｋ　１，２，２４，４８、
　ａｃｉｄ　ｂｌｕｅ　１，７，９，１５，１８，２３，２５，２７，２９，４０～４５，６２，７０，７４，８０，８３，８６，８７，９０，９２，１０３，１１２，１１３，１２０，１２９，１３８，１４７，１５８，１７１，１８２，１９２，２４３，３２４：１、
ａｃｉｄ　ｃｈｒｏｍｅ　ｖｉｏｌｅｔ　Ｋ、
ａｃｉｄ　Ｆｕｃｈｓｉｎ；ａｃｉｄ　ｇｒｅｅｎ　１，３，５，９，１６，２５，２７，５０、
ａｃｉｄ　ｏｒａｎｇｅ　６，７，８，１０，１２，５０，５１，５２，５６，６３，７４，９５、
ａｃｉｄ　ｒｅｄ　１，４，８，１４，１７，１８，２６，２７，２９，３１，３４，３５，３７，４２，４４，５０，５１，５２，５７，６６，７３，８０，８７，８８，９１，９２，９４，９７，１０３，１１１，１１４，１２９，１３３，１３４，１３８，１４３，１４５，１５０，１５１，１５８，１７６，１８３，１９８，２１１，２１５，２１６，２１７，２４９，２５２，２５７，２６０，２６６，２７４、
ａｃｉｄ　ｖｉｏｌｅｔ　６Ｂ，７，９，１７，１９、
ａｃｉｄ　ｙｅｌｌｏｗ　１，３，７，９，１１，１７，２３，２５，２９，３４，３６，４２，５４，７２，７３，７６，７９，９８，９９，１１１，１１２，１１４，１１６，１８４，２４３、
Ｆｏｏｄ　Ｙｅｌｌｏｗ　３
　上述した酸性染料の誘導体も好ましく用いられる。また、上記以外の、アゾ系、キサンテン系、フタロシアニン系の酸性染料も好ましく、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　４４、３８；Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　ｏｒａｎｇｅ　４５；Ｒｈｏｄａｍｉｎｅ　Ｂ、Ｒｈｏｄａｍｉｎｅ　１１０等の酸性染料及びこれらの染料の誘導体も好ましく用いられる。
　なかでも、染料としては、トリアリールメタン系、アントラキノン系、アゾメチン系、ベンジリデン系、オキソノール系、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、ピラゾールアゾ系、アニリノアゾ系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、アンスラピリドン系ピロメテン系から選ばれる着色剤であることが好ましい。
　さらに、顔料と染料を組み合わせて使用してもよい。 Specific examples of the acid dye are shown below, but are not limited thereto.
acid alizarin violet N,
acid black 1, 2, 24, 48,
acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,
acid chroma violet K,
acid Fuchsin; acid green 1,3,5,9,16,25,27,50,
acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95,
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 266, 274,
acid violet 6B, 7, 9, 17, 19,
acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184 243,
Food Yellow 3
The acid dye derivatives described above are also preferably used. Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
Among them, as the dye, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo A colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene is preferable.
Further, pigments and dyes may be used in combination.
　また、本発明では、ビスベンゾフラノン系顔料、アゾメチン系顔料、ペリレン系顔料、アゾ系染料などを用いることもできる。
　ビスベンゾフラノン系顔料としては、特表２０１２－５２８４４８号公報、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３４号公報などに記載のものが挙げられ、例えば、ＢＡＳＦ社製の「ＩＲＧＡＰＨＯＲ　ＢＫ」として入手可能である。
　アゾメチン系顔料としては、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。
　アゾ染料は、特に限定されないが、下記式（Ａ－１）で表される化合物等を好適に挙げることができる。 In the present invention, bisbenzofuranone pigments, azomethine pigments, perylene pigments, azo dyes, and the like can also be used.
Examples of the bisbenzofuranone pigment include those described in JP-A-2012-528448, JP-A-2010-534726, JP-A-2012-515234, and the like. For example, “IRGAPHOR BK” manufactured by BASF Is available as
Examples of the azomethine pigment 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 azo dye is not particularly limited, and preferred examples include compounds represented by the following formula (A-1).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　本発明において、着色剤の好ましい態様としては、黄色着色剤と青色着色剤とを少なくとも含むことが好ましく、赤色着色剤と黄色着色剤と青色着色剤と紫色着色剤とを含有することがより好ましい。また、着色剤は、顔料を含有することが好ましく、黄色顔料と青色顔料とを含有することがより好ましく、赤色顔料と黄色顔料と青色顔料と紫色顔料とを含有することが更に好ましい。この態様によれば、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜を形成可能な着色組成物を得ることができる。
　赤色顔料は、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４が好ましい。黄色顔料は、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９が好ましい。青色顔料は、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６が好ましい。紫色顔料は、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３が好ましい。 In the present invention, as a preferred embodiment of the colorant, it is preferable to include at least a yellow colorant and a blue colorant, and it is more preferable to include a red colorant, a yellow colorant, a blue colorant, and a purple colorant. . The colorant preferably contains a pigment, more preferably contains a yellow pigment and a blue pigment, and more preferably contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment. According to this aspect, it is possible to obtain a colored composition capable of forming a film capable of transmitting near-infrared rays with little visible light-derived noise.
Examples of red pigments include C.I. I. Pigment Red 254 is preferred. Examples of yellow pigments include C.I. I. Pigment Yellow 139 is preferred. Examples of the blue pigment include C.I. I. Pigment Blue 15: 6 is preferred. Purple pigments include, for example, C.I. I. Pigment Violet 23 is preferred.
　また、着色剤の別の好ましい態様としては、着色剤は、ビスベンゾフラノン系顔料、アゾメチン系顔料、ペリレン系顔料およびアゾ系染料から選ばれる少なくとも１種以上を含有することが好ましく、ビスベンゾフラノン系顔料、アゾメチン系顔料およびペリレン系顔料から選ばれる１種以上を含有することがより好ましい。 In another preferred embodiment of the colorant, the colorant preferably contains at least one selected from bisbenzofuranone pigments, azomethine pigments, perylene pigments, and azo dyes. It is more preferable to contain one or more selected from pigments, azomethine pigments and perylene pigments.
　また、赤色着色剤と黄色着色剤と青色着色剤とを組み合わせてなる場合、赤色着色剤の着色剤全量に対する質量比が０．１～０．５であり、黄色着色剤の着色剤全量に対する質量比が０．１～０．４であり、青色着色剤の着色剤全量に対する質量比が０．２～０．６であることが好ましい。赤色着色剤の着色剤全量に対する質量比が０．３～０．５であり、黄色着色剤の着色剤全量に対する質量比が０．１～０．３であり、青色着色剤の着色剤全量に対する質量比が０．４～０．６であることがより好ましい。
　また、黄色着色剤と青色着色剤と紫色着色剤とを組み合わせてなる場合、黄色着色剤の着色剤全量に対する質量比が０．１～０．４であり、青色着色剤の着色剤全量に対する質量比が０．２～０．６であり、紫色着色剤の着色剤全量に対する質量比が０．０１～０．３であることが好ましい。黄色着色剤の着色剤全量に対する質量比が０．２～０．３であり、青色着色剤の着色剤全量に対する質量比が０．４～０．６であり、紫色着色剤の着色剤全量に対する質量比が０．１～０．２５であることがより好ましい。
　また、赤色着色剤と黄色着色剤と青色着色剤と紫色着色剤とを組み合わせてなる場合、赤色着色剤の着色剤全量に対する質量比が０．１～０．５であり、黄色着色剤の着色剤全量に対する質量比が０．１～０．４であり、青色着色剤の着色剤全量に対する質量比が０．２～０．６であり、紫色着色剤の着色剤全量に対する質量比が０．０１～０．３であることが好ましい。赤色着色剤の着色剤全量に対する質量比が０．３～０．５であり、黄色着色剤の着色剤全量に対する質量比が０．１～０．３であり、青色着色剤の着色剤全量に対する質量比が０．３～０．５であり、紫色着色剤の着色剤全量に対する質量比が０．０１～０．２であることがより好ましい。赤色着色剤の着色剤全量に対する質量比が０．３５～０．４１であり、黄色着色剤の着色剤全量に対する質量比が０．１３～０．１．９であり、青色着色剤の着色剤全量に対する質量比が０．３４～０．４０であり、紫色着色剤の着色剤全量に対する質量比が０．０６～０．１２であることが特に好ましい。
　上述した各態様によれば、着色組成物の波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａと、波長５８０ｎｍ以上７７０ｎｍ以下の範囲における最小値Ｂとの比率Ａ／Ｂが０．３～３であり、波長４００ｎｍ以上７５０ｎｍ以下の範囲における吸光度の最小値Ｃと、波長８５０ｎｍ以上１３００ｎｍ以下の範囲における吸光度の最大値Ｄとの比率Ｃ／Ｄが５以上である着色組成物を得ることができる。
　本発明の着色組成物において、着色剤の含有量は、着色組成物の全固形分の１～９０質量％であることが好ましく、３～８０質量％であることがより好ましく、３～７０質量％であることが更に好ましい。 Further, when the red colorant, the yellow colorant and the blue colorant are combined, the mass ratio of the red colorant to the total amount of the colorant is 0.1 to 0.5, and the mass ratio of the yellow colorant to the total amount of the colorant The ratio is preferably 0.1 to 0.4, and the mass ratio of the blue colorant to the total amount of the colorant is preferably 0.2 to 0.6. The mass ratio of the red colorant to the total amount of colorant is 0.3 to 0.5, the mass ratio of the yellow colorant to the total amount of colorant is 0.1 to 0.3, and the blue colorant is based on the total amount of colorant. The mass ratio is more preferably 0.4 to 0.6.
Further, when the yellow colorant, the blue colorant and the purple colorant are combined, the mass ratio of the yellow colorant to the total amount of the colorant is 0.1 to 0.4, and the mass of the blue colorant relative to the total amount of the colorant The ratio is preferably 0.2 to 0.6, and the mass ratio of the purple colorant to the total amount of the colorant is preferably 0.01 to 0.3. The mass ratio of the yellow colorant to the total amount of colorant is 0.2 to 0.3, the mass ratio of the blue colorant to the total amount of colorant is 0.4 to 0.6, and the purple colorant is based on the total amount of colorant. The mass ratio is more preferably 0.1 to 0.25.
Further, when the red colorant, the yellow colorant, the blue colorant and the purple colorant are combined, the mass ratio of the red colorant to the total amount of the colorant is 0.1 to 0.5, and the yellow colorant is colored. The mass ratio to the total amount of the colorant is 0.1 to 0.4, the mass ratio of the blue colorant to the total amount of the colorant is 0.2 to 0.6, and the mass ratio of the purple colorant to the total amount of the colorant is 0.00. It is preferably 01 to 0.3. The mass ratio of the red colorant to the total amount of colorant is 0.3 to 0.5, the mass ratio of the yellow colorant to the total amount of colorant is 0.1 to 0.3, and the blue colorant is based on the total amount of colorant. More preferably, the mass ratio is 0.3 to 0.5, and the mass ratio of the purple colorant to the total amount of the colorant is 0.01 to 0.2. The color ratio of the red colorant to the total amount of the colorant is 0.35 to 0.41, the mass ratio of the yellow colorant to the total amount of the colorant is 0.13 to 0.1.9, and the colorant of the blue colorant The mass ratio with respect to the total amount is preferably 0.34 to 0.40, and the mass ratio of the purple colorant to the total amount of the colorant is particularly preferably 0.06 to 0.12.
According to each aspect described above, the ratio A / B between the minimum value A of the absorbance in the wavelength range from 400 nm to less than 580 nm and the minimum value B in the wavelength range from 580 nm to 770 nm is 0.3 to 3 A colored composition having a ratio C / D of 5 or more between the minimum absorbance C in the wavelength range of 400 nm to 750 nm and the maximum absorbance D in the wavelength range of 850 nm to 1300 nm can be obtained. .
In the colored composition of the present invention, the content of the colorant is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and more preferably 3 to 70% by mass of the total solid content of the colored composition. % Is more preferable.
＜＜＜顔料分散液＞＞＞
　本発明の着色組成物において、着色剤として顔料を用いる場合、顔料を、樹脂、有機溶剤、顔料誘導体等と共に分散させた顔料分散液の形態で用いることが好ましい。以下に顔料分散液の組成、顔料分散液の調製方法について詳述する。 <<< Pigment dispersion >>>
In the colored composition of the present invention, when a pigment is used as the colorant, it is preferably used in the form of a pigment dispersion in which the pigment is dispersed together with a resin, an organic solvent, a pigment derivative and the like. The composition of the pigment dispersion and the method for preparing the pigment dispersion are described in detail below.
＜＜＜＜顔料＞＞＞＞
　顔料の平均粒子径は、２０～３００ｎｍが好ましく、２５～２５０ｎｍがより好ましく、３０～２００ｎｍが更に好ましい。ここでいう「平均粒子径」とは、顔料の一次粒子（単微結晶）が集合した二次粒子についての平均粒子径を意味する。顔料の平均粒子径は、走査型電子顕微鏡（ＳＥＭ）あるいは透過型電子顕微鏡（ＴＥＭ）で観察し、粒子が凝集していない部分で粒子サイズを１００個計測し、平均値を算出することによって求めることができる。
　また、顔料の二次粒子の粒子径分布（以下、単に「粒子径分布」という。）は、（平均粒子径±１００）ｎｍに入る二次粒子が全体の７０質量％以上、好ましくは８０質量％以上であることが好ましい。なお、本発明においては、粒子径分布は、散乱強度分布を用いて測定した値である。 <<<<< Pigment >>>>
The average particle diameter of the pigment is preferably 20 to 300 nm, more preferably 25 to 250 nm, and still more preferably 30 to 200 nm. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average particle diameter of the pigment is obtained by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value. be able to.
The particle size distribution of the secondary particles of the pigment (hereinafter, simply referred to as “particle size distribution”) is 70% by mass or more, preferably 80% by mass, of secondary particles falling into (average particle size ± 100) nm. % Or more is preferable. In the present invention, the particle size distribution is a value measured using a scattering intensity distribution.
　上述した平均粒子径及び粒子径分布を有する顔料は、市販の顔料を、好ましくは樹脂及び有機溶剤と混合し、例えばビーズミル、ロールミル等の粉砕機を用いて、粉砕しつつ混合・分散することにより調製することができる。このようにして得られる顔料は、通常、顔料分散液の形態をとる。 The pigment having the average particle size and particle size distribution described above is obtained by mixing and dispersing a commercially available pigment, preferably with a resin and an organic solvent, and using a pulverizer such as a bead mill or a roll mill while pulverizing. Can be prepared. The pigment thus obtained is usually in the form of a pigment dispersion.
－顔料の微細化－
　本発明においては、微細でかつ整粒化された顔料を用いることが好ましい。顔料の微細化は、顔料と有機溶剤と水溶性無機塩類と共に高粘度な液状組成物を調製し、湿式粉砕装置等を使用して、応力を付加して摩砕する工程を経ることで達成される。 -Refinement of pigment-
In the present invention, it is preferable to use a fine and sized pigment. Refinement of the pigment is achieved by preparing a high-viscosity liquid composition together with the pigment, the organic solvent, and the water-soluble inorganic salts, and applying a stress and grinding using a wet pulverizer. The
　顔料の微細化工程に使用される有機溶剤としては、水溶性有機溶剤が好ましい。水溶性有機溶剤としては、例えば、メタノール、エタノール、イソプロパノール、ｎ－プロパノール、イソブタノール、ｎ－ブタノール、エチレングリコール、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。
　微細化工程における水溶性有機溶剤の使用量は、顔料１００質量部に対して５０～３００質量部が好ましく、１００～２００質量部がより好ましい。
　また、水溶性は低いか、或いは、水溶性を有しない他の溶剤を、廃水中に流失しない範囲で用いてもよい。他の溶剤としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ニトロベンゼン、アニリン、ピリジン、キノリン、テトラヒドロフラン、ジオキサン、酢酸エチル、酢酸イソプロピル、酢酸ブチル、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、シクロヘキサン、メチルシクロヘキサン、ハロゲン化炭化水素、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ－メチルピロリドン等が挙げられる。
　顔料の微細化工程に使用する有機溶剤は、１種のみでもよく、必要に応じて２種類以上を混合して使用してもよい。 As the organic solvent used in the pigment refinement step, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl. Examples include ether acetate.
The amount of the water-soluble organic solvent used in the miniaturization step is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the pigment.
Moreover, you may use the other solvent which is low in water solubility or does not have water solubility in the range which does not wash away in waste water. Examples of other solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, and undecane. , Dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.
Only one organic solvent may be used in the pigment refining step, or two or more organic solvents may be mixed and used as necessary.
　顔料の微細化工程に使用される水溶性無機塩類としては、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化バリウム、硫酸ナトリウム等が挙げられる。
　微細化工程における水溶性無機塩類の使用量は、顔料１質量部に対し１～５０質量部が好ましく、１～１０質量部がより好ましい。また、水分が１％以下の水溶性無機塩類を用いることが好ましい。 Examples of the water-soluble inorganic salts used in the pigment refinement process include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the miniaturization step is preferably 1 to 50 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the pigment. Moreover, it is preferable to use water-soluble inorganic salts having a water content of 1% or less.
　顔料の微細化工程における湿式粉砕装置の運転条件については特に制限はないが、粉砕メディアによる磨砕を効果的に進行させるため、装置がニーダーの場合の運転条件は、装置内のブレードの回転数は、１０～２００ｒｐｍが好ましく、また２軸の回転比が相対的に大きいほうが摩砕効果が大きく好ましい。運転時間は乾式粉砕時間と併せて１～８時間が好ましく、装置の内温は５０～１５０℃が好ましい。また粉砕メディアである水溶性無機塩は粉砕粒度が５～５０μｍで粒子径の分布がシャープで、且つ球形が好ましい。 There are no particular restrictions on the operating conditions of the wet pulverizer in the pigment refinement process. However, in order to effectively carry out the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably from 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of a high grinding effect. The operation time is preferably 1 to 8 hours together with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt as a grinding medium preferably has a grinding particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.
＜＜＜＜樹脂（分散樹脂）＞＞＞＞
　顔料分散液の調製に用いうる樹脂（分散樹脂）としては、高分子分散剤〔例えば、アミン基を有する樹脂（ポリアミドアミンとその塩など）、オリゴイミン系樹脂、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン等の界面活性剤等を挙げることができる。 <<<<< Resin (dispersed resin) >>>>
Resins (dispersion resins) that can be used in the preparation of pigment dispersions include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight Unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol Surfactants such as amines can be mentioned.
　高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。
　顔料表面へのアンカー部位を有する末端変性型高分子としては、例えば、特開平３－１１２９９２号公報、特表２００３－５３３４５５号公報等に記載の末端にリン酸基を有する高分子、特開２００２－２７３１９１号公報等に記載の末端にスルホン酸基を有する高分子、特開平９－７７９９４号公報等に記載の有機色素の部分骨格や複素環を有する高分子などが挙げられる。また、特開２００７－２７７５１４号公報に記載の高分子末端に２個以上の顔料表面へのアンカー部位（酸基、塩基性基、有機色素の部分骨格やヘテロ環等）を導入した高分子も分散安定性に優れ好ましい。
　顔料表面へのアンカー部位を有するグラフト型高分子としては、例えば、特開昭５４ー３７０８２号公報、特表平８－５０７９６０号公報、特開２００９－２５８６６８公報等に記載のポリ（低級アルキレンイミン）とポリエステルの反応生成物、特開平９－１６９８２１号公報等に記載のポリアリルアミンとポリエステルの反応生成物、特開平１０－３３９９４９号、特開２００４－３７９８６号公報等に記載のマクロモノマーと、窒素原子モノマーとの共重合体、特開２００３－２３８８３７号公報、特開２００８－９４２６号公報、特開２００８－８１７３２号公報等に記載の有機色素の部分骨格や複素環を有するグラフト型高分子、特開２０１０－１０６２６８号公報等に記載のマクロモノマーと酸基含有モノマーの共重合体などが挙げられる。
　顔料表面へのアンカー部位を有するグラフト型高分子をラジカル重合で製造する際に用いるマクロモノマーとしては、公知のマクロモノマーを用いることができる。例えば、東亜合成（株）製のマクロモノマーＡＡ－６（末端基がメタクリロイル基であるポリメタクリル酸メチル）、ＡＳ－６（末端基がメタクリロイル基であるポリスチレン）、ＡＮ－６Ｓ（末端基がメタクリロイル基であるスチレンとアクリロニトリルの共重合体）、ＡＢ－６（末端基がメタクリロイル基であるポリアクリル酸ブチル）、ダイセル化学工業（株）製のプラクセルＦＭ５（メタクリル酸２－ヒドロキシエチルのε－カプロラクトン５モル当量付加品）、ＦＡ１０Ｌ（アクリル酸２－ヒドロキシエチルのε－カプロラクトン１０モル当量付加品）、及び特開平２－２７２００９号公報に記載のポリエステル系マクロモノマー等が挙げられる。これらの中でも、特に柔軟性且つ親溶剤性に優れるポリエステル系マクロモノマーが、顔料の分散性、分散安定性、及び顔料分散物を用いた着色組成物が示す現像性の観点から特に好ましく、更に、特開平２－２７２００９号公報に記載のポリエステル系マクロモノマーで表されるポリエステル系マクロモノマーが最も好ましい。
　顔料表面へのアンカー部位を有するブロック型高分子としては、特開２００３－４９１１０号公報、特開２００９－５２０１０号公報等に記載のブロック型高分子が好ましい。 The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
Examples of the terminal-modified polymer having an anchor site to the pigment surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like. Examples thereof include polymers having a sulfonic acid group at the terminal end described in JP-A-273191 and the like, and polymers having a partial skeleton of an organic dye and a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
Examples of the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. And a reaction product of polyester, a reaction product of polyallylamine and polyester described in JP-A-9-169821 and the like, a macromonomer described in JP-A-10-339949, JP-A-2004-37986 and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. A copolymer of a macromonomer and an acid group-containing monomer described in JP 2010-106268 A, etc. It is below.
A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization. For example, macromonomer AA-6 (polymethyl methacrylate whose terminal group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (terminal group is methacryloyl) manufactured by Toa Gosei Co., Ltd. Copolymer of styrene and acrylonitrile, AB-6 (polybutyl acrylate whose terminal group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd. (ε-caprolactone of 2-hydroxyethyl methacrylate) 5 molar equivalent addition product), FA10L (epsilon-caprolactone 10 molar equivalent addition product of 2-hydroxyethyl acrylate), polyester macromonomer described in JP-A-2-272009, and the like. Among these, a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion. A polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is most preferred.
As the block type polymer having an anchor site to the pigment surface, block type polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
　樹脂は、下記式（１）～式（４）のいずれかで表される構造単位を含むクラフト共重合体を用いることもできる。 As the resin, a kraft copolymer containing a structural unit represented by any one of the following formulas (1) to (4) can also be used.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　Ｘ1、Ｘ2、Ｘ3、Ｘ4、及び、Ｘ5はそれぞれ独立に水素原子或いは１価の有機基を表し、水素原子または炭素数１～１２のアルキル基が好ましく、水素原子またはメチル基がより好ましく、メチル基が特に好ましい。
　Ｗ1、Ｗ2、Ｗ3、及び、Ｗ4はそれぞれ独立に酸素原子またはＮＨを表し、酸素原子が好ましい。
　Ｒ3は、分岐若しくは直鎖のアルキレン基（炭素数は１～１０が好ましく、２又は３であることがより好ましい）を表し、分散安定性の観点から、－ＣＨ2－ＣＨ（ＣＨ3）－で表される基、又は、－ＣＨ（ＣＨ3）－ＣＨ2－で表される基が好ましい。
　Ｙ1、Ｙ2、Ｙ3、及び、Ｙ4はそれぞれ独立に２価の連結基を表す。
　上記クラフト共重合体については、特開２０１２－２５５１２８号公報の段落番号００２５～００６９の記載を参酌でき、本明細書には上記内容が組み込まれることとする。
　上記クラフト共重合体の具体例としては、例えば、以下が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号００７２～００９４に記載の樹脂を用いることができる。
X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom or a methyl group Are more preferable, and a methyl group is particularly preferable.
W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH, preferably an oxygen atom.
R 3 represents a branched or straight chain alkylene group (preferably having 1 to 10 carbon atoms, more preferably 2 or 3), and —CH 2 —CH (CH 3 ) from the viewpoint of dispersion stability. A group represented by — or a group represented by —CH (CH 3 ) —CH 2 — is preferred.
Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group.
Regarding the craft copolymer, the description of paragraph numbers 0025 to 0069 of JP2012-255128A can be referred to, and the above contents are incorporated in this specification.
Specific examples of the craft copolymer include the following. Further, resins described in JP-A-2012-255128, paragraphs 0072 to 0094 can be used.
　また、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オリゴイミン系樹脂を用いることもできる。オリゴイミン系樹脂としては、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する繰り返し単位と、原子数４０～１０，０００の側鎖Ｙ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。
　オリゴイミン系樹脂は、例えば、下記式（Ｉ－１）で表される繰り返し単位と、式（Ｉ－２）で表される繰り返し単位、および／または、式（Ｉ－２ａ）で表される繰り返し単位を含む樹脂などが挙げられる。 Further, as the resin, an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used. The oligoimine resin includes a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain. A resin having a basic nitrogen atom on one side is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
The oligoimine resin includes, for example, a repeating unit represented by the following formula (I-1), a repeating unit represented by the formula (I-2), and / or a repeating unit represented by the formula (I-2a). Examples include resins containing units.
Figure JPOXMLDOC01-appb-C000006
 　Ｒ1及びＲ2は、各々独立に、水素原子、ハロゲン原子又はアルキル基（炭素数１～６が好ましい）を表す。ａは、各々独立に、１～５の整数を表す。＊は繰り返し単位間の連結部を表す。
　Ｒ8及びＲ9はＲ1と同義の基である。
　Ｌは単結合、アルキレン基（炭素数１～６が好ましい）、アルケニレン基（炭素数２～６が好ましい）、アリーレン基（炭素数６～２４が好ましい）、ヘテロアリーレン基（炭素数１～６が好ましい）、イミノ基（炭素数０～６が好ましい）、エーテル基、チオエーテル基、カルボニル基、またはこれらの組合せに係る連結基である。なかでも、単結合もしくは－ＣＲ5Ｒ6－ＮＲ7－（イミノ基がＸもしくはＹの方になる）であることが好ましい。ここで、Ｒ5Ｒ6は各々独立に、水素原子、ハロゲン原子、アルキル基（炭素数１～６が好ましい）を表す。Ｒ7は水素原子または炭素数１～６のアルキル基である。
　ＬaはＣＲ8ＣＲ9とＮとともに環構造形成する構造部位であり、ＣＲ8ＣＲ9の炭素原子と合わせて炭素数３～７の非芳香族複素環を形成する構造部位であることが好ましい。さらに好ましくは、ＣＲ8ＣＲ9の炭素原子及びＮ（窒素原子）を合わせて５～７員の非芳香族複素環を形成する構造部位であり、より好ましくは５員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。この構造部位はさらにアルキル基等の置換基を有していてもよい。
　ＸはｐＫａ１４以下の官能基を有する基を表す。
　Ｙは原子数４０～１０，０００の側鎖を表す。
　上記樹脂（オリゴイミン系樹脂）は、さらに式（Ｉ－３）、式（Ｉ－４）、および、式（Ｉ－５）で表される繰り返し単位から選ばれる１種以上を共重合成分として含有していてもよい。上記樹脂が、このような繰り返し単位を含むことで、顔料の分散性能を更に向上させることができる。
Figure JPOXMLDOC01-appb-C000006
 R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
R 8 and R 9 are the same groups as R 1 .
L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). Are preferred), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a combination group thereof. Among these, a single bond or —CR 5 R 6 —NR 7 — (imino group is X or Y) is preferable. Here, R 5 R 6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
L a is a structural site ring structure formed together with CR 8 CR 9 and N, it is preferable together with the carbon atom of CR 8 CR 9 is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms . More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom of CR 8 CR 9 and N (nitrogen atom), more preferably a 5-membered non-aromatic heterocyclic ring. It is a structural part to be formed and is particularly preferably a structural part to form pyrrolidine. This structural part may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa14 or less.
Y represents a side chain having 40 to 10,000 atoms.
The resin (oligoimine-based resin) further contains, as a copolymerization component, one or more selected from repeating units represented by formula (I-3), formula (I-4), and formula (I-5) You may do it. When the resin contains such a repeating unit, the dispersion performance of the pigment can be further improved.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　Ｒ1、Ｒ2、Ｒ8、Ｒ9、Ｌ、Ｌａ、ａ及び＊は式（Ｉ－１）、（Ｉ－２）、（Ｉ－２ａ）における規定と同義である。
　Ｙａはアニオン基を有する原子数４０～１０，０００の側鎖を表す。式（Ｉ－３）で表される繰り返し単位は、主鎖部に一級又は二級アミノ基を有する樹脂に、アミンと反応して塩を形成する基を有するオリゴマー又はポリマーを添加して反応させることで形成することが可能である。 R 1 , R 2 , R 8 , R 9 , L, La, a and * are as defined in the formulas (I-1), (I-2) and (I-2a).
Ya represents a side chain having an anionic group having 40 to 10,000 atoms. The repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed.
　上述したオリゴイミン系樹脂については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、本明細書には上記内容が組み込まれることとする。オリゴイミン系樹脂の具体例としては、例えば、以下が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号０１６８～０１７４に記載の樹脂を用いることができる。
Figure JPOXMLDOC01-appb-C000008
 Regarding the oligoimine-based resin described above, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the oligoimine resin include the following. Also, resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
Figure JPOXMLDOC01-appb-C000008
　樹脂は、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「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミドアミン燐酸塩）、１０７（カルボン酸エステル）、１１０、１１１（酸基を含む共重合物）、１３０（ポリアミド）、１６１、１６２、１６３、１６４、１６５、１６６、１７０（高分子共重合物）」、「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和ポリカルボン酸）、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０～４０１０～４１６５（ポリウレタン系）、ＥＦＫＡ４３３０～４３４０（ブロック共重合体）、４４００～４４０２（変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（高分子量ポリカルボン酸塩）、６２２０（脂肪酸ポリエステル）、６７４５（フタロシアニン誘導体）、６７５０（アゾ顔料誘導体）」、味の素ファンテクノ社製「アジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８８０、ＰＢ８８１」、共栄社化学社製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（アクリル系共重合体）」、楠本化成社製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王社製「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン重縮合物）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン重縮合物）」、「ホモゲノールＬ－１８（高分子ポリカルボン酸）」、「エマルゲン９２０、９３０、９３５、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、日本ルーブリゾール（株）製「ソルスパース５０００（フタロシアニン誘導体）、２２０００（アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１７０００、２７０００（末端部に機能部を有する高分子）、２４０００、２８０００、３２０００、３８５００（グラフト型高分子）」、日光ケミカル社製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）」、川研ファインケミカル（株）製　ヒノアクトＴ－８０００Ｅ等、信越化学工業（株）製、オルガノシロキサンポリマーＫＰ３４１、裕商（株）製「Ｗ００１：カチオン系界面活性剤」、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等のノニオン系界面活性剤、「Ｗ００４、Ｗ００５、Ｗ０１７」等のアニオン系界面活性剤、森下産業（株）製「ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０」、サンノプコ（株）製「ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００」等の高分子分散剤、（株）ＡＤＥＫＡ製「アデカプルロニックＬ３１、Ｆ３８、Ｌ４２、Ｌ４４、Ｌ６１、Ｌ６４、Ｆ６８、Ｌ７２、Ｐ９５、Ｆ７７、Ｐ８４、Ｆ８７、Ｐ９４、Ｌ１０１、Ｐ１０３、Ｆ１０８、Ｌ１２１、Ｐ－１２３」、及び三洋化成（株）製「イオネットＳ－２０」等が挙げられる。 The resin is also available as a commercial product. Specific examples of such resins include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group) manufactured by BYK Chemie. Polymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”, manufactured by EFKA “EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 ( Fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo pigment derivatives), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fan Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 ”,“ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”manufactured by Kao Corporation,“ Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (poly Xylethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, manufactured by Nippon Lubrizol Co., Ltd. ” 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxy) manufactured by Nikko Chemical Co., Ltd. ” Ethylene monostearate) ”, Kawaken Fine Chemical Co., Ltd., Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd.“ W001: Cationic Surfactant ” Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Surfactant, anionic surfactant such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, manufactured by Morishita Sangyo Co., Ltd. EFKA Polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "manufactured by San Nopco Polymer dispersant, manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 And “Ionet S-20” manufactured by Sanyo Chemical Co., Ltd.
　これらの樹脂は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。また、樹脂は、顔料表面へのアンカー部位を有する末端変性型高分子、グラフト型高分子、ブロック型高分子と伴に、後述するアルカリ可溶性樹脂をさらに併用しても良い。アルカリ可溶性樹脂としては、（メタ）アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボン酸を有する酸性セルロース誘導体、ヒドロキシル基を有するポリマーに酸無水物を変性した樹脂が挙げられるが、特に（メタ）アクリル酸共重合体が好ましい。また、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマー共重合体、特開２００４－３００２０４号公報に記載のエーテルダイマー共重合体、特開平７－３１９１６１号公報に記載の重合性基を含有するアルカリ可溶性樹脂も好ましい。 These resins may be used alone or in combination of two or more. In addition, the resin may be used in combination with an alkali-soluble resin to be described later together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acidic cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300922, an ether dimer copolymer described in JP-A-2004-300204, and a polymerizable group described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.
　顔料分散液における樹脂（分散樹脂）の含有量は、顔料１００質量部に対して、１～１００質量部が好ましい。上限は、８０質量部以下が好ましく、７０質量部以下が好ましく、６０質量部以下がより好ましい。下限は、５質量部以上が好ましく、１０質量部以上がより好ましい。
　ここで、顔料の量は、着色剤全量に含まれる顔料の総量を意味する。 The content of the resin (dispersion resin) in the pigment dispersion is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.
Here, the amount of pigment means the total amount of pigment contained in the total amount of colorant.
＜＜＜＜顔料誘導体＞＞＞＞
　顔料分散液は、更に、顔料誘導体を含有することが好ましい。
　顔料誘導体とは、顔料の一部分を、酸性基、塩基性基、フタルイミドメチル基などで置換した構造を有する化合物である。顔料誘導体としては、分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体を含有することが好ましい。
　顔料誘導体を構成するための顔料としては、ジケトピロロピロール顔料、アゾ顔料、フタロシアニン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、ペリノン顔料、ペリレン顔料、チオインジゴ顔料、イソインドリン顔料、イソインドリノン顔料、キノフタロン顔料、スレン顔料、金属錯体顔料等が挙げられる。
　顔料誘導体が有する酸性基としては、スルホン酸、カルボン酸及びその４級アンモニウム塩が好ましく、カルボン酸基及びスルホン酸基がさらに好ましく、スルホン酸基が特に好ましい。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、特に三級アミノ基が好ましい。
　顔料誘導体としては、キノリン顔料誘導体、ベンズイミダゾロン顔料誘導体及びイソインドリン顔料誘導体が好ましく、キノリン顔料誘導体及びベンズイミダゾロン顔料誘導体が特に好ましい。
　顔料分散液における顔料誘導体の含有量は、顔料の全質量に対し、１～５０質量％が好ましく、３～３０質量％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。 <<<<< Pigment derivative >>>>
The pigment dispersion preferably further contains a pigment derivative.
The pigment derivative is a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a phthalimidomethyl group, or the like. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
As pigments for constituting the pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindolinone pigment, isoindolinone pigment, Examples include quinophthalone pigments, selenium pigments, and metal complex pigments.
As an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
As the pigment derivative, a quinoline pigment derivative, a benzimidazolone pigment derivative and an isoindoline pigment derivative are preferable, and a quinoline pigment derivative and a benzimidazolone pigment derivative are particularly preferable.
The content of the pigment derivative in the pigment dispersion is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
＜＜＜＜有機溶剤＞＞＞＞
　顔料分散液は有機溶剤を含有することが好ましい。
　有機溶剤は、顔料分散液中に含まれる各成分の溶解性や、顔料分散液を着色組成物に応用した場合の塗布性などにより選択される。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類が用いられる。中でも、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、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールメチルエーテル、プロピレングリコールモノメチルエーテルアセテートが好ましい。また、後述する着色組成物に含むことができる有機溶剤を用いることも好ましい。
　顔料分散液における有機溶剤の含有量としては、５０～９５質量％が好ましく、７０～９０質量％がより好ましい。 <<<<< Organic solvent >>>>
The pigment dispersion preferably contains an organic solvent.
The organic solvent is selected depending on the solubility of each component contained in the pigment dispersion and the coating property when the pigment dispersion is applied to the coloring composition. As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate are preferred. Moreover, it is also preferable to use the organic solvent which can be contained in the coloring composition mentioned later.
The content of the organic solvent in the pigment dispersion is preferably 50 to 95% by mass, more preferably 70 to 90% by mass.
＜＜重合性化合物＞＞
　本発明の着色組成物は、重合性化合物を含有する。
　重合性化合物は、重合性基を有する化合物であって、ラジカルにより重合可能な公知の重合性化合物を用いることができる。重合性基としては、エチレン性不飽和結合を有する基が好ましい。エチレン性不飽和結合を有する基としては、ビニル基、アリル基、メタリル基、アクリロイル基、メタクリロイル基、アリルオキシカルボニル基、メタリルオキシカルボニル基などが挙げられる。
　重合性化合物は、例えば、モノマー、プレポリマー、すなわち２量体、３量体及びオリゴマー、又はそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。
　重合性化合物は、感度の観点から、重合性基を１個以上有する化合物が好ましく、重合性基を２個以上有する化合物がより好ましい。中でも、重合性基を４個以上有する４官能以上の多官能重合性化合物が好ましく、５官能以上の多官能重合性化合物がさらに好ましい。 << polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound.
The polymerizable compound is a compound having a polymerizable group, and a known polymerizable compound that can be polymerized by a radical can be used. As the polymerizable group, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, methallyl group, acryloyl group, methacryloyl group, allyloxycarbonyl group, and methallyloxycarbonyl group.
The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof.
From the viewpoint of sensitivity, the polymerizable compound is preferably a compound having one or more polymerizable groups, and more preferably a compound having two or more polymerizable groups. Among them, a polyfunctional polymerizable compound having 4 or more functional groups having 4 or more polymerizable groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.
＜＜アルキレンオキシ鎖を有する重合性化合物＞＞
　本発明は、重合性化合物として、アルキレンオキシ基を繰り返し単位として２以上含む鎖（すなわち、アルキレンオキシ基の繰り返し単位数が２以上の鎖。アルキレンオキシ鎖）を有する重合性化合物を含有するものを用いる。アルキレンオキシ鎖を有する重合性化合物は、柔軟性を有しているため、重合性化合物の硬化に伴う膜の収縮を抑制でき、膜表面の皺の発生を効果的に抑制できる。
　本発明において、アルキレンオキシ鎖は、アルキレンオキシ基の繰り返し単位数が２～３０であることが好ましく、２～２０がより好ましく、５～１５が更に好ましい。
　本発明において、アルキレンオキシ基の炭素数は、２以上が好ましく、２～１０がより好ましく、２～４が更に好ましく、２が特に好ましい。アルキレンオキシ基は、直鎖、分岐のいずれであってもよいが、直鎖が好ましい。アルキレンオキシ基は、無置換であることが好ましい。
　すなわち、アルキレンオキシ鎖は、「－（（ＣＨ2）a－Ｏ）b－」で表されることが好ましい。式中、ａは２以上が好ましく、２～２０がより好ましい。ｂは、２以上が好ましく、２～１０がより好ましい。
　本発明において、アルキレンオキシ鎖を有する重合性化合物は、エチレンオキシ基を繰り返し単位として２以上含む鎖（すなわち、エチレンオキシ基の繰り返し単位数が２以上の鎖。エチレンオキシ鎖ともいう）を有する重合性化合物であることが好ましい。エチレンオキシ鎖を有する重合性化合物は、柔軟性が特に優れているので、膜表面の皺の発生をより効果的に抑制できる。 << Polymerizable compound having an alkyleneoxy chain >>
The present invention includes a polymerizable compound containing a polymerizable compound having a chain containing two or more alkyleneoxy groups as repeating units (that is, a chain having 2 or more repeating units of alkyleneoxy groups; an alkyleneoxy chain). Use. Since the polymerizable compound having an alkyleneoxy chain has flexibility, the shrinkage of the film accompanying the curing of the polymerizable compound can be suppressed, and the generation of wrinkles on the film surface can be effectively suppressed.
In the present invention, the alkyleneoxy chain preferably has 2 to 30 repeating units of an alkyleneoxy group, more preferably 2 to 20, and still more preferably 5 to 15.
In the present invention, the alkyleneoxy group preferably has 2 or more carbon atoms, more preferably 2 to 10, more preferably 2 to 4, and particularly preferably 2. The alkyleneoxy group may be either linear or branched, but is preferably linear. The alkyleneoxy group is preferably unsubstituted.
That is, the alkyleneoxy chain is preferably represented by “— ((CH 2 ) a —O) b —”. In the formula, a is preferably 2 or more, more preferably 2 to 20. b is preferably 2 or more, more preferably 2 to 10.
In the present invention, the polymerizable compound having an alkyleneoxy chain is a polymer having a chain containing two or more ethyleneoxy groups as repeating units (that is, a chain having two or more ethyleneoxy group repeating units, also referred to as an ethyleneoxy chain). It is preferable that it is an ionic compound. Since the polymerizable compound having an ethyleneoxy chain is particularly excellent in flexibility, generation of wrinkles on the film surface can be more effectively suppressed.
　アルキレンオキシ鎖を有する重合性化合物は、分子量が１００～２０００が好ましく、１０００～２０００がより好ましい。また、重合性化合物の分子量の値を、重合性化合物中に含まれる重合性基の数で割った値は、１００～３００が好ましく、２００～３００がより好ましい。この態様によれば、重合性化合物の架橋密度が適度であるので、皺の発生をより効果的に抑制できる。
　なお、重合性化合物の分子量の値は、重合性化合物がモノマーの場合は、分子構造から求めた理論値であり、重合性化合物がオリゴマー又はポリマーの場合は、重量平均分子量を意味する。 The polymerizable compound having an alkyleneoxy chain preferably has a molecular weight of 100 to 2000, more preferably 1000 to 2000. Further, the value obtained by dividing the molecular weight value of the polymerizable compound by the number of polymerizable groups contained in the polymerizable compound is preferably 100 to 300, more preferably 200 to 300. According to this aspect, since the crosslinking density of the polymerizable compound is moderate, the generation of wrinkles can be more effectively suppressed.
The molecular weight value of the polymerizable compound is a theoretical value obtained from the molecular structure when the polymerizable compound is a monomer, and means a weight average molecular weight when the polymerizable compound is an oligomer or a polymer.
　アルキレンオキシ鎖を有する重合性化合物は、環状構造を有することが好ましい。環状構造を有することで、密着性が向上する。
　環状構造としては、芳香族環構造、脂環構造、ヘテロ環構造などが挙げられる。好ましくはヘテロ環構造である。ヘテロ環構造のヘテロ環は、５員環または６員環が好ましい。ヘテロ環は、単環、または、縮合環が好ましく、単環が好ましい。ヘテロ環を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子などが挙げられ、窒素原子が好ましい。ヘテロ原子の数は、１～３が好ましく、２～３がより好ましく、３が特に好ましい。
　本発明において、アルキレンオキシ鎖を有する重合性化合物は、下記一般式（１）で表される部分構造を有することが好ましい。式中の＊は連結手である。
Figure JPOXMLDOC01-appb-C000009
 The polymerizable compound having an alkyleneoxy chain preferably has a cyclic structure. Adhesiveness improves by having a cyclic structure.
Examples of the cyclic structure include an aromatic ring structure, an alicyclic structure, and a heterocyclic structure. A heterocyclic structure is preferred. The heterocyclic ring is preferably a 5-membered ring or a 6-membered ring. The heterocycle is preferably a monocycle or a condensed ring, and preferably a monocycle. Examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom is preferable. The number of heteroatoms is preferably 1 to 3, more preferably 2 to 3, and particularly preferably 3.
In the present invention, the polymerizable compound having an alkyleneoxy chain preferably has a partial structure represented by the following general formula (1). * In the formula is a connecting hand.
Figure JPOXMLDOC01-appb-C000009
　環状構造を有する重合性化合物は、例えば、「Ａｒ－（Ｌ－Ｘ）n」で表される化合物などが挙げられる。
　Ａｒは、芳香族環構造、脂環構造またはヘテロ環構造を表す。Ｌは、単結合または連結基を表す。Ｘは、水素原子または重合性基を表し、ｎが１の場合は、Ｘは重合性基を表し、ｎが２以上の場合は、複数のＸの少なくとも一つは、重合性基を表す。
　重合性基としては、ビニル基、アリル基、メタリル基、アクリロイル基、メタクリロイル基、アリルオキシカルボニル基、メタリルオキシカルボニル基から選ばれる１種以上が好ましく、アクリロイル基、メタクリロイル基がより好ましい。 Examples of the polymerizable compound having a cyclic structure include a compound represented by “Ar— (L—X) n ”.
Ar represents an aromatic ring structure, an alicyclic structure, or a heterocyclic structure. L represents a single bond or a linking group. X represents a hydrogen atom or a polymerizable group. When n is 1, X represents a polymerizable group. When n is 2 or more, at least one of the plurality of Xs represents a polymerizable group.
As the polymerizable group, one or more selected from a vinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, an allyloxycarbonyl group, and a methallyloxycarbonyl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.
　上記式（１）で表す部分構造を有する重合性化合物としては、例えば、下記一般式（１ａ）で表される重合性化合物などが挙げられる。
Figure JPOXMLDOC01-appb-C000010
 Examples of the polymerizable compound having a partial structure represented by the formula (1) include a polymerizable compound represented by the following general formula (1a).
Figure JPOXMLDOC01-appb-C000010
　一般式（１ａ）において、Ｘ1～Ｘ3は、それぞれ独立に水素原子または重合性基を表し、Ｘ1～Ｘ3の少なくとも一つは、重合性基を表す。
　重合性基としては、ビニル基、アリル基、メタリル基、アクリロイル基、メタクリロイル基、アリルオキシカルボニル基、メタリルオキシカルボニル基から選ばれる１種以上が好ましく、アクリロイル基、メタクリロイル基がより好ましい。
　一般式（１ａ）において、Ｘ1～Ｘ3が複数存在する場合、複数存在するＸ1～Ｘ3は、それぞれ同一であってもよく、異なっていてもよい。 In formula (1a), X 1 ~ X 3 each independently represent a hydrogen atom or a polymerizable group, at least one of X 1 ~ X 3 represents a polymerizable group.
As the polymerizable group, one or more selected from a vinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, an allyloxycarbonyl group, and a methallyloxycarbonyl group are preferable, and an acryloyl group and a methacryloyl group are more preferable.
In the general formula (1a), when there are a plurality of X 1 to X 3 , the plurality of X 1 to X 3 may be the same or different.
　一般式（１ａ）において、Ｌ1は、（１＋ｎ１）価の連結基を表し、Ｌ2は、（１＋ｎ２）価の連結基を表し、Ｌ3は、（１＋ｎ３）価の連結基を表し、Ｌ1～Ｌ3の少なくとも一つは、－（（ＣＨ2）a－Ｏ）b－を含む連結基を表す。ａは２以上の整数を表し、ｂは２以上の整数を表す。
　Ｌ1～Ｌ3が表す連結基としては、例えば、２価の連結基の場合、－（（ＣＨ2）a－Ｏ）b－、－（ＣＨ2）c－、－ＣＯ－、および、－ＮＨ－から選ばれる１種または２種以上を組み合わせてなる基が挙げられる。
　ａは、２以上の整数を表し、２～１０が好ましく、２～４がより好ましく、２が更に好ましい。
　ｂは、２以上の整数を表し、２～３０が好ましく、２～２０がより好ましく、５～１５が更に好ましい。
　ｃは、１以上の整数を表し、１～３０が好ましく、１～２０がより好ましく、１～１０が更に好ましい。
　Ｌ1～Ｌ3が表す連結基が、３価以上の連結基の場合、上述した２価の連結基の例として挙げた基のうち、１個以上の水素原子を取り除いた基が挙げられる。 In the general formula (1a), L 1 represents a (1 + n1) -valent linking group, L 2 represents a (1 + n2) -valent linking group, L 3 represents a (1 + n3) -valent linking group, L At least one of 1 to L 3 represents a linking group containing — ((CH 2 ) a —O) b —. a represents an integer of 2 or more, and b represents an integer of 2 or more.
As the linking group represented by L 1 to L 3 , for example, in the case of a divalent linking group, — ((CH 2 ) a —O) b —, — (CH 2 ) c —, —CO—, and — Examples thereof include a group formed by combining one or more selected from NH-.
a represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 4, and still more preferably 2.
b represents an integer of 2 or more, preferably 2 to 30, more preferably 2 to 20, and still more preferably 5 to 15.
c represents an integer of 1 or more, preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 10.
When the linking group represented by L 1 to L 3 is a trivalent or higher linking group, among the groups listed as examples of the divalent linking group described above, a group in which one or more hydrogen atoms have been removed can be used.
　一般式（１ａ）において、ｎ１～ｎ３は、それぞれ独立に、１以上の整数を表す。１又は２が好ましい。 In the general formula (1a), n1 to n3 each independently represents an integer of 1 or more. 1 or 2 is preferred.
　一般式（１ａ）で表される重合性化合物としては、例えば、以下の化合物などが具体例として挙げられる。 Specific examples of the polymerizable compound represented by the general formula (1a) include the following compounds.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　一般式（１ａ）で表される重合性化合物の市販品としては、例えば、新中村化学社製のＵＡ－７２００などが挙げられる。 Examples of commercially available polymerizable compounds represented by the general formula (1a) include UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
　本発明において、アルキレンオキシ鎖を有する重合性化合物としては、例えば、下記一般式（Ｚ－４）または（Ｚ－５）で表される化合物の群から選択される少なくとも１種を用いることもできる。 In the present invention, as the polymerizable compound having an alkyleneoxy chain, for example, at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5) can also be used. .
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　一般式（Ｚ－４）および（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ2）yＣＨ2Ｏ）
－、または－（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、アクリロイル基、メタクリロイル基、水素原子、またはカルボキシル基を表す。
　一般式（Ｚ－４）中、アクリロイル基およびメタクリロイル基の合計は３個または４個であり、ｍは各々独立に０～１０の整数を表し、ｍの少なくとも一つは２～１０の整数を表し、各ｍの合計は２～４０の整数である。
　一般式（Ｚ－５）中、アクリロイル基およびメタクリロイル基の合計は５個または６個であり、ｎは各々独立に０～１０の整数を表し、ｎの少なくとも一つは２～１０の整数を表し、各ｎの合計は２～６０の整数である。 In general formulas (Z-4) and (Z-5), each E independently represents — ((CH 2 ) y CH 2 O).
— Or — ((CH 2 ) y CH (CH 3 ) O) —, each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, methacryloyl group, hydrogen atom Or a carboxyl group.
In general formula (Z-4), the total number of acryloyl groups and methacryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and at least one of m represents an integer of 2 to 10 And the sum of each m is an integer from 2 to 40.
In general formula (Z-5), the total number of acryloyl groups and methacryloyl groups is 5 or 6, and each n independently represents an integer of 0 to 10, and at least one of n represents an integer of 2 to 10 And the sum of each n is an integer from 2 to 60.
　一般式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　一般式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。
　また、一般式（Ｚ－４）または一般式（Ｚ－５）中の－（（ＣＨ2）yＣＨ2Ｏ）－または－（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In addition, — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — in general formula (Z-4) or general formula (Z-5) is oxygen A form in which the end on the atom side is bonded to X is preferred.
　一般式（Ｚ－４）または一般式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、一般式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態が好ましい。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.
　一般式（Ｚ－４）または一般式（Ｚ－５）で表される化合物は、従来公知の工程である、ペンタエリスリト－ルまたはジペンタエリスリト－ルにエチレンオキシドまたはプロピレンオキシドを開環付加反応により開環骨格を結合する工程と、開環骨格の末端水酸基に、例えば（メタ）アクリロイルクロライドを反応させて（メタ）アクリロイル基を導入する工程と、から合成することができる。各工程は良く知られた工程であり、当業者は容易に一般式（Ｚ－４）または一般式（Ｚ－５）で表される化合物を合成することができる。 The compound represented by the general formula (Z-4) or (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or the general formula (Z-5).
　一般式（Ｚ－４）または一般式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体および／またはジペンタエリスリトール誘導体がより好ましい。
　具体的には、下記式（ａ）～（ｆ）で表される化合物（以下、「例示化合物（ａ）～（ｆ）」ともいう。）が挙げられ、中でも、例示化合物（ａ）、（ｂ）、（ｅ）、（ｆ）が好ましい。 Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　一般式（Ｚ－４）、（Ｚ－５）で表され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鎖を４個有する４官能アクリレートであるＳＲ－４９４、日本化薬株式会社製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０などが挙げられる。 Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
　本発明の着色組成物に用いる重合性化合物は、上述したアルキレンオキシ鎖を有する重合性化合物を、重合性化合物の全量に対して、５０～１００質量％含有することが好ましく、８０～１００質量％がより好ましく、９５～１００質量％が更に好ましく、アルキレンオキシ鎖を有する重合性化合物のみで構成されていることが特に好ましい。 The polymerizable compound used in the colored composition of the present invention preferably contains 50-100% by mass of the above-mentioned polymerizable compound having an alkyleneoxy chain, based on the total amount of the polymerizable compound, and 80-100% by mass. Is more preferable, and 95 to 100% by mass is still more preferable, and it is particularly preferable that it is composed only of a polymerizable compound having an alkyleneoxy chain.
＜＜＜他の重合性化合物＞＞＞
　本発明の着色組成物は、アルキレンオキシ鎖を有する重合性化合物以外の重合性化合物（以下、「他の重合性化合物」という）を含有してもよい。他の重合性化合物としては、特に限定はなく、従来公知の重合性化合物を用いることができる。
　例えば、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類、並びにこれらの多量体が挙げられる。好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、及び不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類、並びにこれらの多量体が挙げられる。
　また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も用いることができる。
　また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更に、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も用いることができきる。
　また、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。
　これらの具体的な化合物としては、特開２００９－２８８７０５号公報の段落番号〔００９５〕～〔０１０８〕に記載されている化合物を本発明においても用いることができる。 <<< other polymerizable compounds >>>
The colored composition of the present invention may contain a polymerizable compound other than the polymerizable compound having an alkyleneoxy chain (hereinafter referred to as “other polymerizable compound”). There is no limitation in particular as another polymeric compound, A conventionally well-known polymeric compound can be used.
For example, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and multimers thereof can be mentioned. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and a multimer thereof can be used.
Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid can also be used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol can also be used.
Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be used in the present invention.
　また、他の重合性化合物としては、少なくとも１個の付加重合可能なエチレン基を有する、常圧下で１００℃以上の沸点を持つエチレン性不飽和基を持つ化合物を用いることもできる。その例としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能の（メタ）アクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、特公昭４８－４１７０８号、特公昭５０－６０３４号、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタアクリレート及びこれらの混合物を挙げることができる。
　多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和基を有する化合物を反応させ得られる多官能（メタ）アクリレートなども挙げることができる。
　また、特開２０１０－１６０４１８号、特開２０１０－１２９８２５号各公報、特許４３６４２１６号明細書等に記載される、フルオレン環を有し、エチレン性不飽和基を２官能以上有する化合物、カルド樹脂も使用することもできる。 In addition, as the other polymerizable compound, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure, which has at least one addition-polymerizable ethylene group can be used. Examples include monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate A polyfunctional alcohol such as glycerin or trimethylolethane is added with ethylene oxide or propylene oxide and then (meth) acrylated. Urethane (meth) acrylates as described in each publication, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, there are also compounds and cardo resins described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc., having a fluorene ring and having two or more functional ethylenically unsaturated groups. It can also be used.
　また、他の重合性化合物としては、常圧下で１００℃以上の沸点を有し、少なくとも１個の付加重合可能なエチレン性不飽和基を持つ化合物として、特開２００８－２９２９７０号公報の段落番号＜０２５４＞～＜０２５７＞に記載の化合物を用いることもできる。 In addition, as another polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group is disclosed in paragraph No. of JP-A-2008-292970. The compounds described in <0254> to <0257> can also be used.
　また、他の重合性化合物としては、下記一般式（ＭＯ－１）～（ＭＯ－５）で表される、重合性化合物を用いることができる。
　なお、一般式（ＭＯ－１）～（ＭＯ－５）において、Ｔがアルキレンオキシ基の場合には、炭素原子側の末端がＲに結合する。 As other polymerizable compounds, polymerizable compounds represented by the following general formulas (MO-1) to (MO-5) can be used.
In the general formulas (MO-1) to (MO-5), when T is an alkyleneoxy group, the terminal on the carbon atom side is bonded to R.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　一般式（ＭＯ－１）～（ＭＯ－５）において、ｎは０～１４であり、ｍは１～８である。一分子内に複数存在するＲ、Ｔは、それぞれ同一であっても、異なっていてもよい。
　一般式（ＭＯ－１）～（ＭＯ－５）において、複数存在するＲの少なくとも１つは、－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ2、又は、－ＯＣ（＝Ｏ）Ｃ（ＣＨ3）＝ＣＨ2で表される基を表す。
　一般式（ＭＯ－１）～（ＭＯ－５）で表される重合性化合物の具体例としては、特開２００７－２６９７７９号公報の段落番号０２４８～段落番号０２５１に記載されている化合物を本発明においても好適に用いることができる。 In the general formulas (MO-1) to (MO-5), n is 0 to 14 and m is 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH 2 or —OC (═O) C (CH 3 ) ═ A group represented by CH 2 is represented.
As specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979 are disclosed in the present invention. Can also be suitably used.
　また、他の重合性化合物としては、特開平１０－６２９８６号公報において一般式（１）及び（２）としてその具体例と共に記載の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物を用いることができる。 Further, as other polymerizable compounds, after adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, ) Acrylated compounds can be used.
　また、他の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；日本化薬株式会社製）、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；日本化薬株式会社製）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；日本化薬株式会社製）、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；日本化薬株式会社製）、エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート（市販品としてはＡ－ＤＰＨ－１２Ｅ；新中村化学株式会社製）及びこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介している構造などを用いることもできる。 Further, as other polymerizable compounds, 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) Yakuhin 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; manufactured by Nippon Kayaku Co., Ltd.), ethyleneoxy-modified dipentaerythritol hexaacrylate (as a commercial product, A -DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues can also be used.
　また、重合性化合物としては、２－（メタ）アクリロイロキシエチルカプロエートアシッドホスフェート（市販品としては日本化薬株式会社製のＰＭ－２０）、ウレタンアクリレート（市販品としては新中村化学社製のＵ－６ＬＰＡ）、ペンタエリスリトールトリ又はテトラアクリレート（市販品としては東亞合成株式会社製のＭ－３０３、Ｍ－３０５、Ｍ－３０６、Ｍ－４５０、Ｍ－４５２など）も好適に挙げられる。 As the polymerizable compound, 2- (meth) acryloyloxyethyl caproate acid phosphate (PM-20 manufactured by Nippon Kayaku Co., Ltd. as a commercial product), urethane acrylate (Shin Nakamura Chemical Co., Ltd. as a commercial product) Preferable examples include U-6LPA manufactured by U.S.A., pentaerythritol tri- or tetraacrylate (commercially available products such as M-303, M-305, M-306, M-450, and M-452 manufactured by Toagosei Co., Ltd.). .
　また、他の重合性化合物としては、カプロラクトン構造を有する重合性化合物を用いることができる。
　カプロラクトン構造を有する重合性化合物としては、その分子内にカプロラクトン構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸およびε－カプロラクトンをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートを挙げることができる。なかでも下記一般式（Ｚ－１）で表されるカプロラクトン構造を有する重合性化合物が好ましい。 Moreover, as other polymerizable compounds, polymerizable compounds having a caprolactone structure can be used.
The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, diester. Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　一般式（Ｚ－１）中、６個のＲは全てが下記一般式（Ｚ－２）で表される基であるか、または６個のＲのうち１～５個が下記一般式（Ｚ－２）で表される基であり、残りが下記一般式（Ｚ－３）で表される基である。 In the general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six R are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　一般式（Ｚ－２）中、Ｒ1は水素原子またはメチル基を示し、ｍは１または２を示し、「＊」は結合手であることを示す。 In general formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　一般式（Ｚ－３）中、Ｒ1は水素原子またはメチル基を示し、「＊」は結合手であることを示す。 In general formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
　このような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（上記式（Ｚ－１）～（Ｚ－３）においてｍ＝１、式（Ｚ－２）で表される基の数＝２、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－３０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝３、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－６０（同式、ｍ＝１、式（Ｚ－２）で表される基の数＝６、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－１２０（同式においてｍ＝２、式（Ｚ－２）で表される基の数＝６、Ｒ1が全て水素原子である化合物）等を挙げることができる。 Such a polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = in the above formulas (Z-1) to (Z-3)) 1, the number of groups represented by formula (Z-2) = 2, a compound in which all R 1 are hydrogen atoms, DPCA-30 (same formula, m = 1, represented by formula (Z-2) Number of groups = 3, compound in which R 1 is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, R 1 is all hydrogen atoms And the like, and DPCA-120 (a compound in which m = 2, the number of groups represented by formula (Z-2) = 6, and all R 1 are hydrogen atoms).
　本発明の着色組成物において、重合性化合物の含有量は、着色組成物の全固形分の２５～６５質量％が好ましく、２５～６０質量％がより好ましく、２５～５０質量％が更に好ましい。重合性化合物の含有量が上記範囲であれば、膜厚の大きい膜を形成しやすい。
　また、重合性化合物を、上述したアルキレンオキシ鎖を有する重合性化合物のみで構成し、他の重合性化合物を含まない構成にすることで、膜状に適用した着色組成物の、膜表面と膜内部における硬化性をより均一にでき、皺の発生をより効果的に抑制できる。更には、パターン形成時における残渣の発生をより効果的に抑制できる。
　本発明の着色組成物において、着色組成物に含まれる着色剤の質量Ｐと、着色組成物に含まれる重合性化合物の質量Ｍとの比率Ｐ／Ｍは、０．０５～０．３５が好ましく、０．１～０．３５がより好ましい。この態様によれば、膜状に適用した着色組成物の、膜表面と膜内部における硬化性をほぼ均一にでき、皺の発生をより効果的に抑制できる。また、可視光由来のノイズがより少ない状態で近赤外線を透過可能な膜を形成することができる。更には、パターン形成時における残渣の発生を抑制できる。 In the colored composition of the present invention, the content of the polymerizable compound is preferably 25 to 65% by mass, more preferably 25 to 60% by mass, and further preferably 25 to 50% by mass based on the total solid content of the colored composition. If content of a polymeric compound is the said range, it will be easy to form a film | membrane with a large film thickness.
In addition, by forming the polymerizable compound only with the above-described polymerizable compound having an alkyleneoxy chain and not including any other polymerizable compound, the film surface and the film of the colored composition applied in the form of a film can be obtained. The inside curability can be made more uniform, and the generation of wrinkles can be more effectively suppressed. Furthermore, the generation of residues during pattern formation can be more effectively suppressed.
In the colored composition of the present invention, the ratio P / M between the mass P of the colorant contained in the colored composition and the mass M of the polymerizable compound contained in the colored composition is preferably 0.05 to 0.35. 0.1 to 0.35 is more preferable. According to this aspect, the curability of the coloring composition applied in the form of a film can be made substantially uniform on the film surface and inside the film, and the generation of wrinkles can be more effectively suppressed. In addition, it is possible to form a film that can transmit near-infrared rays with less visible light-derived noise. Furthermore, the generation of residues during pattern formation can be suppressed.
＜＜多官能チオール化合物＞＞
　本発明の着色組成物は、重合性化合物の反応を促進させることなどを目的として、分子内に２個以上のメルカプト基を有する多官能チオール化合物を含んでいてもよい。多官能チオール化合物は、２級のアルカンチオール類であることが好ましく、特に下記一般式（Ｉ）で表される構造を有する化合物であることが好ましい。 << Polyfunctional thiol compound >>
The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (I).
一般式（Ｉ）
Figure JPOXMLDOC01-appb-C000020
 （式中、ｎは２～４の整数を表し、Ｌは２～４価の連結基を表す。） Formula (I)
Figure JPOXMLDOC01-appb-C000020
 (In the formula, n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
　上記一般式（Ｉ）において、連結基Ｌは炭素数２～１２の脂肪族基であることが好ましく、ｎが２であり、Lが炭素数２～１２のアルキレン基であることが特に好ましい。多官能チオール化合物の具体的としては、下記の構造式（ＩＩ）～（ＩＶ）で表される化合物が挙げられ、（ＩＩ）で表される化合物が特に好ましい。これらの多官能チオールは１種または複数組み合わせて使用することが可能である。 In the above general formula (I), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　本発明の着色組成物中の多官能チオール化合物の配合量については、溶剤を除いた全固形分の０．３～８．９質量％が好ましく、０．８～６．４質量％がより好ましい。
　多官能チオール化合物は、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。
　また、多官能チオールは安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。 The blending amount of the polyfunctional thiol compound in the colored composition of the present invention is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass based on the total solid content excluding the solvent. .
The polyfunctional thiol compound may contain only 1 type, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含有することが好ましい。なお、本発明において、樹脂には、上述したアルキレンオキシ鎖を有する重合性化合物を含まないこととする。
　本発明において、樹脂は、ヒドロキシル基を有していることが好ましい。ヒドロキシル基を有することにより、シリコン基板などの支持材に対する密着性を向上できる。
　本発明の着色組成物において、樹脂の含有量は、着色組組成物の全固形分の１０～８０質量％が好ましく、２０～７０質量％がより好ましく、３０～６０質量％が更に好ましい。
　本発明の着色組成物は、着色組成物に含まれる重合性化合物の質量Ｍと、着色組成物に含まれる樹脂の質量重合性化合物の質量Ｂとの比率Ｍ／Ｂは、０．４～３．０が好ましく、０．４～０．９がより好ましく、０．４～０．８が更に好ましい。この態様によれば、膜状に適用した着色組成物の、膜表面と膜内部における硬化性をほぼ均一にでき、皺の発生をより効果的に抑制できる。
　樹脂は、上述した分散樹脂や、以下に示す、アルカリ可溶性樹脂などが挙げられる。
　以下、アルカリ可溶性樹脂について説明する。 << Resin >>
The colored composition of the present invention preferably contains a resin. In the present invention, the resin does not include the above-described polymerizable compound having an alkyleneoxy chain.
In the present invention, the resin preferably has a hydroxyl group. By having a hydroxyl group, adhesion to a support material such as a silicon substrate can be improved.
In the colored composition of the present invention, the resin content is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass of the total solid content of the colored composition.
In the colored composition of the present invention, the ratio M / B between the mass M of the polymerizable compound contained in the colored composition and the mass B of the mass polymerizable compound of the resin contained in the colored composition is 0.4-3. 0.0 is preferable, 0.4 to 0.9 is more preferable, and 0.4 to 0.8 is still more preferable. According to this aspect, the curability of the coloring composition applied in the form of a film can be made substantially uniform on the film surface and inside the film, and the generation of wrinkles can be more effectively suppressed.
Examples of the resin include the dispersion resins described above and alkali-soluble resins described below.
Hereinafter, the alkali-soluble resin will be described.
＜＜＜アルカリ可溶性樹脂＞＞＞
　本発明の着色組成物は、樹脂としてアルカリ可溶性樹脂を含有することができる。アルカリ可溶性樹脂を含有することにより、現像性・パターン形成性が向上する。
　アルカリ可溶性樹脂の分子量としては、特に定めるものではないが、重量平均分子量（Ｍｗ）が５０００～１００，０００であることが好ましくい。また、数平均分子量（Ｍｎ）は、１０００～２０，０００であることが好ましい。
　アルカリ可溶性樹脂としては、線状有機高分子重合体であってもよく、分子（好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。 <<< Alkali-soluble resin >>>
The coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation are improved.
The molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably from 5000 to 100,000. The number average molecular weight (Mn) is preferably 1000 to 20,000.
The alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
　アルカリ可溶性樹脂としては、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。
　アルカリ可溶性を促進する基（以下、酸基ともいう）としては、例えば、カルボキシル基、リン酸基、スルホン酸基、フェノール性ヒドロキシル基などが挙げられるが、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、（メタ）アクリル酸が特に好ましいものとして挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。 The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
　アルカリ可溶性樹脂の製造には、例えば、公知のラジカル重合法による方法を適用することができる。ラジカル重合法でアルカリ可溶性樹脂を製造する際の温度、圧力、ラジカル開始剤の種類及びその量、溶剤の種類等々の重合条件は、当業者において容易に設定可能であり、実験的に条件を定めるようにすることもできる。 For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions are determined. It can also be done.
　アルカリ可溶性樹脂としては、側鎖にカルボン酸を有するポリマーが好ましく、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック型樹脂などのアルカリ可溶性フェノール樹脂等、並びに側鎖にカルボン酸を有する酸性セルロース誘導体、ヒドロキシル基を有するポリマーに酸無水物を付加させたもの挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他の単量体との共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他の単量体としては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレート及びアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等、ビニル化合物としては、スチレン、α-メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、Ｎ-ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等、特開平１０－３００９２２号公報に記載のＮ位置換マレイミドモノマーとして、Ｎ―フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等を挙げることができる。なお、これらの（メタ）アクリル酸と共重合可能な他の単量体は１種のみであってもよいし、２種以上であってもよい。 As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples thereof include maleic acid copolymers, alkali-soluble phenol resins such as novolak type resins, acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having hydroxyl groups added with acid anhydrides. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.
　アルカリ可溶性フェノール樹脂は、本発明の着色組成物をポジ型の組成物とする場合に好適に用いることができる。アルカリ可溶性フェノール樹脂としては、例えば、ノボラック樹脂、又はビニル重合体等が挙げられる。
　ノボラック樹脂としては、例えば、フェノール類とアルデヒド類とを酸触媒の存在下に縮合させて得られるものが挙げられる。上記フェノール類としては、例えば、フェノール、クレゾール、エチルフェノール、ブチルフェノール、キシレノール、フェニルフェノール、カテコール、レゾルシノール、ピロガロール、ナフトール、又はビスフェノールＡ等が挙げられる。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、又はベンズアルデヒド等が挙げられる。フェノール類及びアルデヒド類は、単独若しくは２種以上を組み合わせて用いることができる。
　ノボラック樹脂の具体例としては、例えば、メタクレゾール、パラクレゾール又はこれらの混合物とホルマリンとの縮合生成物が挙げられる。
　ノボラック樹脂は分別等の手段を用いて分子量分布を調節してもよい。又、ビスフェノールＣやビスフェノールＡ等のフェノール系ヒドロキシル基を有する低分子量成分をノボラック樹脂に混合してもよい。 The alkali-soluble phenol resin can be suitably used when the colored composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like. Phenols and aldehydes can be used alone or in combination of two or more.
Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
The molecular weight distribution of the novolak resin may be adjusted using a means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with a novolak resin.
　また、本発明における着色組成物の架橋効率を向上させるために、重合性基を有したアルカリ可溶性樹脂を使用してもよい。重合性基としては、アリル基、メタリル基、（メタ）アクリロイル基等が挙げられる。重合性基を有したアルカリ可溶性樹脂は、重合性基を側鎖に含有したアルカリ可溶性樹脂等が有用である。
　重合性基を含有するアルカリ可溶性樹脂は、予めイソシアネート基とヒドロキシル基を反応させ、未反応のイソシアネート基を１つ残し、かつ（メタ）アクリロイル基等の重合性基を含む化合物と、カルボキシル基を含むアクリル樹脂とを反応させて得られるウレタン変性したアルカリ可溶性樹脂；カルボキシル基を含むアクリル樹脂と、分子内にエポキシ基及び重合性二重結合を有する化合物との反応によって得られるアルカリ可溶性樹脂；酸ペンダント型エポキシアクリレート樹脂；ヒドロキシル基を含むアクリル樹脂と重合性二重結合を有する２塩基酸無水物を反応させて得られるアルカリ可溶性樹脂；ヒドロキシル基を含むアクリル樹脂と、イソシアネート及び重合性基を有する化合物を反応させて得られるアルカリ可溶性樹脂；特開２００２-２２９２０７号公報及び特開２００３-３３５８１４号公報に記載されるα位又はβ位にハロゲン原子或いはスルホネート基などの脱離基を有するエステル基を側鎖に有する樹脂を塩基性処理を行うことで得られるアルカリ可溶性樹脂などが好ましい。
　重合性基を含有するアルカリ可溶性樹脂としては、ダイヤナ－ルＮＲシリーズ（三菱レイヨン株式会社製）、Ｐｈｏｔｏｍｅｒ６１７３（ＣＯＯＨ含有　ｐｏｌｙｕｒｅｔｈａｎｅ　ａｃｒｙｌｉｃ　ｏｌｉｇｏｍｅｒ．Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．Ｌｔｄ．，製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業株式会社製）、サイクロマーＰシリーズ、プラクセル　ＣＦ２００シリーズ（いずれもダイセル化学工業株式会社製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー株式会社製）などが挙げられる。 Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. Examples of the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing a polymerizable group in a side chain is useful.
The alkali-soluble resin containing a polymerizable group is prepared by reacting an isocyanate group and a hydroxyl group in advance, leaving one unreacted isocyanate group and containing a polymerizable group such as a (meth) acryloyl group, and a carboxyl group. Urethane-modified alkali-soluble resin obtained by reacting with an acrylic resin containing; an alkali-soluble resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having an epoxy group and a polymerizable double bond in the molecule; acid Pendant-type epoxy acrylate resin; alkali-soluble resin obtained by reacting an acrylic resin containing a hydroxyl group with a dibasic acid anhydride having a polymerizable double bond; an acrylic resin containing a hydroxyl group, an isocyanate and a polymerizable group An alkali-soluble resin obtained by reacting a compound; Basic treatment of a resin having in the side chain an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2002-229207 and JP-A-2003-335814 Alkali-soluble resin obtained by 1 is preferable.
Examples of the alkali-soluble resin containing a polymerizable group include NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH containing polyurethane acrylic oligomer. 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation) and the like.
　アルカリ可溶性樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクレート／メタクリル酸共重合体なども好ましく用いることができる。 Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.
　アルカリ可溶性樹脂は、下記一般式（ＥＤ）で表される化合物、および／または、下記一般式（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。）を含む単量体成分を重合してなる樹脂（ａ）も好ましい。 The alkali-soluble resin is a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). A resin (a) obtained by polymerizing a monomer component containing is also preferred.
Figure JPOXMLDOC01-appb-C000022
 　一般式（ＥＤ）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-C000022
 In general formula (ED), 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.
一般式（ＥＤ２）
Figure JPOXMLDOC01-appb-C000023
 　一般式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。一般式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 General formula (ED2)
Figure JPOXMLDOC01-appb-C000023
 In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.
　一般式（ＥＤ）中、Ｒ1及びＲ2で表される炭化水素基は、炭素数１～２５の炭化水素基であることが好ましい。炭化水素基は、置換基を有していてもよい。
　上記炭化水素基としては、特に制限はないが、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ｔ－アミル、ステアリル、ラウリル、２－エチルヘキシル等の直鎖状又は分岐状のアルキル基；フェニル等のアリール基；シクロヘキシル、ｔ－ブチルシクロヘキシル、ジシクロペンタジエニル、トリシクロデカニル、イソボルニル、アダマンチル、２－メチル－２－アダマンチル等の脂環式基；１－メトキシエチル、１－エトキシエチル等のアルコキシで置換されたアルキル基；ベンジル等のアリール基で置換されたアルキル基；等が挙げられる。これらの中でも特に、メチル、エチル、シクロヘキシル、ベンジル等のような酸や熱で脱離しにくい１級又は２級炭素の炭化水素基が耐熱性の点で好ましい。 In the general formula (ED), the hydrocarbon group represented by R 1 and R 2 is preferably a hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group may have a substituent.
The hydrocarbon group is not particularly limited. For example, straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl, etc. An aryl group such as phenyl; an alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; And alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon hydrocarbon group which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.
　エーテルダイマーの具体例としては、例えば、ジメチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジエチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ｎ－プロピル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（イソプロピル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ｎ－ブチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（イソブチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ｔ－ブチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ｔ－アミル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ステアリル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ラウリル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（２－エチルヘキシル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（１－メトキシエチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（１－エトキシエチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジベンジル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジフェニル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジシクロヘキシル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ｔ－ブチルシクロヘキシル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（ジシクロペンタジエニル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（トリシクロデカニル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（イソボルニル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジアダマンチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジ（２－メチル－２－アダマンチル）－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート等が挙げられる。これらの中でも特に、ジメチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジエチル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジシクロヘキシル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエート、ジベンジル－２，２’－［オキシビス（メチレン）］ビス－２－プロペノエートが好ましい。これらエーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 Specific examples of ether dimers include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) Dicyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.
　単量体成分における、エーテルダイマーの含有量は、特に制限されないが、２～６０質量％が好ましく、５～５５質量％がより好ましく、５～５０質量％が更に好ましい。
　樹脂（ａ）は、エーテルダイマーと共に、その他の単量体を共重合させた共重合体であってもよい。 The content of the ether dimer in the monomer component is not particularly limited, but is preferably 2 to 60% by mass, more preferably 5 to 55% by mass, and still more preferably 5 to 50% by mass.
The resin (a) may be a copolymer obtained by copolymerizing other monomers together with the ether dimer.
　エーテルダイマーと共に共重合しうるその他の単量体としては、例えば、酸基を導入するための単量体、ラジカル重合性二重結合を導入するための単量体、エポキシ基を導入するための単量体、及び、これら以外の他の共重合可能な単量体が挙げられる。このような単量体は、１種のみを用いてもよいし、２種以上を用いてもよい。上述したその他の単量体については、例えば、特開２００４－３００２０４号公報の００１６～００２２の記載を参酌でき、本明細書にはこれらの内容が組み込まれることとする。 Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types. With respect to the other monomers described above, for example, the description in JP-A-2004-300204, 0016 to 0022 can be referred to, and these contents are incorporated in this specification.
　樹脂（ａ）の重量平均分子量（Ｍｗ）は、特に制限されないが、着色組成物の粘度、及び着色組成物により形成される膜の耐熱性の観点から、好ましくは５０００～２０００００であり、より好ましくは５０００～１０００００であり、更に好ましくは５０００～２００００である。
　また、樹脂（ａ）が酸基を有する場合には、酸価は３０～５００ｍｇＫＯＨ／ｇが好ましく、５０～４００ｍｇＫＯＨ／ｇがより好ましい。 The weight average molecular weight (Mw) of the resin (a) is not particularly limited, but is preferably 5000 to 200000, more preferably from the viewpoint of the viscosity of the colored composition and the heat resistance of the film formed from the colored composition. Is from 5,000 to 100,000, more preferably from 5,000 to 20,000.
When the resin (a) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.
　樹脂（ａ）は、エーテルダイマーを含有する単量体を重合することにより、容易に得ることができる。このとき、重合と同時にエーテルダイマーの環化反応が進行してテトラヒドロピラン環構造が形成される。
　樹脂（ａ）の合成に適用される重合方法としては、特に制限はなく、従来公知の各種重合方法を採用することができるが、特に、溶液重合法によることが好ましい。詳細には、例えば、特開２００４－３００２０４号公報に記載される樹脂（ａ）の合成方法に準じて、樹脂（ａ）を合成することができる
　以下、樹脂（ａ）の例示化合物を示すが、本発明はこれらに限定されるものではない。下記に示す例示化合物の組成比はモル％である。 The resin (a) can be easily obtained by polymerizing a monomer containing an ether dimer. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
There is no restriction | limiting in particular as a polymerization method applied to the synthesis | combination of resin (a), Although conventionally well-known various polymerization methods can be employ | adopted, It is especially preferable by a solution polymerization method. Specifically, for example, the resin (a) can be synthesized according to the synthesis method of the resin (a) described in JP-A-2004-300204. Hereinafter, exemplary compounds of the resin (a) are shown. However, the present invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　アルカリ可溶性樹脂としては、下記式（Ｘ）で示されるエチレン性不飽和単量体に由来する構造単位を含む樹脂を用いることもできる。 As the alkali-soluble resin, a resin containing a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X) can also be used.
Figure JPOXMLDOC01-appb-C000025
 （式（Ｘ）において、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。）
Figure JPOXMLDOC01-appb-C000025
 (In 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 a benzene ring which may contain a benzene ring. And represents an alkyl group of 20. n represents an integer of 1 to 15.)
　上記式（Ｘ）において、Ｒ2のアルキレン基の炭素数は、２～３が好ましい。また、Ｒ3のアルキル基の炭素数は１～１０が好ましい。Ｒ3のアルキル基はベンゼン環を含んでもよい。Ｒ3で表されるベンゼン環を含むアルキル基としては、ベンジル基、２－フェニル
（イソ）プロピル基等を挙げることができる。
　上記式（Ｘ）で示されるエチレン性不飽和単量体に由来する構造単位を含む樹脂の具体例としては、特開２０１２－２４７５９１号公報、特開２０１３－２４９３４号公報に記載されている樹脂等が挙げられる。 In the above formula (X), the alkylene group of R 2 preferably has 2 to 3 carbon atoms. The carbon number of the alkyl group of R 3 is preferably 1-10. The alkyl group of R 3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
Specific examples of the resin containing a structural unit derived from the ethylenically unsaturated monomer represented by the above formula (X) include resins described in JP2012-247591A and JP2013-24934A Etc.
　アルカリ可溶性樹脂の酸価は、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、２００ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下が更に好ましく、１２０ｍｇＫＯＨ／ｇ以下が最も好ましい。
　アルカリ可溶性樹脂の含有量は、着色組成物の全固形分に対して、１０～８０質量％が好ましく、２０～７０質量％がより好ましく、３０～６０質量％が更に好ましい。 The acid value of the alkali-soluble resin 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 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
The content of the alkali-soluble resin is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass with respect to the total solid content of the coloring composition.
＜＜光重合開始剤＞＞
　本発明の着色組成物は、光重合開始剤を含有することが好ましい。
　光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する光重合開始剤であってもよく、重合性化合物の種類に応じてカチオン重合を開始させるような光重合開始剤であってもよい。 << photopolymerization initiator >>
The coloring composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be a photopolymerization initiator that generates an active radical by causing some action with a photoexcited sensitizer, and is a photopolymerization initiator that initiates cationic polymerization according to the type of polymerizable compound. May be.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有するもの、オキサジアゾール骨格を有するもの、など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物（例えば、ベンゾフェノン、２－メチルベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノ－１－プロパノン、ベンゾイン、ベンゾインメチルエーテル、アクリドン、Ｎ－メチルアクリドン、２－ベンジル－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノンなど）、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノンなどが挙げられる。これらの中でも、オキシム化合物が好ましい。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds (eg, benzophenone, 2-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzoin, benzoin methyl ether, acridone, N-methylacridone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone), aromatic onium salts, Ketoxime ether, Mino acetophenone compounds, such as hydroxy acetophenone. Among these, oxime compounds are preferable.
　トリアジン骨格を有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報記載の化合物、独国特許３３３７０２４号明細書記載の化合物、Ｆ．Ｃ．ＳｃｈａｅｆｅｒなどによるＪ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報記載の化合物、特開平５－２８１７２８号公報記載の化合物、特開平５－３４９２０号公報記載の化合物、米国特許第４２１２９７６号明細書に記載の化合物（例えば、オキサジアゾール骨格を有する化合物）などが挙げられる。 Examples of halogenated hydrocarbon compounds having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 Examples thereof include compounds described in the specification (for example, compounds having an oxadiazole skeleton).
　また、上記以外の光重合開始剤として、アクリジン誘導体（例えば、９－フェニルアクリジン、１，７－ビス（９，９’－アクリジニル）ヘプタンなど）、Ｎ－フェニルグリシンなど、ポリハロゲン化合物（例えば、四臭化炭素、フェニルトリブロモメチルスルホン、フェニルトリクロロメチルケトンなど）、クマリン類（例えば、３－（２－ベンゾフラノイル）－７－ジエチルアミノクマリン、３－（２－ベンゾフロイル）－７－（１－ピロリジニル）クマリン、３－ベンゾイル－７－ジエチルアミノクマリン、３－（２－メトキシベンゾイル）－７－ジエチルアミノクマリン、３－（４－ジメチルアミノベンゾイル）－７－ジエチルアミノクマリン、３，３’－カルボニルビス（５，７－ジ－ｎ－プロポキシクマリン）、３，３’－カルボニルビス（７－ジエチルアミノクマリン）、３－ベンゾイル－７－メトキシクマリン、３－（２－フロイル）－７－ジエチルアミノクマリン、３－（４－ジエチルアミノシンナモイル）－７－ジエチルアミノクマリン、７－メトキシ－３－（３－ピリジルカルボニル）クマリン、３－ベンゾイル－５，７－ジプロポキシクマリン、７－ベンゾトリアゾール－２－イルクマリン、また、特開平５－１９４７５号公報、特開平７－２７１０２８号公報、特開２００２－３６３２０６号公報、特開２００２－３６３２０７号公報、特開２００２－３６３２０８号公報、特開２００２－３６３２０９号公報などに記載のクマリン化合物など）、アシルホスフィンオキサイド類（例えば、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフェニルホスフィンオキサイド、ＬｕｃｉｒｉｎＴＰＯなど）、メタロセン類（例えば、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフロロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム、η５－シクロペンタジエニル－η６－クメニル－アイアン（１＋）－ヘキサフロロホスフェート（１－）など）、特開昭５３－１３３４２８号公報、特公昭５７－１８１９号公報、同５７－６０９６号公報、及び米国特許第３６１５４５５号明細書に記載された化合物などが挙げられる。 Further, as photopolymerization initiators other than those mentioned above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc. Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1 -Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-ca Bonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP No. 2002-363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Zinc oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.
　光重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、及び、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号公報に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９，ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、及び、ＩＲＧＡＣＵＲＥ－３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるＩＲＧＡＣＵＲＥ－８１９やＤＡＲＯＣＵＲ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。 As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
　光重合開始剤として、より好ましくはオキシム化合物が挙げられる。
　着色組成物が、光重合開始剤としてオキシム化合物を含有することにより、着色組成物の塗布から露光までの時間（ＰＣＤ：Ｐｏｓｔ　Ｃｏａｔｉｎｇ　Ｄｅｌａｙ）に対するパターンの特性依存性（以下、単に、「ＰＣＤ依存性」とも言う）が良好なものとなる。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、特開２００６－３４２１６６号公報記載の化合物を用いることができる。 More preferred examples of the photopolymerization initiator include oxime compounds.
When the coloring composition contains an oxime compound as a photopolymerization initiator, the pattern property dependency on the time from application of the coloring composition to exposure (PCD: Post Coating Delay) (hereinafter simply referred to as “PCD dependency”). Is also good).
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
　光重合開始剤として好適に用いられるオキシム化合物としては、例えば、３－ベンゾイロキシイミノブタン－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－ベンゾイロキシイミノ－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。 Examples of the oxime compound suitably used as the photopolymerization initiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2 -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane- Examples include 2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
　オキシム化合物としては、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号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、特開２００６－３４２１６６号公報の各公報に記載の化合物等が挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ－０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦ社製）、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０４、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０９、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０５（常州強力電子新材料有限公司社（ＣＨＡＮＧＺＨＯＵ　ＴＲＯＮＬＹ　ＮＥＷ　ＥＬＥＣＴＲＯＮＩＣ　ＭＡＴＥＲＩＡＬＳ　ＣＯ．，ＬＴＤ）製）、アデカアークルズＮＣＩ－８３１、アデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）も好適に用いられる。 Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
Commercially available products include IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (Changzhou Power Electronics New Materials Limited) A company (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arkles NCI-831, Adeka Arkles NCI-930 (Adeka) are also preferably used.
　また、上記以外のオキシム化合物として、カルバゾールのＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報および米国特許公開２００９－２９２０３９号記載の化合物、国際公開特許２００９－１３１１８９号公報に記載のケトオキシム系化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有し、ｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報記載の化合物などを用いてもよい。
　好ましくは、例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌することができ、この内容は本願明細書に組み込まれる。
　具体的には、オキシム化合物としては、下記一般式（ＯＸ－１）で表される化合物が好ましい。なお、オキシムのＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、（Ｚ）体のオキシム化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。 Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used. .
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following general formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　一般式（ＯＸ－１）中、ＲおよびＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。
　一般式（ＯＸ－１）中、Ｒで表される一価の置換基としては、一価の非金属原子団であることが好ましい。一価の非金属原子団としては、アルキル基、アリール基、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、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等が挙げられる。これらの基は、１以上の置換基を有していてもよい。置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
　一般式（ＯＸ－１）中、Ｂで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
　一般式（ＯＸ－１）中、Ａで表される二価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、アルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。 In general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
　以下、好適に用いられるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　オキシム化合物は、３５０ｎｍ～５００ｎｍの波長領域に吸収極大波長を有するものであり、３６０ｎｍ～４８０ｎｍの波長領域に吸収波長を有するものであることが好ましく、３６５ｎｍ及び４５５ｎｍの吸光度が高いものが特に好ましい。
　オキシム化合物は、３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１,０００～３００，０００であることが好ましく、２,０００～３００，０００であることがより好ましく、５,０００～２００，０００であることが特に好ましい。
　化合物のモル吸光係数は、公知の方法を用いることができる。具体的には、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｒｙ－５　ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチルを用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound has an absorption maximum wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, it is preferable to measure at a concentration of 0.01 g / L using ethyl acetate in an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian).
　光重合開始剤の含有量は、着色組成物の全固形分に対して、０．１～２０質量％が好ましく、０．５～１０質量％がより好ましく、１～８質量％が特に好ましい。この範囲内であると、良好な感度とパターン形成性が得られる。
　光重合開始剤は、１種のみを用いてもよく、２種以上を組み合わせて使用してもよい。２種以上を組み合わせて用いる場合は、合計の含有量が上記範囲であることが好ましい。 The content of the photopolymerization initiator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass with respect to the total solid content of the coloring composition. Within this range, good sensitivity and pattern formability can be obtained.
A photoinitiator may use only 1 type and may use it in combination of 2 or more type. When using 2 or more types in combination, the total content is preferably in the above range.
＜＜紫外線吸収剤＞＞
　本発明の着色組成物は、紫外線吸収剤を含有することができる。
　紫外線吸収剤は、波長３６５ｎｍにおける１ｇ当りの吸光係数が１００超であってかつ波長４００ｎｍ以上における１ｇ当りの吸光係数が１０以下である化合物が好ましい。波長３６５ｎｍにおける１ｇ当りの吸光係数が１００超であれば、少量であっても優れた紫外線吸収効果が得られる。また、波長４００ｎｍ以上における１ｇ当りの吸光係数が１０以下であれば、可視領域のデバイス分光への影響を低減できる。なお、吸光係数は、紫外可視分光光度計（Ｖａｒｉａｎ社製、Ｃａｒｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチルを用いて０．０１ｇ／Ｌの濃度で測定される値である。 << UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber.
The ultraviolet absorber is preferably a compound having an extinction coefficient per 1 g at a wavelength of 365 nm of more than 100 and an extinction coefficient per 1 g at a wavelength of 400 nm or more. If the extinction coefficient per gram at a wavelength of 365 nm exceeds 100, an excellent ultraviolet absorption effect can be obtained even with a small amount. In addition, if the extinction coefficient per gram at a wavelength of 400 nm or more is 10 or less, the influence on device spectroscopy in the visible region can be reduced. The extinction coefficient is a value measured with an ultraviolet-visible spectrophotometer (Varian, Carry-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate.
　紫外線吸収剤としては、共役ジエン系化合物である下記一般式（Ｉ）で表される化合物が好ましい。この共役ジエン系化合物を用いると、特に低照度露光を行なった際のその後の現像性能変動が抑えられ、パターンの線幅、膜厚、分光スペクトル等のパターン形成性に関係する露光照度依存性をより効果的に抑制することができる。 As the ultraviolet absorber, a compound represented by the following general formula (I) which is a conjugated diene compound is preferable. When this conjugated diene compound is used, fluctuations in development performance after exposure, especially when low-illuminance exposure is performed, can be suppressed, and exposure illuminance dependence related to pattern formability such as pattern line width, film thickness, and spectral spectrum can be reduced. It can suppress more effectively.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　一般式（Ｉ）において、Ｒ1及びＲ2は、各々独立に、水素原子、炭素原子数１～２０のアルキル基、又は炭素原子数６～２０のアリール基を表し、Ｒ1とＲ2とは互いに同一でも異なっていてもよい。ただし、Ｒ1とＲ2が同時に水素原子を表すことはない。
　Ｒ3及びＲ4は、電子吸引基を表す。電子吸引基は、ハメットの置換基定数σp値（以下、単に「σp値」という。）が、０．２０以上１．０以下の電子吸引性基が好ましく、σp値が０．３０以上０．８以下の電子吸引性基がより好ましい。
　ハメット則は、ベンゼン誘導体の反応又は平衡に及ぼす置換基の影響を定量的に論ずるために、１９３５年にＬ．　Ｐ．　Ｈａｍｍｅｔｔにより提唱された経験則であるが、これは今日広く妥当性が認められている。ハメット則により求められた置換基定数には、σp値とσm値とがあり、これらの値は多くの一般的な成書に記載があるが、例えば、Ｊ．Ａ．　Ｄｅａｎ編「Ｌａｎｇｅ’ｓ　Ｈａｎｄｂｏｏｋ　ｏｆ　Ｃｈｅｍｉｓｔｒｙ」第１２版、１９７９年（Ｍｃ　Ｇｒａｗ－Ｈｉｌｌ）や「化学の領域増刊」、１２２号、９６～１０３頁、１９７９年（南江堂）、Ｃｈｅｍｉｃａｌ　Ｒｅｖｉｅｗｓ，　９１巻、１６５頁～１９５頁、１９９１年に詳しい。本発明では、これらの成書に記載の文献既知の値がある置換基にのみ限定されるという意味ではなく、その値が文献未知であってもハメット則に基づいて測定した場合にその範囲内に含まれる限り包含されることは勿論である。
　Ｒ3としては、シアノ基、－ＣＯＯＲ5、－ＣＯＮＨＲ5、－ＣＯＲ5、－ＳＯ2Ｒ5より選択される基が好ましい。Ｒ4としては、シアノ基、－ＣＯＯＲ6、－ＣＯＮＨＲ6、－ＣＯＲ6、－ＳＯ2Ｒ6より選択される基が好ましい。Ｒ5及びＲ6は、各々独立に、炭素原子数１～２０のアルキル基、又は炭素原子数６～２０のアリール基を表す。
　Ｒ3及びＲ4は、互いに結合して環を形成してもよい。
　Ｒ1、Ｒ2、Ｒ3、及びＲ4の少なくとも１つは、連結基を介して、ビニル基と結合したモノマーより導かれるポリマーの形になっていてもよい。また、他のモノマーとの共重合体であってもよい。 In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 May be the same as or different from each other. However, R 1 and R 2 do not represent a hydrogen atom at the same time.
R 3 and R 4 represent an electron withdrawing group. The electron-withdrawing group is preferably an electron-withdrawing group having a Hammett's substituent constant σ p value (hereinafter simply referred to as “σ p value”) of 0.20 or more and 1.0 or less, and the σ p value is 0.30. The electron withdrawing group of 0.8 or less is more preferable.
Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants obtained by Hammett's rule include a σ p value and a σ m value, and these values are described in many general books. A. Dean's “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Area of Chemistry”, 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, detailed in 1991. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.
R 3 is preferably a group selected from a cyano group, —COOR 5 , —CONHR 5 , —COR 5 , and —SO 2 R 5 . R 4 is preferably a group selected from a cyano group, —COOR 6 , —CONHR 6 , —COR 6 , and —SO 2 R 6 . R 5 and R 6 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
R 3 and R 4 may combine with each other to form a ring.
At least one of R 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. Moreover, the copolymer with another monomer may be sufficient.
　以下、一般式（Ｉ）で表される化合物の好ましい具体例〔例示化合物（１）～（１４）〕を示す。但し、本発明においては、これらに制限されるものではない。 Hereinafter, preferred specific examples of the compound represented by the general formula (I) [Exemplary compounds (1) to (14)] are shown. However, the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　一般式（Ｉ）で表される化合物は、特公昭４４－２９６２０号公報、特開５３－１２８３３３号公報、特開昭６１－１６９８３１号公報、特開昭６３－５３５４３号公報、特開昭６３－５３５４４号公報、特開昭６３－５６６５１号公報に記載の方法により合成することができる。 The compounds represented by the general formula (I) are disclosed in JP-B-44-29620, JP-A-53-128333, JP-A-61-169831, JP-A-63-53543, JP-A-63-63. -53544 and JP-A-63-56651.
　本発明の着色組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の着色組成物の全固形分に対して、０．０１～１０質量％が好ましく、０．０１～５質量％がより好ましい。紫外線吸収剤の含有量が上記範囲であれば、感度が良好で、さらには、微細なパターン形状（特に矩形）を精細に形成できる。
　紫外線吸収剤は１種のみを用いてもよく、２種以上を組み合わせて使用してもよい。２種以上を組み合わせて用いる場合は、合計の含有量が上記範囲であることが好ましい。
　本発明の着色組成物が、光重合開始剤と紫外線吸収剤とを含む場合、光重合開始剤の質量（Ｄ）と紫外線吸収剤の質量（Ｂ）との比率（Ｄ／Ｂ）は、０．２５～１．２５が好ましく、０．３～１．１がより好ましく、０．４～１．０の範囲が特に好ましい。前述した比率が上記範囲であれば、感度が良好で、さらには、微細なパターン形状（特に矩形）を精細に形成できる。 The colored composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.01 to from the total solid content of the colored composition of the present invention. 10% by mass is preferable and 0.01 to 5% by mass is more preferable. If the content of the ultraviolet absorber is in the above range, the sensitivity is good, and furthermore, a fine pattern shape (in particular, a rectangle) can be finely formed.
Only one type of ultraviolet absorber may be used, or two or more types may be used in combination. When using 2 or more types in combination, the total content is preferably in the above range.
When the coloring composition of the present invention contains a photopolymerization initiator and an ultraviolet absorber, the ratio (D / B) between the mass (D) of the photopolymerization initiator and the mass (B) of the ultraviolet absorber is 0. .25 to 1.25 is preferable, 0.3 to 1.1 is more preferable, and a range of 0.4 to 1.0 is particularly preferable. If the above-mentioned ratio is within the above range, the sensitivity is good, and furthermore, a fine pattern shape (in particular, a rectangle) can be finely formed.
＜＜有機溶剤＞＞
　本発明の着色組成物は、有機溶剤を含有することができる。有機溶剤は、各成分の溶解性や着色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が、特に紫外線吸収剤、アルカリ可溶性樹脂等の溶解性、着色組成物の塗布性、安全性を考慮して選ばれることが好ましい。 << Organic solvent >>
The coloring composition of the present invention can contain an organic solvent. The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but particularly the solubility of an ultraviolet absorber, an alkali-soluble resin, etc., the coating property of the coloring composition, It is preferable to select in consideration of safety.
　有機溶剤の例としては、例えば、以下のものが挙げられる。
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸シクロヘキシル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル（例えば、オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－オキシプロピオン酸アルキルエステル類（例えば、３－オキシプロピオン酸メチル、３－オキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、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等））、２－オキシプロピオン酸アルキルエステル類（例：２－オキシプロピオン酸メチル、２－オキシプロピオン酸エチル、２－オキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－オキシ－２－メチルプロピオン酸メチル及び２－オキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等、並びに、芳香族炭化水素類として、例えば、トルエン、キシレン等が好適に挙げられる。 Examples of the organic solvent include the following.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Alkyl acetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (For example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc. ), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate) Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2- Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2- Ethyl oxobutanoate, etc. For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons Preferred examples include toluene and xylene.
　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。
　有機溶剤を２種以上組み合わせて用いる場合、特に好ましくは、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、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メチルエーテル、及びプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液である。 An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more organic solvents are used in combination, particularly preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, A mixed solution composed of two or more selected from heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
　着色組成物に含まれる有機溶剤の量としては、着色組成物の全量に対し、１０～９０質量％が好ましく、２０～８０質量％がより好ましく、２５～７５質量％が更に好ましい。 The amount of the organic solvent contained in the colored composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass with respect to the total amount of the colored composition.
＜＜増感剤＞＞
　本発明の着色組成物は、光重合開始剤のラジカル発生効率の向上、感光波長の長波長化の目的で、増感剤を含有していてもよい。
　増感剤としては、増感剤としては、３００ｎｍ～４５０ｎｍの波長領域に吸収波長を有する増感剤が挙げられる。増感剤は、光重合開始剤に対し、電子移動機構又はエネルギー移動機構で増感させるものが好ましい。
　増感剤としては、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のような多核芳香族類、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガルのようなキサンテン類、チオキサントン類、シアニン類、メロシアニン類、フタロシアニン類、チオニン、メチレンブルー、トルイジンブルーのようなチアジン類、アクリジン類、アントラキノン類、スクアリウム類、クマリン類、フェノチアジン類、フェナジン類、スチリルベンゼン類、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ジスチリルベンゼン類、カルバゾール類、ポルフィリン、スピロ化合物、キナクリドン、インジゴ、スチリル、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、ベンゾフェノン、ミヒラーズケトンなどの芳香族ケトン化合物、Ｎ－アリールオキサゾリジノンなどのヘテロ環化合物などが挙げられる。
　また、例えば、特開２００８－３２８０３号公報の段落番号〔０１０１〕～〔０１５４〕に記載される化合物が挙げられる。
　着色組成物中における増感剤の含有量は、深部への光吸収効率と開始分解効率の観点から、固形分換算で、０．１～２０質量％であることが好ましく、０．５～１５質量％がより好ましい。
　増感剤は、１種単独で用いてもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。 << Sensitizer >>
The colored composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength.
Examples of the sensitizer include sensitizers having an absorption wavelength in the wavelength region of 300 nm to 450 nm. The sensitizer is preferably one that sensitizes the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizer include polynuclear aromatics such as phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxyanthracene, xanthene such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal. Thioxanthones, cyanines, merocyanines, phthalocyanines, thiazines such as thionine, methylene blue and toluidine blue, acridines, anthraquinones, squariums, coumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds , Diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazo Triazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N- aryl oxazolidinone and the like.
Examples thereof include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the coloring composition is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency in the deep part and initiation decomposition efficiency, and preferably 0.5 to 15%. The mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
＜＜連鎖移動剤＞＞
　本発明の着色組成物には、用いる光重合開始剤によっては、連鎖移動剤を加えることが好ましい。連鎖移動剤としては、Ｎ，Ｎ-ジアルキルアミノ安息香酸アルキルエステルやチオール系化合物があげられ、チオール系化合物としては、２-メルカプトベンゾチアゾール、２-メルカプト-１-フェニルベンズイミダゾール、３-メルカプトプロピオン酸、などを単独又は２種以上混合して使用することができる。 << Chain transfer agent >>
Depending on the photopolymerization initiator used, it is preferable to add a chain transfer agent to the colored composition of the present invention. Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds. Examples of thiol compounds include 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, and 3-mercaptopropion. An acid etc. can be used individually or in mixture of 2 or more types.
＜＜重合禁止剤＞＞
　本発明における着色組成物は、着色組成物の製造中又は保存中において、重合性化合物の不要な熱重合を阻止するために、重合禁止剤を含有させてもよい。
　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－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－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－ｔ－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。
　重合禁止剤の添加量は、着色組成物の質量に対して、０．０１～５質量％が好ましい。 << Polymerization inhibitor >>
The colored composition in the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, p-methoxyphenol is preferred.
The addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the mass of the colored composition.
＜＜基板密着剤＞＞
　本発明の着色組成物は、基板密着性を向上させる目的で、基板密着剤を含有させてもよい。
　基板密着剤としては、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤を用いることが好ましい。シラン系カップリング剤としては、例えば、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－アクリロキシプロピルトリメトキシシラン、γ－アクリロキシプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、フェニルトリメトキシシラン、等が挙げられる。中でも、基板密着剤としては、γ－メタクリロキシプロピルトリメトキシシランが好ましい。
　基板密着剤の含有量は、着色組成物を露光、現像した際に、未露光部に残渣が残らないようにする観点から、着色組成物の全固形分に対して、０．１～３０質量％が好ましく、０．５～２０質量％がより好ましく、１～１０質量％が特に好ましい。 << Substrate adhesion agent >>
The coloring composition of the present invention may contain a substrate adhesion agent for the purpose of improving the substrate adhesion.
As the substrate adhesion agent, it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Examples of silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyl. Examples include trimethoxysilane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane. Among these, γ-methacryloxypropyltrimethoxysilane is preferable as the substrate adhesive.
The content of the substrate adhesion agent is from 0.1 to 30 masses based on the total solid content of the colored composition from the viewpoint of leaving no residue in the unexposed areas when the colored composition is exposed and developed. %, More preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass.
＜＜界面活性剤＞＞
　本発明の着色組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。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、シリコーン系界面活性剤などの各種界面活性剤を使用できる。 << Surfactant >>
The colored composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
　本発明の着色組成物にフッ素系界面活性剤を含有させることで、塗布液として調製したときの液特性（特に、流動性）がより向上し、塗布厚の均一性や省液性をより改善することができる。即ち、フッ素系界面活性剤を含有する着色組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力が低下して、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、厚みムラの小さい均一厚の膜形成をより好適に行うことができる。 By including a fluorosurfactant in the colored composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved. can do. That is, when a film is formed using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is reduced. Is improved, and the coating property to the coated surface is improved. Therefore, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
　フッ素系界面活性剤は、フッ素含有率が３～４０質量％であることが好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。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-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more 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、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ３９３、同ＫＨ－４０（以上、旭硝子（株）製）等が挙げられる。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
　ノニオン系界面活性剤として具体的には、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、グリセリンエトキシレート等）、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（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１、ソルスパース２００００（日本ルーブリゾール（株）製）等が挙げられる。 Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin 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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sparse 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
　カチオン系界面活性剤として具体的には、フタロシアニン誘導体（商品名：ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等が挙げられる。 Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）社製）等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
　シリコー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）、ＫＰ３４１、ＫＦ６００１、ＫＦ６００２（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 silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone 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), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
　界面活性剤は、１種のみを用いてもよいし、２種類以上を組み合わせてもよい。
　界面活性剤の含有量は、組成物の全質量に対して、０．００１～２．０質量％が好ましく０．００５～１．０質量％がより好ましい。 Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the composition.
＜＜その他成分＞＞
　本発明における着色組成物は、必要に応じて、熱重合開始剤、熱重合成分、エポキシ化合物、ジオクチルフタレートなどの可塑剤、低分子量有機カルボン酸などの現像性向上剤、その他充填剤、酸化防止剤、凝集防止剤などの各種添加物を含有することができる。 << Other ingredients >>
In the present invention, the coloring composition comprises a thermal polymerization initiator, a thermal polymerization component, an epoxy compound, a plasticizer such as dioctyl phthalate, a developability improver such as a low molecular weight organic carboxylic acid, other fillers, and an antioxidant. Various additives such as an agent and an anti-aggregation agent can be contained.
＜着色組成物の調製＞
　本発明の着色組成物は、上述した各成分を混合することで調製することができる。
　なお、本発明の着色組成物の調製に際しては、着色組成物を構成する各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して着色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２つ以上の溶液・分散液としておいて、使用時（塗布時）にこれらを混合して組成物として調製してもよい。 <Preparation of coloring composition>
The coloring composition of this invention can be prepared by mixing each component mentioned above.
In preparing the colored composition of the present invention, the components constituting the colored composition may be blended together, or may be sequentially blended after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, a colored composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (application). May be mixed to prepare a composition.
　本発明の着色組成物の調製に際して、異物の除去や欠陥の低減などの目的で、フィルタで濾過することが好ましい。
　フィルタとしては、従来から濾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。
　フィルタの材質の例としては、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－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、超高分子量を含む）；等が挙げられる。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）が好ましい。
　フィルタの孔径は特に限定はないが、例えば０．０１～７．０μｍが好ましく、０．０１～２．５μｍがより好ましく、０．０１～２．０μｍが更に好ましい。フィルタの孔径を上記範囲とすることにより、微細な粒子をより効果的に取り除くことができ、着色組成物の濁度をより低減することができる。ここで、フィルタの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。 In preparing the colored composition of the present invention, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects.
Any filter can be used without any particular limitation as long as it is a filter that has been used for filtration.
Examples of filter materials include: fluorine resins such as polytetrafluoroethylene (PTFE); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is not particularly limited, but is preferably 0.01 to 7.0 μm, more preferably 0.01 to 2.5 μm, and still more preferably 0.01 to 2.0 μm. By setting the pore size of the filter in the above range, fine particles can be more effectively removed, and the turbidity of the coloring composition can be further reduced. Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
　フィルタ濾過では、２種以上のフィルタを組み合わせて用いてもよい。
　例えば、まず第１のフィルタを用いて濾過を行い、次に、第１のフィルタとは孔径が異なる第２のフィルタを用いて濾過を行うことができる。
　その際、第１のフィルタでのフィルタリング及び第２のフィルタでのフィルタリングは、それぞれ、１回のみでもよいし、２回以上行ってもよい。
　第２のフィルタは、上述した第１のフィルタと同様の材料等で形成されたものを使用することができる。 In filter filtration, two or more types of filters may be used in combination.
For example, filtration can be performed first using a first filter, and then using a second filter having a hole diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.
＜着色組成物の特性＞
　本発明の着色組成物は、２５℃における粘度が１～２００ｍＰａ・ｓが好ましく、５０～２００ｍＰａ・ｓがより好ましく、１００～１５０ｍＰａ・ｓが特に好ましい。
　また、膜厚が、０．１～２μｍの膜（カラーフィルタ）を形成する場合は、着色組成物は、１～５０ｍＰａ・ｓが好ましく、１～２０ｍＰａ・ｓがより好ましく、１～１５ｍＰａ・ｓが特に好ましい。
　また、膜厚が、２～２０μｍの膜（カラーフィルタ）を形成する場合は、着色組成物は、５０～２００ｍＰａ・ｓが好ましく、５０～１５０ｍＰａ・ｓがより好ましく、１００～１５０ｍＰａ・ｓが特に好ましい。
　粘度は、例えば、東機産業製　粘度計　ＲＥ８５Ｌ（ローター：１°３４’×Ｒ２４測定範囲０．６～１２００ｍＰａ・ｓ）を使用し、２５℃に温度調整を施した状態で測定することができる。
　本発明の着色組成物は、乾燥後の膜厚が１２．０μｍの膜を製膜した際に、膜の厚み方向における光の透過率であって、波長４００～７８０ｎｍの範囲における透過率の最大値が１５％以下であり、波長８５０の透過率が８０％以上であることが好ましい。波長４００～７８０ｎｍの範囲における透過率の最大値は、１５％以下が好ましく、１０％以下がより好ましく、５％以下が特に好ましい。波長８５０ｎｍの透過率は、８０％以上が好ましく、８５％以上がより好ましく、９０％以上が特に好ましい。また、波長８５０～１３００ｎｍの範囲における透過率の最小値は、８０％以上が好ましく、８５％以上がより好ましく、９０％以上が特に好ましい。 <Characteristics of colored composition>
The colored composition of the present invention has a viscosity at 25 ° C. of preferably 1 to 200 mPa · s, more preferably 50 to 200 mPa · s, and particularly preferably 100 to 150 mPa · s.
When a film (color filter) having a film thickness of 0.1 to 2 μm is formed, the colored composition is preferably 1 to 50 mPa · s, more preferably 1 to 20 mPa · s, and more preferably 1 to 15 mPa · s. Is particularly preferred.
When a film (color filter) having a thickness of 2 to 20 μm is formed, the coloring composition is preferably 50 to 200 mPa · s, more preferably 50 to 150 mPa · s, and particularly preferably 100 to 150 mPa · s. preferable.
The viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
The colored composition of the present invention has a light transmittance in the thickness direction of a film when a film having a thickness of 12.0 μm after drying is formed, and has a maximum transmittance in a wavelength range of 400 to 780 nm. The value is preferably 15% or less, and the transmittance at a wavelength 850 is preferably 80% or more. The maximum value of transmittance in the wavelength range of 400 to 780 nm is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less. The transmittance at a wavelength of 850 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Further, the minimum transmittance in the wavelength range of 850 to 1300 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.
＜膜＞
　次に、本発明における膜について説明する。
　本発明の膜は、上述した本発明の着色組成物を硬化してなるものである。かかる膜はカラーフィルタに好ましく用いられる。
　本発明の膜は、膜の厚み方向における光の透過率の、波長４００～７８０ｎｍの範囲における最大値が１５％以下であり、波長８５０～１３００ｎｍの範囲における最小値が８０％以上であることが好ましい。このような分光特性を有することにより、可視光由来のノイズが少ない状態で近赤外線を透過可能な膜とすることができる。
　本発明の膜の分光特性は、紫外可視近赤外分光光度計（日立ハイテクノロジーズ社製　Ｕ－４１００）の分光光度計（ｒｅｆ．ガラス基板）を用いて、波長３００～１３００ｎｍの範囲において透過率を測定した値である。
　本発明の膜の膜厚は、特に限定はないが、０．１～２０μｍが好ましく、０．５～１５μｍがより好ましく、３～１５μｍが特に好ましい。上記分光特性を有する膜は、膜厚が大きくなるほど、膜表面に皺が発生し易い傾向にあったが、本発明によれば、膜厚が大きくても皺の発生を抑制できるので、膜厚が大きい場合において、本発明の効果が顕著に得られる。 <Membrane>
Next, the film | membrane in this invention is demonstrated.
The film of the present invention is formed by curing the above-described colored composition of the present invention. Such a film is preferably used for a color filter.
In the film of the present invention, the maximum value of light transmittance in the film thickness direction is 15% or less in the wavelength range of 400 to 780 nm, and the minimum value in the wavelength range of 850 to 1300 nm is 80% or more. preferable. By having such spectral characteristics, it is possible to obtain a film that can transmit near-infrared rays with less visible light-derived noise.
Spectral characteristics of the film of the present invention are as follows: a transmittance in a wavelength range of 300 to 1300 nm using a spectrophotometer (ref. Glass substrate) of an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). Is a measured value.
The thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and particularly preferably 3 to 15 μm. The film having the above spectral characteristics tended to generate wrinkles on the film surface as the film thickness increased. However, according to the present invention, the generation of wrinkles can be suppressed even when the film thickness is large. When the value is large, the effect of the present invention is remarkably obtained.
＜パターン形成方法、カラーフィルタおよびカラーフィルタの製造方法＞
　次に、本発明におけるパターン形成方法およびカラーフィルタについて、その製造方法を通じて詳述する。また、本発明のパターン形成方法を用いたカラーフィルタの製造方法についても説明する。
　本発明のパターン形成方法は、着色組成物を支持体上に適用して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含む。このようなパターン形成方法は、カラーフィルタの着色層の製造に用いられる。すなわち、本発明では、本発明のパターン形成方法を含むカラーフィルタの製造方法についても開示する。
　以下、本発明のパターン形成方法における各工程については、固体撮像素子用カラーフィルタの製造方法を通じて詳細に説明するが、本発明はこの方法に限定されるものではない。以下、固体撮像素子用カラーフィルタを単に「カラーフィルタ」ということがある。 <Pattern Forming Method, Color Filter, and Color Filter Manufacturing Method>
Next, the pattern forming method and the color filter in the present invention will be described in detail through the manufacturing method. A method for producing a color filter using the pattern forming method of the present invention will also be described.
The pattern forming method of the present invention includes a step of applying a colored composition on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and developing and removing an unexposed portion. Forming a colored pattern. Such a pattern forming method is used for manufacturing a colored layer of a color filter. That is, the present invention also discloses a method for manufacturing a color filter including the pattern forming method of the present invention.
Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.
＜＜着色組成物層を形成する工程＞＞
　着色組成物層を形成する工程では、支持体上に、本発明の着色組成物を適用して着色組成物層を形成する。 << Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed by applying the colored composition of the present invention on the support.
　支持体としては、例えば、基板（例えば、シリコン基板）上に、ＣＣＤ、ＣＭＯＳ等の撮像素子（受光素子）が設けられた固体撮像素子用基板、シリコン基板、無アルカリガラス基板、ソーダガラス基板、パイレックス（登録商標）ガラス基板、石英ガラス基板、及びこれらに透明導電膜を付着させたもの等が挙げられる。これらの基板は、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、これらの支持体上には、必要により、上部の層との密着改良、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を設けてもよい。 As the support, for example, a substrate for a solid-state imaging device in which an imaging device (light receiving device) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate), a silicon substrate, a non-alkali glass substrate, a soda glass substrate, Examples include a Pyrex (registered trademark) glass substrate, a quartz glass substrate, and those obtained by attaching a transparent conductive film thereto. In some cases, a black matrix for isolating each pixel is formed on these substrates.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.
　支持体上への本発明の着色組成物の適用方法としては、スリット塗布、インクジェット法、回転塗布（スピンコート）、流延塗布、ロール塗布、スクリーン印刷法等の各種の塗布方法を適用することができる。 As a method for applying the coloring composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, spin coating, roll coating, and screen printing are applied. Can do.
　支持体上に塗布された着色組成物層の乾燥（プリベーク）は、ホットプレート、オーブン等で５０～１４０℃の温度で１０～３００秒で行うことができる。 Drying (pre-baking) of the colored composition layer coated on the support can be performed at a temperature of 50 to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.
　着色組成物層の乾燥後（プリベーク後）の膜厚としては、０．５～３０μｍが好ましく、０．６０～２５μｍがより好ましく、０．７０～２０μｍが更に好ましく、０．８０μｍ～１５μｍが特に好ましい。 The thickness of the colored composition layer after drying (after pre-baking) is preferably 0.5 to 30 μm, more preferably 0.60 to 25 μm, still more preferably 0.70 to 20 μm, and particularly preferably 0.80 μm to 15 μm. preferable.
＜＜露光する工程＞＞
　露光工程では、着色組成物層を、例えば、ステッパー等の露光装置を用い、所定のマスクパターンを有するマスクを介してパターン露光する。これにより、硬化膜が得られる。
　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線等の紫外線が好ましく、ｉ線がより好ましく用いられる。照射量（露光量）は３０～１５００ｍＪ／ｃｍ2が好ましく、５０～１０００ｍＪ／ｃｍ2がより好ましく、８０～５００ｍＪ／ｃｍ2が特に好ましい。 << Exposure Step >>
In the exposure step, the colored composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thereby, a cured film is obtained.
Radiation (light) that can be used for exposure is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferably used. Irradiation dose (exposure dose) is preferably 30 ~ 1500mJ / cm 2, more preferably 50 ~ 1000mJ / cm 2, particularly preferably 80 ~ 500mJ / cm 2.
＜＜現像工程＞＞
　露光工程に次いで、現像工程を行うことにより、露光後の未硬化部を現像液に溶出させ、光硬化した部分を残存させる。この現像工程により、着色パターンを形成することができる。
　現像方式は、デイップ方式、シャワー方式、スプレー方式、パドル方式などいずれでもよく、これらにスウィング方式、スピン方式、超音波方式などを組み合わせてもよい。
　現像液に触れる前に、被現像面を予め水等で湿しておくことで、現像むらを防ぐこともできる。 << Development process >>
Following the exposure step, a development step is performed to elute the uncured portion after exposure into the developer and leave the photocured portion. By this development step, a colored pattern can be formed.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined with these.
Unevenness of development can be prevented by pre-wetting the surface to be developed with water or the like before touching the developer.
　現像液としては、下地の回路などにダメージを起さない、有機アルカリ現像液が望ましい。現像温度は、２０～３０℃が好ましい。現像時間は２０～９０秒が好ましい。
　現像液は、アルカリ剤を含むことが好ましい。アルカリ剤としては、例えば、アンモニア水、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、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、テトラブ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、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、水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸水素カリウム等の無機化合物等が挙げられる。
　現像液は、上述したアルカリ剤を、０．００１～１０質量％、好ましくは０．０１～１質量％となるように、純水で希釈したアルカリ性水溶液が好ましく使用される。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後、純水で洗浄（リンス）して余剰の現像液を洗浄除去し、乾燥を施すことが好ましい。 As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is preferably 20 to 30 ° C. The development time is preferably 20 to 90 seconds.
The developer preferably contains an alkaline agent. Examples of the alkaline agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8. -Organic alkaline compounds such as -diazabicyclo- [5,4,0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
As the developer, an alkaline aqueous solution obtained by diluting the above-mentioned alkaline agent with pure water so as to be 0.001 to 10% by mass, preferably 0.01 to 1% by mass is preferably used. When a developer composed of such an alkaline aqueous solution is used, it is generally preferable that after development, the excess developer is washed and removed by rinsing with pure water, followed by drying.
　本発明においては、現像工程後に、乾燥を施した後、加熱処理（ポストベーク）や後露光により硬化する硬化工程を行ってもよい。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、通常１００℃～２７０℃の熱硬化処理を行う。
　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。
　光を用いる場合には、ｇ線、ｈ線、ｉ線、ＫｒＦやＡｒＦなどのエキシマレーザ、電子線、Ｘ線等により行うことができるが、既存の高圧水銀灯で２０～５０℃程度の低温で行うことが好ましい。照射時間としては、１０～１８０秒が好ましく、３０～６０秒がより好ましい。後露光と後加熱との併用の場合、後露光を先に実施することが好ましい。 In the present invention, after the development step, after drying, a curing step of curing by heat treatment (post-baking) or post-exposure may be performed. Post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 270 ° C. is performed.
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. .
In the case of using light, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but with an existing high-pressure mercury lamp at a low temperature of about 20 to 50 ° C. Preferably it is done. The irradiation time is preferably 10 to 180 seconds, more preferably 30 to 60 seconds. In the case of combined use of post-exposure and post-heating, post-exposure is preferably performed first.
　以上説明した、各工程を行うことにより、カラーフィルタが作製される。
　なお、本発明の特定の分光特性を示す着色画素だけでカラーフィルタを構成してもよいし、上記した分光特性を示す着色画素と、赤、緑、青、マゼンタ、黄、シアン、黒、無色等の着色画素とを有するカラーフィルタを構成してもよい。他の色の画素と共にカラーフィルタを構成する場合は、本発明の特定の分光特性を示す着色画素を先に設けても、後から設けてもよい。 A color filter is manufactured by performing each process demonstrated above.
Note that the color filter may be configured with only the colored pixels exhibiting the specific spectral characteristics of the present invention, or the colored pixels exhibiting the spectral characteristics described above, and red, green, blue, magenta, yellow, cyan, black, and colorless. You may comprise the color filter which has coloring pixels, such as. When a color filter is configured with pixels of other colors, the colored pixels exhibiting the specific spectral characteristics of the present invention may be provided first or later.
　本発明における着色組成物は、例えば、塗布装置吐出部のノズル、塗布装置の配管部、塗布装置内等に付着した場合でも、公知の洗浄液を用いて容易に洗浄除去することができる。また、着色組成物に対する洗浄液の浸透性を向上させるために、洗浄液には、着色組成物が含有しうる界面活性剤として上述した界面活性剤を添加してもよい。 The colored composition in the present invention can be easily washed and removed using a known cleaning liquid even when it adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus. Moreover, in order to improve the permeability of the cleaning liquid with respect to the coloring composition, the surfactant described above may be added to the cleaning liquid as a surfactant that the coloring composition may contain.
　本発明のカラーフィルタは、ＣＣＤイメージセンサ、ＣＭＯＳイメージセンサ、有機ＣＭＯＳイメージセンサ、ＣＩＧＳイメージセンサ等の固体撮像素子に好適に搭載されることができる。特に１００万画素を超えるような高解像度の固体撮像素子に搭載されることが好適である。本発明のカラーフィルタは、例えば、ＣＣＤイメージセンサを構成する各画素の受光部と、集光するためのマイクロレンズとの間に配置されることができる。 The color filter of the present invention can be suitably mounted on a solid-state imaging device such as a CCD image sensor, a CMOS image sensor, an organic CMOS image sensor, or a CIGS image sensor. In particular, it is suitable to be mounted on a high-resolution solid-state imaging device exceeding 1 million pixels. The color filter of the present invention can be disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and a microlens for collecting light.
＜固体撮像素子＞
　本発明の固体撮像素子は、前述した本発明のカラーフィルタを備える。本発明の固体撮像素子の構成としては、本発明におけるカラーフィルタが備えられた構成であり、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 includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
　支持体上に、固体撮像素子（ＣＣＤイメージセンサ、ＣＭＯＳ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タングステン等からなる遮光膜を有し、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、本発明の固体撮像素子用カラーフィルタを有する構成である。
　さらに、デバイス保護層上であってカラーフィルタの下（支持体に近い側）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。 The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). A light-shielding film made of tungsten or the like having an opening only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. In addition, the solid-state image sensor color filter of the present invention is included.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protection layer and under the color filter (on the side close to the support), a structure having the light condensing means on the color filter, etc. It may be.
＜赤外線センサ＞
　本発明の赤外線センサは、本発明のカラーフィルタを備える。本発明の赤外線センサの構成としては、本発明のカラーフィルタが備えられた構成であり、赤外線センサ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。 <Infrared sensor>
The infrared sensor of the present invention includes the color filter of the present invention. The configuration of the infrared sensor of the present invention is a configuration provided with the color filter of the present invention and is not particularly limited as long as it is a configuration that functions as an infrared sensor. For example, the following configurations can be given.
　基板上に、固体撮像素子（ＣＣＤセンサ、ＣＭＯＳセンサ、有機ＣＭＯＳ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及びポリシリコン等からなる転送電極を有し、フォトダイオード及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タングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面及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、本発明のカラーフィルタを有する構成である。
　更に、デバイス保護層上であって本発明の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、本発明の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。 On the substrate, there are a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.), a transfer electrode made of polysilicon, etc., and a photodiode on the photodiode and the transfer electrode A light-shielding film made of tungsten or the like that is open only in the light-receiving part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. In addition, the color filter of the present invention is included.
Furthermore, it has a condensing means (for example, a microlens etc., the same shall apply hereinafter) on the device protective layer and below the color filter of the present invention (on the side close to the substrate), or condensing on the color filter of the present invention. The structure etc. which have a means may be sufficient.
　なお、有機ＣＭＯＳセンサは、光電変換層として薄膜のパンクロ感光性有機光電変換膜とＣＭＯＳ信号読み出し基板を含んで構成され、光を捕捉しそれを電気信号に変換する役割を有機材料が担い、電気信号を外部に取り出す役割を無機材料が担う２層構成のハイブリッド構造であり、原理的には入射光に対して開口率を１００％にすることができる。有機光電変換膜は構造フリーの連続膜でＣＭＯＳ信号読みだし基板上に敷設できるので、高価な微細加工プロセスを必要とせず、画素微細化に適している。 The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and the organic material plays a role of capturing light and converting it into an electric signal. This is a two-layer hybrid structure in which an inorganic material plays a role of taking out a signal to the outside. In principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film that can be laid on a CMOS signal reading substrate, and therefore does not require an expensive fine processing process and is suitable for pixel miniaturization.
　以下、本発明の赤外線センサの一実施形態について、図１を用いて説明する。
　図１に示す赤外線センサ１００において、図番１１０は、固体撮像素子である。
　固体撮像素子１１０上に設けられている撮像領域は、近赤外線吸収フィルタ１１１とカラ－フィルタ１１２を有する。
　近赤外線吸収フィルタ１１１は、可視光領域の光（例えば、波長３００～７００ｎｍの光）を透過し、赤外領域の光（例えば、波長８００～１３００ｎｍの光、好ましくは波長９００～１３００ｎｍの光、更に好ましくは波長１０００～１３００ｎｍの光）を遮蔽するもので構成されている。
　カラーフィルタ１１２は、可視光領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタなどが用いられる。
　近赤外線透過フィルタ１１３と固体撮像素子１１０との間には近赤外線吸収フィルタ１１１が形成されていない領域１１４が設けられている。領域１１４には、赤外線透過フィルタ１１３を透過した波長の光が透過可能な樹脂層（例えば、透明樹脂層など）が配置されている。
　近赤外線透過フィルタ１１３は、可視光遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタであって、上述した分光を有する本発明のカラーフィルタで構成されている。近赤外線透過フィルタ１１３は、例えば、波長４００～７８０ｎｍの光を遮光し、波長８５０～１３００ｎｍの光を透過させることが好ましい。
　カラ－フィルタ１１２および近赤外線透過フィルタ１１３の入射光ｈν側には、マイクロレンズ１１５が配置されている。マイクロレンズ１１５を覆うように平坦化層１１６が形成されている。
　図１に示す実施形態では、領域１１４に樹脂層が配置されているが、領域１１４に赤外線透過フィルタ１１３を形成してもよい。すなわち、固体撮像素子１１０上に、赤外線透過フィルタ１１３を形成してもよい。
　また、図１に示す実施形態では、カラ－フィルタ１１２の膜厚と、赤外線透過フィルタ１１３の膜厚が同一であるが、両者の膜厚は異なっていてもよい。
　また、図１に示す実施形態では、カラ－フィルタ１１２が、近赤外線吸収フィルタ１１１よりも入射光ｈν側に設けられているが、近赤外線吸収フィルタ１１１と、カラ－フィルタ１１２との順序を入れ替えて、近赤外線吸収フィルタ１１１を、カラ－フィルタ１１２よりも入射光ｈν側に設けてもよい。
　また、図１に示す実施形態では、近赤外線吸収フィルタ１１１とカラ－フィルタ１１２は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていても良い。
　この赤外線センサによれば、画像情報を同時に取り込むことができるため、動きを検知する対象を認識したモーションセンシングなどが可能である。更には、距離情報を取得できるため、３Ｄ情報を含んだ画像の撮影等も可能である。 Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to FIG.
In the infrared sensor 100 shown in FIG. 1, reference numeral 110 is a solid-state image sensor.
The imaging region provided on the solid-state imaging device 110 has a near infrared absorption filter 111 and a color filter 112.
The near-infrared absorption filter 111 transmits light in the visible light region (for example, light having a wavelength of 300 to 700 nm) and light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1300 nm, More preferably, it is configured to shield light having a wavelength of 1000 to 1300 nm.
The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used.
A region 114 where the near infrared absorption filter 111 is not formed is provided between the near infrared transmission filter 113 and the solid-state imaging device 110. In the region 114, a resin layer (for example, a transparent resin layer) that can transmit light having a wavelength that has passed through the infrared transmission filter 113 is disposed.
The near-infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays having a specific wavelength, and is configured by the color filter of the present invention having the above-described spectrum. For example, the near infrared transmission filter 113 preferably blocks light having a wavelength of 400 to 780 nm and transmits light having a wavelength of 850 to 1300 nm.
On the incident light hv side of the color filter 112 and the near-infrared transmission filter 113, a microlens 115 is disposed. A planarization layer 116 is formed so as to cover the microlens 115.
In the embodiment shown in FIG. 1, the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state image sensor 110.
In the embodiment shown in FIG. 1, the thickness of the color filter 112 and the thickness of the infrared transmission filter 113 are the same, but the thickness of both may be different.
In the embodiment shown in FIG. 1, the color filter 112 is provided closer to the incident light hν than the near-infrared absorption filter 111. However, the order of the near-infrared absorption filter 111 and the color filter 112 is changed. Thus, the near-infrared absorption filter 111 may be provided on the incident light hν side with respect to the color filter 112.
In the embodiment shown in FIG. 1, the near-infrared absorption filter 111 and the color filter 112 are stacked adjacent to each other. However, both filters are not necessarily adjacent to each other, and another layer is provided between them. May be.
According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes a target whose motion is to be detected is possible. Furthermore, since distance information can be acquired, an image including 3D information can be taken.
　次に、本発明の赤外線センサを適用した例として撮像装置について説明する。撮像装置としては、カメラモジュールなどが挙げられる。
　図２は、撮像装置の機能ブロック図である。撮像装置は、レンズ光学系１と、固体撮像素子１０と、信号処理部２０と、信号切替部３０と、制御部４０と、信号蓄積部５０と、発光制御部６０と、赤外光を発光する発光素子の赤外ＬＥＤ７０と、画像出力部８０および８１とを備える。なお、固体撮像素子１０としては、上述した赤外線センサ１００を用いることができる。また、固体撮像素子１０とレンズ光学系１以外の構成は、そのすべてが、または、その一部が、同一の半導体基板に形成することもできる。撮像装置の各構成については、特開２０１１－２３３９８３号公報の段落００３２～００３６を参酌することができ、この内容は本願明細書に組み込まれる。 Next, an imaging apparatus will be described as an example to which the infrared sensor of the present invention is applied. Examples of the imaging device include a camera module.
FIG. 2 is a functional block diagram of the imaging apparatus. The imaging device emits infrared light, the lens optical system 1, the solid-state imaging device 10, the signal processing unit 20, the signal switching unit 30, the control unit 40, the signal storage unit 50, the light emission control unit 60, and the like. Infrared LED 70 of the light emitting element and image output units 80 and 81 are provided. Note that the infrared sensor 100 described above can be used as the solid-state imaging device 10. In addition, the configuration other than the solid-state imaging device 10 and the lens optical system 1 may be formed entirely or partially on the same semiconductor substrate. Regarding each configuration of the imaging apparatus, paragraphs 0032 to 0036 of JP 2011-233983 A can be referred to, and the contents thereof are incorporated in the present specification.
　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。なお、特に断りのない限り、「部」、「％」は、質量基準である。
〔顔料分散液Ｂ－１の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－１を調製した。
・赤色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４）及び黄色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９）からなる混合顔料
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１４．８部
・分散樹脂１（ＢＹＫ社製　ＢＹＫ－１１１）　　　　　　　　　　　６．８部
・有機溶剤：プロピレングリコールメチルエーテルアセテート　　　７８．４部 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. Unless otherwise specified, “part” and “%” are based on mass.
[Preparation of pigment dispersion B-1]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-1 was prepared.
-14.8 parts of mixed pigment composed of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139)-Dispersing resin 1 (BYK-111 manufactured by BYK) 6.8 parts-Organic Solvent: 78.4 parts propylene glycol methyl ether acetate
〔顔料分散液Ｂ－２の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－２を調製した。
・青色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６）及び紫色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３）からなる混合顔料
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１２．８部
・分散樹脂１（ＢＹＫ社製　ＢＹＫ－１１１）　　　　　　　　　　　２．０部
・アルカリ可溶性樹脂１　　　　　　　　　　　　　　　　　　　　　３．２部
・有機溶剤：シクロヘキサノン　　　　　　　　　　　　　　　　　３１．０部
・有機溶剤：プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　５１．０部 [Preparation of pigment dispersion B-2]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-2 was prepared.
-12.8 parts of mixed pigment consisting of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23)-Dispersing resin 1 (BYK-111 BYK-111) 2.0 parts・ Alkali-soluble resin 1 3.2 parts ・ Organic solvent: Cyclohexanone 31.0 parts ・ Organic solvent: Propylene glycol methyl ether acetate (PGMEA)
51.0 parts
〔顔料分散液Ｂ－３の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－３を調製した。
・赤色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４）　　　　　１３．５部
・分散樹脂２　　　　　　　　　　　　　　　　　　　　　　　　　　２．０部
・アルカリ可溶性樹脂２　　　　　　　　　　　　　　　　　　　　　２．０部
・有機溶剤：プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　８２．５部 [Preparation of pigment dispersion B-3]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-3 was prepared.
Red pigment (CI Pigment Red 254) 13.5 parts Dispersion resin 2 2.0 parts Alkali-soluble resin 2 2.0 parts Organic solvent: Propylene glycol methyl ether acetate (PGMEA)
82.5 parts
〔顔料分散液Ｂ－４の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－４を調製した。
・赤色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６）　　　１３．５部
・分散樹脂３　　　　　　　　　　　　　　　　　　　　　　　　　　４．０部
・有機溶剤：プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　８２．５部 [Preparation of pigment dispersion B-4]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-4 was prepared.
-Red pigment (CI Pigment Blue 15: 6) 13.5 parts-Dispersing resin 3 4.0 parts-Organic solvent: Propylene glycol methyl ether acetate (PGMEA)
82.5 parts
〔顔料分散液Ｂ－５の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－５を調製した。
・黄色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９　　　１４．８部
・分散樹脂１：ＢＹＫ社製　ＢＹＫ－１１１　　　　　　　　　　　　３．０部
・アルカリ可溶性樹脂２　　　　　　　　　　　　　　　　　　　　　２．２部
・有機溶剤：プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　８０．０部 [Preparation of pigment dispersion B-5]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-5 was prepared.
Yellow pigment (CI Pigment Yellow 139 14.8 parts Dispersion resin 1: BYK manufactured BYK-111 3.0 parts Alkali-soluble resin 2 2.2 parts Organic solvent: Propylene glycol methyl ether acetate (PGMEA )
80.0 parts
〔顔料分散液Ｂ－６の調製〕
　下記組成の混合液を、０．３ｍｍ径のジルコニアビーズを使用して、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））で、３時間、混合、分散して、顔料分散液Ｂ－６を調製した。
・紫色顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３）　　　１４．８部
・分散樹脂１：ＢＹＫ社製　ＢＹＫ－１１１　　　　　　　　　　　　３．０部
・アルカリ可溶性樹脂１　　　　　　　　　　　　　　　　　　　　　２．２部
・有機溶剤：プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　８０．０部
［樹脂］
・分散樹脂１：　商品名；ＢＹＫ－１１１（ＢＹＫ社製）
・分散樹脂２：下記構造（Ｍｗ：７９５０）
Figure JPOXMLDOC01-appb-C000033
 ・分散樹脂３：下記構造（Ｍｗ：３００００）
Figure JPOXMLDOC01-appb-C000034
 ・アルカリ可溶性樹脂１：下記構造（繰り返し単位における比はモル比である）
Figure JPOXMLDOC01-appb-C000035
 ・アルカリ可溶性樹脂２：下記構造（繰り返し単位における比はモル比である）
Figure JPOXMLDOC01-appb-C000036
 [Preparation of pigment dispersion B-6]
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion B-6 was prepared.
Purple pigment (CI Pigment Violet 23) 14.8 parts Dispersion resin 1: BYK-made BYK-111 3.0 parts Alkali-soluble resin 1 2.2 parts Organic solvent: Propylene glycol methyl ether acetate ( PGMEA)
80.0 parts [resin]
-Dispersing resin 1: trade name; BYK-111 (manufactured by BYK)
Dispersing resin 2: the following structure (Mw: 7950)
Figure JPOXMLDOC01-appb-C000033
 -Dispersing resin 3: the following structure (Mw: 30000)
Figure JPOXMLDOC01-appb-C000034
 -Alkali-soluble resin 1: the following structure (ratio in repeating units is molar ratio)
Figure JPOXMLDOC01-appb-C000035
 Alkali-soluble resin 2: the following structure (ratio in repeating units is molar ratio)
Figure JPOXMLDOC01-appb-C000036
　（実施例１）
〔着色組成物の調製〕
　下記の成分を混合して、実施例１の着色組成物を調製した。
・顔料分散液Ｂ－１（各顔料の質量比は下記表１を参照）　　　　　１１．２部
・顔料分散液Ｂ－２（各顔料の質量比は下記表１を参照）　　　　　　９．１部
・下記アルカリ可溶性樹脂１の４０質量％ＰＧＭＥＡ溶液　　　　　５４．２部
・下記重合性化合物１　　　　　　　　　　　　　　　　　　　　　１３．６部
・下記光重合開始剤１：　　　　　　　　　　　　　　　　　　　　　２．０部
・界面活性剤１：ＤＩＣ株式会社製Ｍｅｇａｆａｃ
　Ｆ－７８１Ｆの１０質量％ＰＧＭＥＡ溶液　　　　　　　　　　　０．４２部
・下記紫外線吸収剤１：　　　　　　　　　　　　　　　　　　　　０．４１部
・重合禁止剤：ｐ－メトキシフェノール　　　　　　　　　　　　　０．０１部
・有機溶剤１：ＰＧＭＥＡ　　　　　　　　　　　　　　　　　　　　９．２部 Example 1
(Preparation of coloring composition)
The following components were mixed to prepare the coloring composition of Example 1.
-Pigment dispersion B-1 (see Table 1 below for the mass ratio of each pigment) 11.2 parts-Pigment dispersion B-2 (See Table 1 below for the mass ratio of each pigment) 9.1 parts-below 40 mass% PGMEA solution of alkali-soluble resin 1 54.2 parts ・ The following polymerizable compound 1 13.6 parts ・ The following photopolymerization initiator 1: 2.0 parts ・ Surfactant 1: Megafac manufactured by DIC Corporation
0.42 part of 10% by mass PGMEA solution of F-781F, the following UV absorber 1: 0.41 part, polymerization inhibitor: 0.01 part of p-methoxyphenol, organic solvent 1: PGMEA 9.2 parts
　（実施例２～６、比較例１～２）
　実施例１の着色組成物の調製において、顔料分散液、アルカリ可溶性樹脂、重合性化合物、光重合開始剤、界面活性剤及び有機溶剤を下記表２に示すもの及び量（質量部）に変更して（顔料分散液における各顔料の質量比は表１を参照。また、表２中、数値が無いものは使用していないことを意味する。）、実施例２～６及び比較例１～２の着色組成物を調製した。 (Examples 2-6, Comparative Examples 1-2)
In the preparation of the colored composition of Example 1, the pigment dispersion, alkali-soluble resin, polymerizable compound, photopolymerization initiator, surfactant and organic solvent were changed to those shown in Table 2 below and in amounts (parts by mass). (Refer to Table 1 for the mass ratio of each pigment in the pigment dispersion. Also, in Table 2, it means that those without numerical values are not used.) Examples 2 to 6 and Comparative Examples 1 to 2 A colored composition was prepared.
Figure JPOXMLDOC01-appb-T000037
 　表１における各顔料比率は、全顔料に占める各顔料の比率（質量換算）である。
Figure JPOXMLDOC01-appb-T000037
 Each pigment ratio in Table 1 is the ratio (in terms of mass) of each pigment in the total pigment.
Figure JPOXMLDOC01-appb-T000038
 　表２において、アルカリ可溶性樹脂１は、４０質量％ＰＧＭＥＡ溶液での値（質量部）である。また、アルカリ可溶性樹脂２は、４０質量％ＰＧＭＥＡ溶液での値（質量部）である。また、界面活性剤１は、１０質量％ＰＧＭＥＡ溶液での値（質量部）である。
Figure JPOXMLDOC01-appb-T000038
 In Table 2, the alkali-soluble resin 1 is a value (part by mass) in a 40% by mass PGMEA solution. Moreover, alkali-soluble resin 2 is a value (mass part) in a 40 mass% PGMEA solution. Surfactant 1 is a value (parts by mass) in a 10% by mass PGMEA solution.
　表２中の各成分の略語は以下である。
　アルカリ可溶性樹脂１：下記構造（繰り返し単位における比はモル比である）
Figure JPOXMLDOC01-appb-C000039
 　アルカリ可溶性樹脂２：下記構造（繰り返し単位における比はモル比である）
Figure JPOXMLDOC01-appb-C000040
 　重合性化合物１：下記構造（ＵＡ－７２００、新中村化学社製、（分子量／重合性基数）＝２９０）
Figure JPOXMLDOC01-appb-C000041
 　重合性化合物２：下記構造（ＫＡＹＡＲＡＤ　ＲＰ－１０４０、日本化薬製、（分子量／重合性基数）＝１２０）
Figure JPOXMLDOC01-appb-C000042
 　重合性化合物３：下記構造（Ｍ－３０５（トリアクリレートが５５～６３質量％)（東亜合成社製、（分子量／重合性基数）＝９４）
Figure JPOXMLDOC01-appb-C000043
 　重合性化合物４：下記構造（（分子量／重合性基数）＝３００）
Figure JPOXMLDOC01-appb-C000044
 　光重合開始剤１：下記構造
Figure JPOXMLDOC01-appb-C000045
 　光重合開始剤２：下記構造
Figure JPOXMLDOC01-appb-C000046
 　紫外線吸収剤１：下記構造
Figure JPOXMLDOC01-appb-C000047
 Abbreviations for each component in Table 2 are as follows.
Alkali-soluble resin 1: following structure (ratio in repeating unit is molar ratio)
Figure JPOXMLDOC01-appb-C000039
 Alkali-soluble resin 2: the following structure (ratio in repeating units is molar ratio)
Figure JPOXMLDOC01-appb-C000040
 Polymerizable compound 1: structure (UA-7200, manufactured by Shin-Nakamura Chemical Co., Ltd., (molecular weight / polymerizable group number) = 290)
Figure JPOXMLDOC01-appb-C000041
 Polymerizable compound 2: the following structure (KAYARAD RP-1040, manufactured by Nippon Kayaku, (molecular weight / number of polymerizable groups) = 120)
Figure JPOXMLDOC01-appb-C000042
 Polymerizable compound 3: the following structure (M-305 (55 to 63% by mass of triacrylate) (manufactured by Toa Gosei Co., Ltd., (molecular weight / polymerizable group number) = 94)
Figure JPOXMLDOC01-appb-C000043
 Polymerizable compound 4: the following structure ((molecular weight / number of polymerizable groups) = 300)
Figure JPOXMLDOC01-appb-C000044
 Photopolymerization initiator 1: structure shown below
Figure JPOXMLDOC01-appb-C000045
 Photopolymerization initiator 2: Structure shown below
Figure JPOXMLDOC01-appb-C000046
 Ultraviolet absorber 1: The following structure
Figure JPOXMLDOC01-appb-C000047
［吸光度および透過率の測定］
　着色組成物をガラス基板上にスピンコートし、ポストベーク後の膜厚が１２μｍとなるように塗布し、１００℃、１２０秒間ホットプレートで乾燥し、乾燥した後、さらに、２００℃のホットプレートを用いて３００秒間加熱処理（ポストベーク）を行った。
　着色層を有する基板を、紫外可視近赤外分光光度計Ｕ－４１００（日立ハイテク製）（ｒｅｆ．ガラス基板）を用いて、波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａ、波長５８０ｎｍ以上７７０ｎｍ以下の範囲における吸光度の最小値Ｂ、波長４００ｎｍ以上７５０ｎｍ以下の範囲における吸光度の最小値Ｃ、波長８５０ｎｍ以上１３００ｎｍ以下の範囲における吸光度の最大値Ｄ、波長４００～７８０ｎｍの範囲における透過率の最小値、波長８５０ｎｍの透過率を測定した。 [Measurement of absorbance and transmittance]
The colored composition is spin-coated on a glass substrate, applied so that the film thickness after post-baking is 12 μm, dried on a hot plate at 100 ° C. for 120 seconds, dried, and further heated at 200 ° C. Using this, heat treatment (post-bake) was performed for 300 seconds.
A substrate having a colored layer is measured using a UV-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech) (ref. Glass substrate), and a minimum absorbance A in a wavelength range of 400 nm to less than 580 nm, a wavelength of 580 nm or more. Minimum absorbance B in the range of 770 nm or less, Minimum absorbance C in the wavelength range of 400 nm to 750 nm, Maximum absorbance D in the wavelength range of 850 nm to 1300 nm, Minimum transmittance in the wavelength range of 400 to 780 nm Value, transmittance at a wavelength of 850 nm was measured.
［粘度の測定］
　着色組成物の２５℃における粘度を、Ｂ型粘度計（ＴＯＫＩ産業製）を用いて測定した。 [Measurement of viscosity]
The viscosity at 25 ° C. of the colored composition was measured using a B-type viscometer (manufactured by TOKI Sangyo).
［カラーフィルタの作製］
　着色組成物を、シリコンウェハ上に乾燥後の膜厚が１２μｍになるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行った。
　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用して、１．４μｍ角の正方形ピクセルパターンが形成されるフォトマスクを用いて５０～７５０ｍＪ／ｃｍ2まで５０ｍＪ／ｃｍ2ずつ上昇させて、上記正方形ピクセルパターンを解像する最適露光量を決定し、この最適露光量にて露光を行った。
　その後、露光された塗布膜が形成されているシリコンウェハをスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ－２０６０（富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で６０秒間パドル現像を行い、シリコンウェハ上に着色パターンを形成した。
　着色パターンが形成されたシリコンウェハを純水でリンス処理を行い、その後スプレー乾燥した。
　さらに、２００℃のホットプレートを用いて３００秒間加熱処理（ポストベーク）を行い、それぞれ、実施例１～６および比較例１～２のカラーフィルタとしての、着色パターンを有するシリコンウェハを得た。 [Production of color filter]
The coloring composition was applied onto a silicon wafer using a spin coater so that the film thickness after drying was 12 μm, and heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C.
Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), 50 mJ / cm 2 up to 50 ~ 750mJ / cm 2 using a photomask having a square pixel pattern of 1.4μm angle is formed The optimum exposure amount for resolving the square pixel pattern was determined by increasing each time, and exposure was performed at this optimum exposure amount.
Thereafter, the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. to form a colored pattern on the silicon wafer.
The silicon wafer on which the colored pattern was formed was rinsed with pure water and then spray-dried.
Furthermore, a heat treatment (post-bake) was performed for 300 seconds using a 200 ° C. hot plate to obtain silicon wafers having colored patterns as color filters of Examples 1 to 6 and Comparative Examples 1 and 2, respectively.
＜評価＞
［ノイズ］
　可視光領域（波長４００～７００ｎｍ）での平均透過率ｔ１と、波長８２５～１３００ｎｍでの平均透過率ｔ２の比（ｔ１／ｔ２）を求め、以下の評価基準でノイズを評価した。ｔ１／ｔ２の値が小さいほど、可視光由来のノイズの少ないカラーフィルタである。
３：ｔ１／ｔ２が０．０８５未満
２：ｔ１／ｔ２が０．０８５以上０．１未満
１：ｔ１／ｔ２が０．１以上
［皺］
　カラーフィルタの表面をＡＦＭ（原子間力顕微鏡）にて測定し、表面粗さ（Ｒａ）を計算により求めた。
３：表面粗さ（Ｒａ）が１０ｎｍ未満
２：表面粗さ（Ｒａ）が１０ｎｍ以上、２０ｎｍ未満
１：表面粗さ（Ｒａ）が２０ｎｍ以上
［密着］
現像後のカラーフィルタを光学式顕微鏡にて観察し、パターンが剥がれている数をカウントした。
３：パターンの剥がれが見られない
２：パターンの剥がれが１０個未満
１：パターンの剥がれが１０個以上 <Evaluation>
[noise]
A ratio (t1 / t2) between the average transmittance t1 in the visible light region (wavelength 400 to 700 nm) and the average transmittance t2 in the wavelength 825 to 1300 nm was determined, and noise was evaluated according to the following evaluation criteria. The smaller the value of t1 / t2, the less the noise derived from visible light.
3: t1 / t2 is less than 0.085 2: t1 / t2 is 0.085 or more and less than 0.1 1: t1 / t2 is 0.1 or more [皺]
The surface of the color filter was measured with an AFM (atomic force microscope), and the surface roughness (Ra) was obtained by calculation.
3: Surface roughness (Ra) is less than 10 nm 2: Surface roughness (Ra) is 10 nm or more, less than 20 nm 1: Surface roughness (Ra) is 20 nm or more [adhesion]
The developed color filter was observed with an optical microscope, and the number of peeled patterns was counted.
3: No peeling of the pattern is observed 2: Less than 10 peeling of the pattern 1: 10 or more peeling of the pattern
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　本発明の着色感組成物を用いた実施例１～６はいずれも、可視光由来のノイズが少ない状態で近赤外線を透過可能で、かつ、皺の抑制された膜を形成することができた。また、実施例１～６は、密着性にも優れていた。
　一方、比較例１～２は、膜表面の皺が多かった。 In each of Examples 1 to 6 using the colored sensation composition of the present invention, it was possible to form a film capable of transmitting near-infrared rays with less visible light-derived noise and having no wrinkles. . In addition, Examples 1 to 6 were excellent in adhesion.
On the other hand, Comparative Examples 1 and 2 had many wrinkles on the film surface.
１：レンズ光学系、１０：固体撮像素子、２０：信号処理部、３０：信号切替部、４０：制御部、５０：信号蓄積部、６０：発光制御部、７０：赤外ＬＥＤ、８０、８１：画像出力部、１００：赤外線センサ、１１０：固体撮像素子、１１１：近赤外線吸収フィルタ、１１２：カラ－フィルタ、１１３：近赤外線透過フィルタ、１１４：領域、１１５：マイクロレンズ、１１６：平坦化層、ｈν：入射光 1: lens optical system, 10: solid-state imaging device, 20: signal processing unit, 30: signal switching unit, 40: control unit, 50: signal storage unit, 60: light emission control unit, 70: infrared LED, 80, 81 : Image output unit, 100: Infrared sensor, 110: Solid-state imaging device, 111: Near-infrared absorption filter, 112: Color filter, 113: Near-infrared transmission filter, 114: Region, 115: Micro lens, 116: Flattening layer , Hν: incident light

Claims (18)

  1. 着色剤と重合性化合物とを含む着色組成物であって、
    前記重合性化合物は、アルキレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有し、
    前記着色組成物の、波長４００ｎｍ以上５８０ｎｍ未満の範囲における吸光度の最小値Ａと、波長５８０ｎｍ以上７７０ｎｍ以下の範囲における吸光度の最小値Ｂとの比率Ａ／Ｂが０．３～３であり、波長４００ｎｍ以上７５０ｎｍ以下の範囲における吸光度の最小値Ｃと、波長８５０ｎｍ以上１３００ｎｍ以下の範囲における吸光度の最大値Ｄとの比率Ｃ／Ｄが５以上である、着色組成物。     A coloring composition comprising a coloring agent and a polymerizable compound,
    The polymerizable compound contains a polymerizable compound having a chain in which the number of repeating units of the alkyleneoxy group is 2 or more,
    The colored composition has a ratio A / B of 0.3 to 3 between the minimum absorbance A in the wavelength range of 400 nm to less than 580 nm and the minimum absorbance B in the wavelength range of 580 nm to 770 nm. A coloring composition having a ratio C / D of 5 or more between a minimum value C of absorbance in a range of 400 nm to 750 nm and a maximum value D of absorbance in a wavelength range of 850 nm to 1300 nm.
  2. 着色剤と重合性化合物とを含む着色組成物であって、
    前記重合性化合物は、アルキレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有し、
    前記着色剤は、赤色着色剤および紫色着色剤から選ばれる１種以上の着色剤Ａと、黄色着色剤と、青色着色剤と、を少なくとも含み、前記赤色着色剤および前記紫色着色剤から選ばれる前記着色剤Ａの着色剤全量に対する質量比である着色剤Ａ／全着色剤が、０．０１～０．７であり、前記黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．０５～０．５であり、前記青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．０５～０．６である、着色組成物。     A coloring composition comprising a coloring agent and a polymerizable compound,
    The polymerizable compound contains a polymerizable compound having a chain in which the number of repeating units of the alkyleneoxy group is 2 or more,
    The colorant includes at least one colorant A selected from a red colorant and a purple colorant, a yellow colorant, and a blue colorant, and is selected from the red colorant and the purple colorant. The colorant A / total colorant, which is a mass ratio of the colorant A to the total amount of colorant, is 0.01 to 0.7, and the yellow colorant / total colorant is the mass ratio of the yellow colorant to the total amount of colorant. A coloring composition having a colorant of 0.05 to 0.5 and a blue colorant / total colorant in a mass ratio of the blue colorant to the total amount of colorant of 0.05 to 0.6.
  3. 前記着色剤は、前記赤色着色剤と、前記紫色着色剤と、前記黄色着色剤と、前記青色着色剤とを含み、前記赤色着色剤の着色剤全量に対する質量比である赤色着色剤／全着色剤が０．１～０．５であり、前記黄色着色剤の着色剤全量に対する質量比である黄色着色剤／全着色剤が０．１～０．４であり、前記青色着色剤の着色剤全量に対する質量比である青色着色剤／全着色剤が０．２～０．６であり、前記紫色着色剤の着色剤全量に対する質量比である紫色着色剤／全着色剤が０．０１～０．３である、請求項２に記載の着色組成物。 The colorant includes the red colorant, the purple colorant, the yellow colorant, and the blue colorant, wherein the red colorant / total color is a mass ratio of the red colorant to the total amount of the colorant. The colorant of the blue colorant is 0.1 to 0.5, and the yellow colorant / total colorant in a mass ratio of the yellow colorant to the total amount of the colorant is 0.1 to 0.4. The blue colorant / total colorant, which is the mass ratio to the total amount, is 0.2 to 0.6, and the purple colorant / total colorant, which is the mass ratio of the purple colorant to the total amount of colorant, is 0.01 to 0. The colored composition according to claim 2, which is .3.
  4. 前記重合性化合物は、エチレンオキシ基の繰り返し単位数が２以上の鎖を有する重合性化合物を含有する、請求項１～３のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 3, wherein the polymerizable compound contains a polymerizable compound having a chain in which the number of repeating units of an ethyleneoxy group is 2 or more.
  5. 前記重合性化合物は、前記重合性化合物の分子量の値を、前記重合性化合物中に含まれる重合性基の数で割った値が１００～３００である、請求項１～４のいずれか１項に記載の着色組成物。 5. The polymerizable compound according to claim 1, wherein a value obtained by dividing the molecular weight value of the polymerizable compound by the number of polymerizable groups contained in the polymerizable compound is 100 to 300. The coloring composition as described in.
  6. 前記重合性化合物は、環状構造を有する、請求項１～５のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 5, wherein the polymerizable compound has a cyclic structure.
  7. 前記重合性化合物は、ヘテロ環構造を有する、請求項１～５のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 5, wherein the polymerizable compound has a heterocyclic structure.
  8. 前記重合性化合物は、下記一般式（１）で表される部分構造を有する、請求項１～７のいずれか１項に記載の着色組成物；ただし、式中の＊は連結手である。
    Figure JPOXMLDOC01-appb-C000001
         The colored composition according to any one of claims 1 to 7, wherein the polymerizable compound has a partial structure represented by the following general formula (1); wherein * is a connecting hand.
    Figure JPOXMLDOC01-appb-C000001
  9. 更に、樹脂および光重合開始剤を含有する、請求項１～８のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 8, further comprising a resin and a photopolymerization initiator.
  10. 前記樹脂は、ヒドロキシル基を有する樹脂を含有する、請求項９に記載の着色組成物。 The colored composition according to claim 9, wherein the resin contains a resin having a hydroxyl group.
  11. 乾燥後の膜厚が１２．０μｍの膜を形成した際に、波長４００～７８０ｎｍの範囲における透過率の最大値が１５％以下であり、波長８５０ｎｍの透過率が８０％以上である、請求項１～１０のいずれか１項に記載の着色組成物。 The maximum transmittance in a wavelength range of 400 to 780 nm is 15% or less and the transmittance at a wavelength of 850 nm is 80% or more when a film having a thickness of 12.0 μm after drying is formed. The coloring composition according to any one of 1 to 10.
  12. ２５℃における粘度が１００～１５０ｍＰ・ｓである、請求項１～１１のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 11, having a viscosity of 100 to 150 mP · s at 25 ° C.
  13. 請求項１～１２のいずれか１項に記載の着色組成物を硬化してなる膜。 A film formed by curing the colored composition according to any one of claims 1 to 12.
  14. 請求項１３に記載の膜を有するカラーフィルタ。 A color filter having the film according to claim 13.
  15. 請求項１～１２のいずれか１項に記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、前記着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含むパターン形成方法。 A step of applying a colored composition according to any one of claims 1 to 12 on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and an unexposed state Forming a colored pattern by developing and removing the portion.
  16. 請求項１５に記載のパターン形成方法を含む、カラーフィルタの製造方法。 A method for producing a color filter, comprising the pattern forming method according to claim 15.
  17. 請求項１４に記載のカラーフィルタまたは請求項１６に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。 The solid-state image sensor which has a color filter obtained by the manufacturing method of the color filter of Claim 14, or the color filter of Claim 16.
  18. 請求項１４に記載のカラーフィルタまたは請求項１６に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する赤外線センサ。 An infrared sensor having a color filter according to claim 14 or a color filter obtained by the method for producing a color filter according to claim 16.
PCT/JP2015/061804 2014-05-27 2015-04-17 Coloring composition, film, color filter, pattern formation method, method for producing color filter, solid-state imaging element, and infrared ray sensor WO2015182277A1 (en)

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