JP2015232642A - Colored composition for solid-state image sensor, color filter for solid-state image sensor, and solid-state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a solid-state image sensor, which shows sufficient fastness and excellent spectral characteristics, a color filter for a solid-state image sensor using the above composition, and a solid-state image sensor having excellent sensitivity and color reproducibility using the color filter.SOLUTION: The colored composition for a solid-state image sensor comprises a colorant, a binder resin, and an organic solvent. The colorant comprises a cyanine dye (ZC) represented by general formula (1) and a pigment (B).

Description

  The present invention relates to a color filter for a solid-state imaging device that is mounted on a solid-state imaging device typified by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device: Charge Coupled Device), The present invention relates to a solid-state imaging device including the color filter and a coloring composition for the solid-state imaging device.

  Solid-state image sensors such as C-MOS and CCD are provided with color filters each including a filter segment of an additive color mixture of B (blue), G (green), and R (red) on the light receiving element. Generally, color separation is performed. In recent years, the area per pixel tends to decrease due to the miniaturization and increase in the number of pixels of the solid-state imaging device. As a result, it is required to reduce the thickness of the color filter mounted on the image sensor and to increase the concentration of the coloring component.

  The color filter manufacturing method includes a dyeing method using a dye as a color material, a dye dispersion method, a pigment dispersion method using a pigment as a color material, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a disadvantage that the heat resistance and the light resistance are slightly inferior because the dye is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as the color material of the color filter, and the pigment dispersion method is often used as the manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive in a pigment in which pigment particles, which are pigments, are dispersed in a transparent resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In recent years, there has been an increasing demand for color characteristics for color filters, such as transmittance, brightness, color purity, coating uniformity when forming filter segments, sensitivity, developability, and pattern shape. Especially for color filters used in solid-state image sensors used in video cameras, digital cameras, color scanners, etc., high definition, high brightness, and high color reproducibility are required, and the transmittance is high. There is a need for a color filter having excellent color reproducibility and color separation.

  In recent years, a technique of using a dye as a colorant has been proposed in order to realize a color filter excellent in high transmittance, high color reproducibility, and high color separation (for example, Patent Document 1). However, if only a dye itself such as a direct dye or an acid dye is used, the color developability is good, but the heat resistance and light resistance are often poor (Patent Document 2). Therefore, in the use of dyes, a solution to the technical problem of achieving both fastness and color characteristics is required.

Further, in a solid-state imaging device using a color filter, there is a problem of a decrease in color reproducibility caused by noise due to color mixing. In particular, it is known that the red filter causes a deterioration in image quality due to a “bump” (hereinafter referred to as a “bump”) in which the transmittance near 530 nm increases locally. For this reason, a technique of using Pigment Red 166 to erase the bumps near 530 nm is disclosed (see Patent Document 3). However, simply removing this bump using Pigment Red 166 is not practical because the transmittance of 600 nm to 700 nm is low and the sensitivity of the solid-state imaging device is lowered.
Further, in the spectrum of the red filter, the floating of the spectrum of 400 to 450 nm causes a color mixture with blue, and the color reproducibility of blue is deteriorated.

JP-A-6-75375 JP-A-8-327811 Japanese Patent No. 2010-085457

  An object of the present invention is a coloring composition for a solid-state imaging device that satisfies fastness and has excellent spectral characteristics, a color filter for a solid-state imaging device using the same, and a solid-state imaging excellent in sensitivity and color reproducibility using the same It is to provide an element.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have developed a coloring for a solid-state imaging device containing a cyanine dye (ZC) represented by the general formula (1) and a pigment (B). The present inventors have found that the above-mentioned problems can be solved by a composition.

［一般式（１）において、Ａは置換基もしくは水素原子を有する炭素原子、または硫黄原子を表す。Ｒ^３〜Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子、ニトロ基、置換もしくは無置換の炭素数１〜４のアルキル基、置換もしくは無置換の炭素数１〜４のアルコキシ基、置換もしくは無置換のアリール基、または置換もしくは無置換のアシル基を表す。Ｒ^１１は、水素原子、置換もしくは無置換の炭素数１〜４のアルキル基、またはハロゲン原子を表す。Ｒ^１２およびＲ^１３は、それぞれ独立に水素原子、ハロゲン原子、重合性官能基を有する有機基、または置換もしくは無置換の炭素数１〜６のアルキル基を示す。Ｙ⁻は、無機または有機のアニオン化合物を表す。ただし、Ｙ⁻がハロゲン化物イオンである場合は除く。］ That is, the present invention is a colored composition for a solid-state imaging device containing a colorant, a binder resin, and an organic solvent, wherein the colorant is a cyanine dye (ZC) represented by the following general formula (1) and a pigment ( B) and a coloring composition for a solid-state imaging device.

[In General Formula (1), A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom. R ^{3 to} R ¹⁰ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Y ⁻ represents an inorganic or organic anionic compound. However, Y ^- is excluded if a halide ion. ]

［一般式（２）において、Ｒ^２１およびＲ^２２はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］

［一般式（３）において、Ｒ^３１〜Ｒ^３４はそれぞれ独立に、フッ素原子で置換されていても良いアルキル基、シアノ基、水素原子、フッ素原子、フッ素原子で置換されていても良いアリール基を表し、Ｒ^３１〜Ｒ^３４のうち少なくとも一つは、フッ素原子で置換されていても良いアルキル基、フッ素原子、またはフッ素原子で置換されていても良いアリール基を表す。
ただし、Ｒ^３１〜Ｒ^３４がすべてフッ素原子である場合は除く。］

［一般式（４）において、Ｒ^４１〜Ｒ^４３はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、または置換基を有してもよい芳香族炭化水素基を表す。］

［一般式（５）中、Ｒ^５１は水素原子、または置換もしくは無置換のアルキル基を表す。Ｑは置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、−ＣＯＮＨ−Ｒ^５２−、または−ＣＯＯ−Ｒ^５２−を表し、Ｒ^５２は置換もしくは無置換のアルキレン基を表す。Ｐ⁻は、―ＳＯ_３ ⁻、または−ＣＯＯ⁻を表す。］ In the present invention, the anion represented by Y- is represented by the imido acid anion represented by the following general formula (2), the fluorine group-containing boron anion represented by the following general formula (3), and the following general formula (4). The solid-state imaging device coloring described above, characterized in that it is at least one selected from the group consisting of a methide acid anion and a vinyl resin having an anionic group containing a structural unit represented by the following general formula (5) Relates to the composition.

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group that may have a substituent, an alicyclic hydrocarbon group that may have a substituent, or a substituent. An aromatic hydrocarbon group which may have or a heterocyclic group which may have a substituent. ]

[In General Formula (3), R ^{31 to} R ³⁴ are each independently an alkyl group optionally substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom, or an aryl group optionally substituted with a fluorine atom. And at least one of R ^{31 to} R ³⁴ represents an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, it excludes when R < ³¹ > -R < ³⁴ > is all fluorine atoms. ]

[In General Formula (4), R ^{41 to} R ⁴³ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. ]

[In General Formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —CONH—R ⁵² —, or —COO—R ⁵² —, and R ⁵² represents a substituted or unsubstituted alkylene group. P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]

  In addition, the present invention relates to the colored composition for a solid-state imaging device, wherein the pigment (B) is at least one selected from the group consisting of a yellow pigment and a red pigment.

  In the present invention, the yellow pigment is C.I. I. Pigment Yellow 139 is included, and the present invention relates to the coloring composition for a solid-state imaging device.

  In the present invention, the red pigment is C.I. I. Pigment red 254 and C.I. I. It contains at least one selected from the group consisting of CI Pigment Red 177.

  In addition, the present invention relates to the colored composition for a solid-state imaging device, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one red filter segment is formed of the colored composition for a solid-state imaging device. A color filter for a solid-state imaging device.

  The present invention also relates to a solid-state image sensor including the color filter for the solid-state image sensor.

  The colored composition for a solid-state imaging device of the present invention can provide a color filter for a solid-state imaging device capable of satisfying both spectral characteristics and fastness (heat resistance). Furthermore, by using this to create a solid-state imaging device, it is possible to form a solid-state imaging device with excellent sensitivity and color reproducibility.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

  The coloring composition for a solid-state imaging device of the present invention is a coloring composition for a solid-state imaging device containing a coloring agent, a resin, and an organic solvent, and the coloring agent is a cyanine dye represented by the general formula (1) ( ZC) and the pigment (B).

<Colorant>
The colored composition for a solid-state imaging device of the present invention contains a cyanine dye (ZC) represented by the general formula (1) and a pigment (B) as a colorant.

  In the colored composition for a solid-state imaging device of the present invention, the concentration of the colorant with respect to all nonvolatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Yes, most preferably 20-80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the color composition May become unstable.

(Cyanine dye (ZC) represented by general formula (1))
The cyanine dye of the present invention has a structure represented by the general formula (1). By using such a dye, it has excellent color characteristics and fastness such as heat resistance. It is suitable as a coloring composition for a solid-state imaging device.
In particular, when used in a red coloring composition used for a red filter segment, solid-state imaging is possible because there is no “bump” in which the transmittance near 530 nm increases locally and the transmittance from 600 nm to 700 nm is high. The device can have excellent color separation characteristics.

  The cyanine dye of the present invention is a salt-forming compound having a structure in which a cation moiety and an anion moiety are salt-formed as represented by the general formula (1). The cationic site is a cationic cyanine dye represented by the following general formula (1-2), and the anion site is an inorganic or organic anion other than halide ions. In particular, the cyanine dye of the present invention is a salt-forming compound of a cationic cyanine dye represented by the general formula (1-2) and an anion represented by the general formula (2), (3) or (4). It is desirable. Alternatively, a salt-forming compound with a vinyl resin having an anionic group containing the structural unit represented by the general formula (5) is preferable because of excellent color characteristics and resistance for a solid-state imaging device.

［一般式（１）において、Ａは置換基もしくは水素原子を有する炭素原子、または硫黄原子を表す。Ｒ^３〜Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子、ニトロ基、置換もしくは無置換の炭素数１〜４のアルキル基、置換もしくは無置換の炭素数１〜４のアルコキシ基、置換もしくは無置換のアリール基、または置換もしくは無置換のアシル基を表す。Ｒ^１１は、水素原子、置換もしくは無置換の炭素数１〜４のアルキル基、またはハロゲン原子を表す。Ｒ^１２およびＲ^１３は、それぞれ独立に水素原子、ハロゲン原子、重合性官能基を有する有機基、または置換もしくは無置換の炭素数１〜６のアルキル基を示す。Ｙ−は、無機または有機のアニオン性化合物を表す。ただし、Ｙ−がハロゲン化物イオンである場合は除く。］

[In General Formula (1), A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom. R ^{3 to} R ¹⁰ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Y- represents an inorganic or organic anionic compound. However, it excludes when Y- is a halide ion. ]

≪Cationic cyanine dye≫
[Cationic cyanine dye represented by formula (1-2)]
The cationic cyanine dye of the present invention has a cation represented by the following general formula (1-2).

[In General Formula (1-2), A represents a carbon atom which has a substituent or a hydrogen atom, or a sulfur atom. R ^{3 to} R ¹⁰ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

  As the aryl group, phenyl group, biphenylyl group, terphenylyl group, quarterphenylyl group, pentarenyl group, indenyl group, naphthyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, azulenyl group, heptalenyl group, biphenylenyl group, indacenyl Group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl Group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexyl group Seniru group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  These aryl groups may have a substituent. In this case, examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an aryl group.

  Examples of the acyl group include acetyl group, ethanoyl group, propanoyl group, isopropanoyl group, butanoyl group, isobutanoyl group, sec-butanoyl group, tert-butanoyl group and the like.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The organic group having a polymerizable functional group referred to in the present invention is composed of an atomic group that includes a polymerizable functional group, contains a carbon atom-hydrogen atom bond as a whole, and may contain atoms other than carbon as necessary. Represents a group. Specifically, there are a case where it consists of only a polymerizable functional group and a case where it contains a polymerizable functional group and a linking group.
Here, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, and an isocyanate group.
As the linking group (as viewed from the cyanine skeleton), an alkylene group (hereinafter referred to as -X-), -XO- group, -XNH- group, arylene group, aryleneoxy group, -XCONH- group,- XCOO- group, -XOCO- group, -XCOOX- group, -XOCOX- group, -XCOOXCOO- group, -XOCOXCOO- group, and the like.
Specific examples of the organic group having a polymerizable functional group are as shown in the following table (DC-5 to 8 etc.).

A carbon atom and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ¹² , A carbon atom and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹³ may each independently or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure.

Specific examples of the cationic cyanine dye include the following cationic cyanine dyes, but the present invention is not limited thereto. Further, when salt formation is performed, the counters of the cationic cyanine dyes (DC-1 to DC-91) shown below are halide ions, and are Cl ^−, Br ⁻ or I ⁻ .

≪Anion Y ⁻ ≫
In the general formula (1), Y- represents an inorganic or organic anion, and any compound having an anion can be used. However, the case of halide ions (Cl-, etc.) is excluded.

Typical examples include halogen ions (chloride ions, bromide ions, etc.), triflate ions (CF ₃ SO ₃ ⁻ ), benzoate ions (C ₆ H ₅ COO ⁻ ), oxalate ions (C ₂ O ₄ ^2−). ), Perhalogenate ions (ClO ₄ ⁻ , FO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ etc.), thiocyanate ions (SCN ⁻ etc.), sulfate ions (SO ₄ ²⁻ , HSO ₄ ⁻ etc.), heteropolyacids , Organic carboxylate ion, organic sulfonate ion (eg, alkyl sulfonate having 1 to 20 carbon atoms, benzene sulfonate, etc.), fatty acid ion (such as aliphatic carboxylate having 1 to 20 carbon atoms), sulfonate group-containing nitrogen anion, fluorine group Containing boron anion, methide acid anion, fluorine group containing phosphorus anion, cyano group containing nitrogen anion Or like anionic acid dye having a conjugate base of an organic acid having a halogenated hydrocarbon group, as long as these anions, there is no problem in resistance and color properties, can be preferably used.

  Among these anions Y-, from the viewpoint of heat resistance, a sulfate ion, an organic sulfonate ion, a sulfonate group-containing nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is preferable, and an organic sulfonate ion and a sulfonate group are contained. A nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is more preferable, and a sulfonic acid group-containing nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is particularly preferable.

  Among the sulfonic acid group-containing nitrogen anions, among the imido acid anion represented by the general formula (2) and the fluorine group-containing boron anion, the fluorine group-containing boron anion represented by the general formula (3) is methide acid. Among the anions, the methide acid anion represented by the general formula (4) is most preferable.

  Alternatively, a resin having these anionic groups in the side chain can be used, and among these resins, a resin in which the anion portion is —SO 3 — or —COO— is preferable, and most preferably, heat resistance It is a vinyl resin having an anionic group represented by the following general formula (5) from the viewpoint of color and color characteristics.

Specifically as these anions,
Heteropolyacids include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, cytungstomolybdic acid, phosphotungstic acid, Anions such as phosphomolybdic acid, silicotungstic acid, silicomolybdic acid and the like can be mentioned.

  Examples of organic carboxylate ions include tetrachlorophthalic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, gallenic acid, arachidonic acid, α- Examples include anions of anionic compounds such as linolenic acid, stearidonic acid, eicosapentaenoic acid, and docosahexaenoic acid.

  Preferred compounds as organic sulfonate ions are methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, dodecylsulfone. Acid, hexadecanesulfonic acid, icosanesulfonic acid, benzenesulfonic acid 1-naphthalenesulfonic acid, 4-phenylaminobenzenesulfonic acid, 1-naphthylamine-4,8-disulfonic acid, 1-naphthylamine-3,8-disulfonic acid, 1-naphthylamine-5,7-disulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 1-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine-6,8-disulfonic acid, 2-naphthylamine -1,6 Disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid (amino-R acid), 2-naphthylamine-5,7-disulfonic acid (amino J acid), 1-naphthol -4,8-disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,6,8-trisulfonic acid, 2- Naphthol-6,8-disulfonic acid, 2-naphthol-3,6-disulfonic acid (R acid), 2-naphthol-3,6,8-trisulfonic acid, N-phenyl-1-naphthylamine-8-sulfonic acid N-p-tolyl-1-naphthylamine-8-sulfonic acid, N-phenyl-1-naphthylamine-5-sulfonic acid, N-phenyl-2-naphthylamine-6-sulfonic acid, N-acetyl-7-amino-1-naphthol-3-sulfonic acid, N-phenyl-7-amino-1-naphthol-3-sulfonic acid, N-acetyl-6-amino-1-naphthol-3-sulfonic acid N-phenyl-6-amino-1-naphthol-3-sulfonic acid, 1,8-dihydro-3,6-disulfonic acid (chromotropic acid), 8-amino-1-naphthol-3,6-disulfonic acid 8-amino-1-naphthol-5,7-disulfonic acid, 1,6-diamino-2-naphthol-4-sulfonic acid, 1-amino-2-naphthol-6,8-disulfonic acid, 1-amino- 2-naphthol-3,6-disulfonic acid, 2,8-diamino-1-naphthol-5,7-disulfonic acid, 2,7-diamino-1-naphthol-3-sulfonic acid, 2,6-diamino Anions of anionic compounds such as 1-naphthol-3-sulfonic acid, 2,8-diamino-1-naphthol-3,6-disulfonic acid, 2-amino-7-phenylamino-1-naphthol-3-sulfonic acid Can be given.

  Also anthracene sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1-sulfonic acid, 2-amino-1-naphthalenesulfonic acid (tobias acid), 4-amino-1-naphthalenesulfonic acid (naphthoic acid), 8-amino -1-naphthalenesulfonic acid (peric acid), 2-amino-6-naphthalenesulfonic acid (brenamic acid), 1-amino-5-naphthalenesulfonic acid (Lorentzic acid), 5-amino-2-naphthalenesulfonic acid (molecular weight) 223), anions of anionic compounds such as 1-amino-6-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, and 3-amino-1-naphthalenesulfonic acid can also be used.

  Examples of fatty acid ions include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, serotic acid, decylene acid, dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petrothelic acid, vacenoic acid, linoleic acid, eleostearic acid Examples include anions of anionic compounds such as acid, licanoic acid, parinaric acid, taliphosphoric acid, gadoleic acid, cetreic acid, and ceracolic acid.

Examples of the sulfonic acid group-containing nitrogen anion include trifluoromethanesulfonamide anion, N- (trimethylsilyl) trifluoromethanesulfonamide anion, N- (2-methoxyethyl) trifluoromethanesulfonamide anion, and p-trifluoromethylbenzenesulfonamide anion. In addition, a sulfonyl imido acid anion is mentioned.
Among these, a sulfonyl imido acid anion is preferable in terms of heat resistance, and an imido acid anion represented by the general formula (2) described below is particularly preferable.

Examples of the fluorine group-containing boron anion include BF _4- or a fluorine group-containing boron anion represented by the general formula (3).
Among these, a fluorine group-containing boron anion represented by the general formula (3) described later is particularly preferable from the viewpoint of heat resistance.

Fluorine group-containing phosphorus anions include PF ₆ ⁻ , (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF ^{_{] 2 PF 4 -, [(}} CF 3) 2 CF] 3 PF 3 -, (n-C 3 F 7) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ _{, (n-C 4 F 9} ) 2 PF 4 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F 3 H 2 ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^{— and the} like.
Among these, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , ((n-C ₃ F ₇ ) ₃ PF ₃ ⁻ , (n-C ₄₎ F ₉ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , [( CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^— is preferred.

As the cyano group-containing nitrogen anion, [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ^{_{3 CF 2 SO 2)] -}} , [(FSO 2) N {(CF 3) 2 CFSO 2}] -, [(FSO 2) N (CF 3 CF 2 CF 2 SO 2)] -, [(FSO 2 ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like.

The conjugate base of the organic acid having a halogenated hydrocarbon group is not particularly limited, but examples of the organic acid having a halogenated hydrocarbon group include sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimide acid _(-SO 2 NHSO ₂ -) and the like.

Examples of the acid dyes include anthraquinone acid dyes, monoazo acid dyes, disazo acid dyes, oxazine acid dyes, amino ketone acid dyes, quinoline acid dyes, and triarylmethane acid dyes.
The hue can also be controlled by using an acid dye.

  Among them, in the present invention, the imido acid anion represented by the general formula (2), the fluorine group-containing boron anion represented by the following general formula (3), the methide acid anion represented by the following general formula (4), and the following general formula Use of any one of vinyl resins having an anionic group containing the structural unit represented by (5) is desirable in terms of heat resistance and color characteristics.

［一般式（２）において、Ｒ^２１およびＲ^２２はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ [Imidate anion represented by general formula (2)]

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group that may have a substituent, an alicyclic hydrocarbon group that may have a substituent, or a substituent. An aromatic hydrocarbon group which may have or a heterocyclic group which may have a substituent. ]

In the general formula (2), examples of the “aliphatic hydrocarbon group” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Linear alkyl groups such as tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group and pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group And the like.
In the general formula (2), examples of the “alicyclic hydrocarbon group” include cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cycloalkyl groups such as cyclononyl groups, cyclodecyl groups, and the like. It is done.
In the general formula (2), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.

  In the general formula (2), examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline And a ring.

R ²¹ and R ²² may form an aliphatic saturated hydrocarbon ring structure.

  In the general formula (2), examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group; polymerizable functional groups such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group and epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; phenoxy Aryloxy groups such as benzyloxy groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfa Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyls Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; can be nitro group, a cyano group and the like; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

In the general formula (2), R ²¹ represents an aliphatic hydrocarbon group that may have a substituent, an alicyclic hydrocarbon group that may have a substituent, or an aromatic that may have a substituent. It is preferably a hydrocarbon group, and R ²² is preferably an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.

R ^{21 in the} general formula (2) is preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group substituted with a fluorine atom, and having 1 to 20 carbon atoms substituted with a fluorine atom. An alkyl group is more preferable, and a trifluoromethyl group is particularly preferable.

Of these, R ^{22 in the} general formula (2) is preferably an aromatic hydrocarbon group substituted with a fluorine atom, more preferably a p-fluorophenyl group or a pentafluorophenyl group.

Specific examples of the imido acid anion include the following imido acid anions, but the present invention is not limited thereto. Moreover, l and n show the integer of 1-5. In addition, when performing salt formation, the counter of the anionic compound which has the imido acid anion (IC-1 to IC-59) shown below is Na ^<+> or K ^<+> or tetrabutylammonium or trimethylammonium.

［一般式（３）において、Ｒ^３１〜Ｒ^３４はそれぞれ独立に、フッ素原子で置換されていても良いアルキル基、シアノ基、水素原子、フッ素原子、フッ素原子で置換されていても良いアリール基を表し、Ｒ^３１〜Ｒ^３４のうち少なくとも一つは、フッ素原子で置換されていても良いアルキル基、フッ素原子、またはフッ素原子で置換されていても良いアリール基を表す。
ただし、Ｒ^３１〜Ｒ^３４がすべてフッ素原子である場合は除く。］ [Fluorine group-containing boron anion represented by general formula (3)]

[In General Formula (3), R ^{31 to} R ³⁴ are each independently an alkyl group optionally substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom, or an aryl group optionally substituted with a fluorine atom. And at least one of R ^{31 to} R ³⁴ represents an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, it excludes when R < ³¹ > -R < ³⁴ > is all fluorine atoms. ]

In general formula (3), examples of the alkyl group represented by R ^{31 to} R ³⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A pentyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, a dodecyl group, a pentadecyl group and an octadecyl group, which may be substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, and 2 to 12 carbon atoms from the viewpoints of solubility in organic solvents, brightness, heat resistance, and contrast ratio. More preferably.

In general formula (3), the aryl group represented by R ^{31 to} R ³⁴ has a group containing a benzene ring, a group containing a condensed ring having aromaticity, two or more benzene rings, or aromaticity. A group having a structure in which fused rings are directly bonded, a group in which two or more benzene rings or a condensed ring having aromaticity are bonded via a group such as vinylene are included. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. Examples of the aryl group substituted with a fluorine atom include a phenyl group which may have a fluorine group, a 1-naphthyl group which may have a fluorine group, and a fluorine group which may have 2 -A naphthyl group is mentioned. From the viewpoint of heat resistance, lightness, and contrast ratio, it is preferable that a fluorine atom has a substituent.

Specific examples of the fluorine group-containing boron anion represented by the general formula (3) include (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ and (CF ₃ ) BF _{3. ^{-, (C 2 F 5)}} 4 B -, (C 2 F 5) 3 BF -, (C 2 F 5) BF 3 -, (C 2 F 5) 2 BF 2 -, (CF 3) (C 2 F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ^{− _{, B (CN) 3 F -}} , (CF 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (C ^{_{) -, (C 2 F 5}} ) 2 B (CN) 2 -, (n-C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n- _{C 4 F 9) 2 B (} CN) 2 -, (n-C 6 F 3) 3 B (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 - , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F _{5 ^{) 2 B (CN) 2 -}} , (CH 2 CH 2 C 3 F 7) 2 B (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5 ) ₃ B (CN) ^-, and the like.
Among these, B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ are preferable.

In addition, in general formula (3), at least one of R ^{31 to} R ³⁴ is represented by the general formula, such as (C ₆ F ₅ ) ₄ B ⁻ or [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^—. A structure represented by (3-2) is preferable.

［一般式（３−２）において、Ｒ^３５〜Ｒ^３９は、それぞれ独立に、水素原子、またはフッ素原子を示す。ただし、Ｒ^３５〜Ｒ^３９がすべて水素原子である場合は除く。］

[In General Formula (3-2), R ^{35 to} R ³⁹ each independently represent a hydrogen atom or a fluorine atom. ^However, when R 35 ^{to R 39} are all hydrogen atoms is excluded. ]

Examples of the substituent represented by the general formula (3-2) include a pentafluorophenyl group (C ₆ F ₅ ), a trifluorophenyl group (C ₆ H ₂ F ₃ ), and a tetrafluorophenyl group (C ₆ HF _4). ), Trifluoromethylphenyl group (CF ₃ C ₆ H ₄ ), bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₂ CF ₃ C ₆ H ₄₎ ), Bis (pentafluoroethyl) phenyl group ((CF ₂ CF ₃ ) ₂ C ₆ H ₃ ), fluoro-trifluoromethylphenyl group (CF ₃ C ₆ H ₃ F), fluoro-bis (trifluoromethyl) phenyl group _{((CF 3) 2 C 6} H 2 F), fluoro - pentafluoroethyl phenyl group _{(CF 3 CF 2 C 6 H} 3 F), fluoro - bis ( Such pointer fluoroethyl) phenyl group _{((CF 3 CF 2) 2} C 6 H 2 F) can be mentioned.

That is, the fluorine group-containing boron anion represented by the general formula (3) includes [B (C ₆ F ₅ ) ₄ ] ⁻ _, [(C ₆ H] from the viewpoint of brightness, heat resistance, and color characteristics. ₅ ) B (C ₆ F ₅ ) ₃ ] ^— _, [(C ₆ H ₅ ) ₂ B (C ₆ F ₅ ) ₂ ] ^— _, [(C ₆ H ₅ ) ₃ B (C ₆ F ₅ )] ^— _, [(C ₆ H ₅ ) B (C ₆ H ₃ (CF ₃ ) ₂ ) ₃ ³ ] ^{— and the} like. Among these, [B (C ₆ F ₅ ) ₄ ] ^— is preferable.

［一般式（４）において、Ｒ^４１〜Ｒ^４３はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、または置換基を有してもよい芳香族炭化水素基を表す。］ [Methidoacid anion represented by general formula (4)]

[In General Formula (4), R ^{41 to} R ⁴³ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. ]

In the general formula (4), examples of the “aliphatic hydrocarbon group” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Linear alkyl groups such as tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group and pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group A cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group;
In the general formula (4), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.

  In the general formula (4), examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group; polymerizable functional groups such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group and epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; phenoxy Aryloxy groups such as benzyloxy groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfa Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyls Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; a nitro group, can be mentioned a cyano group.

R ^{41 to} R ^{43 in} the general formula (4) are preferably a halogenated aliphatic hydrocarbon group or a halogenated aromatic hydrocarbon group. From the viewpoint of ^{availability,} it is preferred that R 41 ^{to R 43} are the same.

  In the general formula (4), examples of the “halogenated aliphatic hydrocarbon group” include trifluoromethyl group, difluoromethyl group, monofluoromethyl group, dichloromethyl group, monochloromethyl group, dibromomethyl group, difluorochloromethyl. Group, pentafluoroethyl group, tetrafluoroethyl group, trifluoroethyl group, trifluorochloroethyl group, difluoroethyl group, monofluoroethyl group, trifluoroiodoethyl group, heptafluoropropyl group, hexafluoropropyl group, pentafluoro Propyl group, tetrafluoropropyl group, trifluoropropyl group, difluoropropyl group, monofluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorooctylethyl group, pentaf Oro group, heptafluoroisopropyl group, can be perfluoro-3-methylbutyl group, a perfluoro-3-methylhexyl group and the like exemplified.

  In the general formula (4), examples of the “halogenated aromatic hydrocarbon group” include pentafluorophenyl group, tetrafluorophenyl group, trifluorophenyl group, difluorophenyl group, monofluorophenyl group, fluorochlorophenyl group, fluoro Examples thereof include a chlorophenyl group, a trichlorophenyl group, a dichlorophenyl group, a monochlorophenyl group, a bromophenyl group, an iodophenyl group, and a difluorobromophenyl group.

Among R ^{41 to} R ^{43 in} the general formula (4), among these, an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom is preferable, and substituted with a fluorine atom. An aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable in terms of heat resistance.

Specific examples of the methide acid anion include the following methide acid anions, but the present invention is not limited thereto. In addition, when performing salt formation, the counter of the anionic compound which has a methide acid anion (MC-1 to MC-26) shown below is Na ^<+> or K ^<+> or Cs ^<+> , tetrabutylammonium.

"Salt formation of cationic cyanine dyes and anionic compounds"
The salt-forming compound of the present invention is prepared by stirring or vibrating an aqueous solution in which the anionic compound having the anion Y ⁻ and the cationic cyanine dye are dissolved, or an aqueous solution of the anionic compound and an aqueous solution of the cationic cyanine dye. Are mixed with stirring or under vibration, a salt-forming compound can be easily obtained. In the aqueous solution, the anionic group of the anionic compound and the cationic group of the cationic cyanine dye are ionized, and these are ionically bonded, the ion-bonded portion becomes water-insoluble, and the salt-forming compound is precipitated. On the contrary, a salt composed of a counter anion of an anionic compound and a counter anion of a cationic cyanine dye is water-soluble, and therefore can be removed by washing with water. As the anionic compound and the cationic cyanine dye to be used, only a single type or a plurality of types having different structures may be used.
If the cationic cyanine dye or anionic compound is insoluble in water, each is appropriately dissolved in a soluble organic solvent, heated and stirred, and then the organic solvent is distilled off under reduced pressure or normal pressure. Then, a solid product may be obtained, and by adding water to the slurry and reslurry, the salt as a by-product may be removed, and then the solid product may be filtered to obtain a salt-forming compound. At this time, the water-soluble organic solvent mentioned later can be used for the organic solvent to be used.

  The salt-forming compound of the present invention is preferably a salt-forming compound obtained by removing a salt composed of a counter cation of an anionic compound and a counter anion of a cationic cyanine dye. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the anionic compound and the cationic cyanine dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the anionic compound to the cationic cyanine dye is that the molar ratio of the anionic unit of the anionic compound to the total cationic groups of the cationic cyanine dye is in the range of 10/1 to 1/4. The salt-forming compound can be suitably adjusted, and it is more preferable if it is in the range of 2/1 to 1/2.

[Vinyl resin having an anionic group represented by the general formula (5)]
Among resins having an anionic group in the side chain, it is preferable from the viewpoint of heat resistance to use a vinyl resin having an anionic group represented by the general formula (5). Of these, acrylic resins are preferably used.

［一般式（５）中、Ｒ^５１は水素原子、または置換もしくは無置換のアルキル基を表す。Ｑは置換もしくは無置換のアルキレン基、置換もしくは無置換のアリーレン基、−ＣＯＮＨ−Ｒ^５２−、または−ＣＯＯ−Ｒ^５２−を表し、Ｒ^５２は置換もしくは無置換のアルキレン基を表す。Ｐ⁻は、―ＳＯ_３ ⁻、または−ＣＯＯ⁻を表す。］

[In General Formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —CONH—R ⁵² —, or —COO—R ⁵² —, and R ⁵² represents a substituted or unsubstituted alkylene group. P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]

In general formula (5), examples of the alkyl group in R ⁵¹ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. It is done. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ⁵¹ is most preferably a hydrogen atom or a methyl group.

P ⁻ in the general formula (5) represents —SO ₃ ^— or —COO ^— , and —SO ₃ ^— is more preferable from the viewpoint of heat resistance.

In the general formula (5), acrylic site and P ^- component of Q connecting the alkylene group, an arylene ^{group, -CONH-R 52 -, -} COO-R 52 - ^represents, but ^{R 52} represents an alkylene group, Among these, —CONH—R ⁵² — and —COO—R ⁵² — are preferable because of polymerizability and availability.

In the general formula (5) constituting the resin, a cationic component is present as a counter ion at the stage of the cationic cyanine dye and the precursor before salt formation. In this case, the cation that can be employed is an inorganic or organic cation, and any known cation can be employed without limitation. Specifically, hydrogen, an alkali metal, an alkaline earth metal, an ammonium compound, and the like can be given. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. The ammonium compound is NH ⁴⁺ or a compound in which H is substituted with a hydrocarbon group or the like.

  In order to obtain a vinyl resin containing a structural unit represented by the following general formula (5) which is a preferred embodiment of the present invention, a method of copolymerizing monomers having a sulfonic acid group and / or a carboxyl group as a monomer component Is mentioned.

  Below, the specific example of the ethylenically unsaturated monomer which has a sulfonic acid group or carboxyl group which can be used in order to obtain the vinyl resin containing the structural unit represented by General formula (5) is shown.

[Carboxyl group-containing ethylenically unsaturated monomer]
Examples of the ethylenically unsaturated monomer having a carboxyl group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, and examples of the monomer having a carboxyl group include Further, a monomer having a carboxylic acid anhydride group is also included, and examples of the monomer having a carboxylic acid anhydride group include maleic anhydride and itaconic anhydride.

[Sulphonic acid group-containing ethylenically unsaturated monomer]
Monomers having sulphonic acid groups are monomers of the formula (IV) and their water-soluble salts, in particular alkali metal salts, such as potassium and very particularly preferably sodium and ammonium salts.
Formula (IV)
^{R 56 (R 57) C =} C (R 58) -X-SO 3 H
[Wherein R ⁵⁶ , R ⁵⁷ and R ⁵⁸ independently represent -H, a linear or branched alkyl group having 1 to 12 C atoms, or a linear or branched C atom of 2 to 12 atoms. A monounsaturated or polyunsaturated alkenyl group with the latter two groups being unsubstituted or substituted by one or more groups —NH ₂ , —OH or —COOH , —COOH or —COOR ⁵⁹ , and R ⁵⁶ is XSO ₃ H; R ⁵⁹ is a saturated or unsaturated hydrocarbon having 1 to 12 straight or branched C atoms; , A single bond, — (CH ₂ ) n— wherein n = 1 to 4, phenylene, preferably 1,4-phenylene, —CH ₂ —O-phenylene (preferably 1,4), —CH ₂ —O—. _{CH 2 -CH (OH) -CH 2} -, k It is _{1~6 -COO- (CH 2) k -} , - CO-NH-, m = 0~3 a is -CO-NH-CR'R '' - (CH 2) m or -CO-NH- CH ₂ —CH (OH) —CH ₂ —; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or —CH ₃ . ]

Particularly advantageous among the monomers having sulfonic acid groups are the monomers of formula (IVa), (IVb) and / or (IVc).
_{H 2 C = CH-X-} SO 3 H (IVa)
_{H 2 C = C (CH 3} ) -X-SO 3 H (IVb)
HO ₃ S—X— (R ⁵⁰⁰ ) C═C (R ⁵¹¹ ) —X—SO ₃ H (IVc)
[Wherein R ⁵⁰⁰ and R ⁵¹¹ independently of one another are —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ or —CH (CH ₃ ) ₂ and X is a single group. bond, n = 1 to 4 of the - _(CH 2) n-, phenylene, preferably 1,4-phenylene, _-CH 2 -O- phenylene (preferably _{1,4), - CH 2 -O-} CH 2 - _{CH (OH) -CH 2 -,} k = 1~6 of _{-COO- (CH 2) k -,} - CO-NH-, m = 0~3 of -CO-NH-CR'R '' - (CH ₂ ) m- or —CO—NH—CH ₂ —CH (OH) —CH ₂ —; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or -CH _3. ]

  Very advantageous sulfonic acid group-containing monomers are 1-acrylamide-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamide-2- Methylpropanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 3-methacrylamide-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid (2-methyl-2-propene- 1-sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, p-styrenesulfonic acid, vinylsulfonic acid, isoprene Sulfonic acid, 3-sulfopropyla Lilate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts and esters of the acids mentioned, alkali metal salts and alkaline earth metal salts It is advantageous to be in the form of Na salts and K salts.

  Particularly preferred monomers having sulfonic acid groups are 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid or 2-sodium sulfoethyl methacrylate.

[Other copolymerizable ethylenically unsaturated monomers]
Other examples of ethylenically unsaturated monomers that can be used include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (Meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such an ethylenically unsaturated monomer include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Preferred are methyl (meth) acrylate, lauryl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, or benzyl (meth) acrylate, 2-Methyl (meth) acrylate, methyl (meth) acrylate, lauryl (meth) acrylate or styrene is more preferable from the viewpoint of the storage stability of the colored composition using the salt-forming compound.

[Other ethylenically unsaturated monomers containing copolymerizable thermally crosslinkable functional groups]
By copolymerizing an ethylenically unsaturated monomer containing a heat-crosslinkable functional group, a cross-linking with an acrylic resin having a heat-crosslinkable functional group or a binder resin is formed in the heating step in the production of the color filter. . Thereby, a strong film is formed, color change of the film can be prevented, that is, heat resistance can be improved, and solvent resistance is also improved.

The preferred structure of the thermally crosslinkable functional group is not particularly limited. For example, a hydroxyl group, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, an epoxy group, a mercapto group, an isocyanate group, An allyl group, a (meth) acryl group, etc. are mentioned.
Of these, hydroxyl group, oxetanyl group, t-butyl group, isocyanate group, and (meth) acryl group are preferable from the viewpoint of storage stability and reactivity with other materials in use as a color filter coloring composition, and particularly hydroxyl group. It is preferable to have.

  One method for introducing a thermally crosslinkable functional group in a vinyl resin having an anionic group into a vinyl resin having an anionic group used in the present invention is to use an ethylenically unsaturated monomer having a thermally crosslinkable functional group. This is a method of copolymerizing the product with an ethylenically unsaturated monomer corresponding to the anionic group represented by the general formula (5).

  Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (addition mole number is preferably 1 to 5).

  Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl) 3-hexyloxetane and the like.

  Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, and the like.

  The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

  Examples of commercially available ethylenically unsaturated monomers having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Examples include 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

  Moreover, as an ethylenically unsaturated monomer which has a block isocyanate group, a commercial item can be used, and it can also prepare and use by a well-known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization and distillation are performed. It can obtain by separating using.

  Another method for introducing a thermally crosslinkable functional group in an anionic group-containing vinyl resin used in the present invention can react with the functional group of the vinyl resin after obtaining the vinyl resin. In this method, a compound having a functional group and a thermally crosslinkable functional group is reacted. For example, by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group is obtained. Can be obtained.

At least one kind of the heat-crosslinkable functional group needs to be contained in the resin, and two or more kinds may be contained.

  Examples of a method for obtaining a vinyl resin containing a structural unit represented by the general formula (5) suitable for the present invention include anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The total of the structural units having a sulfonic acid group and a carboxyl group present in the vinyl resin containing the structural unit represented by the general formula (5) suitable for the present invention is 2 out of the total 100% by weight of the copolymer composition. It is preferably a copolymer containing ˜50% by weight, more preferably a copolymer containing 5˜35% by weight. When the total of the structural units having a sulfonic acid group and a carboxyl group is less than 2% by weight, the proportion of the cationic dye in which salt formation reaction occurs is low. For this reason, the amount of the unsalted cationic dye increases, and as a result, the solvent solubility is lowered and a phenomenon such as precipitation of foreign matters may occur. Further, in order to prevent the precipitation of foreign substances, it is necessary to increase the amount of organic solvent in the resist material, but in this case, the coatability may be significantly deteriorated. On the other hand, if it exceeds 50% by weight, the amount of the cationic dye salted in the vinyl resin containing the structural unit represented by the general formula (5) becomes too large, and the heat resistance may deteriorate. is there.

  The molecular weight of the vinyl resin containing the structural unit represented by the following general formula (5) used in the present invention is not particularly limited, but is a converted weight average measured by gel permeation chromatography (GPC). The molecular weight is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by following General formula (5) suitable for this invention has the characteristic melt | dissolved in the organic solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is preferable to dissolve in glycol acetates, especially propylene glycol monomethyl ether acetate.

"Salt formation of cationic cyanine dyes and vinyl resins having anionic groups"
The salt-forming compound of the present invention is prepared by stirring or vibrating an aqueous solution in which a vinyl resin having an anionic group and a cationic cyanine dye are dissolved, or an aqueous solution of a resin having an anionic group and a cationic cyanine dye. A salt-forming compound can be easily obtained by mixing with an aqueous solution under stirring or vibration. In the aqueous solution, the anionic group of the resin and the cationic group of the dye are ionized, and these are ionically bonded, so that the ion-bonded portion becomes water-insoluble and the salt-forming compound is precipitated. On the contrary, the salt composed of the counter cation of the resin and the counter anion of the basic dye is water-soluble and can be removed by washing with water. The resin having an anionic group and the cationic cyanine dye to be used may each be a single type or a plurality of types having different structures.

  The salt-forming compound of the present invention comprises mixing a vinyl resin having an anionic group and a cationic cyanine dye in an aqueous solution to form a salt comprising a counter cation of the resin having an anionic group and a counter anion of the cationic dye. It is a compound formed by removal, or a vinyl resin having a cationic group and an anionic cyanine dye are mixed in an aqueous solution, and a counter anion of the resin having a cationic group and a counter cation of the anionic dye are used. A compound obtained by removing the salt is preferable from the viewpoints of heat resistance and storage stability. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

  Mixing water and water-soluble organic solvent to dissolve the resin having an anionic group and the cationic dye, or to dissolve the resin having the cationic group and the anionic dye, as an aqueous solution to be used at the time of salt formation A solution may be used. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the resin having an anionic group and the cationic cyanine dye is such that the molar ratio of the total anionic unit of the resin to the total cationic group of the cationic cyanine dye is in the range of 10/1 to 1/4. It is more preferable if the salt-forming compound of the invention can be suitably adjusted and is in the range of 2/1 to 1/2.

(Pigment (B))
The pigment (B) is further used in the colored composition for a solid-state imaging device of the present invention. This makes it possible to adjust the hue and improve resistance. In addition, the color separation characteristics for the solid-state imaging device can be excellent.
The use ratio of the cyanine dye (ZC) and the pigment (B) is preferably 1 to 200 parts by weight of the cyanine dye (ZC) with respect to 100 parts by weight of the pigment (B). More preferably, it is 50-150 weight part. When the amount of the cyanine dye (ZC) added is within this range, the hue and reproducible chromaticity region can be excellent.

As the pigment used in combination, the following are used for each color filter segment.
≪Pigment forming red filter segment≫
As a red pigment for a red coloring composition forming a red filter segment,
C. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 224, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP 2011-523433, or JP2013 Although the naphthol azo pigment etc. which are described in -161025 gazette are mentioned, it is not limited in particular.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Red 177, 242, 254, or 269 is preferably used. More preferably, C.I. I. Pigment Red 177 or 254.

  In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026, but not limited thereto. .
Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used. More preferably, C.I. I. Pigment Yellow 139.

  These pigments can be used alone or in admixture of two or more at any ratio as required.

≪Pigment forming blue filter segment≫
As a blue pigment for a blue coloring composition forming a blue filter segment,
C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not particularly limited thereto.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 or the like, but not limited thereto.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Blue 15: 1 or 15: 6 is preferably used.

≪Pigment forming green filter segment≫
As a green pigment for a green coloring composition forming a green filter segment,
C. I. Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigment described in JP 2008-193833 A, JP 2007-320986 A, JP 2004-70342 A, etc., or Japanese Patent No. 4893859 The aluminum phthalocyanine pigment described in 1) is mentioned, but it is not particularly limited thereto.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Green 7, 36, or 58 is preferably used.

  In addition, a yellow pigment can be used in combination with the green coloring composition in order to adjust the hue.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026, etc. Not.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used.

[Miniaturization of pigment]
The pigment (B) of the present invention is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

  It is also preferable to add the cyanine dye (ZC) of the present invention at the same time when the salt is milled (miniaturized). When the pigment is refined, a good colorant can be obtained by adding it together.

(Other colorants)
The coloring composition for a solid-state imaging device of the present invention may further be used in combination with other dyes.
Examples of the dyes that can be used in combination include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Oil-soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
In addition, according to the chemical structure, azo dyes, cyanine dyes other than cyanine dyes (ZC), triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, xanthene dyes, squarylium dyes, Examples include acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes.

<Binder resin>
The binder resin in the present invention disperses or permeates the colorant, and examples thereof include thermoplastic resins and thermosetting resins. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, a fat that functions as an affinity group for the colorant carrier and the organic solvent. Resin having an acid value of 20 to 300 mgKOH / g is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured portion, and the durability. Is preferably used. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics. Is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be widened by such a composition ratio of the colorant.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These organic solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The colored composition for a solid-state imaging device of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the coloring composition for solid-state imaging devices from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing. The rate can be increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the colored composition for a solid-state imaging device (100% by weight), because the brightness and sensitivity are good. preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a coloring agent in a coloring agent carrier such as a binder resin and / or an organic solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill. Further, it can be produced by finely dispersing using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, the cyanine dye (ZC), the pigment (B), and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. If the colorant has high solubility, specifically, it is highly soluble in the organic solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, an organic solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed on the support by the colored composition for a solid-state imaging device of the present invention. The color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a coloring composition for a solid-state imaging device of the present invention. It is preferable to use a product. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  When having a filter segment other than at least one filter segment formed by the colored composition for a solid-state imaging device of the present invention, an ordinary red colored composition, green colored composition, or blue colored composition is used. Can be formed.

<Color filter manufacturing method>
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  In the method for producing a color filter of the present invention, the colored composition for a solid-state imaging device of the present invention is applied directly or via another layer on a substrate (and then dried as necessary) to form a colored layer. A colored layer forming step, an exposure step of exposing the colored layer through a mask (for example, in a pattern), and a developing step of developing the exposed colored layer to form a pattern are provided. Moreover, you may provide the process of hardening a pattern by a heating and / or exposure as needed, and the post-baking process which performs a post-baking process to the developed colored layer. Through these steps, a colored pattern can be formed.

The colored composition of the present invention described above is used for forming a pattern of a color filter for a solid-state imaging device such as a CCD, and is particularly effective for forming a fine pattern.
Specifically, it is effective for forming a pattern having a pattern dimension of 2.5 μm or less, and is particularly effective for forming a pattern having a pattern dimension of 2.0 μm or less. Further, the film thickness of the pattern is effective for forming a pattern with a film thickness of 1.5 μm or less, and is particularly effective for forming a pattern with a film thickness of 1.0 μm or less.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated in detail.
In the colored layer forming step, the colored composition is applied onto the substrate by a coating method such as spin coating, cast coating, roll coating, slit coating, and the like, and further dried as necessary to form a colored layer.
Examples of the substrate include a silicon substrate, and a solid-state imaging device such as a CCD or CMOS. In some cases, a black matrix for isolating each pixel is formed on these substrates. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion with a layer provided on the substrate, prevent diffusion of substances, or planarize the substrate surface.

  In the exposure step, a specific pattern is exposed to the colored layer formed in the colored layer forming step through a mask. As the radiation used for exposure, ultraviolet rays such as g-line, h-line and i-line are preferably used. Among these, i-line is particularly preferable from the viewpoint of forming a finer pattern.

In the development step, the exposed colored layer is developed with an alkali developer or the like.
Any alkali developer may be used as long as it dissolves the unexposed portion of the colored photocurable composition of the present invention and does not dissolve the exposed portion (radiation irradiated portion). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the organic solvents described in the above <Organic solvent> section.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved as such is mentioned.
When a developer composed of an alkaline aqueous solution is used, it is generally preferable to wash with water after development.

The alkaline developer is preferably an alkaline aqueous solution adjusted to have an alkali concentration of preferably pH 11 to 13, more preferably pH 11.5 to 12.5. When the alkali concentration is within the above range, pattern roughness and peeling can be more effectively suppressed, the remaining film rate can be further improved, and the development rate is reduced and the generation of development residues is further reduced. It can be effectively suppressed.
In the development step, it is preferable to perform development with a developer composed of such an alkaline aqueous solution. Examples of the developing method include a dipping method, a spray method, a paddle method, and the like, and the temperature is preferably 15 to 40 ° C.

  In the method for producing a color filter of the present invention, it is preferable that a post-baking process is performed in the post-baking step in order to sufficiently cure the coated film after development. 100-300 degreeC is preferable and the heating temperature in a post-baking process has more preferable 150-250 degreeC. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

The color filter of the present invention is used for the production of a solid-state imaging device, and is suitable for an image sensor such as a CCD, particularly a high-resolution CCD device or a CMOS device that exceeds 1 million pixels. The color filter of the present invention is more preferably used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.
Among them, it is more suitable to use as a color filter having a pattern size of 2.5 μm or less (more preferably 2.0 μm or less), and a pattern film having a pattern size of 2.5 μm or less (more preferably 2.0 μm or less). It is optimal to use as a color filter having a thickness of 1.5 μm or less (more preferably 1.0 μm or less).

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Prior to the examples, a method for measuring the weight average molecular weight of the resin will be described.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Subsequently, binder resins, cationic cyanine dyes used in Examples and Comparative Examples, imido acid anion compounds represented by general formula (2), fluorine group-containing boron anion compounds represented by general formula (3), general formulas (4) a methide acid anion compound, a vinyl resin having an anionic group represented by the general formula (5), a cyanine dye solution, a xanthene dye solution, a method for producing a fine pigment, and a resin-type dispersant The method for preparing the solution, the pigment dispersion, and the method for producing the photosensitive coloring composition will be described.

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized resin solution had a non-volatile content of 20% by weight. Ethyl ether acetate was added to prepare an acrylic resin solution 1.

<Synthesis Method of Cationic Cyanine Dye>
The following cationic cyanine dyes were synthesized with reference to J. Org. Chem., 1995, 60 (8), pp 2411-2422, J. Am. Chem. Soc., 2011, 133 (40), pp 15870-15873. .
Cationic cyanine dyes in the present invention were synthesized according to the following reaction schemes 1 to 3, respectively.

(Cationic cyanine dye (A-1))
In the cationic cyanine dye (A-1), first, the intermediate (a-1) was synthesized, and then the target product, the cationic cyanine dye (A-1), was synthesized in the next step.
(Reaction Scheme 1)

“Synthesis of Intermediate (a-1)”
To a 100 ml four-necked flask equipped with a thermometer, a dropping funnel and a cooling tube, 5 parts of 2,3,3-trimethylindolenine, 7.35 parts of iodoethane and 10 ml of acetonitrile were added, and the mixture was heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 ml of diethyl ether was added, washed and filtered with suction. 8.61 parts of product were obtained. The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 188.25 (molecular weight 188.14).

“Synthesis of Cationic Cyanine Dye (A-1)”
Add 8.61 parts of intermediate (a-1) and 15 ml of acetic anhydride to a 100 ml four-necked flask equipped with a thermometer, a dropping funnel, a condenser, and a nitrogen flow tube, and then add triethyl orthoformate using the dropping funnel. 05 parts were added dropwise and heated to reflux. After 1 hour, the mixture was cooled to room temperature to precipitate a solid. The precipitated solid was filtered off with suction and washed with 30 ml of ethyl acetate and 30 ml of ion-exchanged water. It was dried by heating overnight at 40 ° C. in a hot air dryer to obtain 6.16 parts of product. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 385.33 (molecular weight 385.26).

中間体（ａ−１）のヨードエタンをヨードブタンに変更した以外は、中間体（ａ−１）と同様に合成し、９．４９部の生成物（中間体（ａ−２））を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２１６．２９（分子量２１６．１７）で目的物であることを確認した。中間体（ａ−２）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．６８部のカチオン性シアニン染料（Ａ−２）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４４１．４５（分子量４４１．３３）で目的物であることを確認した。 (Cationic cyanine dye (A-2))

The intermediate (a-1) was synthesized in the same manner as the intermediate (a-1) except that iodoethane was changed to iodobutane to obtain 9.49 parts of the product (intermediate (a-2)). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 216.29 (molecular weight 216.17). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-2) was used to obtain 6.68 parts of a cationic cyanine dye (A-2). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 441.45 (molecular weight: 441.33).

中間体（ａ−１）のヨードエタンをヨードヘキサンに変更した以外は、中間体（ａ−１）と同様に合成し、９．７９部の生成物（中間体（ａ−３））を得た。収率は８４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２４４．３５（分子量２４４．２１）で目的物であることを確認した。中間体（ａ−３）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．９２部のカチオン性シアニン染料（Ａ−３）を得た。収率は８４％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４９７．５１（分子量４９７．３９）で目的物であることを確認した。 (Cationic cyanine dye (A-3))

The intermediate (a-1) was synthesized in the same manner as the intermediate (a-1) except that the iodoethane was changed to iodohexane to obtain 9.79 parts of the product (intermediate (a-3)). . The yield was 84%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 244.35 (molecular weight 244.21). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-3) was used to obtain 6.92 parts of a cationic cyanine dye (A-3). The yield was 84%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 497.51 (molecular weight 497.39).

中間体（ａ−１）のヨードエタンを３−ヨードプロピレンに変更した以外は、中間体（ａ−１）と同様に合成し、９．０４部の生成物（中間体（ａ−４））を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２００．２８（分子量２００．１４）で目的物であることを確認した。中間体（ａ−４）を用い、反応温度を８０ ℃に変更した以外は、カチオン性シアニン染料（Ａ−１）と同様に合成した。４．６０部のカチオン性シアニン染料（Ａ−４）を得た。収率は６２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４０９．３６（分子量４０９．２６）で目的物であることを確認した。 (Cationic cyanine dye (A-4))

The intermediate (a-1) was synthesized in the same manner as the intermediate (a-1) except that the iodoethane was changed to 3-iodopropylene, and 9.04 parts of the product (intermediate (a-4)) was obtained. Obtained. The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 200.28 (molecular weight 200.14). Synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-4) was used and the reaction temperature was changed to 80 ° C. 4.60 parts of cationic cyanine dye (A-4) was obtained. The yield was 62%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 409.36 (molecular weight 409.26).

(Cationic cyanine dye (A-5))
As for the cationic cyanine dye (A-5), first, the intermediate (a-5) was synthesized, and then the cationic cyanine dye (A-5) as the target product was synthesized in the next step.
(Reaction Scheme 2)

“Synthesis of Intermediate (a-5)”
In a 100 ml four-necked flask equipped with a thermometer, a dropping funnel and a condenser, 2,3,3-trimethylindolenine, 5 parts, 2- (4-bromo-butoxymethyl) -oxirane, 9.85 parts, potassium iodide 5 .21 parts and 10 ml of acetonitrile were added and heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 ml of diethyl ether was added, washed and filtered with suction. 5.87 parts of product (intermediate (a-5)) were obtained. The yield was 52%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 288.31 (molecular weight 288.20).

"Synthesis of cationic cyanine dye (A-5)"
The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-5) was used to obtain 5.54 parts of the cationic cyanine dye (A-5). The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 585.49 (molecular weight 585.37).

中間体（ａ−５）の２−（４−ブロモ−ブトキシメチル）−オキシランを（４−ブロモ−ブチル）−カルバミック酸ビニルエステルに変更した以外は、中間体（ａ−５）と同様に合成し、７．９３部の生成物（中間体（ａ−６））を得た。収率は５９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３０１．３１（分子量３０１．１９）で目的物であることを確認した。中間体（ａ−６）を用いた以外はカチオン性シアニン染料（Ａ−１）と同様に合成し、３．７６部のカチオン性シアニン染料（Ａ−６）を得た。収率は５５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６１１．４８（分子量６１１．３６）で目的物であることを確認した。 (Cationic cyanine dye (A-6))

Synthesis similar to Intermediate (a-5) except that 2- (4-bromo-butoxymethyl) -oxirane of intermediate (a-5) was changed to (4-bromo-butyl) -carbamic acid vinyl ester 7.93 parts of product (intermediate (a-6)) was obtained. The yield was 59%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 301.31 (molecular weight 301.19). The compound was synthesized in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-6) was used to obtain 3.76 parts of a cationic cyanine dye (A-6). The yield was 55%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 611.48 (molecular weight 611.36).

(Cationic cyanine dye (A-7))
The cationic cyanine dye (A-7) is prepared by first synthesizing the intermediate (a-7a), then synthesizing the intermediate (a-7b) in the next step, and in the next step, the target cationic compound. A cyanine dye (A-7) was synthesized.
(Reaction Scheme 3)

“Synthesis of Intermediate (a-7a)”
The intermediate (a-5) was synthesized in the same manner as the intermediate (a-5) except that 2- (4-bromo-butoxymethyl) -oxirane was changed to 3-bromopropionic acid, and 5.87 parts of The product (intermediate (a-7a)) was obtained. The yield was 52%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). m / z = 232.25 (molecular weight 232.13), which confirmed the intended product.

“Synthesis of Intermediate (a-7b)”
In a 100 ml three-necked flask equipped with a thermometer, a dropping funnel and a condenser, 9.81 parts of intermediate (a-7a), 15 ml of dichloromethane, 0.40 parts of 4- (N, N dimethyl) aminopyridine, 2-hydroxy 2.55 parts of ethyl methacrylate and 3.44 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added and stirred at room temperature for 24 hours. The liquid separation operation was performed twice with 30 ml of ion-exchanged water, and then the organic layer was washed twice with 50 ml of saturated saline. After adding 5 parts of magnesium sulfate and stirring for 30 minutes, the magnesium sulfate was filtered and the solvent was distilled off. The mixture was heated and dried overnight at 40 ° C. in a vacuum drier to obtain 5.46 parts of the product (intermediate (a-7b)). The yield was 71%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 344.31 (molecular weight 344.19).

“Synthesis of Cationic Cyanine Dye (A-7)”
The compound was synthesized in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-7b) was used. 5.54 parts of product (A-7) were obtained. The yield was 58%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 824.38 (molecular weight 824.25).

中間体（ａ−１）の２，３，３−トリメチルインドレニンを２，３，３−トリメチル−４，５−ベンゾ−３Ｈ−インドールに変更した以外は、中間体（ａ−１）と同様に合成し、７．５９部の生成物（中間体（ａ−８））を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３８．２８（分子量２３８．１６）で目的物であることを確認した。中間体（ａ−８）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、５．７９部のカチオン性シアニン染料（Ａ−８）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４８５．４２（分子量４８５．３０）で目的物であることを確認した。 (Cationic cyanine dye (A-8))

Same as intermediate (a-1) except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 2,3,3-trimethyl-4,5-benzo-3H-indole To obtain 7.59 parts of the product (intermediate (a-8)). The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 238.28 (molecular weight 238.16). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-8) was used to obtain 5.79 parts of a cationic cyanine dye (A-8). The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 485.42 (molecular weight 485.30).

中間体（ａ−１）の２,３,３−トリメチルインドレニンを５−ブロモ−２,３,３−トリメチルインドレニンに変更した以外は、中間体（ａ−１）と同様に合成し、７．５３部の生成物（中間体（ａ−９））を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２６６．１８（分子量２６６．０５）で目的物であることを確認した。中間体（ａ−９）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、５．８９部のカチオン性シアニン染料（Ａ−９）を得た。収率は９２％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５４１．２０（分子量５４１．０８）で目的物であることを確認した。 (Cationic cyanine dye (A-9))

Synthesized in the same manner as intermediate (a-1) except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 5-bromo-2,3,3-trimethylindolenine, 7.53 parts of product (intermediate (a-9)) were obtained. The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). The product was confirmed to be the target product with a cationic component m / z = 266.18 (molecular weight 266.05). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-9) was used, and 5.89 parts of the cationic cyanine dye (A-9) was obtained. The yield was 92%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed to be the target product by a cationic component m / z = 541.20 (molecular weight: 541.08).

中間体（ａ−９）のヨードエタンをヨードブタンに変更した以外は、中間体（ａ−９）と同様に合成し、７．８０部の生成物（中間体（ａ−１０））を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２９４．２０（分子量２９４．０９）で目的物であることを確認した。中間体（ａ−１０）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．０４部のカチオン性シアニン染料（Ａ−１０）を得た。収率は９０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５９９．５９（分子量５９９．４６）で目的物であることを確認した。 (Cationic cyanine dye (A-10))

The intermediate (a-9) was synthesized in the same manner as the intermediate (a-9) except that iodoethane was changed to iodobutane to obtain 7.80 parts of the product (intermediate (a-10)). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). The product was confirmed to be the target product with a cationic component m / z = 294.20 (molecular weight 294.09). Synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-10) was used to obtain 6.04 parts of a cationic cyanine dye (A-10). The yield was 90%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 599.59 (molecular weight 599.46).

中間体（ａ−９）のヨードエタンをヨードヘキサンに変更した以外は、中間体（ａ−９）と同様に合成し、８．０４部の生成物（中間体（ａ−１１））を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝３２２．２４（分子量３２２．１２）で目的物であることを確認した。中間体（ａ−１１）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．１４部のカチオン性シアニン染料（Ａ−１１）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝６５３．３３（分子量６５３．２１）で目的物であることを確認した。 (Cationic cyanine dye (A-11))

The intermediate (a-9) was synthesized in the same manner as the intermediate (a-9) except that the iodoethane was changed to iodohexane to obtain 8.04 parts of the product (intermediate (a-11)). . The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 322.24 (molecular weight 322.12). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-11) was used to obtain 6.14 parts of a cationic cyanine dye (A-11). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 653.33 (molecular weight 653.21).

中間体（ａ−１）の２,３,３−トリメチルインドレニンを５−クロロ−２,３,３−トリメチルインドレニンに変更した以外は、中間体（ａ−１）と同様に合成し、８．１２部の生成物（中間体（ａ−１２））を得た。収率は９０％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２２２．２３（分子量２２２．１０）で目的物であることを確認した。中間体（ａ−１２）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．１５部のカチオン性シアニン染料（Ａ−１２）を得た。収率は９１％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４５３．３０（分子量４５３．１９）で目的物であることを確認した。 (Cationic cyanine dye (A-12))

Synthesized in the same manner as intermediate (a-1) except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 5-chloro-2,3,3-trimethylindolenine, 8.12 parts of product (intermediate (a-12)) were obtained. The yield was 90%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 222.23 (molecular weight 222.10). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-12) was used to obtain 6.15 parts of a cationic cyanine dye (A-12). The yield was 91%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 453.30 (molecular weight 453.19).

中間体（ａ−１２）のヨードエタンをヨードブタンに変更した以外は、中間体（ａ−１２）と同様に合成し、８．５８部の生成物（中間体（ａ−１３））を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２５０．２８（分子量２５０．１４）で目的物であることを確認した。中間体（ａ−１３）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．４４部のカチオン性シアニン染料（Ａ−１３）を得た。収率は８９％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５０９．３８（分子量５０９．２５）で目的物であることを確認した。 (Cationic cyanine dye (A-13))

The intermediate (a-12) was synthesized in the same manner as the intermediate (a-12) except that iodoethane was changed to iodobutane to obtain 8.58 parts of the product (intermediate (a-13)). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 250.28 (molecular weight 250.14). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-13) was used, to obtain 6.44 parts of a cationic cyanine dye (A-13). The yield was 89%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 509.38 (molecular weight 509.25).

中間体（ａ−１２）のヨードエタンをヨードヘキサンに変更した以外は、中間体（ａ−１２）と同様に合成し、９．１１部の生成物（中間体（ａ−１４））を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２７８.２７（分子量２７８．１７）で目的物であることを確認した。中間体（ａ−１４）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．８５部のカチオン性シアニン染料（Ａ−１４）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５６５．４４（分子量５６５．３１）で目的物であることを確認した。 (Cationic cyanine dye (A-14))

The intermediate (a-12) was synthesized in the same manner as the intermediate (a-12) except that the iodoethane was changed to iodohexane to obtain 9.11 parts of the product (intermediate (a-14)). . The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a desired product with a cationic component m / z = 278.27 (molecular weight 278.17). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-14) was used to obtain 6.85 parts of a cationic cyanine dye (A-14). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 565.44 (molecular weight 565.31).

中間体（ａ−１）の２,３,３−トリメチルインドレニンを２,３,３,５−テトラメチルインドレニンに、ヨードエタンをヨードブタンに変更した以外は中間体（ａ−１）と同様に合成し、９．０７部の生成物（中間体（ａ−１５））を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２３０．３１（分子量２３０．１９）で目的物であることを確認した。中間体（ａ−１５）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．４４部のカチオン性シアニン染料（Ａ−１５）を得た。収率は８５％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝４６９．４６（分子量４６９．３６）で目的物であることを確認した。 (Cationic cyanine dye (A-15))

Same as intermediate (a-1) except that 2,3,3-trimethylindolenine in intermediate (a-1) was changed to 2,3,3,5-tetramethylindolenine and iodoethane was changed to iodobutane Synthesized to obtain 9.07 parts of product (intermediate (a-15)). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 230.31 (molecular weight 230.19). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-15) was used to obtain 6.44 parts of a cationic cyanine dye (A-15). The yield was 85%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 469.46 (molecular weight 469.36).

中間体（ａ−１）の２,３,３−トリメチルインドレニンを５−メトキシ−２,３,３−トリメチルインドレニンに、ヨードエタンをヨードブタンに変更した以外は、中間体（ａ−１）と同様に合成し、８．５８部の生成物（中間体（ａ−１６））を得た。収率は８７％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝２４６．３２（分子量２４６．１９）で目的物であることを確認した。中間体（ａ−１６）を用いた以外は、カチオン性シアニン染料（Ａ−１）と同様に合成し、６．３６部のカチオン性シアニン染料（Ａ−１６）を得た。収率は８８％であった。質量分析装置（ＴＯＦ−ＭＳ：ブルカー・ダルトニクス社製 ａｕｔｏｆｌｅｘＩＩ）で化合物の同定を行なった。カチオン成分ｍ／ｚ＝５０１．４６（分子量５０１．３５）で目的物であることを確認した。 (Cationic cyanine dye (A-16))

The intermediate (a-1) and the intermediate (a-1) were changed except that 2,3,3-trimethylindolenine in the intermediate (a-1) was changed to 5-methoxy-2,3,3-trimethylindolenine and iodoethane was changed to iodobutane. The same synthesis was performed to obtain 8.58 parts of the product (intermediate (a-16)). The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 246.32 (molecular weight 246.19). The synthesis was performed in the same manner as the cationic cyanine dye (A-1) except that the intermediate (a-16) was used to obtain 6.36 parts of a cationic cyanine dye (A-16). The yield was 88%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 501.46 (molecular weight 501.35).

温度計、撹拌機、冷却管を具備した４つ口セパラブルフラスコに、トリフルオロメタンスルホンアミド３．５８部（１．１当量）と炭酸カリウム５．５３部（２当量）、アセトニトリル６０ｍｌを加えた後、ペンタフルオロベンゼンスルホニルクロリド３．５３部を分割添加し、５時間加熱還流した。室温まで冷却後、アセトニトリル４００ｍｌを加えてよく撹拌した後、吸引ろ過により得られたろ液を濃縮して、７．３０部の生成物を得た。^１Ｈ、^１３Ｃ−ＮＭＲスペクトル（溶剤：重水素化クロロホルム）測定により、得られた化合物が目的化合物（イミド酸アニオン化合物（Ｇ−１））であることを確認した。 <The manufacturing method of the imido acid anion compound represented by General formula (2)>
(Imidic acid anion compound (G-1))

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 3.58 parts (1.1 equivalents) of trifluoromethanesulfonamide, 5.53 parts (2 equivalents) of potassium carbonate, and 60 ml of acetonitrile were added. Thereafter, 3.53 parts of pentafluorobenzenesulfonyl chloride was added in portions and heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 7.30 parts of product. It was confirmed by ¹ H, ¹³ C-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was the target compound (imido acid anion compound (G-1)).

イミド酸アニオン化合物（Ｇ−１）の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−フルオロベンゼンスルホニルクロリドを使用した以外は同様にして、イミド酸アニオン化合物（Ｇ−２）を得た。 (Imic acid anion compound (G-2))

In the synthesis of imido acid anion compound (G-1), imido acid anion compound (G-2) was obtained in the same manner except that p-fluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

イミド酸アニオン化合物（Ｇ−１）の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−トリフルオロメチルベンゼンスルホニルクロリドを使用した以外は同様にして、イミド酸アニオン化合物（Ｇ−３）を得た。 (Imidic acid anion compound (G-3))

In the synthesis of the imido acid anion compound (G-1), imido acid anion compound (G-3) was obtained in the same manner except that p-trifluoromethylbenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride. .

イミド酸アニオン化合物（Ｇ−１）の合成において、トリフルオロメタンスルホンアミドに代えてｐ−トリフルオロメチルベンゼンスルホンアミドを使用した以外は同様にして、イミド酸アニオン化合物（Ｇ−４）を得た。 (Imidic acid anion compound (G-4))

In the synthesis of the imido acid anion compound (G-1), imido acid anion compound (G-4) was obtained in the same manner except that p-trifluoromethylbenzenesulfonamide was used instead of trifluoromethanesulfonamide.

<Method for Producing Fluorine Group-Containing Boron Anion Compound Represented by General Formula (3)>
Hereinafter, a fluorine group-containing boron anion compound was synthesized with reference to JP2011-201803A.

(Fluorine group-containing boron anion compound (FBA-1))
A reaction vessel purged with deaerated nitrogen is charged with 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran, and cooled to 18 ° C. in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged into a dropping funnel and added dropwise so that the internal temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 3.0 parts of dichlorophenylborane is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 65 ° C. for 2 hours to complete the reaction.
This solution is added to 50 parts of a saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the resulting ethyl acetate layer is added to the previously separated organic layer. added. The organic layer was removed, and the residue was washed twice with hexane, and the residue was dried under reduced pressure to obtain sodium phenyltris (pentafluorophenyl) borate (fluorine group-containing boron anion compound (FBA-1)). ) 10.4 parts, yield 90% (purity 98% or more). The product (FBA-1) was identified by ¹ H-NMR and ¹⁹ F-NMR. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Fluorine group-containing boron anion compound (FBA-2))
A reaction vessel purged with deaerated nitrogen is charged with 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran, and cooled to 18 ° C. in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged into a dropping funnel and added dropwise so that the internal temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 2.4 parts of boron trifluoride diethyl ether complex is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. The reaction is continued at 65 ° C. for 12 hours after completion of the dropping.
This solution is added to 50 parts of a saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the resulting ethyl acetate layer is added to the previously separated organic layer. added. The organic layer was removed, and the residue was washed twice with hexane, and the residue was dried under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate (fluorine group-containing boron anion compound (FBA-2)) as the target product. 5.8 parts, yield 40% (purity 98% or more). The product (FBA-2) was identified by ¹⁹ F-NMR. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

<Method for Producing Methetic Acid Anion Compound Represented by General Formula (4)>
The methide acid anion was synthesized with reference to JP 2009-155206 A.

ＰＴＦＥ撹拌子（１５ｍｍ、φ＝６ｍｍ）を入れた３つ口フラスコに、温度計を取り付け、塩化カルシウムを通した窒素気流下で１．０Ｍメチルマグネシウムブロミド−テトラヒドロフラン溶液（東京化成工業製）２１５．７部を加えて氷冷後、内温１５℃以下でトリフルオロメタンスルホニルフルオリド１１部を添加した。一旦内温４０℃まで加熱撹拌し、再びトリフルオロメタンスルホニルフルオリド５部加え、室温にて２４時間撹拌した。０．３Ｍ塩化カリウム水溶液を２００加えてよく撹拌した後、エバポレーターにてテトラヒドロフランを留去した。析出物を吸引ろ過にてろ別し、得られたろ物を水による再結晶にて精製し、カリウムトリス（トリフルオロメタンスルホニル）メチド（メチド酸アニオン化合物（Ｍ−１））を収量８．２部で得た。¹⁹Ｆ-ＮＭＲにて目的物であることを確認した。 (Methido acid anion compound (M-1))

A thermometer was attached to a three-necked flask containing a PTFE stirrer (15 mm, φ = 6 mm), and a 1.0 M methylmagnesium bromide-tetrahydrofuran solution (manufactured by Tokyo Chemical Industry Co., Ltd.) under a nitrogen stream through calcium chloride 215. After adding 7 parts and cooling with ice, 11 parts of trifluoromethanesulfonyl fluoride was added at an internal temperature of 15 ° C. or lower. The mixture was once heated and stirred to an internal temperature of 40 ° C., 5 parts of trifluoromethanesulfonyl fluoride was added again, and the mixture was stirred at room temperature for 24 hours. After adding 200M 0.3M potassium chloride aqueous solution and stirring well, tetrahydrofuran was distilled off by the evaporator. The precipitate was filtered off with suction filtration, and the obtained filtrate was purified by recrystallization with water to obtain potassium tris (trifluoromethanesulfonyl) methide (methideic acid anion compound (M-1)) in a yield of 8.2 parts. Obtained. It was confirmed to be the target product by ¹⁹ F-NMR.

<Method for Producing Vinyl Resin Having Anionic Group Represented by General Formula (5)>
(Resin having an anionic group (AJ-1))
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 20.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12.5 parts of methyl methacrylate, 20.0 parts of n-butyl methacrylate, 20.0 parts of 2-ethylhexyl methacrylate, 3.0 parts of methacrylic acid, 2 -16.5 parts of hydroxyethyl methacrylate, 6.5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were made uniform and charged into a dropping funnel. It was attached to a separable flask and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 3390, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin (AJ-1) having a resin component having 47% by weight of an anionic group was obtained.

(Resin having an anionic group (AJ-2 to 4))
Resins (AJ-2 to 4) were obtained in the same manner as the resin (AJ-1) except that the material composition was changed to those shown in Table 1.

<Cyanine dye (ZC) represented by general formula (1)>
(Cyanine dye (ZC-1))
A cyanine dye (ZC-1) comprising a cationic cyanine dye and a resin having an anionic group (AJ-1) was produced by the following procedure.

  A resin (AJ-1) having 57.1 parts of an anionic group and 1.5 parts of sodium hydroxide are added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution in which 10 parts of the cationic cyanine dye (A-1) is dissolved in 45 parts of water and 45 parts of methanol is prepared and added dropwise to the above resin solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. Thereafter, the solvent was removed by evaporation under reduced pressure using an evaporator, the concentrated solution was dropped into 1000 parts of water while stirring, and the resulting precipitate was taken out by suction filtration, washed with water, and then left on the filter paper. The salt compound was dried with a dryer to obtain a cyanine dye (ZC-1) which is a salt-forming compound of 32 parts of the cationic cyanine dye (A-1) and an anionic group-containing resin (AJ-1). . By-products such as salt and salt exchange reactions between dyes and resins, trace amounts of unreacted dyes, and unreacted resins can be removed during suction filtration because they dissolve in water when the concentrate is added dropwise to water while stirring. . In addition, by-products that remain slightly in the subsequent washing with water are completely removed.

(Cyanine dyes (ZC-2 to ZC-19, ZC-27))
A cationic cyanine dye and an anionic group are the same as the cyanine dye (ZC-1) except that the type and blending amount (parts by weight) of the resin having a cationic cyanine dye and an anionic group shown in Table 2 are changed. Cyanine dyes (ZC-2 to ZC-19, ZC-27), which are salt-forming compounds composed of a resin having a pH value, were produced. About Basic.Red.12 (CI basic red 12) used for ZC-27, Aizen Astra Phloxine manufactured by Hodogaya Chemical Co., Ltd. was used.

(Cyanine dye (ZC-20))
A cyanine dye (ZC-20), which is a salt-forming compound composed of a cationic cyanine dye and an imido acid anion compound (G-1), was produced by the following procedure.

  In a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone, and 100 parts of acetone, 8.23 parts of imidoanion anion (G-1) and 10 parts of cationic cyanine dye (A-13) are dissolved. The mixture was stirred at 60 ° C. for 240 minutes and sufficiently reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The taken out salt-forming compound was dried with a dryer, and 14.3 parts of a cyanine dye (ZC-) which is a salt-forming compound of the cationic cyanine dye (A-13) and the imido acid anion compound (G-1). 20) was obtained.

(Cyanine dye (ZC-21 to ZC-23, 28, 30))
Various cationic cyanine dyes and various kinds in the same manner as the cyanine dye (ZC-20) except that the types and blending amounts (parts by weight) of the cationic cyanine dye and imido acid anion compound were changed to the contents shown in Table 2. Cyanine dyes (ZC-21 to ZC-23, 28, 30), which are salt-forming compounds composed of an imido acid anion compound, were produced.

(Cyanine dye (ZC-24))
A cyanine dye (ZC-24), which is a salt-forming compound composed of a cationic cyanine dye and a fluorine group-containing boron anion compound (FBA-1), was produced by the following procedure.

  A cationic cyanine dye (A-13) in a mixed solvent of 300 parts of methanol, 100 parts of methyl ethyl ketone and 100 parts of acetone is dissolved, and 12.79 parts of a fluorine group-containing boron anion compound (FBA-1) in 1000 parts of water in advance. ) Is dissolved dropwise. Then, it stirred for 240 minutes at 60 degreeC and fully reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The taken out salt-forming compound was dried with a dryer, and a cyanine dye (ZC) which is a salt-forming compound of 14.3 parts of cationic cyanine dye (A-13) and a fluorine-containing boron anion compound (FBA-1). -24) was obtained.

(Cyanine dye (ZC-25, 29, 31, 32))
Various kinds of cationic cyanines similar to the salt-forming compounds (ZC-24) except that the types and blending amounts (parts by weight) of the cationic cyanine dye and fluorine-containing boron anion compound were changed to the contents shown in Table 2. Cyanine dyes (ZC-25, 29, 31, 32), which are salt-forming compounds of dyes and various fluorine group-containing boron anion compounds, were produced.

(Cyanine dye (ZC-26))
A cyanine dye (ZC-26), which is a salt-forming compound composed of a cationic cyanine dye and a methide acid anion compound (M-1), was produced by the following procedure.

  Dissolve 9.94 parts of methide acid anion compound (M-1) and 10 parts of cationic cyanine dye (A-13) in a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone, and 100 parts of acetone. The mixture was stirred at 60 ° C. for 240 minutes and sufficiently reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The taken out salt-forming compound was dried with a drier, and 12.1 parts of a cyanine dye (ZC-) which is a salt-forming compound of a cationic cyanine dye (A-13) and a methide acid anion compound (M-1). 26) was obtained.

(Cyanine dye (ZC-32))
A cyanine dye (ZC-32), which is a salt-forming compound composed of a cationic cyanine dye and a tetrafluoroboron anion compound, was produced by the following procedure.

  The cationic cyanine dye (A-1) in 300 parts of methanol, 100 parts of methyl ethyl ketone and 10 parts of acetone was dissolved in 2.5 parts of sodium tetrafluoroboron in 1000 parts of water in advance. Mix the solution dropwise. Then, it stirred for 240 minutes at 60 degreeC and fully reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The extracted salt-forming compound was dried with a dryer to obtain a cyanine dye (ZC-32) which is a salt-forming compound of 14.3 parts of cationic cyanine dye (A-1) and a perchlorate anion compound. .

(Cyanine dye (ZC-33))
A cyanine dye (ZC-33), which is a salt-forming compound composed of a cationic cyanine dye and a perchlorate anion compound, was produced by the following procedure.

  The cationic cyanine dye (A-1) in 300 parts of methanol, 100 parts of methyl ethyl ketone and 10 parts of acetone was dissolved in 2.5 parts of sodium perchlorate in 1000 parts of water in advance. Mix the solution dropwise. Then, it stirred for 240 minutes at 60 degreeC and fully reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The extracted salt-forming compound was dried with a dryer to obtain a cyanine dye (ZC-33) which is a salt-forming compound of 14.3 parts of cationic cyanine dye (A-1) and a perchlorate anion compound. .

<Method for producing xanthene dye>
(Xanthene dye (ZX-1))
A resin (AJ-1) having 50 parts of an anionic group and 2000 parts of sodium hydroxide are added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts C.I. in 45 parts water, 45 parts methanol. I. An aqueous solution in which Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rhodamine B) is prepared is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. Thereafter, the solvent was removed by evaporation under reduced pressure using an evaporator, the concentrated solution was dropped into 1000 parts of water while stirring, and the resulting precipitate was taken out by suction filtration, washed with water, and then left on the filter paper. The salt compound is dried in a dryer, and C.I. I. A xanthene dye (ZX-1) which is a salt-forming compound of Basic Violet 10 and a resin having an anionic group (AJ-1) was obtained. By-products such as salt and salt exchange reactions between dyes and resins, trace amounts of unreacted dyes, and unreacted resins can be removed during suction filtration because they dissolve in water when the concentrate is added dropwise to water while stirring. . In addition, by-products that remain slightly in the subsequent washing with water are completely removed.

<Method for producing cyanine dye solution and xanthene dye solution>
(Cyanine dye solution (SY-1))
The following mixture was subjected to ultrasonic irradiation for 1 hour to obtain a cyanine dye solution (SY-1).

Cyanine dye (ZC-1): 4.0 parts Acrylic resin solution 1: 30.0 parts Cyclohexanone: 16.0 parts

(Cyanine dye solution and xanthene dye solution (SY-2-37))
Except for changing the cyanine dye (ZC-1) in the production of the cyanine dye solution (SY-1) to the composition described in Table 3, the cyanine dye solution was obtained in the same manner as in the case of the cyanine dye solution (SY-1). And a xanthene dye solution (SY-2 to 37) was obtained.

<Production method of fine pigment>
(Miniaturized yellow pigment (PY 139-1))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Pariotor Yellow D1819” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY139-1) was obtained.

(Miniaturized yellow pigment (PY150-1))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Miniaturized red pigment (PR254-1))
Red pigment C.I. I. Pigment Red 254 (BASF “B-CF”) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. And a refined red pigment (PR254-1) was obtained.

(Miniaturized red pigment (PR177-1))
Red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. And a refined red pigment (PR177-1) was obtained.

(Miniaturized red pigment (PR166-1))
Red pigment C.I. I. 200 parts of Pigment Red 166 (“CHROMOPHTAL SCARLET D 3540” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Then, a refined red pigment (PR166-1) was obtained.

(Miniaturized red pigment (PR224-1))
Red pigment C.I. I. 200 parts of Pigment Red 224 ("Perylene Red 224 R6420" manufactured by Sun Chemical Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Then, a refined red pigment (PR224-1) was obtained.

(Miniaturized green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine green pigment (PG58-1) was obtained.

(Miniaturized blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 80 ° C. For 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine blue pigment (PB15: 6-1) was obtained.

(Miniaturized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A dioxazine-based purple refined purple pigment (PV23-1) was obtained.

<Preparation of resin-type dispersant solution>
(Resin Dispersant Solution 1)
A resin type dispersant solution 1 was prepared by using a commercially available resin type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate to prepare a 40 wt% nonvolatile content solution.

<Method for producing pigment dispersion>
(Pigment dispersion (P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (P-1) whose non-volatile component is 20 weight% was produced.

Refined yellow pigment (PR139-1): 11.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate: 49.0 parts Resin-type dispersant solution 1: 5.0 parts

(Pigment dispersion (P-2 to 9))
Pigment dispersion was performed in the same manner as for Pigment Dispersion (P-1), except that the type of refined organic pigment (PR254-1) pigment used in the production of Pigment Dispersion (P-1) was changed as shown in Table 4. The body (P-2-9) was produced.

<The manufacturing method of a red coloring composition>
[Example 1]
(Red coloring composition (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a red colored composition (DP-1).

Cyanine dye solution (SY-1): 40.0 parts Pigment dispersion (P-1): 10.0 parts

[Examples 2-36, Comparative Examples 1-6]
(Red coloring composition (DP-2 to 42))
Except for changing the cyanine dye solution (SY-1) and pigment dispersion (P-1) to the types and amounts (parts by weight) of the cyanine dye solution, xanthene dye solution, and pigment dispersion shown in Table 5, respectively. Produced red coloring compositions (DP-2 to 41) in the same manner as the red coloring composition (DP-1).

<Evaluation of red coloring composition>
Using the obtained red coloring composition (DP-1 to 42), spectral characteristics and heat resistance of the prepared coating film were evaluated by the following methods. Table 6 shows the evaluation results. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical level, and x is a level which is not suitable for practical use.

(Spectral characteristic evaluation)
The obtained colored composition was applied on a 1.1 mm-thick glass substrate using a spin coater so that the wavelength at which the spectral transmittance was 50% was between 580 nm and 590 nm. And dried for 20 minutes, and further heated at 230 ° C. for 60 minutes to obtain a coated substrate. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

"400nm transmittance"
○ ... The transmittance at 400 nm is less than 15.0% Δ ... The transmittance at 400 nm is 15.0% to less than 20.0% × ... The transmittance at 400 nm is 20.0% or more Transmittance "
◎ ・ ・ ・ Transmittance at 530 nm is less than 1.0% ○ ・ ・ ・ Transmittance at 530 nm is 1.0% or more and less than 3.0% × ・ ・ ・ Transmittance at 530 nm is 3.0% or more Transmittance "
A transmittance of 600 nm is 90.0% or more. A transmittance of 600 nm is 80.0% or more and less than 90.0%. A transmittance of 600 nm is less than 80.0%.

(Heat resistance evaluation)
For the substrate obtained by the brightness evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). Then, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0
○: ΔEab * is 3.0 or more and less than 5.0
Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  From Table 5, the coloring composition using the cyanine dye (ZC) and the pigment (B) of the present invention was excellent in spectral characteristics and heat resistance.

<Method for producing red photosensitive coloring composition>
[Example 37]
(Red photosensitive coloring composition (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (R-1).

Red coloring composition (DP-1): 70.0 parts Trimethylolpropane triacrylate: 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 26.0 parts

[Examples 38 to 72, Comparative Examples 6 to 11]
(Red photosensitive coloring composition (R-2 to 42)
The red photosensitive coloring composition (R-2) was the same as the red photosensitive coloring composition (R-1) except that the red coloring composition (DP-1) was changed to the type of red coloring composition shown in Table 7. To 42).

<Evaluation of red photosensitive coloring composition>
Using the resulting photosensitive coloring composition (R-1 to 42), the spectral characteristics and heat resistance of the prepared coating film were evaluated by the following methods. The results are shown in Table 7. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical level, and x is a level which is not suitable for practical use.

(Spectral characteristic evaluation)
The obtained colored composition was applied on a 1.1 mm-thick glass substrate using a spin coater so that the wavelength at which the spectral transmittance was 50% was between 580 nm and 590 nm. And dried for 20 minutes, and further heated at 230 ° C. for 60 minutes to obtain a coated substrate. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

"400nm transmittance"
○ ... The transmittance at 400 nm is less than 15.0% Δ ... The transmittance at 400 nm is 15.0% to less than 20.0% × ... The transmittance at 400 nm is 20.0% or more Transmittance "
◎ ・ ・ ・ Transmittance at 530 nm is less than 1.0% ○ ・ ・ ・ Transmittance at 530 nm is 1.0% or more and less than 3.0% × ・ ・ ・ Transmittance at 530 nm is 3.0% or more Transmittance "
A transmittance of 600 nm is 90.0% or more. A transmittance of 600 nm is 80.0% or more and less than 90.0%. A transmittance of 600 nm is less than 80.0%.

(Heat resistance evaluation)
For the substrate obtained by the brightness evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). Then, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0
○: ΔEab * is 3.0 or more and less than 5.0
Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  From Table 7, the coloring composition for solid-state image sensors using the cyanine dye (ZC) and the pigment (B) of the present invention was excellent in spectral characteristics and heat resistance.

<The manufacturing method of a blue coloring composition>
[Example 73]
(Blue coloring composition (DP-43))
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue colored composition (DP-43).

Cyanine dye solution (SY-9): 12.5 parts Pigment dispersion (P-8): 37.5 parts

[Examples 74 to 76, Comparative Examples 12 to 14]
(Blue coloring composition (DP-44 to 49))
Except for changing the cyanine dye solution (SY-16) and pigment dispersion (P-8) to the types and amounts (parts by weight) of the cyanine dye solution, xanthene dye solution, and pigment dispersion shown in Table 5, respectively. Produced blue colored compositions (DP-44 to 49) in the same manner as the blue colored composition (DP-43).

<Evaluation of blue coloring composition>
Using the obtained blue coloring composition (DP-43 to 49), spectral characteristics and heat resistance of the prepared coating film were evaluated by the following methods. Table 9 shows the evaluation results. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical level, and x is a level which is not suitable for practical use.

(Spectral characteristic evaluation)
The obtained colored composition was applied on a 1.1 mm thick glass substrate using a spin coater so that the wavelength at which the spectral transmittance was 50% was 500 nm, and after drying at 70 ° C. for 20 minutes, A coated substrate was obtained by heating at 230 ° C. for 60 minutes. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

"Transmission at 450nm"
○ ... The transmittance at 400 nm is 90.0% or more × ... The transmittance at 400 nm is less than 90.0% "transmittance at 540 nm"
○ ... The transmittance at 550 nm is less than 10.0% × ... The transmittance at 550 nm is 10.0% or more

(Heat resistance evaluation)
For the substrate obtained by the brightness evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). Then, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0
○: ΔEab * is 3.0 or more and less than 5.0
Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  From Table 9, the coloring composition using the cyanine dye (ZC) and the pigment (B) of the present invention was excellent in spectral characteristics and heat resistance.

<Method for producing blue photosensitive coloring composition>
[Example 77]
(Blue photosensitive coloring composition (B-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a blue photosensitive coloring composition (B-1).

Blue coloring composition (DP-43): 70.0 parts Trimethylolpropane triacrylate: 3.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 26.0 parts

[Examples 78 to 80, Comparative Examples 15 to 17]
(Blue photosensitive coloring composition (B-2 to 7)
The blue photosensitive coloring composition (B-2) was the same as the blue photosensitive coloring composition (B-1) except that the blue coloring composition (DP-43) was changed to the type of blue coloring composition shown in Table 10. To 7).

<Evaluation of blue photosensitive coloring composition>
Using the obtained blue photosensitive coloring composition (B-1 to 7), spectral characteristics and heat resistance of the prepared coating film were evaluated by the following methods. Table 10 shows the evaluation results. In addition, (double-circle) is a very favorable level, (circle) is a favorable level, (triangle | delta) is a practical level, and x is a level which is not suitable for practical use.

(Spectral characteristic evaluation)
The obtained colored composition was applied on a 1.1 mm thick glass substrate using a spin coater so that the wavelength at which the spectral transmittance was 50% was 500 nm, and after drying at 70 ° C. for 20 minutes, A coated substrate was obtained by heating at 230 ° C. for 60 minutes. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

"Transmission at 450nm"
○ ... The transmittance at 400 nm is 90.0% or more × ... The transmittance at 400 nm is less than 90.0% "transmittance at 540 nm"
○ ... The transmittance at 550 nm is less than 10.0% × ... The transmittance at 550 nm is 10.0% or more

(Heat resistance evaluation)
For the substrate obtained by the brightness evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). Then, as a heat resistance test, it was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

A: ΔEab * is less than 3.0
○: ΔEab * is 3.0 or more and less than 5.0
Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  From Table 10, the coloring composition for solid-state image sensors using the cyanine dye (ZC) and the pigment (B) of the present invention was excellent in spectral characteristics and heat resistance.

<Method for producing color filter for solid-state imaging device>
(Green photosensitive coloring composition (G-1))
A mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (G-1).

Pigment dispersion (P-7): 38.5 parts Pigment dispersion (P-2): 16.5 parts Acrylic resin solution 1: 3.5 parts Trimethylolpropane triacrylate: 3.7 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 36.8 parts

(Color filter for solid-state image sensor)
On a 6-inch silicon wafer, a planarization film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) was applied by a spin coating method, and heat-treated for 6 minutes on a hot plate at 100 ° C. as a prebake. Furthermore, it processed in 230 degreeC oven for 1 hour, the coating film was hardened, the 1.0 micrometer planarizing film was formed, and the wafer with a planarizing film was obtained.

  The green photosensitive coloring composition (G-1) was applied onto a silicon wafer with a flattened film by a spin coater, and heat-treated for 1 minute on a hot plate at 100 ° C. as a prebake. The film thickness after pre-baking was adjusted to 0.9 μm.

Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), a pattern is formed at a dose of 150 mJ / cm ² through a photomask for forming a 1.0 μm square red pixel at a wavelength of 365 nm. Exposure was performed.

  The exposed coating film was subjected to paddle development with an organic alkali developer for 1 minute. After the paddle development, rinsing with pure water was performed in a spin shower for 20 seconds, followed by washing with pure water for 20 seconds. Thereafter, water droplets remaining on the wafer were blown with high-pressure air, the substrate was naturally dried, and further heated for 5 minutes on a hot plate having a surface temperature of 230 ° C. to form a square pixel pattern. The film thickness of the green pattern after the heat treatment was 0.80 μm.

  Next, the red photosensitive coloring composition (R-1) is used, the red coloring pixel layer is formed in the same manner as the green coloring pixel layer, and further the blue photosensitive coloring composition (B-1) is used. A blue colored pixel layer was formed to obtain a color filter (CF-1).

The color filter for a solid-state image sensor thus produced was very excellent in spectral characteristics.
Particularly, in the red filter, bumps around 530 nm are suppressed, the spectral characteristics are good, and the heat resistance is excellent. Therefore, the solid-state image sensor using the color filter for the solid-state image sensor is particularly skin-colored. Excellent reproducibility.

Claims (8)

A coloring composition for a solid-state imaging device containing a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains a cyanine dye (ZC) represented by the following general formula (1) and a pigment (B) A coloring composition for a solid-state imaging device.

[In General Formula (1), A represents a carbon atom having a substituent or a hydrogen atom, or a sulfur atom. R ^{3 to} R ¹⁰ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted acyl group. R ¹¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Y- represents an inorganic or organic anion. However, Y ^- is excluded if a halide ion. ] An anion represented by Y- is an imido acid anion represented by the following general formula (2), a fluorine group-containing boron anion represented by the following general formula (3), a methide acid anion represented by the following general formula (4), and 2. The colored composition for a solid-state imaging device according to claim 1, wherein the coloring composition is at least one selected from the group consisting of vinyl resins having an anionic group containing a structural unit represented by the following general formula (5). .

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group that may have a substituent, an alicyclic hydrocarbon group that may have a substituent, or a substituent. An aromatic hydrocarbon group which may have or a heterocyclic group which may have a substituent. ]

[In General Formula (3), R ^{31 to} R ³⁴ are each independently an alkyl group optionally substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom, or an aryl group optionally substituted with a fluorine atom. And at least one of R ^{31 to} R ³⁴ represents an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, it excludes when R < ³¹ > -R < ³⁴ > is all fluorine atoms. ]

[In General Formula (4), R ^{41 to} R ⁴³ each independently represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. ]

[In General Formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Q represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —CONH—R ⁵² —, or —COO—R ⁵² —, and R ⁵² represents a substituted or unsubstituted alkylene group. P ^- is, -SO ₃ ^-, or -COO ^- represents a. ]   The colored composition for a solid-state imaging device according to claim 1 or 2, wherein the pigment (B) is at least one selected from the group consisting of a yellow pigment and a red pigment.   The yellow pigment is C.I. I. The colored composition for a solid-state imaging device according to claim 3, comprising Pigment Yellow 139.   The red pigment is C.I. I. Pigment red 254 and C.I. I. The colored composition for a solid-state imaging device according to claim 3, comprising at least one selected from the group consisting of CI Pigment Red 177.   Furthermore, the coloring composition for solid-state image sensors of any one of Claims 1-5 containing a photopolymerizable monomer and / or a photoinitiator.   The color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one red filter segment is colored for a solid-state imaging device according to any one of claims 1 to 6. A color filter for a solid-state image sensor formed of a composition.   The solid-state image sensor provided with the color filter for solid-state image sensors of Claim 7.