TWI651372B - Coloring composition, coloring cured film, display element, solid-state photographic element, and colorant dispersion - Google Patents

Abstract

The present invention provides a coloring composition using a diketopyrrolopyrrole-based pigment as a colorant, and can form a cured film having excellent chromaticity characteristics and being less likely to cause defects even at low exposure.

The coloring composition of the present invention is a coloring composition comprising (A) a colorant, (C) a binder resin, and (D) a polymerizable compound, wherein (A) the colorant contains a pigment represented by the following formula (1) The coloring composition further includes (B1) a phosphate ester and (B2) a dispersant having a nitrogen atom.

[In formula (1), R ¹ and R ² each independently represent a chlorine atom or a bromine atom].

Description

Colored composition, colored cured film, display element, solid-state imaging element, and colorant dispersion liquid

The present invention relates to a colored composition, a colored cured film, and a display element and a solid-state imaging element. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display element, a solid-state imaging element, and an organic EL display element. , A coloring composition for forming a coloring cured film such as electronic paper, a coloring cured film formed using the coloring composition, and a display element and a solid-state imaging element including the coloring cured film.

When manufacturing a color filter using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is irradiated with radiation. A desired pattern shape (hereinafter referred to as "exposure") is developed to obtain pixels of each color (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). Furthermore, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, refer to Patent Document 4).

In terms of a coloring composition for forming a red colored hardened film, the use of diketopyrrolopyrrole-based pigments such as CI Pigment Red 254 has been studied as a colorant from the viewpoint of the chromaticity characteristics of the colored hardened film (for example, (Refer to Patent Document 5), and in recent years, it has been proposed to brominate A diketopyrrolopyrrole-based pigment is a coloring agent capable of forming a red colored hardened film having more excellent chromaticity characteristics (for example, refer to Patent Documents 6 to 8).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Patent Document 2] Japanese Unexamined Patent Publication No. 3-52201

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-35188

[Patent Document 4] Japanese Patent Laid-Open No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open No. 11-231516

[Patent Document 6] Japanese Patent Laid-Open No. 2012-211969

[Patent Document 7] Japanese Patent Application Publication No. 2012-211970

[Patent Document 8] Japanese Patent Laid-Open No. 2013-014750

However, according to research by the present inventors, it has been found that the pixels formed from a coloring composition containing a diketopyrrolopyrrole-based pigment described in Patent Documents 6 to 8 have excellent chromaticity characteristics but are prone to defects. problem.

In addition, in the technical field of color filters in recent years, reducing the exposure amount and shortening the takt time has become mainstream, and it is required that the pixel and the black matrix pattern shape formed under a low exposure amount are excellent. However, according to research and studies by the present inventors, it is known that when the exposure amount of a colored composition containing a diketopyrrolopyrrole-based pigment is reduced, pattern defects are likely to occur. Therefore, it is difficult to obtain a good pattern shape while shortening the cycle. Shaped pixels and black matrix.

Therefore, the subject of the present invention is to provide a coloring composition using a diketopyrrolopyrrole pigment as a colorant, which is excellent in chromaticity characteristics even at a low exposure amount, and can form a hardened film that is hard to cause defects. . In addition, an object of the present invention is to provide a colored cured film formed using the colored composition, and a display element and a solid-state imaging element including the colored cured film. Furthermore, the subject of this invention is providing the coloring agent dispersion liquid containing the diketopyrrolopyrrole pigment as a coloring agent.

As a result of intensive research, the present inventors have found that the above problems can be solved by using a diketopyrrolopyrrole-based pigment in combination with a specific compound.

That is, the present invention provides a coloring composition comprising (A) a colorant, (C) a binder resin, and (D) a polymerizable compound, wherein (A) the colorant includes a pigment represented by the following formula (1) The coloring composition further comprises (B1) a phosphate ester and (B2) a dispersant having a nitrogen atom,

[In formula (1), R ¹ and R ² each independently represent a chlorine atom or a bromine atom. ]

The present invention also provides a colored cured film formed using the above-mentioned colored composition, and a display element and a solid-state imaging element including the colored cured film. Here, the "colored cured film" refers to pixels, black matrices, black spacers, etc. of each color used in display elements and solid-state imaging elements.

Furthermore, the present invention provides a colorant dispersion liquid comprising (A) a colorant and (F) a solvent, wherein (A) the colorant contains a pigment represented by the following formula (1), and the colorant dispersion liquid further Dispersant containing (B1) phosphate and (B2) having a nitrogen atom.

[In formula (1), R ¹ and R ² each independently represent a chlorine atom or a bromine atom. ]

The diketopyrrolopyrrole pigment of the coloring agent dispersion liquid of the present invention has good dispersibility, maintains a low viscosity, and has excellent coatability. In addition, if the colored composition of the present invention is used, a colored hardened film having excellent chromaticity characteristics and less likely to be damaged can be formed even at a low exposure amount. Moreover, the developing speed of the colored composition of the present invention is also excellent, and the cycle can be shortened.

Therefore, the colored composition of the present invention is extremely suitable for the production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.

[Form of Implementing Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored composition of the present invention will be described in detail.

-(A) Colorant-

The coloring composition of the present invention contains a pigment represented by the following formula (1) as a (A) colorant.

[In formula (1), R ¹ and R ² each independently represent a chlorine atom or a bromine atom. ]

It is preferable that both R ¹ and R ² are chlorine atoms or that both R ¹ and R ² are bromine atoms, and it is more preferable that both R ¹ and R ² are bromine atoms. The pigment represented by the following formula (1) can be produced by a conventional method. For example, a pigment in which both R ¹ and R ² are bromine atoms can be produced by a method described in International Publication No. 2009/144115. .

The coloring composition of the present invention may contain a coloring agent (hereinafter also referred to as "other coloring agent") other than the pigment represented by the formula (1). Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application, and any one of pigments, dyes, and natural pigments other than the pigments represented by formula (1) may be used. Among them, organic pigments and organic dyes are preferred in the sense of obtaining pixels with high brightness and color purity.

Examples of the organic pigment include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists). Among them, Japanese Patent Application Laid-Open No. 2001-081348 and Japanese Patent Application Laid-Open No. 2010- 026334, Japanese Patent Laid-Open No. 2010-191304, Japanese Patent Laid-Open No. 2010-237384, Japanese Patent Laid-Open No. 2010-237569, Japanese Patent Laid-Open No. 2011-006602, Japanese Patent Laid-Open No. 2011-145346 Recorded lake pigments; CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 , CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment 185, CI Pigment Yellow Organic pigments other than lake pigments such as 211, CI Pigment Yellow 215, CI Pigment Orange 38, and CI Pigment Violet 23 are preferred. and Among the lake pigments, triarylmethane-based lake pigments, dibenzopiperan-based lake pigments, and azo-based lake pigments are preferred. Triarylmethane-based lake pigments and dibenzopiperan-based lake pigments are preferred. Lake pigments are better.

In the present invention, the pigment represented by the formula (1) and other pigments used arbitrarily may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. . In addition, the pigment may be used by modifying the surface of the particles with a resin as required. Examples of the resin in which the particle surface of the pigment is modified include, for example, a vehicle resin described in Japanese Patent Application Laid-Open No. 2001-108817, or various commercially available resins for dispersing pigments. As a method for coating the carbon black surface, for example, the methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, and Japanese Patent Application Laid-Open No. 9-124969 can be used. In addition, organic pigments can also be used by miniaturizing primary particles by so-called salt milling. As the method of salt grinding, for example, the method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be used.

In the present invention, in addition to the pigment represented by the formula (1) and other pigments used arbitrarily, it may further contain a conventional dispersing auxiliary agent. Examples of conventional dispersion aids include pigment derivatives such as copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. In the present invention, when a dispersing assistant is used, a diketopyrrolopyrrole sulfonic acid derivative is preferred.

Examples of the organic dyes include dibenzopiperan-based dyes, triarylmethane-based dyes, methine-based dyes, anthraquinone-based dyes, and azo-based dyes. More specifically, it can be enumerated: Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Laid-Open No. 2010-254964, Japanese Patent Laid-Open No. 2011-138094, International Publication No. 2010/123071, Japanese Patent Laid-Open No. 2011-116803, Japanese Patent Laid-Open No. 2011 Organic dyes described in JP-117995, JP 2011-133844, JP 2011-174987, and the like.

Among them, the above-mentioned organic dye is preferably a dibenzopiperan-based dye.

Examples of the dibenzopiperan-based dye include compounds having a structure represented by the following formula.

The dibenzopiperan dye may have an anion when it is cationic, so that the dibenzopiperan dye becomes electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, and a carboxylic acid. Acid anion, sulfuric acid anion, organic sulfonic acid anion, nitrogen anion, methylate anion, anion having a transition metal complex of an azo compound, and the like. Examples of the nitrogen anion system include the nitrogen anions described in JP-A-2011-133844, JP-A-2011-116803, and JP-A-2010-090341. Examples of the anion system of the transition metal complex having an azo compound as the ligand include those described in Japanese Patent Application Laid-Open No. 2009-163226 and Japanese Patent Application Laid-Open No. 2012-212089.

In addition, a dibenzopiperan-based acid dye having an ammonium cation and a dibenzopiperan-based acid dye having a fluorene cation can also be applied. Here, the dibenzopiperan-based acid dye means a dibenzopiperan-based dye in which the anion moiety becomes a chromophore. Typical examples of the dibenzopiperan-based acid dye having an ammonium cation include the dyes described in Japanese Patent No. 4492760 and Japanese Patent Application Laid-Open No. 2011-242752.

In the present invention, other colorants may be used alone or in combination of two or more.

The coloring composition of the present invention is preferably used in the formation of a red pixel. In this case, the colorant (A) includes a pigment represented by the formula (1) and a pigment selected from the group consisting of a red pigment, a red dye, and a purple pigment other than the pigment represented by the formula (1) as another colorant. Preferably, at least one selected from the group consisting of cyanine, purple dye, yellow pigment, and orange pigment.

The red pigment is preferably a pigment classified as C.I. Pigment Red, and more preferably C.I. Pigment Red 177, C.I. Pigment Red 179, and C.I. Pigment Red 264. The purple pigment is preferably C.I. Pigment Violet 23.

The above-mentioned red and purple dyes are based on dibenzopiperan dyes. good. More specifically, the same may be mentioned.

The aforementioned yellow pigments are preferably C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185. The orange pigment is preferably C.I. Pigment Orange 38.

In view of the fact that even at low exposures, pixels with excellent chromaticity characteristics and no defects can be formed, or black matrices and black spacers with excellent light-shielding properties, the content of (A) the colorant is in the solid of the coloring composition. Among the ingredients, it is generally 5 to 70% by mass, and preferably 10 to 60% by mass. The solid content here is a component other than the solvent mentioned later.

When other colorants are used, the content ratio of the other colorants is preferably 99% by mass or less, and more preferably 95% by mass or less with respect to the total content of the colorant. The lower limit value is not particularly limited, and it may be at least 0.01% by mass.

-(B) ingredients-

The coloring composition of the present invention includes (B1) phosphate ester (hereinafter also referred to as "(B1) component") as a component (B) and (B2) a dispersant having a nitrogen atom (hereinafter also referred to as "(B2) Dispersant"). The component (B1) and the dispersant (B2) of the present invention are those that disperse the pigment represented by formula (1) and any other pigments used as a dispersant. As a result of intensive research conducted by the present inventors, it was found that by using a combination of the (B1) component and the (B2) dispersant, a diketopyrrolopyrrole-based pigment can be prepared with good dispersibility and reduced viscosity and spreadability. It is an excellent colorant dispersion liquid, and as a result, it was found that the chromaticity characteristics are excellent even at a low exposure amount, and a hardened film is hardly formed. One of the advantages is that the development speed of the colored composition of the present invention is fast.

(B1) The component is not particularly limited as long as it is a phosphate ester, and may be a phosphate monoester, a phosphate diester, and a phosphate triester, or a mixture of two or more of these. The phosphate may be in the form of a salt, and examples of the salt include an amine salt, an alkali metal salt, and an alkaline earth metal salt. (B1) The component can be synthesized by a conventional method, or a commercially available one can be used, for example: Solsperse 41000 (made by Lubrizol (stock); polyether phosphate polymer, 100% by mass of non-volatile components, acid value 50mgKOH / g), Disperbyk-111 (manufactured by BYK Chemie (BYK); phosphate polymer, non-volatile component 95% by mass, acid value 129mgKOH / g), Phosphanol RE-610, Phosphanol RS-710 (alkyl Ether phosphate, acid value 65mgKOH / g) (all above are manufactured by Toho Chemical Industry), Disparlon PW-36 (50% by mass of non-volatile components, acid value 55mgKOH / g), Disparlon DA-375 (Polyether phosphate polymerization Substances, non-volatile ingredients 100% by mass, acid value 14mgKOH / g), Disparlon DA-325 (amine salt of polyether phosphate, non-volatile ingredients 100% by mass, acid value 14mgKOH / g) (all above are Nancheng Chemical system) and so on. Among these, the (B1) component is preferably a polyether phosphate-based polymer from the viewpoint of dispersibility, viscosity, and coatability of a diketopyrrolopyrrole-based pigment.

(B1) The acid value of the component is preferably 1 to 150 mgKOH / g, more preferably 5 to 90 mgKOH / g, and even more preferably 10 to 60 mgKOH / g. Such a state is preferable from the viewpoint of dispersibility, viscosity, and coatability of diketopyrrolopyrrole-based pigments. Here, the "acid value" in the present invention means the number of mg of KOH required to neutralize 1 g of a non-volatile component excluding a solvent of a dispersant solution.

The colored composition of the present invention contains (B1) component and (B2) component Powder.

(B2) Examples of the nitrogen atom of the dispersant include primary amine groups, secondary amine groups, tertiary amine groups, quaternary ammonium groups, amidoamine groups, imine groups, and urethane groups. Nitrogen atom.

The (B2) dispersant in the present invention is selected from, for example, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, a polyethylene glycol diester dispersant, and a sorbitan fat. Ester-based dispersant, polyester-based dispersant and dispersant in (meth) acrylic-based dispersant, can be applied: having at least one selected from the group consisting of amine, quaternary ammonium, amido and imine groups Dispersant with characteristic group, urethane-based dispersant, polyethyleneimine-based dispersant. Moreover, the amine group may be a primary amine group, or a secondary amine group or a tertiary amine group.

Among them, the (B2) dispersant may be a (meth) acrylic dispersant or a polyester dispersant, and preferably has one or more characteristics selected from the group consisting of an amine group, a quaternary ammonium group, a sulfonium group, and an imine group. At least one of a base dispersant and a urethane-based dispersant, more preferably one (methyl) having one or more characteristic groups selected from the group consisting of amine, quaternary ammonium, amido, and imine. ) Acrylic dispersant.

The (meth) acrylic-based dispersant may have a crosslinkable functional group in addition to the above-mentioned characteristic group having a nitrogen atom. Examples of the crosslinkable functional group include an oxygen-containing saturated heterocyclic group such as an epoxyethyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropiperanyl group, an ethylenically unsaturated group, and a ring. Thio group, (dithio) carbonate group and the like. Among these crosslinkable functional groups, an oxygen-containing saturated heterocyclic group is preferable, and an oxetanyl group and a tetrahydrofuranyl group are more preferable. In addition, a (meth) acrylic dispersion having a crosslinkable functional group The agent can be synthesized by, for example, a method described in Japanese Patent Application Laid-Open No. 2012-118505. According to this aspect, the effects expected by the present invention can be further obtained.

(B2) As long as the dispersant has a nitrogen atom, it can also be used commercially. For example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, and BYK-LPN21116 as (meth) acrylic dispersants. (40% by mass of non-volatile components), BYK-LPN22102 (the above are manufactured by BYK Chemie (BYK)), etc .; Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk as urethane-based dispersants -167, Disperbyk-170, Disperbyk-182 (all of which are manufactured by BYK Chemie (BYK)); Solsperse 76500 (made by Lubrizol (stock); non-volatile content 50% by mass); etc .; as polyethylene dispersant Solsperse 24000 (manufactured by Lubrizol), etc .; Ajisper PB821 (100% by mass of non-volatile components), Ajisper PB822, Ajisper PB880, Ajisper PB881 (Ajinomoto Fine-Techno (shares)) (Manufactured by BYK), and also BYK-LPN21324 (40% by mass of non-volatile components) (manufactured by BYK Chemie (BYK)).

(B2) A dispersant can be used individually or in mixture of 2 or more types.

The coloring composition of the present invention can appropriately select the content ratio of the (B1) component and the (B2) dispersant, but the ratio of the content of the component (B1) w ₁ to the content of the dispersant w ₂ (w ₁ / w ₂ ) In terms of mass ratio, it is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and even more preferably 30/70 to 70/30.

In the present invention, the total content of (B1) component and (B2) dispersant With respect to 100 parts by mass of the coloring agent (A), 5 to 300 parts by mass is preferred, 10 to 200 parts by mass is more preferred, and 20 to 100 parts by mass is even more preferred. With such a configuration, the desired effect of the present invention can be easily obtained.

-(C) Adhesive resin-

The (C) binder resin of the present invention is not particularly limited, but a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferred. Among them, a polymer having a carboxyl group (hereinafter also referred to as a “carboxyl-containing polymer”) is preferred, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as an “unsaturated monomer”). (c1) ") and a copolymerizable other copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as" unsaturated monomer (c2) ").

Examples of the unsaturated monomer (c1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloxyethyl ester], and ω- Carboxyl polycaprolactone mono (meth) acrylate, p-vinyl benzoic acid and the like.

These unsaturated monomers (c1) can be used alone or in combination of two or more.

In addition, as for the unsaturated monomer (c2), for example, N-phenylmaleimide and N-cyclohexylmaleimide may be substituted at the N-position of maleimide. ; Such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinyl benzyl glycidyl ether, and aromatic vinyl compounds of pinene; such as (methyl) Methyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, (meth) ) Benzyl acrylate, polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol ( Degree of polymerization 2 to 10) Mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, ( (5.2.1.0 ^2,6 ) decane-8-yl methacrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylic acid-4- Hydroxyphenyl ester, modified by ethylene oxide of p-cumylphenol (A ) Acrylate, glycidyl (meth) acrylate, -3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) acryloxymethyl 1-oxetane, 3-[(Meth) acryloxymethyl] -3-ethyloxetane (meth) acrylates; such as cyclohexyl vinyl ether, isofluorenyl vinyl ether, tricyclic [5.2 .1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3- (vinyloxymethyl) -3-ethyloxetane; For example, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, macromolecule monomers with a mono (meth) acrylfluorene group at the end of the polymer molecular chain of polysiloxane .

These unsaturated monomers (c2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass and 10 to 40% by mass. % Is better. By copolymerizing the unsaturated monomer (c1) within such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Copolymerization of unsaturated monomer (c1) and unsaturated monomer (c2) Specific examples of the object include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, and Japanese Patent Laid-Open No. Copolymers disclosed in JP 11-174224, JP 11-258415, JP 2000-56118, and JP 2004-101728.

In addition, the present invention can also use, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. 11-140144. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain disclosed in Japanese Patent Application Publication No. 2008-181095 and the like is used as a binder resin.

The weight average molecular weight (Mw) of the polystyrene resin converted from the binder resin in the present invention measured by a gel permeation chromatography (hereinafter referred to as GPC) (eluent: tetrahydrofuran) is generally 1,000 to 100,000, and 3,000 to 50,000. Better. In such a state, the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. The term “Mn” used herein refers to the number average molecular weight of polystyrene in terms of GPC (eluent: tetrahydrofuran).

The binder resin in the present invention can be produced by a conventional method, and for example, it can be prepared by Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open The method disclosed in 2006-259680, International Publication No. 07/029871, and the like is used to control the structure or Mw, Mw / Mn.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the binder resin is generally 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass with respect to 100 parts by mass of the colorant (A). In such a state, it is possible to further improve alkali developability, storage stability of the coloring composition, pattern shape, and chromaticity characteristics.

-(D) polymerizable compound-

In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, Caprolactone modified polyfunctional (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, hydroxyl (meth) acrylate with polyfunctional isocyanate A functional polyurethane (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride, and the like.

Among them, examples of the aliphatic polyhydroxy compound include For example: divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; such as trivalent glycerol, trimethylolpropane, neopentyl tetraol, and dipentaerythritol Above aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, and neopentyl tetratriol Group) acrylate, dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. As for the acid anhydride, for example, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride and dibasic acid anhydrides; such as pyromelite anhydride Tetracarboxylic dianhydride of biphenyltetracarboxylic dianhydride and diphenylketone tetracarboxylic dianhydride.

The polyfunctional (meth) acrylate modified with caprolactone includes, for example, compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. As for the above-mentioned polyfunctional (meth) acrylate modified by alkylene oxide, bisphenol A di (meth) acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, Tris (meth) acrylate isocyanurate modified with at least one selected from ethylene oxide and propylene oxide, trimethylolpropane modified with at least one selected from ethylene oxide and propylene oxide Tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate modified by at least one selected from ethylene oxide and propylene oxide, modified by at least one selected from ethylene oxide and propylene oxide Quality neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate modified by at least one selected from ethylene oxide and propylene oxide, to One less selected from the group consisting of ethylene oxide and propylene oxide modified dipentaerythritol hexa (meth) acrylate and the like.

Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure means that one or more Ring or three substituted with phenyl The chemical structure of a ring as a basic skeleton is a concept that also includes melamine, benzoguanamine, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine , N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycol urea and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and polyfunctional (formaldehyde modified by caprolactone) are preferred. Acrylate), polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N ', N', N ", N" -hexa (alkane) (Oxymethyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and less occurrence of scum and film residue on the substrate of the unexposed portion and the light-shielding layer, the use of trivalent or higher aliphatic polyhydroxy compounds Among the polyfunctional (meth) acrylates obtained by reacting with (meth) acrylic acid, trimethylolpropane triacrylate, neopentaerythritol triacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate; among polyfunctional (meth) acrylates having a carboxyl group, particularly preferred is neopentaerythritol triacrylate and succinic acid A compound obtained by the reaction of an anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride.

In this invention, (D) polymerizable compound can be used individually or in mixture of 2 or more types.

In the present invention, the content of the (D) polymerizable compound is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and 80 to 500 parts by mass with respect to 100 parts by mass of the colorant (D). For even better. In such a state, it is possible to further improve the hardenability and alkali developability, and to suppress the occurrence of scum and film residue on the substrate or the light-shielding layer of the unexposed portion at a high level.

-(E) Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. This can impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates active species that can initiate polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, Compounds, O-fluorenyl oxime compounds, onium salt compounds, benzoin compounds, diphenyl ketone compounds, α-diketone compounds, polycyclic quinone compounds, diazonium compounds, and sulfonium sulfonate compounds.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, Preferably, at least one of the group of the compound and the O-fluorenyl oxime compound is used.

Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl Thiothioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropylthioxanthone and the like.

In addition, specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-N- Phenylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-N- Phenylphenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-N- Phenylphenyl) butane-1-one and the like.

Moreover, as a specific example of the said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi Imidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

In addition, when using a biimidazole compound as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination in order to improve sensitivity. The so-called "hydrogen donor" refers to a compound capable of supplying a hydrogen atom with respect to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo Thiol hydrogen precursors such as azoles, 4,4'-bis (dimethylamino) diphenyl ketones, 4,4'-bis (diethylamino) diphenyl ketones, etc. . In the present invention, the hydrogen donors can be used alone or in combination of two or more kinds, and the combination of one or more thiol hydrogen donors and one or more amine hydrogen donors can further improve the sensitivity, which is preferable.

And, just the above three Specific examples of the compound include: 2,4,6-tris (trichloromethyl) -s-tri , 2-methyl-4,6-bis (trichloromethyl) -s-tri , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-tri Halomethyl Compound.

In addition, specific examples of the O-fluorenyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzidine oxime ), Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime), ethyl ketone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl]-, 1- (O-acetimoxime), Ethyl ketone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl} -9H -Carbazol-3-yl]-, 1- (O-acetimoxime) and the like. Commercially available products of O-fluorenyl oxime compounds include NCI-831, NCI-930 (above manufactured by ADEKA Co., Ltd.), DFI-020, DFI-091 (above manufactured by Daito Chemix Co., Ltd.), and the like.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) diphenyl ketone, 4,4'-bis (diethylamino) diphenyl ketone, and 4-diethyl Aminoaminoacetophenone, 4-dimethylaminophenylacetone, 4-dimethylamino Ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino- 3- (4-Diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone and the like.

In the present invention, the content of the (E) photopolymerization initiator is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass, relative to 100 parts by mass of the polymerizable compound (D). By adopting such a state, it is possible to further improve the hardenability and the coating characteristics.

-(F) Solvent-

The coloring composition of the present invention contains the above-mentioned components (A) to (D) and other components arbitrarily added, but generally it is a solvent composition to prepare a liquid composition.

(F) The solvent can be appropriately selected and used as long as it disperses or dissolves the components (A) to (D) and other components constituting the colored composition, does not react with these components, and has a moderate volatility.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono (Poly) olefin-based glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; alkyl lactates such as methyl lactate and ethyl lactate; (Cyclo) alkanols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol; diacetone alcohol, etc. Keto alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxyacetate (Poly) alkene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Class; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanedione Diacetates such as alcohol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Esters, ethoxyethyl acetate, 3-methyl-3-methoxypropionic acid butyl and other alkoxycarboxylic acid esters; ethyl acetate, N-propyl acid, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isobutyrate Other esters such as propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxobutanoate, etc. Type; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Class, etc.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, and coatability, (poly) olefin-based glycol monoalkyl ethers, alkyl lactates, and (poly) olefin-based glycol monoesters are preferred. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, and other esters, particularly preferred are propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol Alcohol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyethyl butyrate, diethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, butyl 3-methyl-3-methoxypropionate, n-butyl acetate, isopropyl acetate Butyl, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

(F) The content of the solvent is not particularly limited, but the total concentration of each component except the solvent of the coloring composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By being in such a state, a coloring agent dispersion liquid having good dispersibility and stability and a coloring composition having good coatability and stability can be obtained.

-additive-

The coloring composition of the present invention may contain various additives as necessary.

Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) Surfactants; fluorosurfactants, polysiloxane surfactants, etc .; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethylsilane Adhesion promoters such as oxysilane; 2,2-thiobis (4-methyl-6-tertiary-butylphenol), 2,6-di-tertiary-butylphenol, neopentaerythritol tetra [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methyl Phenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, thiodiethyl bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and other antioxidants; 2- (3-tri Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxydiphenyl ketone and other ultraviolet absorbers; anticoagulants such as sodium polyacrylate; malonic acid, Adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino -1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improving agents; succinic acid mono [2- (meth) propenyloxy] Ethyl ester], phthalic acid mono [2- (meth) acryloxyethyl ester], omega-carboxy polycaprolactone mono (meth) acrylate, and other developing improvers.

The coloring composition of the present invention can be prepared by an appropriate method, but a preferable method for preparing the coloring composition is to use the coloring agent of the present invention. Method of dispersion. That is, the coloring agent containing the pigment represented by the formula (1) (A) in the solvent (F) is dispersed with the component (B1) and (B2) using, for example, a bead mill or a roll mill. The dispersing agent and the required (C) binder resin are pulverized together, and mixed and dispersed at the same time to form a colorant dispersion liquid. To the colorant dispersion liquid, (C) binder resin and (D) A method for preparing a polymerizable compound by adding (E) a photopolymerization initiator, and (F) a solvent or an additive, if necessary, and mixing them. In addition, the coloring composition of the present invention (A) colorant, (B1) component, (B2) dispersant, and (F) solvent, as well as a dispersing aid and (C) binder resin added as needed The specific structure is as described above.

In addition, by using the (B1) component and (B2) dispersant in combination in the colorant dispersion liquid of the present invention, the diketopyrrolopyrrole-based pigment is dispersed compared to when the (B1) component and (B2) dispersant are used separately. It has good properties, can reduce viscosity, and has excellent coatability. As a result, it is possible to prepare a colored composition that can form a cured film that is excellent in chromaticity characteristics even at low exposures and hardly causes defects. Specifically, the viscosity of the colorant dispersion can be made preferably 20 mPa. Below s, more preferably 16mPa. Below s, it is more preferably 13mPa. Below s, the best is 11mPa. s or less. Among them, the viscosity is a value measured using an E-type viscometer at 25 ° C.

In addition, when the dyeing composition of the present invention uses both a dye and a pigment as a colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, the following method can be adopted: after passing the dye solution through the first filter, A method in which a dye solution that has passed through the first filter is mixed with a separately prepared pigment dispersion liquid and the like, and the obtained colored composition is passed through the second filter to prepare. In addition, the following method may be adopted: the dye and the above (B) The component (D) and other components used as necessary are dissolved in a solvent. After the obtained solution is passed through the first filter, the solution passed through the first filter is mixed with a separately prepared pigment dispersion liquid, and the obtained color is colored. A method in which the composition is prepared by passing through a second filter. In addition, the following method may be adopted: after passing the dye solution through the first filter, mixing the dye solution passed through the first filter with the above-mentioned components (B) to (D) and other components used as necessary, After dissolving and passing the obtained solution through the second filter, the solution passing through the second filter is further mixed with a pigment dispersion liquid prepared separately, and the obtained colored composition is prepared by passing through the third filter.

Colored hardened film and forming method thereof

The colored hardened film of the present invention is formed using the colored composition of the present invention, and specifically, it refers to pixels, black matrices, black spacers, and the like of each color constituting a color filter.

Hereinafter, a coloring cured film used for a color filter constituting a display element and a solid-state imaging element and a method for forming the same will be described.

As a method of manufacturing a color filter, the following methods can be cited first. First, a light-shielding layer (black matrix) is formed on the surface of the substrate in such a manner that a portion forming a pixel is divided as necessary. Next, on this substrate, for example, a red liquid composition of the radiation-sensitive composition of the present invention is applied, followed by pre-baking to evaporate the solvent to form a coating film. Next, after this coating film is exposed through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is melt | dissolved and removed. Then, a post-bake is performed to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

Next, using each of the radiation-sensitive compositions in green or blue, the same operations as described above are performed to coat, pre-bake, expose, develop, and post-bake each radiation-sensitive composition to sequentially form green ones on the same substrate. Pixel array and blue pixel array. Thus, a color filter can be obtained in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

The black matrix described above can be formed by forming a desired pattern of a thin metal film such as chromium formed by sputtering or vapor deposition using Photolithography, but a radiation-sensitive black dispersion may also be used. The sexually colored composition is formed by performing the same operations as in the formation of the above-mentioned pixels.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyimide, polyimide, imine, and polyimide.

In addition, appropriate pretreatments such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation may be performed in advance on these substrates as required.

When the radiation-sensitive coloring composition is coated on a substrate, appropriate coatings such as a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method (slit coating method), and a bar coating method can be used. However, spin coating and slot die coating are particularly preferred.

Pre-baking is generally performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is generally performed until 50 to 200 Pa. The conditions for heating and drying are generally performed at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness after drying is generally 0.6 to 8 μm, preferably 1.2 to 5 μm.

Examples of the radiation source used when forming at least one type of pixel and black matrix include xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halogen lamps, and medium-pressure mercury. Lamp light sources such as lamps and low-pressure mercury lamps or laser light sources such as argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc. The exposure light source can also be an ultraviolet LED. The wavelength is preferably radiation in the range of 190 to 450 nm.

Generally speaking, the radiation exposure is preferably 10 to 10,000 J / m ² .

In addition, as the alkali developing solution, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazinebicyclo [5.4.0] -7-ten Aqueous solutions of monoene, 1,5-diazinebicyclo [4.3.0] -5-nonene and the like are preferred.

An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant may be added to the alkali developing solution. In addition, after alkali development, washing with water is generally performed.

As the development processing method, a shower development method, a spray development method, a dipping development method, an immersion development method, or the like can be used. The development conditions are preferably 5 to 300 seconds at normal temperature.

Post-baking conditions are generally about 180 to 280 ° C for about 10 to 60 minutes.

The film thickness of the pixels formed in this manner is generally 0.5 to 5 μm, and preferably 1.0 to 3 μm.

In addition, the second method of manufacturing a color filter is a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like. In this method, first, a partition wall having a light shielding function is formed on the surface of the substrate. Next, in the formed partition wall, for example, after the liquid composition of the red thermosetting coloring composition is discharged from the inkjet device, pre-baking is performed to evaporate the solvent. Next, after exposing the coating film as necessary, it is cured by post-baking to form a blue pixel pattern.

Next, using each of the green or blue thermosetting coloring compositions, the same operation as described above is performed to sequentially form a green pixel pattern and a blue pixel pattern on the same substrate. In this way, a color filter is obtained in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, the partition wall not only has a light-shielding function, but also can achieve the function of preventing the thermosetting coloring composition of each color discharged from the zone from mixing colors. Therefore, compared with the black matrix used in the first method, The film thickness is thicker. Therefore, the partition wall is generally formed using a black radiation-sensitive composition.

The substrate or radiation source used when forming the color filter, and the method or conditions for pre-baking or post-baking are the same as the first method described above. The film thickness of the pixel formed by the inkjet operation in this way is the same as the height of the partition wall.

After a protective film is formed on the pixel pattern obtained in this way as necessary, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. The spacer is generally formed using a radiation-sensitive composition, and a spacer (black spacer) having a light-shielding property can also be used. In this case, although a radiation-sensitive composition in which a black coloring agent is dispersed is used, the colored composition of the present invention is also applicable to the formation of the black spacer.

The radiation-sensitive coloring composition of the present invention is also applicable to the formation of a colored hardened film of any of the pixels, black matrices, black spacers, and the like used in the color filter.

The color filter including the colored hardened film of the present invention formed in this way has extremely high brightness and color purity. Therefore, the color filter is used in a color liquid crystal display element, a color photographic tube element, a color sensor, and an organic EL display. Components and electronic paper are extremely useful. In addition, the display element described later may be provided with at least one or more colored hardened films formed using the radiation-sensitive composition of the present invention.

Display element

The display element of the present invention includes the colored hardened film of the present invention. Examples of the display device include a color liquid crystal display device, an organic EL display device, and electronic paper.

The color liquid crystal display element provided with the colored curing film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate other than a driving substrate on which a thin film transistor (TFT) is configured, and the driving substrate and the substrate on which the color filter is formed face to face with a liquid crystal layer interposed therebetween. Also, you can use A structure in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is arranged, and a substrate on which an ITO (indium oxide doped with tin) electrode is formed face to face via a liquid crystal layer. The latter structure has the advantage that the aperture ratio can be further improved and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.

The color liquid crystal display element provided with the colored hardened film of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL: Cold Cathode Fluorescent Lamp). Examples of the white LED system include white LEDs that obtain white light by combining red LEDs, green LEDs, and blue LEDs and combining colors; white LEDs that obtain white light by combining blue LEDs, red LEDs, and green phosphors ; White LED is obtained by combining blue LED, red light emitting phosphor and green light emitting phosphor and mixing colors; white light white LED is obtained by mixing color of blue LED and YAG phosphor; by combining Blue LED, orange light-emitting phosphor and green light-emitting phosphor are mixed to obtain white light; white LED is obtained by combining ultraviolet LED, red light-emitting phosphor, green light-emitting phosphor and blue light-emitting phosphor And get white LED and so on.

The color liquid crystal display element provided with the colored hardened film of the present invention is applicable to TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes Switching) type. VA (Vertical Alignment) type, OCB (Optically Compensated) Birefringence) type.

The organic EL display element provided with the colored cured film of the present invention may have a suitable structure, and examples thereof include the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

Moreover, the electronic paper provided with the colored hardened film of this invention can take an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

Solid-state photographic element

The solid-state imaging element of the present invention includes the colored cured film of the present invention. In addition, the solid-state imaging element of the present invention can adopt a suitable structure. For example, by using the colored composition of the present invention as one embodiment, a colored substrate (colored cured film) can be produced on a semiconductor substrate such as a CMOS substrate by performing the same operations as described above, and color reproduction can be produced in particular. Excellent solid-state imaging element.

[Example]

In the following, examples are given to further specifically describe the embodiments of the present invention. However, the present invention is not limited to the following examples.

<(B2) Synthesis of Dispersant>

Synthesis Example 1

According to Synthesis Example 5 of Japanese Patent Application Laid-Open No. 2012-118505, a quaternary ammonium-containing A block containing about 80 mol% of repeating units derived from dimethylaminoethyl methacrylate, and a source having A block copolymer solution (non-volatile content 40% by mass) of the B block of the repeating unit of n-butyl methacrylate, methyl methacrylate and tetrahydrofurfuryl methacrylate. The obtained block copolymer was used as a "dispersant (B-1)".

<(C) Synthesis of Adhesive Resin>

Synthesis Example 2

In a flask equipped with a condenser and a stirrer, 25.0 g of 3-methacryloxymethyl-3-ethyloxetane, 18.0 g of methacrylic acid, and 14.0 g of methacrylic acid-2 -Hydroxyethyl ester, 24.0 g of benzyl methacrylate, 10.0 g of N-phenylmaleimide and 9.0 g of mono-2-propenyloxyethyl succinate dissolved in 300 g of propylene glycol monomethyl To ether acetate, 5.3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was further added, and then flushed with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. while being stirred and purged with nitrogen, and polymerized for 5 hours to obtain a solution containing 25% by mass of the precursor copolymer (c-1). The polystyrene-equivalent weight average molecular weight (Mw) of the precursor copolymer (c-1) was 10,000.

Next, 200 g of the solution containing the precursor copolymer (c-1), 15.9 g of 2-methacryloxyethyl isocyanate, and 0.2 g of phenanthrene as a polymerization inhibitor The reaction mixture was placed in a flask and reacted at a temperature of 110 ° C for 9 hours. Each reaction solution was washed with 75 g of ion-exchanged water four times and concentrated under reduced pressure to obtain a binder resin solution (C-1) (solid content concentration: 33% by mass). The Mw of the obtained binder resin was 11,500.

Synthesis Example 3

A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen. Heat to 80 ° C., and drop in 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and formaldehyde at the same temperature dropwise over 1 hour. 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, A mixed solution of 15 parts by mass of mono (2-propenyloxyethyl) succinate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), and the temperature was maintained for 2 hours. polymerization. Then, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (C-2) (solid content concentration: 33% by mass). Mw of the obtained binder resin was 12,200 and Mn was 6,500.

<Synthesis of colorants>

Synthesis Example 4

A 200 mL round-bottomed flask with a stir bar was added. 2.9 g (5.0 mmol) of dibenzopiperanic acid dye CI Acid Red 52 and 2.9 mL of ion-exchanged water were added. While stirring, the temperature of the bath was increased in an oil bath Heat to 85 ° C. To this solution, a solution prepared by dissolving 5.2 g (10.26 mmol) of tributylhexadecylphosphonium bromide in 60 g of ion-exchanged water at room temperature was added in small amounts at the same temperature. At the point of all additions, generation of a water-insoluble colored oily substance was confirmed. Then, after stirring at the same temperature for 1 hour, it was cooled to about room temperature using an ice bath. The supernatant was removed by decantation, and the residue was washed with ion-exchanged water. This residue was dissolved in methanol and recovered, and then concentrated under reduced pressure using a rotary evaporator. The obtained oily residue was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.1 g of a red-purple solid.

As a result of ¹ H-NMR spectrum measurement (solvent: deuterated chloroform), the obtained compound was confirmed to be a compound represented by the following formula (A-2). The obtained compound was used as a colorant (A-2).

Synthesis Example 5

With reference to Synthesis Example 3 of Japanese Patent Application Laid-Open No. 2010-032999, a compound represented by the following formula (A-3) was synthesized. This compound was used as a colorant (A-3).

Synthesis Example 6

With reference to Synthesis Example 3 of JP 2012-181505, a compound represented by the following formula (A-4) was synthesized. This compound was used as a colorant (A-4).

Synthesis Example 7

The compound represented by the following formula (A-5) was synthesized with reference to the synthesis example of Patent No. 4492760. This compound was used as a colorant (A-5).

<Preparation and Evaluation of Colorant Dispersions>

Example 1

13 parts by mass of a pigment represented by the following formula (2) (hereinafter also referred to as "colorant (A-1)") was used as a colorant so that the colorant dispersion liquid was 100 parts by mass, (B1 ) 2 parts by mass of Solsperse 41000 (manufactured by Lubrizol (stock); 100% by mass of non-volatile components), 5% by mass of a dispersant (B-1) solution (40% by mass of non-volatile components) as a (B2) dispersant Parts and propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed by a bead mill to prepare a toner dispersion liquid (R-1).

Viscosity of colorant dispersion

The viscosity of the obtained toner dispersion liquid was measured at 25 ° C using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The evaluation results are shown in Table 1.

Examples 2 to 30 and Comparative Examples 1 to 14

In Example 1, the same operations as in Example 1 were performed except that the types and amounts of the components to be mixed and dispersed were changed to those shown in Table 1, to prepare toner dispersion liquids (R-2) to (R- 44). The same operation as in Example 1 was performed to measure the viscosity of the colorant dispersion. The evaluation results are shown in Table 1.

However, in Examples 22 to 25, 15 parts by mass of the binder resin solution (C-1) (solid content concentration: 33% by mass) as the (C) binder resin was added. The solvent in Example 26 was a 9/1 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.

The symbols in Table 1 are as follows.

R177: C.I. Pigment Red 177

R179: C.I. Pigment Red 179

Y150: C.I. Pigment Yellow 150

R254: C.I. Pigment Red 254

S41000: Solsperse 41000 (made by Lubrizol (stock); non-volatile content 100% by mass)

BYK111: Disperbyk-111 (manufactured by BYK Chemie (BYK); non-volatile content 95% by mass)

Dispersant (B-1): Dispersant (B-1) solution synthesized in Synthesis Example 1 (non-volatile component 40% by mass)

LPN21324: BYK-LPN21324 (manufactured by BYK-Chemie (BYK); 40% by mass of non-volatile components)

LPN21116: BYK-LPN21116 (manufactured by BYK-Chemie (BYK); 40% by mass of non-volatile components)

S76500: Solsperse 76500 (made by Lubrizol (stock); 50% by mass of non-volatile components)

PB821: Ajisper PB821 (manufactured by Ajinomoto Fine-Techno (stock); non-volatile content 100% by mass)

In addition, in Table 1, "colorant (A-1) / R177 = 50/50" means that the colorant (A-1) and R177 are mixed at 50/50 (mass ratio). Similarly, "colorant (A-1) / R177 / Y150 = 25/70/5" means that colorant (A-1) is mixed with R177 and Y150 at 25/70/5 (mass ratio), and "coloring Agent (A-1) / R179 = 50/50 "refers to a mixture of colorant (A-1) and R179 at 50/50 (mass ratio)," colorant (A-1) / R179 / R177 = 50 / "30/20" refers to the colorant (A-1) mixed with R179 and R177 at 50/30/20 (mass ratio), "colorant (A-1) / colorant (A-2) = 85/15 "Means colorant (A-1) and colorant (A-2) are mixed at 85/15 (mass ratio)," R254 / R177 = 50/50 "means R254 and R177 are at 50/50 (mass ratio) ) Mixer.

In Comparative Example 7 and Comparative Example 14, since the colorant cannot be dispersed, the viscosity cannot be measured.

<Preparation and Evaluation of Colored Compositions>

Example 101

100 parts by mass of the pigment dispersion liquid (R-1), 35 parts by mass of the binder resin solution (C-1) as the binder resin (C), and dipentaerythritol hexaacrylate as the (D) polymerizable compound 13 parts by mass of a mixture with dipentaerythritol pentaacrylate (hereinafter referred to as "(D-1)"; manufactured by Nippon Kayaku Co., Ltd .; product name KAYARAD DPHA) as a photopolymerization initiator Yl-1- [4- (methylthio) phenyl] -2- (N- 10 parts by mass of propan-1-one, 0.05 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a surfactant, propylene glycol monomethyl ether acetate and 3-methoxy as solvents Butyl acetate was prepared as a colored composition (S-1) so that the solid content concentration was 15% by mass. The content of 3-methoxybutyl acetate was adjusted to 30% by mass of all solvents contained in the coloring composition (S-1).

Evaluation of development speed

The coloring composition (S-1) was coated on a soda glass substrate having a diameter of 4 inches on the surface of which a SiO ₂ film preventing sodium ion elution was formed using a slot die coater, and then performed on a hot plate at 90 ° C. for 1 minute. It was pre-baked to form a coating film with a thickness of 2.0 μm. The developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged from the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and the elution end time (braking time) was measured. Those who reached 25 seconds were rated as "○", those who were 25 seconds or more and less than 30 seconds were rated as "△", and those who were 30 seconds or more were rated as "x". The evaluation results are shown in Table 2. The earlier this time is, the faster the development speed is, which has the advantage of shortening the yield time for manufacturing color filters.

Evaluation of pattern defects

The colored composition (S-1) was coated on a glass substrate using a slot die coater, and then left to stand at room temperature for 20 minutes. After pre-baking for 1 minute on a hot plate at 90 ° C. to form a coating film with a thickness of 2.0 μm, the substrate was cooled to room temperature. A high-pressure mercury lamp is used to expose radiation with wavelengths of 365 nm, 405 nm, and 436 nm through a mask having a stripe pattern with a width of 90 μm at an exposure illuminance of 17 mW, an exposure of 400 J / m ² and a distance of 350 μm between the substrate and the mask. Conditional exposure. Then, the coating film on the substrate was completely peeled off at a developing pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm), and then 0.04 mass% potassium hydroxide containing 23 ° C. was discharged until 30 seconds elapsed. A developing solution in an aqueous solution is subjected to shower development. Next, the ultra-pure water was discharged at a flushing pressure of 1.5 kgf / cm ² (nozzle diameter 1 mm) for 60 seconds to perform a flushing process, and then moisture was removed from the surface of the substrate on which the stripe pattern was formed by blowing air to form a stripe having a width of 90 μm. pattern.

The above five stripe patterns were observed using an optical microscope. Among the five stripe patterns, it was evaluated as "×" when 10 or more defects were observed, "△" when 1 to 9 defects were observed, and "○" when no defects were observed at all. The evaluation results are shown in Table 2.

Comparative evaluation

After the colored composition (S-1) was applied on a glass substrate using a slot die coater, pre-baking was performed on a hot plate at 80 ° C. for 10 minutes to form a coating film. The number of rotations of the spin coater was changed and the same operation was performed to form three coating films with different film thicknesses.

Next, after these substrates were cooled to room temperature, each coating film was exposed to radiation having a wavelength of 365 nm, 405 nm, and 436 nm with an exposure amount of 2,000 J / m ² using a high-pressure mercury lamp without a mask. Then, the developing solution containing 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged from these substrates at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and subjected to shower development for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then dried in a clean oven at 200 ° C. for 30 minutes, thereby forming a hardened film for evaluation.

The substrate on which the cured film is formed is sandwiched between two deflector plates, and the front side deflection plate is rotated by a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and a brightness meter LS-100 (made by Minolta) The maximum and minimum values of transmitted light intensity were measured. Then, for each cured film, a value obtained by dividing the maximum value by the minimum value is used as a contrast. From the measurement results, the contrast at the chromaticity coordinate value y = 0.650 was obtained. The evaluation results are shown in Table 2. The larger the contrast value, the better the meaning.

Examples 102 to 130 and Comparative Examples 101 to 114

In Example 1, except that the colorant dispersion liquid was changed as shown in Table 2, the same operations as in Example 101 were performed to prepare colored compositions (S-2) to (S-44). Next, using the obtained colored composition, the same operations as in Example 101 were performed, and various evaluations were performed. The results are shown in Table 2. However, the evaluation of the contrast was performed in Examples 109 to 126, Example 128, and Comparative Examples 108 to 114 to obtain the contrast at the chromaticity coordinate value y = 0.663.

In Comparative Example 107 and Comparative Example 114, since the colorant dispersion liquid (R-35) and the colorant dispersion liquid (R-44) could not be dispersed, various evaluations of the colored composition could not be performed.

In Comparative Example 105 and Comparative Example 112, a uniform coating film was not obtained using a slot die coater, and evaluation was difficult.

<Production and Evaluation of Colored Hardened Films for Solid-state Photographic Elements>

Modulation example 1

(Preparation of composition for forming base film)

After nitrogen was substituted in the flask, 200 parts by mass of a methyl-3-methoxypropionate solution in which 0.6 parts by mass of 2,2'-azobisisobutyronitrile was dissolved was added, and then tertiary butyl methacrylate was charged. After 37.5 parts by mass of ester and 62.5 parts by mass of glycidyl methacrylate, the mixture was stirred and heated at 70 ° C. for 6 hours. After cooling, a polymer-containing resin solution was obtained.

Next, after diluting 33.3 parts by mass of this resin solution (containing 10 parts of polymer) with 31.9 parts by mass of methyl-3-methoxypropionate and 3.4 parts by mass of propylene glycol monomethyl ether, 0.3 parts by mass of trimellitic acid Parts, 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 0.005 parts by mass of the trade name "FC-4432" (manufactured by Sumitomo 3M Co., Ltd.) were dissolved to prepare a composition for forming a base film.

Example 131

9.0 parts by mass of a coloring agent (A-1), 1396.0 parts by mass of CI Pigment Yellow, and 10.0 parts by mass of BYK-LPN22102 (by BYK Chemie (BYK)) as a (B2) dispersant (solid content concentration = 40% by mass), 2.0 parts by mass of PHOSPHANOL RS-710 (manufactured by Toho Chemical Industry Co., Ltd.) as a component (B1), 5.0 parts by mass of a binder resin solution (C-1) A part (solid content concentration = 40% by mass) and 68.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed with a bead mill to prepare a coloring agent dispersion liquid (R-45).

In addition, BYK-LPN22102 is a (meth) acrylic dispersant having an amine group and a quaternary ammonium group. This (meth) acrylic dispersant is a propylene glycol monomethyl ether of a modified acrylic block copolymer. Acetate / propylene glycol methyl ether = 1/1 (mass ratio) 40% by mass solution (acid value = 0, amine value = 29mgKOH / g). The modified acrylic block copolymer includes a block having repeating units derived from methacryloxyethylbenzyldimethylammonium chloride and dimethylaminoethyl methacrylate, Blocks with repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, and triethylene glycol ethyl ether methacrylate .

Next, 66.7 parts by mass of the toner dispersion liquid (R-45) prepared above, 4.48 parts by mass of the binder resin solution (C-1) as the binder resin (C-1) (solid content concentration = 40% by mass), 2.81 parts by mass of KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd .; dipentaerythritol hexaacrylate modified with ethylene oxide) as a (D) polymerizable compound, and ADEKA as a photopolymerization initiator ARC LUZ NCI-930 (manufactured by ADEKA Co., Ltd.) 0.37 parts by mass, FTERGENT FTX-218 (manufactured by NEOS Co., Ltd.) as a fluorine-based surfactant, 0.004 parts by mass, and propylene glycol monomethyl ether acetate 25.67 parts by mass are mixed A colored composition (S-45) having a solid content concentration of 20% by mass and a pigment concentration of 50% by mass was obtained.

Formation and evaluation of pixel patterns

On a 6-inch silicon wafer, the above-mentioned composition for forming a base film was spin-coated using an automatic coating and developing device (clean track made by Tokyo Electron Corporation; trade name "MARK-Vz"). After coating, baking was performed at 230 ° C. for 300 seconds to form a base film having a thickness of 0.6 μm.

After the coloring composition (S-45) was applied to the base film by a spin coating method, pre-baking was performed at 90 ° C for 150 seconds to form a coating film having a film thickness of 0.75 μm. Then, the obtained substrate was cooled to room temperature, and the coating film on the substrate was sandwiched by a photomask, and a reduction projection exposure machine (NSR-2205i12D manufactured by Nikon Corporation); the numerical aperture of the lens = 0.50 was used, and the wavelength was 365 nm (i-ray ) 30 to 500mJ / cm ² exposure amount of at 10mJ / cm ² exposure interval. Next, in an automatic coating and developing device, a 0.6% tetramethylammonium hydroxide aqueous solution was immersed (liquid-covered) for development in 90 seconds, and then rinsed with ultrapure water. After spin-drying, the plate was subjected to 300 ° C at 200 ° C Bake in seconds to form a red pixel pattern.

Even if the red pixel pattern is an ultra-thin film required for a solid-state imaging element, it is confirmed that the color separation property is excellent. Therefore, the coloring composition of the present invention can be said to be excellent in color reproducibility, and a color filter suitable for a solid-state imaging element can be produced.

Comparative Example 115

9.0 parts by mass of a coloring agent (A-1), 6.0 parts by mass of CI Pigment Yellow 139, 6.0 parts by mass of CI Pigment Yellow 139, and BYK-LPN22102 (manufactured by BYK Chemie (BYK)) as a dispersant (15.0 parts by mass) = 40% by mass), 5.0 parts by mass of the binder resin solution (C-1) (solid content concentration = 40% by mass), and 65.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent, mixed with a bead mill, Disperse and prepare a toner dispersion (R-46).

Next, the same operation as in Example 131 was performed except that the prepared colorant dispersion liquid (R-46) was used instead of the colorant dispersion liquid (R-45) to obtain a solid content concentration of 20% by mass and a pigment concentration. 50% by mass of the colored composition (S-46). Then, the same operation as in Example 131 was performed to form a red pixel pattern.

As a result, many development residues were observed on the red pixel pattern. When the red pixel pattern is used as a color filter for a solid-state imaging device, color mixing due to development residues may occur, and color reproducibility may deteriorate.

Claims (16)

A coloring composition comprising (A) a colorant, (C) a binder resin, and (D) a polymerizable compound, wherein (A) the colorant includes a pigment represented by the following formula (1), and the The coloring composition further contains (B1) a phosphate ester and (B2) a dispersant having a nitrogen atom, and the total content of the (B1) component and (B2) dispersant is 20 to 100 masses based on 100 parts by mass of the (A) colorant. Servings, [In the formula (1), R ¹ and R ² represent a bromine atom]. For example, the coloring composition of claim 1, wherein (B2) the dispersant having a nitrogen atom is a (meth) acrylic dispersant and a polyester dispersant, and has at least one selected from the group consisting of amine, quaternary ammonium, At least one of a dispersant having a characteristic group among an amine group and an imine group, and a urethane-based dispersant. For example, the coloring composition of claim 1, wherein the ratio (w ₁ / w ₂ ) of the content w _{1 of the} phosphate ester (B1) to the content w ₂ of the dispersant having a nitrogen atom (w ₁ / w ₂ ) is 10 / 90 to 90/10. The coloring composition according to claim 1, wherein the acid value of the (B1) phosphate is 1 to 150 mgKOH / g. The coloring composition according to claim 1, wherein the (B1) phosphate is a polyether phosphate polymer. A coloring composition comprising (A) a colorant, (C) a binder resin, and (D) a polymerizable compound, wherein (A) the colorant includes a pigment represented by the following formula (1), and the The coloring composition further contains (B1) phosphate ester and (B2) a dispersant having a nitrogen atom, and the content of (B1) component is 29 to 50% by mass based on the total content of (B1) component and (B2) dispersant, [In the formula (1), R ¹ and R ² represent a bromine atom]. The coloring composition according to claim 6, wherein (B2) the dispersant having a nitrogen atom is a (meth) acrylic dispersant and a polyester dispersant, and has at least one selected from the group consisting of amine groups, quaternary ammonium, At least one of a dispersant having a characteristic group among an amine group and an imine group, and a urethane-based dispersant. The coloring composition of claim 6, wherein the ratio (w ₁ / w ₂ ) of the content w _{1 of the} phosphate ester (B1) to the content w ₂ of the dispersant having a nitrogen atom (w ₁ / w ₂ ) is 10 / in terms of mass ratio. 90 to 90/10. The coloring composition according to claim 6, wherein the acid value of the (B1) phosphate is 1 to 150 mgKOH / g. The coloring composition according to claim 6, wherein the (B1) phosphate is a polyether phosphate polymer. The coloring composition according to any one of claims 1 to 10, wherein the (A) colorant contains a coloring agent other than the pigment represented by the formula (1). A colored hardened film formed by using the colored composition according to any one of claims 1 to 11. A display element including the colored hardened film according to claim 12. A solid-state photographic element including the colored hardened film according to claim 12. A colorant dispersion liquid comprising (A) a colorant and (F) a solvent, characterized in that (A) the colorant includes a pigment represented by the following formula (1), and the colorant dispersion liquid further includes (B1 ) Phosphate ester and (B2) a dispersant having a nitrogen atom, the total content of the component (B1) and the (B2) dispersant is 20 to 100 parts by mass relative to 100 parts by mass of the (A) colorant, [In the formula (1), R ¹ and R ² represent a bromine atom]. A colorant dispersion liquid comprising (A) a colorant and (F) a solvent, characterized in that (A) the colorant includes a pigment represented by the following formula (1), and the colorant dispersion liquid further includes (B1 ) Phosphate ester and (B2) dispersant having nitrogen atom, the content of (B1) component is 29 to 50% by mass relative to the total content of (B1) component and (B2) dispersant, [In the formula (1), R ¹ and R ² represent a bromine atom].