KR102252701B1 - Coloring composition, coloring cured film, display device and solid state imaging device - Google Patents

Abstract

(화학식 (1)에 있어서, R¹ 및 R²는 서로 독립적으로 염소 원자 또는 브롬 원자를 나타냄)An object of the present invention is to provide a colored composition that uses a diketopyrrolopyrrole pigment as a colorant, has excellent chromaticity characteristics even at a low exposure amount, and can form a cured film that is less likely to cause defects.
The solution of the present invention is a coloring composition comprising (A) a colorant, (C) a binder resin and (D) a polymerizable compound, (A) the colorant contains a pigment represented by the following formula (1), and (B1) ) A phosphoric acid 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

A colored composition, a colored cured film, a display device, and a solid-state imaging device TECHNICAL FIELD [COLORING COMPOSITION, COLORING CURED FILM, DISPLAY DEVICE AND SOLID STATE IMAGING DEVICE}

The present invention relates to a colored composition, a colored cured film, a display device, and a solid-state imaging device, and more particularly, to a colored cured film used for a transmissive or reflective color liquid crystal display device, a solid-state imaging device, an organic EL display device, electronic paper, and the like. It relates to a colored composition used for formation, a colored cured film formed by using the colored composition, and a display device and a solid-state imaging device including the colored cured film.

In manufacturing a color filter using a colored radiation-sensitive composition, after applying and drying a pigment-dispersed colored radiation-sensitive composition on a substrate, the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter referred to as ``exposure''). And developing, a method of obtaining a pixel of each color (see, for example, Patent Documents 1 and 2) is known. Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Further, a method of obtaining a pixel of each color by an ink jet method using a pigment-dispersed colored resin composition (for example, see Patent Document 4) is known.

In the colored composition for forming a red colored cured film, from the viewpoint of chromaticity characteristics of the colored cured film, C.I. It has been studied to use a diketopyrrolopyrrole pigment such as Pigment Red 254 as a colorant (see, for example, Patent Document 5). In addition, in recent years, brominated diketopyrrolopyrrole pigments have been proposed as a colorant capable of forming a red colored cured film having more excellent chromaticity properties (see, for example, Patent Documents 6 to 8).

Japanese Patent Laid-Open (Hei) 2-144502 Japanese Patent Laid-Open (Hei) 3-53201 Japanese Patent Publication (Hei) 6-35188 Japanese Patent Publication No. 2000-310706 Japanese Patent Publication (Hei) 11-231516 Japanese Patent Publication No. 2012-211969 Japanese Patent Application Publication No. 2012-211970 Japanese Patent Publication No. 2013-014750

However, according to the investigation of the present inventors, it has been found that the pixels formed from the colored composition containing the diketopyrrolopyrrole pigments described in Patent Documents 6 to 8 have excellent chromaticity characteristics, but there is a problem that defects are likely to occur.

In addition, in the field of technology for color filters in recent years, it is becoming mainstream to shorten the tact time by lowering the exposure amount, and it is required to have excellent pattern shapes of pixels or black matrices formed at a low exposure amount. However, according to the investigation of the present inventors, when the exposure amount of the colored composition containing diketopyrrolopyrrole pigment decreases, defects tend to occur in the pattern, so that the tact time is shortened, and a pixel or black matrix having a good pattern shape is obtained. The difficult thing became clear.

Accordingly, an object of the present invention is to provide a colored composition capable of forming a cured film which is excellent in chromaticity characteristics even at a low exposure amount and hardly causes defects by using a diketopyrrolopyrrole pigment as a colorant. Further, an object of the present invention is to provide a colored cured film formed by using the colored composition, and a display device and a solid-state imaging device including the same. Further, an object of the present invention is to provide a colorant dispersion containing a diketopyrrolopyrrole pigment as a colorant.

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

That is, the present invention is a coloring composition comprising a (A) colorant, (C) a binder resin and (D) a polymerizable compound, (A) the colorant contains a pigment represented by the following formula (1), (B1) It is to provide a colored composition further comprising a phosphoric acid ester and a dispersant having a nitrogen atom (B2).

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

Further, the present invention is to provide a colored cured film formed by using the colored composition, and a display device and a solid-state imaging device including the colored cured film. Here, the "colored cured film" means a pixel of each color, a black matrix, a black spacer, and the like used in a display element or a solid-state imaging element.

In addition, the present invention is a colorant dispersion containing (A) a colorant and (F) a solvent, (A) the colorant contains a pigment represented by the following formula (1), and (B1) a phosphoric acid ester and (B2) a nitrogen atom It is to provide a colorant dispersion further comprising a dispersant having.

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

The colorant dispersion of the present invention has good dispersibility of diketopyrrolopyrrole pigments, suppresses low viscosity, and has excellent coating properties. In addition, when the colored composition of the present invention is used, it is possible to form a colored cured film having excellent chromaticity characteristics even at a low exposure amount and in which defects are less likely to occur. In addition, the coloring composition of the present invention is excellent in development speed and can shorten the tact time.

Therefore, the colored composition of the present invention can be suitably used for manufacturing a color liquid crystal display device, an organic EL display device, a display device such as electronic paper, and a solid-state imaging device such as a CMOS image sensor.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring 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 general formula (1) as the colorant (A).

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

R ¹ and R ² are both chlorine atoms, or R ¹ And R ² are both preferably a bromine atom, more preferably R ¹ and R ² are both bromine atoms. In addition, the pigment represented by the following formula (1) can be produced by a known method. For example ^{, a pigment in which both R 1} and R ² are bromine atoms can be prepared by the method described in International Publication No. 2009/144115. Can be manufactured.

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

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colourists). Among them, Japanese Patent Laid-Open Publication No. 2001-081348, Japan Japanese Patent Application Publication No. 2010-026334, Japanese Patent Application Publication No. 2010-191304, Japanese Patent Application Publication No. 2010-237384, Japanese Patent Application Publication No. 2010-237569, Japanese Patent Application Publication No. 2011-006602, Japan Lake pigment, CI described in Patent Publication No. 2011-145346, etc. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 264, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 15:6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. Pigment Yellow 215, C.I. Pigment Orange 38, C.I. Organic pigments other than lake pigments, such as pigment violet 23, are preferable. In addition, among the lake pigments, a triarylmethane-based lake pigment, a xanthene-based lake pigment, and an azo-based lake pigment are preferable, and a triarylmethane-based lake pigment and a xanthene-based lake pigment are more preferable.

In the present invention, the pigment represented by the formula (1) and other pigments optionally used may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, if necessary, the pigment may be used by modifying the surface of the particle with a resin. Examples of the resin for modifying the surface of the pigment particles include vehicle resins disclosed in Japanese Patent Laid-Open No. 2001-108817 or various commercially available resins for dispersing pigments. As a resin coating method on the surface of carbon black, for example, the method described in Japanese Patent Laid-Open (Hei) 9-71733, Japanese Patent Laid-Open (Hei) 9-95625, Japanese Patent Laid-Open (Hei) 9-124969, etc. Can be employed. In addition, the organic pigment may be used by miniaturizing the primary particles by so-called salt milling. As the salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be adopted.

In the present invention, it is possible to further contain a known dispersion aid together with the pigment represented by the general formula (1) and other pigments to be used arbitrarily. As known dispersion aids, pigment derivatives, such as copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of kinophthalone, are mentioned, for example. In the present invention, when a dispersion aid is used, a sulfonic acid derivative of diketopyrrolopyrrole is preferred.

Further, examples of the organic dye include xanthene-based dyes, triarylmethane-based dyes, methine-based dyes, anthraquinone-based dyes, and azo-based dyes. More specifically, Japanese Unexamined Patent Publication No. 2010-32999, Unexamined Japanese Patent 2010-254964, Unexamined Japanese Patent 2011-138094, Unexamined International 2010/123071, Japanese Unexamined Patent 2011- The organic dyes described in JP-A-116803, JP-A-2011-117995, JP-A-2011-133844, JP-A-2011-174987, and the like are mentioned.

Among them, the organic dye is preferably a xanthene dye.

Examples of xanthene dyes include compounds having a structure represented by the following formula.

When the xanthene dye is cationic, it may have an anion so that the xanthene dye is electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonic acid anion, a nitrogen anion, a methide anion, an anion of a transition metal complex having an azo compound as a ligand. . As the nitrogen anion, the nitrogen anion described in JP 2011-133844 A, JP 2011-116803 A, and JP 2010-090341 A can be mentioned. As the anion of the transition metal complex having an azo compound as a ligand, the anions described in Japanese Patent Application Laid-Open No. 2009-163226 and Japanese Patent Application Laid-Open No. 2012-212089 can be mentioned.

In addition, a xanthene-based acid dye having an ammonium cation and a xanthene-based acid dye having a phosphonium cation can also be preferably used. Here, the xanthene-based acid dye means a xanthene-based dye whose anion moiety becomes a chromophore. Representative examples of the xanthene-based acid dye having an ammonium cation include, for example, the dyes described in Japanese Patent No. 4452760 and Japanese Patent Laid-Open No. 2011-242752.

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

It is preferable to use the coloring composition of this invention for formation of a red pixel. In this case, as the colorant (A), together with the pigment represented by the formula (1), as another colorant, a red pigment other than the pigment represented by the formula (1), a red dye, a purple pigment, a purple dye, a yellow pigment and an orange pigment It is preferable to include at least one selected from the group consisting of.

As the red pigment, C.I. Pigments classified as pigment red are preferred, and C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 264 is more preferred. As the purple pigment, C.I. Pigment violet 23 is preferred.

As the red dye and purple dye, a xanthene-based dye is preferable, and more specifically, the same as described above is mentioned.

As the yellow pigment, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185 is preferred. As the orange pigment, C.I. Pigment Orange 38 is preferred.

(A) The content of the colorant is usually 5 to 70% by mass in the solid content of the colored composition from the viewpoint of forming a pixel with excellent chromaticity characteristics and less defects, or a black matrix having excellent light-shielding properties, and a black spacer even at a low exposure dose. , Preferably it is 10 to 60 mass %. Here, the solid content is a component other than the solvent mentioned later.

In addition, when using another colorant, the content ratio of the other colorant 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 is not particularly limited, and may be 0.01% by mass or more.

-(B) component-

As the component (B), the colored composition of the present invention includes (B1) a phosphate ester (hereinafter, also simply referred to as ``(B1) component''), and (B2) a dispersant having a nitrogen atom (hereinafter, simply ``(B2)) dispersant''. Also referred to as). The component (B1) and the dispersant (B2) of the present invention act as a dispersant for dispersing the pigment represented by the general formula (1) and other pigments optionally used. As a result of intensive study, the present inventors showed that by using a combination of the component (B1) and the dispersant (B2), the dispersibility of the diketopyrrolopyrrole pigment is good, the viscosity is suppressed low, and the colorant dispersion is also excellent in coatability can be prepared. As a result, it was found that the cured film was excellent in chromaticity characteristics even at a low exposure dose, and a cured film in which defects are hard to occur can be formed. It is also mentioned as an advantage that the coloring composition of the present invention has a high development speed.

The component (B1) is not particularly limited as long as it is a phosphoric acid ester, and may be a phosphoric acid monoester, a phosphoric acid diester, a phosphoric acid tryster, or a mixture of two or more of these. Further, the phosphoric acid ester 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. As the component (B1), one synthesized by a known method can be used, but, for example, Solsperse 41000 (manufactured by Lubrizol Co., Ltd., polyether phosphate-based polymer, non-volatile component 100% by mass, acid value 50 mgKOH/ g), Disperbyk-111 (manufactured by BYK Co., Ltd., a phosphate ester polymer, 95% by mass of a non-volatile component, an acid value of 129 mgKOH/g), Phosphenol RE-610, Phosphenol RS-710 (alkyl ether phosphate ester, Acid value 65 mgKOH/g) (above, manufactured by Toho Chemical Industry Co., Ltd.), Dispalon PW-36 (non-volatile component 50 mass%, acid value 55 mgKOH/g), Dispalon DA-375 (polyetherphosphoric acid ester polymer, non-volatile component 100) Mass%, acid value 14 mgKOH/g), dispalon DA-325 (amine salt of polyetherphosphate, non-volatile component 100% by mass, acid value 14 mgKOH/g) (above, manufactured by Gusumoto Kasei), etc. were commercially obtained. You can also use it. Among these, as the component (B1), a polyether phosphate-based polymer is preferable from the viewpoint of dispersibility, viscosity, and coatability of a diketopyrrolopyrrole pigment.

The acid value of the component (B1) is preferably 1 to 150 mgKOH/g, more preferably 5 to 90 mgKOH/g, and even more preferably 10 to 60 mgKOH/g. This form is preferable from the viewpoint of dispersibility, viscosity, and coatability of the diketopyrrolopyrrole pigment. Here, in the present invention, the "acid value" is the number of mg of KOH required to neutralize 1 g of nonvolatile components excluding the solvent of the dispersant solution.

The colored composition of the present invention contains a dispersant (B2) together with the component (B1).

(B2) The nitrogen atom contained in the dispersant includes a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium, an amide group, an imino group, a urethane group, and the like.

As the dispersant (B2) in the present invention, for example, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, a polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, a polyester dispersant, and ( It is a dispersant selected from meth)acrylic dispersants, and a dispersant having at least one characteristic group selected from amino groups, quaternary ammonium, amide groups and imino groups, urethane dispersants, and polyethyleneimine dispersants can be preferably used. In addition, the amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.

Among them, (B2) the dispersant is a (meth)acrylic dispersant or a polyester dispersant, and at least one of a dispersant having at least one characteristic group selected from an amino group, a quaternary ammonium, an amide group and an imino group, and a urethane-based dispersant is preferred. , An amino group, a quaternary ammonium, an amide group, and an (meth)acrylic dispersant having at least one characteristic group selected from an imino group.

The (meth)acrylic dispersant may have a crosslinkable functional group in addition to the above-described characteristic group having a nitrogen atom. Examples of the crosslinkable functional group include an oxygen-containing saturated heterocyclic group such as an oxiranyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group, an ethylenically unsaturated group, an epithio group, and a (dithio) carbonate. 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, the (meth)acrylic dispersant having a crosslinkable functional group can be synthesized by, for example, a method described in Japanese Patent Laid-Open No. 2012-118505. With this form, the desired effect of the present invention can be further obtained.

(B2) The dispersant may be commercially obtained as long as it has a nitrogen atom.For example, as (meth)acrylic dispersants, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (non-volatile component 40 mass) %), BYK-LPN22102 (above, manufactured by BYK), etc., as urethane-based dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, Big Chemie (BYK)), Solsperse 76500 (Lubrizol Co., Ltd., non-volatile component 50% by mass), etc. As a polyethyleneimine-based dispersant, Solsperse 24000 (Lubrizol Co., Ltd. product), etc. , As a polyester-based dispersant, in addition to Azisper PB821 (non-volatile component 100% by mass), Azisper PB822, Azisper PB880, Azisper PB881 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), BYK-LPN 21324 (40% by mass of non-volatile components) (manufactured by BYK), and the like, respectively.

(B2) Dispersants may be used alone or in combination of two or more.

The coloring composition of the present invention, component (B1) and (B2) may be selected appropriately for the content of the dispersing agent, (B1) content of the component (w ₁₎ and (B2) ratio (w ₁ of the content (w ₂₎ of the dispersant /w ₂ ) is preferably 10/90 to 90/10 by mass ratio, more preferably 20/80 to 80/20, and still more preferably 30/70 to 70/30.

In the present invention, the total content of the component (B1) and the dispersant (B2) is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass based on 100 parts by mass of the colorant (A). desirable. By setting it as such a form, it becomes easy to obtain the desired effect of this application.

-(C) Binder resin-

Although it does not specifically limit as (C) binder resin in this invention, It is preferable that it is a resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter, also referred to as a ``carboxyl group-containing polymer'') is preferable, and for example, it is different from an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as ``unsaturated monomer (c1)''). A copolymer of a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (c2)") is mentioned.

Examples of the unsaturated monomer (c1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate and p-vinylbenzoic acid.

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

In addition, as the unsaturated monomer (c2), for example

N-position substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)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 (polymerization degree 2 to 10) mono (meth) acrylate, poly Propylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl ( Meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyl (Meth)acrylic acid esters such as oxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane Vinyl ethers such as;

And macromonomers having a mono(meth)acryloyl group at the terminal of a polymer molecular chain such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, and polysiloxane.

These unsaturated monomers (c2) may 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, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (c1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include, for example, Japanese Patent Application Laid-Open (Hei) 7-140654, Japanese Patent Laid-Open (Hei) 8-259876, and Japanese Patent Laid-Open (Hei). )10-31308, Japanese Patent Laid-Open (Hei) 10-300922, Japanese Patent Laid-Open (Hei) 11-174224, Japanese Patent Laid-Open (Hei) 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728 and the like can be mentioned.

In addition, in the present invention, for example, Japanese Patent Laid-Open (Hei) 5-19467, Japanese Patent Laid-Open (Hei) 6-230212, Japanese Patent Laid-Open (Hei) 7-207211, and Japanese Patent Laid-Open ( As disclosed in Hei) 9-325494, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc., polymerizable unsaturated bonds such as (meth)acryloyl groups in the side chain A carboxyl group-containing polymer having a can also be used as a binder resin.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to It is 50,000. By setting it as such a form, the film remaining rate, pattern shape, heat resistance, electrical properties, and resolution of the film are further increased, and the occurrence of dry foreign matter during application can be suppressed to a high level.

Further, in the present invention, the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the binder resin and the number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In addition, Mn here refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, but disclosed, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. Its structure, Mw, and Mw/Mn can also be controlled by a method that has been established.

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

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass based on 100 parts by mass of the colorant (A). By setting it as such a form, alkali developability, storage stability of a colored composition, pattern shape, and chromaticity characteristics can be further improved.

-(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 oxiranyl 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)acryloyl groups, or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, alkyl Reaction of polyfunctional urethane (meth)acrylate obtained by reacting renoxide-modified polyfunctional (meth)acrylate, (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and (meth)acrylate having a hydroxyl group with an acid anhydride The polyfunctional (meth)acrylate etc. which have a carboxyl group obtained by making it are mentioned.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; And trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. As the (meth)acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropanedi (meth)acrylate, pentaerythritol tri (meth)acrylate, dipentaerythritol penta (Meth)acrylate, glycerol dimethacrylate, etc. are mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. As the acid anhydride, for example, anhydride of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride And tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Further, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955 A. The alkylene oxide-modified polyfunctional (meth)acrylate is selected from bisphenol A di(meth)acrylate modified by at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Isocyanuric acid tri(meth)acrylate modified by at least one type, trimethylolpropane tri(meth)acrylate modified by at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene Pentaerythritol tetra(meth)acrylate modified by at least one selected from pentaerythritol tri(meth)acrylate, ethylene oxide and propylene oxide modified by at least one selected from oxides, ethylene Dipentaerythritol hexa modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from oxide and propylene oxide ( And meth)acrylate.

Further, examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl substituted triazine rings as a basic skeleton, and are concepts including melamine, benzoguanamine, or condensates 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'-tetra (Alkoxymethyl)benzoguanamine, N,N,N',N'-tetra (alkoxymethyl) glycoluril, etc. are mentioned.

Among these polymerizable compounds, polyfunctional (meth)acrylate obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, and polyfunctional urethane (meth)acrylic Rate, polyfunctional (meth)acrylate having a carboxyl group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra( Alkoxymethyl)benzoguanamine is preferred. Among the polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among the polyfunctional (meth)acrylates having a carboxyl group, erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride. It is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and ground contamination, film residue, and the like are difficult to occur on the substrate and the light-shielding layer of the unexposed portion.

In the present invention, the (D) polymerizable compound can be used alone or in combination of two or more.

The content of the (D) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, further preferably 20 to 700 parts by mass, further preferably 80 to 500 parts by mass based on 100 parts by mass of the (D) colorant. By setting it as such a form, hardenability and alkali developability are further improved, and generation|occurrence|production of background contamination, film|membrane residue, etc. can be suppressed to a high level on the substrate of an unexposed part or a light-shielding layer.

-(E) Photoinitiator-

A photoinitiator can be contained in the coloring composition of this invention. Thereby, it is possible to impart radiation-sensitive properties to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, A polynuclear quinone compound, a diazo compound, an imide sulfonate compound, etc. are mentioned.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photoinitiator, at least one selected from the group of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds is preferable.

Among the preferred photoinitiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc. are mentioned.

Further, as specific examples of the acetophenone compound, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

Further, as a specific example of the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 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, etc. are mentioned.

In addition, when a biimidazole compound is used as the photoinitiator, it is preferable to use a hydrogen donor in combination, since sensitivity can be improved. The "hydrogen donor" as used herein means a compound capable of providing a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(di And amine hydrogen donors such as ethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but using a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors can also improve sensitivity. desirable.

Further, specific examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[ 2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4 And triazine compounds having a halomethyl group such as ,6-bis(trichloromethyl)-s-triazine.

In addition, as a specific example of the O-acyloxime compound, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanol, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanol, 1-[9-ethyl-6-(2-methyl-4-tetrahydropra) Nylmethoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanol, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl) -1,3-dioxolanyl)methoxybenzoyl-9H-carbazol-3-yl]-,1-(O-acetyloxime), and the like. Commercially available products of O-acyloxime compounds include NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), DFI-020, DFI-091 (above, manufactured by Daitochemicals, Inc.), etc. You can also use it.

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 sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. , 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl ) Coumarin, 4-(diethylamino)chalcone, etc. are mentioned.

In the present invention, the content of the photoinitiator (E) is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass, based on 100 parts by mass of the (D) polymerizable compound. By setting it as such a form, hardenability and a film|film|coat characteristic can be further improved.

-(F) solvent-

Although the colored composition of the present invention contains the components (A) to (D) and other components optionally added, it is usually prepared as a liquid composition by blending a solvent.

As the (F) solvent, it can be appropriately selected and used as long as it does not react with these components while dispersing or dissolving components (A) to (D) or other components constituting the colored composition and has suitable volatility.

Among these solvents, for example

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, 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-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Alkyl lactate esters such as methyl lactate and ethyl lactate;

(Cyclo)alkyl alcohols, such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, and cyclohexanol;

Keto alcohols such as diacetone alcohol;

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 (Poly)alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Diacetates, such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxyl, such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy ethyl acetate, and 3-methyl-3-methoxybutyl propionate Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate , Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

And amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, or lactams.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coating properties, etc., (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones , Diacetates, alkoxycarboxylic acid esters, and other esters are preferable, and in particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6 -Hexanediol diacetate, ethyl lactate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, acetate i -Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like are preferable.

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

(F) The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By setting it as such a form, a coloring agent dispersion liquid with good dispersibility and stability, and a coloring composition having good coating properties and stability can be obtained.

-additive-

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

Examples of additives include fillers such as glass and alumina; Polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); Surfactants such as fluorine surfactants and silicone surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. Adhesion promoter; 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4) -Hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro[5·5]undecane, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. Antioxidants; Ultraviolet absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenones; Anti-aggregation agents 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-propane Residue improving agents such as diol, 2-amino-1,3-propanediol, and 4-amino-1,2-butanediol; Developability improving agents such as succinate mono [2-(meth)acryloyloxyethyl], phthalic acid mono [2-(meth)acryloyloxyethyl], and ω-carboxypolycaprolactone mono(meth)acrylate I can.

The coloring composition of the present invention can be produced by an appropriate method, but a more preferable method for producing the colored composition is a method using the colorant dispersion of the present invention. That is, (A) the colorant containing the pigment represented by the above formula (1) in the (F) solvent, together with a component (B1) and a dispersant (B2), and a dispersing aid if necessary, and a part of the (C) binder resin. , For example, using a bead mill, roll mill, etc., mixing and dispersing while pulverizing to obtain a colorant dispersion, and in this colorant dispersion, (C) a binder resin and (D) a polymerizable compound, and if necessary (E) photopolymerization The method of manufacturing by further adding an initiator, an additional (F) solvent, or an additive, and mixing is mentioned. In addition, the specific configuration of the (A) colorant, (B1) component, (B2) dispersant and (F) solvent, and a dispersion aid added as necessary, and (C) binder resin in the colorant dispersion of the present invention are as described above. to be.

In addition, the colorant dispersion of the present invention has good dispersibility of diketopyrrolopyrrole pigments compared to the case where the component (B1) and the dispersant (B2) are used alone by using the component (B1) and the dispersant (B2) in combination. It is possible to prepare a colored composition capable of forming a cured film that is less likely to cause defects and has excellent chromaticity characteristics even at a low exposure dose, as a result of which it is possible to manufacture a colored composition that has low viscosity and is excellent in coating properties. Specifically, the viscosity of the colorant dispersion can be preferably 20 mPa·s or less, more preferably 16 mPa·s or less, still more preferably 13 mPa·s or less, and particularly preferably 11 mPa·s or less. Here, the viscosity is a value measured using an E-type viscometer at 25°C.

In addition, in the case where the coloring composition of the present invention uses both a dye and a pigment as a colorant, as disclosed in Japanese Patent Laid-Open Publication No. 2010-132874, after passing the dye solution through the first filter, the first filter A method of preparing a dye solution that has passed through is mixed with a separately prepared pigment dispersion or the like, and then passed the obtained colored composition through a second filter can be adopted. In addition, after dissolving a dye, components (B) to (D), and other components used as necessary in a solvent, and passing the obtained solution through a first filter, a solution that has passed through the first filter is separately prepared. It is also possible to employ a method of mixing with one pigment dispersion and producing the obtained colored composition through a second filter. In addition, after passing the dye solution through the first filter, the dye solution passed through the first filter, the components (B) to (D), and other components used as necessary are mixed and dissolved, and the obtained solution is A method of producing by passing through the second filter and mixing the solution passed through the second filter with a separately prepared pigment dispersion, and passing the obtained colored composition through a third filter can also be employed.

coloring Cured film And its formation method

The colored cured film of the present invention is formed by using the colored composition of the present invention, and specifically means each color pixel constituting a color filter, a black matrix, a black spacer, and the like.

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

As a method of manufacturing a color filter, first, the following method is mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate by dividing a portion for forming a pixel as necessary. Subsequently, on this substrate, for example, after applying the liquid composition of the red radiation-sensitive coloring composition of the present invention, prebaking is performed to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film to light through a photomask, it is developed using an alkali developer, and the unexposed portion of the coating film is dissolved and removed. Thereafter, by post-baking, a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed.

Subsequently, using each of the green or blue radiation-sensitive coloring compositions, in the same manner as described above, application, pre-baking, exposure, development, and post-baking of each radiation-sensitive coloring composition are performed, and the green pixel array and the blue color are Pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which an array of three primary colors of red, green and blue pixels is disposed on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method, but using a radiation-sensitive coloring composition in which a black colorant is dispersed, the pixel It can also be formed in the same manner as in the case of forming.

Examples of the substrate used when forming the color filter include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

Further, if necessary, the substrate may be subjected to appropriate pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. with a silane coupling agent or the like.

When applying the radiation-sensitive coloring composition to the substrate, suitable coating methods such as spray method, roll coating method, rotation coating method (spin coating method), slit die coating method (slit coating method), and bar coating method can be adopted. In particular, it is preferable to employ a spin coating method or a slit die coating method.

Pre-baking is usually carried out in combination of drying under reduced pressure and drying by heating. Drying under reduced pressure is usually performed until it reaches 50 to 200 Pa. In addition, the conditions for heat drying are usually about 1 to 10 minutes at 70 to 110°C.

The coating thickness is usually 0.6 to 8 µm, preferably 1.2 to 5 µm, as the film thickness after drying.

As a light source of radiation used when forming at least one selected from a pixel and a black matrix, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. And laser light sources such as a lamp light source, an argon ion laser, a YAG laser, an XeCl excimer laser, and a nitrogen laser. As the exposure light source, an ultraviolet LED can also be used. The wavelength is preferably radiation in the range of 190 to 450 nm.

In general, the exposure dose of radiation is preferably ^{10 to 10,000 J/m 2.}

In addition, as the alkali developer, for example, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, An aqueous solution such as 1,5-diazabicyclo-[4.3.0]-5-nonene is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer, for example. Moreover, after alkali development, it is usually washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid storage) developing method, or the like can be applied. Development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280°C.

The film thickness of the pixel thus formed is usually 0.5 to 5 µm, preferably 1.0 to 3 µm.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in Japanese Patent Laid-Open (HEI) 7-318723, Japanese Patent Laid-Open No. 2000-310706, etc. Can be adopted. In this method, first, a partition wall that also serves as a light shielding function is formed on the surface of the substrate. Subsequently, a liquid composition of, for example, a red thermosetting coloring composition is discharged into the formed partition wall by an ink jet apparatus, and then prebaking is performed to evaporate the solvent. Subsequently, this coating film is exposed to light as necessary, and then cured by post-baking to form a blue pixel pattern.

Subsequently, each green or blue thermosetting coloring composition is used, and in the same manner as above, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate. Thereby, a color filter in which three primary color pixel patterns of red, green and blue are disposed on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, since the partition wall not only functions to shield light, but also functions to prevent the thermosetting coloring composition of each color discharged into the compartment from being mixed, the film thickness is thicker than that of the black matrix used in the above-described first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

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

On the pixel pattern thus obtained, after forming a protective film as necessary, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but it can also be used as a light-shielding spacer (black spacer). In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention can be suitably used also for formation of such a black spacer.

The radiation-sensitive coloring composition of the present invention can be suitably used in the formation of any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.

The color filter including the colored cured film of the present invention thus formed has extremely high luminance and color purity, and is therefore very useful for a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, and the like. In addition, the display element described later may have at least one colored cured film formed using the radiation-sensitive colored composition of the present invention.

Display element

The display element of the present invention is provided with the colored cured film of the present invention. As a display element, a color liquid crystal display element, an organic EL display element, electronic paper, etc. are mentioned.

The color liquid crystal display device provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and a suitable structure can be adopted. For example, a color filter can be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter are formed can adopt a structure in which the substrate for driving and the substrate on which the color filter is formed are opposed to each other via a liquid crystal layer. have. In addition, the substrate on which the color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed and the substrate on which the ITO (tin-doped indium oxide) electrode is formed are opposed to each other through a liquid crystal layer. You may. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-precision liquid crystal display element is obtained. Further, in the case of employing the latter structure, a black matrix or a black spacer may be formed both on the side of the substrate on which the color filter is formed and on the side of the substrate on which the ITO electrode is formed.

The color liquid crystal display device having the colored cured 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). As a white LED, for example, a white LED that obtains white light by a mixture color by combining a red LED, a green LED and a blue LED, a white LED that obtains white light by a mixture color by a combination of a blue LED and a red LED and a green phosphor, and a blue LED. A white LED that produces white light by a mixture of red and green light-emitting phosphors, a white LED that produces white light by a mixture of blue LEDs and YAG-based phosphors, and a combination of blue LED and orange-emitting phosphors and green-emitting phosphors. And white LEDs that produce white light by mixing color by combining an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor, and the like.

The color liquid crystal display device having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) type. An appropriate liquid crystal mode such as a mold can be applied.

In addition, the organic EL display device provided with the colored cured film of the present invention can have an appropriate structure, and for example, a structure disclosed in Japanese Patent Laid-Open No. 11-307242 is mentioned.

In addition, the electronic paper provided with the colored cured film of the present invention can have a suitable structure, and for example, a structure disclosed in Japanese Unexamined Patent Application Publication No. 2007-41169 is mentioned.

solid Imaging device

The solid-state imaging device of the present invention is provided with the colored cured film of the present invention. Further, the solid-state imaging device of the present invention can adopt an appropriate structure. For example, as one embodiment, by forming a colored pixel (colored cured film) by the same operation as described above on a semiconductor substrate such as a CMOS substrate using the colored composition of the present invention, particularly excellent color reproducibility A solid-state imaging device can be manufactured.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail by taking examples as an example. 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 Laid-Open No. 2012-118505, about 80 mol% of repeating units derived from dimethylaminoethyl methacrylate are quaternary ammonized A blocks, n-butyl methacrylate, and methyl methacryl. A block copolymer solution (non-volatile component 40% by mass) containing a B block having a repeating unit derived from a rate and tetrahydrofurfuryl methacrylate was obtained. The obtained block copolymer is referred to as "dispersant (B-1)".

<(C) Synthesis of binder resin>

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 3-methacryloyloxymethyl-3-ethyloxetane 25.0 g, methacrylic acid 18.0 g, methacrylic acid 2-hydroxylethyl ester 14.0 g, benzyl methacrylate 24.0 g, 10.0 g of N-phenylmaleimide and 9.0 g of succinate mono2-acryloxyethyl were dissolved in 300 g of propylene glycol monomethyl ether acetate, and 2,2'-azobis (2,4-dimethylvaleronitrile) 5.3 g was added, followed by purging with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80°C while stirring and bubbling with nitrogen, and polymerized for 5 hours to obtain a solution containing 25% by mass of the precursor copolymer [c-1]. The weight average molecular weight (Mw) in terms of polystyrene of this precursor copolymer [c-1] was 10,000.

Subsequently, 200 g of a solution containing the precursor copolymer [c-1], 15.9 g of 2-methacryloyloxyethyl isocyanate, and 0.2 g of phenothiazine as a polymerization inhibitor were added to the flask, and at a temperature of 110° C. for 9 hours. Reacted. This reaction solution was washed 4 times with 75 g of ion-exchanged water per time and concentrated under reduced pressure to obtain a binder resin solution (C-1) (solid content concentration of 33% by mass). The obtained binder resin had an Mw of 11,500.

Synthesis Example 3

A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate, followed by nitrogen substitution. At the same temperature by heating to 80°C, 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, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, N-phenylmaleimide 12 parts by mass, succinate mono (2-acryloyloxyethyl) 15 parts by mass and 2,2'-azobis (2,4-dimethylvalero Nitrile) 6 parts by mass of a mixed solution was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100°C, and polymerization was performed for an additional hour to obtain a binder resin solution (C-2) (solid content concentration of 33% by mass). The obtained binder resin had an Mw of 12,200 and a Mn of 6,500.

<Synthesis of coloring agent>

Synthesis Example 4

In a 200 mL eggplant-shaped flask containing a stirrer, a xanthene-based acid dye, C.I. Acid red 52 was added to 2.9 g (5.0 mmol) and ion-exchanged water (29 mL) was added, followed by heating in an oil bath to a bath temperature of 85°C while stirring. To this solution, a solution obtained by dissolving 5.2 g (10.26 mmol) of tributylhexadecylphosphonium bromide in 60 g of ion-exchanged water at room temperature was added little by little at the same temperature. When all were added, it was confirmed that a water-insoluble colored oily substance was formed. Then, after stirring at the same temperature for 1 hour, it was cooled to around room temperature using a cold bath. The supernatant was removed by decantation, and the residue was subsequently washed with ion-exchanged water. After dissolving and recovering this residue in methanol, it was 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-violet solid.

^{By 1} H-NMR spectrum (solvent: deuterated chloroform) measurement, it was confirmed that the obtained compound was a compound represented by the following formula (A-2). The obtained compound is referred to as a coloring agent (A-2).

Synthesis Example 5

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

Synthesis Example 6

With reference to Synthesis Example 3 of Japanese Patent Laid-Open No. 2012-181505, a compound represented by the following formula (A-4) was synthesized. This compound is referred to as a colorant (A-4).

Synthesis Example 7

A compound represented by the following formula (A-5) was synthesized with reference to the synthesis example in the specification of Japanese Patent No. 4452760. This compound is referred to as a colorant (A-5).

<Preparation and evaluation of colorant dispersion>

Example 1

(A) 13 parts by mass of a pigment represented by the following formula (2) (hereinafter, also referred to as ``coloring agent (A-1)'') as a colorant, as a component (B1), Solsperse 41000 (manufactured by Lubrizol Co., Ltd.) , Non-volatile component 100% by mass) 2 parts by mass, (B2) dispersant (B-1) solution (non-volatile component 40% by mass) 5 parts by mass as a dispersant, and propylene glycol monomethyl ether acetate as a solvent as a coloring agent dispersion liquid The mixture was used so as to be 100 parts by mass, and mixed and dispersed by a bead mill to prepare a colorant dispersion (R-1).

Viscosity of colorant dispersion

The viscosity of the obtained colorant dispersion was measured at 25°C using an E-type viscometer (manufactured by Keiki, Tokyo). Table 1 shows the evaluation results.

Examples 2 to 30 and Comparative Examples 1 to 14

In Example 1, colorant dispersions (R-2) to (R-44) were prepared in the same manner as in Example 1 except that the kind and amount of each component to be mixed and dispersed as shown in Table 1 were changed. . And in the same manner as in Example 1, the viscosity of the colorant dispersion was measured. Table 1 shows the evaluation results.

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

In addition, in Table 1, the symbols 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: Solspur 41000 (manufactured by Lubrizol Co., Ltd., non-volatile component 100% by mass)

BYK111: Disperbyk-111 (manufactured by BYK, 95% by mass of non-volatile component)

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

LPN21324: BYK-LPN21324 (manufactured by BYK, non-volatile component 40% by mass)

LPN21116: BYK-LPN21116 (manufactured by BYK, non-volatile component 40% by mass)

S76500: Solsperse 76500 (manufactured by Lubrizol Co., Ltd., non-volatile component 50% by mass)

PB821: Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd., non-volatile component 100% by mass)

In addition, in Table 1, "coloring agent (A-1)/R177=50/50" means that the coloring agent (A-1) and R177 were mixed at 50/50 (mass ratio). Similarly, "colorant (A-1)/R177/Y150=25/70/5" means that the colorant (A-1), R177, and Y150 are mixed at 25/70/5 (mass ratio), and "colorant ( A-1)/R179=50/50" means that the coloring agent (A-1) and R179 were mixed at 50/50 (mass ratio), and "the coloring agent (A-1)/R179/R177=50/30/ 20" means that the colorant (A-1) and R179 and R177 are mixed at 50/30/20 (mass ratio), and "colorant (A-1)/colorant (A-2) = 85/15" is a colorant It means that (A-1) and the colorant (A-2) were mixed at 85/15 (mass ratio), and "R254/R177=50/50" means that R254 and R177 were mixed at 50/50 (mass ratio). it means.

In Comparative Example 7 and Comparative Example 14, since the colorant could not be dispersed, viscosity measurement was not possible.

<Preparation and evaluation of colored composition>

Example 101

Pigment dispersion (R-1) 100 parts by mass, (C) binder resin solution (C-1) 35 parts by mass as binder resin, (D) dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylic as polymerizable compounds 13 parts by mass of a mixture of rates (hereinafter referred to as "(D-1)", manufactured by Nippon Kayaku Co., Ltd., brand name KAYARAD DPHA), 2-methyl-1-[4-(methylthio)phenyl as a photoinitiator ]-2-morpholinopropan-1-one 10 parts by mass, Megaface F-554 (manufactured by DIC Corporation) as a surfactant, 0.05 parts by mass, and propylene glycol monomethyl ether acetate and 3-mer as a solvent. Toxybutyl acetate was mixed so that the solid content concentration was 15% by mass to prepare a colored composition (S-1). In addition, 3-methoxybutyl acetate content was adjusted so that it might become 30 mass% in all the solvents contained in colored composition (S-1).

Evaluation of development speed

The coloring composition (S-1) was applied on _{a 4 inch diameter soda glass substrate with a SiO 2} film that prevents the elution of sodium ions on the surface using a slit die coater, and then freed on a hot plate at 90°C for 1 minute. Baking was performed to form a coating film having a thickness of 2.0 µm. The elution end time (breaking time) was measured by discharging a developer containing a 0.04 mass% potassium hydroxide aqueous solution at 23° C. with respect to the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter 1 mm), and the elution end time (breaking time) was measured to take less than 25 seconds. "○", 25 seconds or more and less than 30 seconds were set as "△", and 30 seconds or more were set as "x". Table 2 shows the evaluation results. The faster this time is, the faster the development speed is, and there is an advantage in that the tact time for manufacturing the color filter can be shortened.

pattern Faulty evaluation

After applying the colored composition (S-1) on a glass substrate using a slit die coater, it was allowed to stand at room temperature for 20 minutes. After pre-baking for 1 minute on a 90°C hot plate to form a 2.0 µm-thick coating, the substrate was cooled to room temperature. Using a high-pressure mercury lamp, through a photomask having a stripe pattern of 90 μm width, the radiation including each wavelength of 365 nm, 405 nm, and 436 nm is exposed, with an illumination intensity of 17 mW, an exposure amount of 400 J/m ² , and a substrate and a mask. The exposure was performed under conditions of a distance of 350 µm. Thereafter, a developer containing a 0.04 mass% potassium hydroxide aqueous solution at 23° C. with respect to 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 further 30 seconds elapsed. The shower phenomenon was performed by discharging until. Subsequently, after performing a rinse treatment by discharging ultrapure water at a rinse pressure of 1.5 kgf/cm ² (nozzle diameter 1 mm) for 60 seconds, water on the surface of the substrate on which the stripe pattern was formed was removed by air blowing, thereby forming a stripe having a width of 90 μm. A pattern was formed.

Using an optical microscope, the five stripe patterns were observed. The case where 10 or more defects were observed among the five stripe patterns was evaluated as "x", the case where 1 to 9 defects were observed was evaluated as "Δ", and the case where no defect was observed at all was evaluated as "○". Table 2 shows the evaluation results.

Contrast evaluation

After applying the coloring composition (S-1) on a glass substrate using a slit die coater, pre-baking was performed on a hot plate at 80°C for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation by changing the number of rotations of the spin coater.

Subsequently, after cooling these substrates to room temperature, using a high-pressure mercury lamp, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was irradiated to each coating film without interposing a photomask at 2,000 J/m ^2. It was exposed at the exposure amount of. Thereafter, a developer containing a 0.04 mass% potassium hydroxide aqueous solution at 23° C. ^{was discharged to the substrate at a developing pressure of 1 kgf/cm 2} (nozzle diameter 1 mm) to perform shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked for 30 minutes in a 200°C clean oven to form a cured film for evaluation.

The substrate on which the cured film was formed was inserted into two deflection plates, and the deflection plate on the front side was rotated while irradiating with a fluorescent lamp (wavelength range 380 to 780 nm) from the rear side, and a luminance meter LS-100 (manufactured by Minolta Co., Ltd.) ), the maximum and minimum values of the transmitted light intensity were measured. And, for each cured film, the value obtained by dividing the maximum value by the minimum value was taken as the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.650 was calculated. Table 2 shows the evaluation results. The larger the contrast ratio, the better.

Examples 102 to 130 and Comparative Examples 101 to 114

In Example 1, as shown in Table 2, except having changed the coloring agent dispersion liquid, it carried out similarly to Example 101, and produced the coloring composition (S-2)-(S-44). Then, using the obtained coloring composition, it carried out similarly to Example 101, and performed various evaluations. The results are shown in Table 2. However, about the evaluation of the contrast, in Examples 109 to 126, Examples 128 and 108 to 114, the contrast ratio at the chromaticity coordinate value y = 0.663 was calculated.

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 colorant composition were also not possible.

In Comparative Examples 105 and 112, evaluation was difficult because a uniform coating film could not be obtained by a slit die coater.

<Production and evaluation of colored cured film for solid-state imaging device>

Manufacturing Example 1

(Preparation of a composition for forming a base film)

After nitrogen substitution in the flask, 200 parts by mass of a methyl-3-methoxypropionate solution obtained by dissolving 0.6 parts by mass of 2,2′-azobisisobutyronitrile was added. Subsequently, 37.5 parts by mass of tert-butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate were added, followed by stirring and heating at 70° C. for 6 hours. After cooling, a resin solution containing a polymer was obtained.

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

Example 131

As a colorant, 9.0 parts by mass of the colorant (A-1), C.I. Pigment Yellow 139 was 6.0 parts by mass, (B2) BYK-LPN22102 (manufactured by BYK) was 10.0 parts by mass (solid content concentration = 40% by mass) as a dispersant, and (B1) Phosphenol RS-710 ( Toho Chemical Co., Ltd.) 2.0 parts by mass, the binder resin solution (C-1) 5.0 parts by mass (solid content concentration = 40% by mass), and 68.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent were used in a bead mill. By mixing and dispersing, a colorant dispersion (R-45) was prepared.

In addition, BYK-LPN 22102 is a (meth)acrylic dispersant having an amino group and a quaternary ammonium group, and the (meth)acrylic dispersant is propylene glycol methyl ether acetate / propylene glycol methyl ether of a modified acrylic block copolymer = 1/1 (mass ratio ) 40 mass% solution (acid value = 0, amine value = 29 mgKOH/g). The modified acrylic block copolymer includes a block having repeating units derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylaminoethylmethacrylate, methylmethacrylate, butylmethacrylate, and 2-ethylhexylmethacrylate. , A block having a repeating unit derived from benzyl methacrylate and triethylene glycol ethyl ether methacrylate.

Next, 66.7 parts by mass of the colorant dispersion (R-45) prepared above, (C) 4.48 parts by mass of the binder resin solution (C-1) as a binder resin (solid content concentration = 40% by mass), (D) as a polymerizable compound Kayaled DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate) 2.81 parts by mass, as a photoinitiator, Adeka Acruze NCI-930 (manufactured by Adeka Co., Ltd.) 0.37 mass Part, as a fluorine-based surfactant, 0.004 parts by mass of Ptergent FTX-218 (manufactured by Neos Co., Ltd.) and 25.67 parts by mass of propylene glycol monomethyl ether acetate are mixed, and a solid content concentration of 20% by mass and a pigment concentration of 50% by mass are mixed. A composition (S-45) was obtained.

Formation and evaluation of pixel patterns

Using an automatic coating and developing device (Clean Track manufactured by Tokyo Electron Co., Ltd., trade name "MARK-Vz") on a 6-inch silicon wafer, the composition for forming a base film was applied by spin coating, and then 300 at 230°C. Baking was performed for a second to form a base film having a thickness of 0.6 µm.

The coloring composition (S-45) was applied on the base film by spin coating, and then prebaked at 90°C for 150 seconds to form a coating film having a thickness of 0.75 µm. Thereafter, the obtained substrate was cooled to room temperature, and a reduction projection exposure machine (NSR-2205i12D manufactured by Nikon Co., Ltd., lens numerical aperture = 0.50) was used through a photomask on the coating film on the substrate, with a wavelength of 365 nm (i-line). 30 to the exposure amount of 500mJ / cm ² was exposed to light from a 10mJ / cm ² intervals. Subsequently, in an automatic coating and developing device, a puddle (liquid reservoir) is developed for 90 seconds with a 0.6% tetramethylammonium hydroxide aqueous solution, rinsed with ultrapure water, spin-dried, and then post on a hot plate at 200°C for 300 seconds. Baking was performed to form a red pixel pattern.

It was confirmed that the red pixel pattern is excellent in color separation even if it is an ultra-thin film required for a solid-state image sensor. Therefore, it can be said that the colored composition of the present invention is excellent in color reproducibility and can produce a color filter suitable for use in a solid-state image sensor.

Comparative Example 115

As a colorant, 9.0 parts by mass of the colorant (A-1), C.I. Pigment Yellow 139 was 6.0 parts by mass, (B2) BYK-LPN22102 (manufactured by BYK) 15.0 parts by mass (solid content concentration = 40% by mass) as a dispersant, and 5.0 parts by mass of the binder resin solution (C-1) A colorant dispersion (R-46) was prepared by mixing and dispersing with a bead mill using parts (solid content concentration = 40% by mass) and 65.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Next, in the same manner as in Example 131, except that the colorant dispersion (R-46) prepared above was used instead of the colorant dispersion (R-45), the coloring composition (S -46). Then, in the same manner as in Example 131, a red pixel pattern was formed.

As a result, many development residues were confirmed on the red pixel pattern. When a color filter for a solid-state image sensor is produced using the red pixel pattern, there is a concern that color mixing due to a developing residue occurs, and color reproducibility may deteriorate.

Claims (10)

It is a coloring composition containing (A) a coloring agent, (C) a binder resin, and (D) a polymeric compound,
(A) the colorant contains a pigment represented by the following formula (1),
(B1) a phosphoric acid ester and (B2) a dispersant having a nitrogen atom,
(B2) The dispersant having a nitrogen atom is a (meth)acrylic dispersant and a polyester dispersant, and is at least one of a dispersant having at least one characteristic group selected from amino groups, quaternary ammonium, amide groups and imino groups, and urethane-based dispersants. Coloring composition.

(In formula (1), R ¹ and R ² each independently represent a chlorine atom or a bromine atom) The ratio (w ₁ /w _{2 ) of the content (w 1} ) of the (B1) phosphoric acid ester _{and the content (w 2} ) of the dispersant having a nitrogen atom (B2) is 10/90 to 90/by mass ratio. 10 person coloring composition. The colored composition according to claim 1 or 2, wherein the (B1) phosphoric acid ester has an acid value of 1 to 150 mgKOH/g. The colored composition according to claim 1 or 2, wherein the (B1) phosphate ester is a polyether phosphate-based polymer. The coloring composition according to claim 1 or 2, wherein the colorant (A) contains a colorant other than the pigment represented by the general formula (1). A colored cured film formed using the colored composition according to claim 1 or 2. A display element comprising the colored cured film according to claim 6. A solid-state imaging device comprising the colored cured film according to claim 6. It is a colorant dispersion containing a colorant (A) and a solvent (F),
(A) the colorant contains a pigment represented by the following formula (1),
(B1) a phosphoric acid ester and (B2) a dispersant having a nitrogen atom,
(B2) The dispersant having a nitrogen atom is a (meth)acrylic dispersant and a polyester dispersant, and is at least one of a dispersant having at least one characteristic group selected from amino groups, quaternary ammonium, amide groups and imino groups, and urethane-based dispersants. Colorant dispersion.

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