TW201341957A - Radiation-sensitive coloring composition, color filter and display device - Google Patents

Abstract

This invention provides a radition-sensitive coloring composition for fabricating color filter with excellent properties even when lake pigment is used as coloring agent, and also provides a color filter and a display device. The radition-sensitive coloring composition includes (A) a coloring agent having a lake pigment, (B) a binder resin, (c) a photopolymerizition initiator, (D) a compound having two or more polymerizable unsaturated group and (E) a polyfuntional thiol. A color filter 1 is fabricated by forming a pixel pattern 3 on a substrate 2 using the radition-sensitive coloring composition, and by disposing a black matrix 4 and a protect film 5 on the substrate 2. The display device is fabricated by using the color filter 1.

Description

Radiation-sensitive coloring composition, color filter, and display element

The present invention relates to a radiation sensitive coloring composition, a color filter, and a display element.

When a color filter is produced using a radiation sensitive coloring composition, a method is known in which a pigment dispersion type color-sensing radiation composition is coated on a substrate and dried, and the dried coating film is irradiated in a desired pattern shape. Radiation (hereinafter referred to as "exposure") and development are performed to obtain pixels of respective colors (Patent Document 1 to Patent Document 2). In addition, a method is also known in which a black matrix is formed using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3).

Further, in order to achieve high luminance and high color purity of the display element or high definition of the solid-state imaging element, it is known to use a dye as a colorant. However, when a dye is used as a coloring agent, there is a problem that heat resistance, light resistance, and the like are inferior. Therefore, for example, Patent Document 4 proposes the use of a lake pigment obtained by subjecting a dye to lake.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-081348

However, the color filter is produced by heating after exposure and development (also referred to as post-baking) or a heating process such as formation of an alignment film such as polyimide or the like, which is usually more than 200° C. Therefore, even if a lake pigment is used, if it is subjected to such a high-temperature heating process, The problem of reduced chroma characteristics cannot be avoided. Further, a color filter using a lake pigment also has a problem that the solvent resistance is insufficient.

Accordingly, an object of the present invention is to provide a radiation sensitive coloring composition which can produce a color filter excellent in characteristics even when a lake pigment is used as a coloring agent. Further, an object of the present invention is to provide a color filter produced by using the radiation sensitive coloring composition and a display element having the color filter.

The inventors of the present invention conducted diligent research and found that the problem can be solved by using a lake pigment together with a polyfunctional thiol.

A first embodiment of the present invention relates to a radiation sensitive coloring composition comprising: (A) a coloring agent containing a lake pigment, (B) a binder resin, (C) a photopolymerization initiator, and (D) A compound having two or more polymerizable unsaturated bonds and (E) a polyfunctional thiol.

In the first embodiment of the present invention, the lake pigment preferably contains at least one selected from the group consisting of a xanthene-based lake pigment and a triarylmethane-based lake pigment.

In the first embodiment of the present invention, the lake pigment is preferably formed by lake chromatography using a heteropoly acid.

In a first embodiment of the present invention, the (E) polyfunctional thiol preferably contains a group selected from the group consisting of aliphatic polyfunctional thiols, decane polyfunctional thiols, and fluorine-containing polyfunctional thiols. At least one of them.

A second embodiment of the present invention relates to a color filter characterized by having a coloring layer formed using the radiation sensitive coloring composition of the first embodiment of the present invention.

A third embodiment of the present invention relates to a display element characterized by having the color filter of the second embodiment of the present invention.

According to the first embodiment of the present invention, it is possible to obtain a radiation sensitive coloring composition which uses a lake pigment as a colorant and is suitable for producing a color filter excellent in characteristics.

According to a second embodiment of the present invention, a color filter can be obtained, A lake pigment is used as a colorant and has excellent properties.

According to the third embodiment of the present invention, it is possible to obtain a display element having a color filter excellent in characteristics using a lake pigment as a colorant.

1‧‧‧Color filters

2, 6‧‧‧ substrate

3‧‧‧ pixel pattern

4‧‧‧Black matrix

5‧‧‧Protective film

7‧‧‧pixel electrode

10‧‧‧Liquid display components

11‧‧‧Common electrode

12‧‧‧Alignment film

13‧‧‧LCD

14‧‧‧Polar plate

16‧‧‧ Sealing material

17‧‧‧ Backlight

20‧‧‧Drive substrate

Fig. 1 is a cross-sectional view schematically showing a configuration of an example of a color filter of the embodiment.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of an example of a liquid crystal display element of the embodiment.

Hereinafter, embodiments of the present invention will be described in detail.

Further, in the present invention, the term "colored layer" means a color pixel pattern, a black matrix, a black spacer, or the like used in a color filter. Further, the "radiation" to be irradiated during exposure includes visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle radiation.

[Sense Radiation Coloring Composition]

The radiation sensitive coloring composition of the present embodiment contains (A) a colorant, (B) a binder resin, (C) a photopolymerization initiator, and (D) a compound having two or more polymerizable unsaturated bonds and ( E) is composed of a polyfunctional thiol.

Hereinafter, the constituent components of the radiation-sensitive coloring composition (hereinafter also simply referred to as "coloring composition") of the present embodiment will be described.

<(A) Colorant>

The coloring composition of the present embodiment contains a lake pigment as (A) a coloring agent (hereinafter also simply referred to as a coloring agent). Here, the term "lake pigment" means a pigment obtained by adjusting a soluble dye to an insoluble pigment by a precipitating agent. In the present embodiment, the lake pigment is not particularly limited, and examples thereof include a dibenzofuran-based lake pigment, a triarylmethane-based lake pigment, an azo-based lake pigment, a phthalocyanine-based lake pigment, and the like. . In the present embodiment, a dibenzofuran-based lake pigment or a triarylmethane-based lake pigment is preferable, and a triarylmethane-based lake pigment is particularly preferable. Specific examples of the lake pigment include a pigment having a color index (C.I.) as described below.

CI Pigment Red 81, CI Pigment Red 81:1, CI Pigment Red 81:2, CI Pigment Red 81:3, CI Pigment Red 81:4, CI Pigment Red 81:5, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1:1, CI Pigment Violet 1:2, CI Pigment Violet 2 and other dibenzoxanthene lake pigments; CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 3, CI Pigment Blue 9, CI Pigment Blue 10, CI Pigment Blue 14, CI Pigment Blue 24, Pigment Blue 24: 1, CI Pigment Blue 56, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Violet 3, CI Pigment Violet 3: 1, CI Pigment Violet 3 :3, CI pigment violet 27, CI pigment violet 39, CI pigment green 1, CI pigment green 4 and other triaryl methane-based lake pigment; CI pigment red 48: 1, CI pigment red 48: 2, CI pigment red 48: 3, CI Pigment Red 48:4, CI Pigment Red 48:5, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 54, CI Pigment Red 57:1, CI Pigment Red 58, CI Pigment Red 58:1, CI Pigment Red 58:2, CI Pigment Red 58:3 , CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 63:3, CI Pigment Yellow 61, CI Pigment Yellow 61 :1, CI Yellow 62, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 247, CI Pigment Red 200, CI Pigment Yellow 100, CI Pigment Yellow 104, CI Pigment Yellow 133, CI Pigment Yellow 168, CI Pigment Yellow 169 , CI Pigment Yellow 183, CI Pigment Yellow 191, CI Pigment Yellow 191:1 and other azo-based lake pigments; CI Pigment Blue 17:1 and other phthalocyanine lake pigments.

On the other hand, examples of the precipitating agent used for the lake formation include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katatanol (Katanol). ), Tamol, isopoly acid, heteropoly acid, and the like. Examples of the polypoly acid include isopolytungstic acid, isopolyvanadate, and homopolymolybdic acid. Examples of the heteropoly acid include phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, and cerium. Tungstomolybdic acid, tungstic acid, lanthanum molybdate, and the like. Among these, a lake pigment obtained by lake-forming with a polyacid or a heteropoly acid as a precipitating agent is preferable, and a lake pigment obtained by lake-forming a heteropoly acid as a precipitating agent is particularly preferable. The lake pigment obtained by coloring with a polyacid or a heteropoly acid as a precipitating agent can be produced, for example, by the method described in JP-A-2011-186043.

In the present embodiment, the lake pigments may be used singly or in combination of two or more.

In the present embodiment, other coloring agents may be used together with the lake pigment as a coloring agent.

The other coloring agent is not particularly limited, and the color or material can be appropriately selected depending on the use of the color filter. Specifically, any of pigments, dyes, and natural colors other than the lake pigment may be used, but high color purity, brightness, contrast, light blocking property, heat resistance, and the like are required for the coloring layer constituting the color filter. Organic pigments and/or organic dyes other than lake pigments are preferred, and organic pigments are particularly preferred.

Preferred specific examples of the organic pigment other than the lake pigment are, in terms of color index (CI), CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red. 254, 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 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23, and the like. Among these, the organic pigment used together with the dibenzoxanthene lake pigment and the triarylmethane lake pigment is preferably CI Pigment Red 177, CI Pigment Red 254, CI Pigment Blue 15:6, CI Pigment Violet 23, and the like. Preferably, CI Pigment Blue 15:6, CI Pigment Violet 23.

The organic dye is preferably a dibenzopyranyl dye, a triarylmethane dye, a cyanine dye, or an anthraquinone dye. More specifically, Japanese Patent Laid-Open Publication No. 2010-32999, Japanese Patent Laid-Open Publication No. 2010-254964, Japanese Patent Laid-Open No. 2011-138094, International Publication No. 10/123071, Japanese Patent Laid-Open No. 2011 An organic dye described in JP-A-2011-174987, JP-A-2011-117987, JP-A-2011-174987, and the like.

In the present embodiment, the organic pigment and the organic dye may be used alone or in combination of two or more.

In the present embodiment, when a pigment is used as the colorant, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination of these methods as needed. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. The resin which modifies the surface of the particle of the pigment, for example, is a vehicle resin described in JP-A-2001-108817, or a commercially available resin for dispersing various pigments. Further, it is preferable that the pigment is used after the primary particles are fined by so-called salt milling. The method of salt milling can be, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111.

From the formation of pixels with high brightness and excellent color purity, or black moments with excellent light blocking properties In the solid content of the coloring composition, the content ratio of the (A) coloring agent in the coloring composition of the present embodiment is 5 mass% to 70 mass%, preferably 5 mass% to 60 mass%. . Here, the "solid component" means a component other than the solvent described later.

In addition, the content ratio of the lake pigment is appropriately adjusted according to the required chromaticity. When the coloring composition of the present embodiment is used, the content ratio of the lake pigment in all the colorants is 20% by mass or more, and further When it is 50% by mass or more, a coloring layer excellent in heat resistance and solvent resistance can be formed.

In the present embodiment, the coloring agent containing the lake pigment may be used together with the dispersing agent as needed. As the dispersing agent, for example, a suitable dispersing agent such as a cationic system, an anionic system or a nonionic system can be used, and a polymer dispersing agent is preferable. Specific examples thereof include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polyethylene glycol diester system. A dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, or the like.

Such a dispersing agent can be obtained commercially, and examples of the acrylic dispersing agent include: Disperbyk (registered trademark)-2000, Disperbyk (registered trademark)-2001, and BYK (BYK, Registered trademark) - LPN6919, BYK (registered trademark) - LPN21116, BYK - LPN21324 (above is BYK Chemie); carbamate dispersant can be exemplified: Disperbyl (registered trademark)-161, Disperbyk (registered trademark)-162, Disperbyk (registered trademark)-165, Disperbyk (registered trademark)-167 , Disperbyk (registered trademark)-170, Disperbyk (registered trademark)-182, Disperbyk (registered trademark)-2164 (above is made by BYK Chemical Co., Ltd.) Solsperse (registered trademark) 76500 (manufactured by Lubrizol Co., Ltd.); polyethyleneimine dispersant: Solsperse (registered trademark) 24000 (Lubrizol) (manufactured by the company); polyester dispersant can be cited: Ajisper (registered trademark) PB821, Ai Ajisper (registered trademark) PB822, Ajisper (registered trademark) PB880, Ajisper (registered trademark) PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) Wait. Further, the content of the dispersing agent can be appropriately determined within the range not detracting from the object of the present invention.

<(B) Adhesive Resin>

The (B) adhesive resin (hereinafter also simply referred to as a binder resin) in the present embodiment is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer". (b1)") a copolymer of another ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)") which can be copolymerized.

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl)acryloxyethyl) ester, and ω-carboxyl group. Polycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used alone or in combination of two or more.

Further, the unsaturated monomer (b2) may, for example, be an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; for example, benzene An aromatic vinyl compound such as ethylene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether or acenaphthylene; for example, (methyl) Methyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (methyl) Benzyl acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene Alcohol (degree of polymerization: 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, (meth) acrylate cyclohexyl, (meth) acrylate Borneol ester, tricyclo[methyl]acrylic acid [5.2.1.0 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (methyl) 4-hydroxyphenyl acrylate, paracumyl phenol ring Oxyethane modified (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) propylene decyloxy a (meth) acrylate such as oxetane or 3-[(meth)acryloxymethyl]-3-ethyloxetane; such as cyclohexyl vinyl ether, isobornyl Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane Such a vinyl ether; such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polyoxyalkylene, having a mono (meth) acrylonitrile at the end of the polymer molecular chain; A macromonomer or the like.

Among these unsaturated monomers (b2), it is preferred to use p-vinylbenzyl glycidyl ether, glycidyl (meth)acrylate, or (meth)acrylic acid-3 from the viewpoint that the desired effect can be enhanced. , 4-epoxycyclohexylmethyl ester, 3-[(meth)acryloxymethyl]oxetane, 3-[(methyl)acryloxymethyl]-3-ethyloxy An ethylenically unsaturated monomer having a cyclic ether structure such as a heterocyclic butane or a 3-(vinyloxymethyl)-3-ethyloxetane (especially an ethylenic acid having an oxetanyl group) Saturated monomer).

The unsaturated monomer (b2) may be used singly or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5% by mass to 50% by mass, more preferably 10% by mass. %~40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Laid-Open No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The copolymer disclosed in JP-A-2004-101728, and the like.

In addition, in the present embodiment, a carboxyl group-containing polymer having a polymerizable unsaturated group such as a (meth) acrylonitrile group in a side chain is used as the binder resin, and the desired effect can be obtained, which is preferable in this respect. Specific examples of such a binder resin are disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. 5-19467, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 11-140144, Japanese Patent Laid-Open No. Hei. No. 2008-181095, and Japanese Patent Laid-Open No. 2010-44365.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) (eluent solvent: tetrahydrofuran) of the adhesive resin in the present embodiment is usually 1,000 to 100,000, preferably 3,000. 50000. If the Mw is too small, the residual film ratio of the obtained film may be lowered, or the pattern shape and heat resistance may be obtained. If the Mw is too large, the resolution may be lowered, or the shape of the pattern may be impaired, or the dry matter may be easily generated in the case of a slit nozzle.

In addition, the ratio (Mw/Mn) of the weight average molecular weight of the binder resin in the present embodiment to the number average molecular weight (Mn) in terms of polystyrene measured by GPC (solution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably Preferably 1.0 to 3.0.

The adhesive resin in the present embodiment can be produced by a known method, and can be disclosed, for example, in Japanese Patent Laid-Open Publication No. 2003-222717, Japanese Patent Laid-Open No. Hei. No. 2006-259680, and International Publication No. 07/029871. The method controls the structure of the adhesive resin or Mw, Mw/Mn.

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

In the present embodiment, the content of the (B) binder resin is preferably 10 parts by mass to 1000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass, based on 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be lowered, or the storage stability of the obtained coloring composition may be lowered. On the other hand, if the content of the binder resin is too large, the concentration of the colorant may be relatively lowered, so that the film is thin. It is difficult to form the target color density.

<(C) Photopolymerization initiator>

The (C) photopolymerization initiator (hereinafter also referred to simply as photopolymerization initiator) used in the present embodiment is a compound produced by exposure of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. A compound of an active species capable of initiating polymerization of a compound having two or more polymerizable unsaturated bonds (D) which will be described later.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-mercaptoquinone compound. An onium salt-based compound, a benzoin-based compound, a benzophenone-based compound, an α-diketone-based compound, a polynuclear oxime-based compound, a diazo-based compound, and a quinone sulfinate-based compound.

In the present embodiment, the photopolymerization initiator may be used singly or in combination of two or more.

The photopolymerization initiator is preferably selected from the group consisting of thioxanthone compounds and acetophenone compounds. At least one selected from the group consisting of a bifurazol compound, a triazine compound, and an O-mercapto quinone compound.

In a preferred photopolymerization initiator of the present embodiment, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthiophene. Tons of ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diiso Propyl thioxanthone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and 2-benzyl group. 2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-? Polinylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based compound include 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, and the like.

Further, in the case where a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include a mercaptan hydrogen donor such as 2-mercaptobenzothiazole or 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, and 4,4'. An amine-based hydrogen donor such as bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, in terms of further improving the sensitivity, it is preferred to supply one or more thiol-based hydrogen donors to one or more amines. Hydrogen is used in combination.

Further, specific examples of the triazine-based compound include 2,4,6-tris(trichloromethyl)-s-triazine and 2-methyl-4,6-bis(trichloromethyl)- Triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl) ) vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis ( Trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-( 4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)- A triazine-based compound having a halogenated methyl group such as a s-triazine or a 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Further, specific examples of the O-mercapto fluorene-based compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene)肟), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), B Ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl) Oxylbenzylidene)-9H-indazol-3-yl]-,1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4 -(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-, 1-(O-ethylindenyl) In addition, the oxime ester compound etc. which are described in the International Publication No. 08/078678, and the Japanese Patent Publication No. 2011-132215 are mentioned. NCI-831, NCI-930 (manufactured by ADEKA Co., Ltd.) or the like which is a commercially available product of an O-fluorenyl compound can also be used.

In the case of using a photopolymerization initiator other than a biimidazole compound such as an acetophenone-based compound, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethylaminoacetophenone. , 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene) Cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present embodiment, the content of the (C) photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass based on 100 parts by mass of the compound having two or more polymerizable unsaturated bonds (D) to be described later. It is particularly preferably 1 part by mass to 100 parts by mass. In this case, if the content of the photopolymerization initiator is too small, the hardening due to exposure may become insufficient. On the other hand, if the content of the photopolymerization initiator is too large, the colored layer formed may be formed. It tends to fall off from the substrate during development.

<(D) Compound having two or more polymerizable unsaturated bonds>

In the present embodiment, (D) a compound having two or more polymerizable unsaturated bonds is not particularly limited, and a compound having two or more (meth) acrylonitrile groups is preferable.

Examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and caprolactone-modified. Polyfunctional (meth) acrylate, polyalkyl (meth) acrylate modified with alkylene oxide, polyfunctional (meth) acrylate amino group obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate A formate or a polyfunctional (meth)acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a binary aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Such a ternary or higher aliphatic polyhydroxy compound Things. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic anhydride and biphenyl. Tetraacid dianhydride such as tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

Further, the polycaprolactone-modified polyfunctional (meth) acrylate is, for example, a compound described in paragraph [0015] to [0018] of JP-A-H11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate may, for example, be an ethylene oxide and/or propylene oxide-modified di(meth)acrylate of bisphenol A or a ring of isocyanuric acid. Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, pentaerythritol epoxy B Alkane and/or propylene oxide modified tri(meth)acrylate, pentaerythritol ethylene oxide and/or propylene oxide modified tetra(meth)acrylate, dipentaerythritol ethylene oxide and/or ring Oxypropane modified penta (meth) acrylate, dipentaerythritol ethylene oxide and/or propylene oxide modified hexa (meth) acrylate, and the like.

Among these, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a caprolactone-modified polyfunctional (meth) acrylate, A polyfunctional (meth)acrylic urethane or a polyfunctional (meth) acrylate having a carboxyl group. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and scumming and residual film on the substrate of the unexposed portion and the light-shielding layer, it is more than three or more aliphatics. Among the polyfunctional (meth) acrylates obtained by reacting a hydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate are particularly preferred. Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable.

In the present embodiment, (D) a compound having two or more polymerizable unsaturated bonds may be used singly or in combination of two or more.

The content of the compound having two or more polymerizable unsaturated bonds in (D) in the present embodiment is preferably 20 parts by mass to 500 parts by mass based on 100 parts by mass of the (B) binder resin. The portion is particularly preferably 50 parts by mass to 300 parts by mass. In this case, if the content of the compound (D) having two or more polymerizable unsaturated bonds is too small, sufficient curability may not be obtained. On the other hand, when the content of the compound (D) having two or more polymerizable unsaturated bonds is too large, the alkali developability is lowered, and scum, residual film, and the like are likely to be generated on the substrate or the light-shielding layer of the unexposed portion. Propensity.

<(E) Polyfunctional Mercaptan>

The coloring composition of the present embodiment is characterized by containing (E) a polyfunctional thiol (hereinafter also referred to simply as a polyfunctional thiol), that is, a compound having two or more sulfanyl groups (-SH). By using a curing system in which a polyfunctional thiol is introduced, the coloring composition of the present embodiment can produce a color filter excellent in characteristics even when a lake pigment is used as a coloring agent, and more specifically, heat resistance can be produced. And a color filter excellent in solvent resistance.

The polyfunctional thiol is not particularly limited as long as it is a compound having two or more thio groups, and examples thereof include an aliphatic polyfunctional thiol, a cyclic polyfunctional thiol, a decane polyfunctional thiol, and a fluorine-containing compound. Polyfunctional thiols and the like.

When the aliphatic polyfunctional thiol is a chain compound having two or more thio groups, it is not particularly limited as long as it has a fluorine atom, and specific examples thereof include hexane-1,6- Dithiol, decane-1,10-dithiol, ethylene glycol bis(mercaptoacetate), propylene glycol bis(mercaptoacetate), glycerol tris(mercaptoacetate), trimethylolpropane three (mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), dipentaerythritol hexa(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), Tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), B Diol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), Octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetrakis(2-mercaptopropionate), dipentaerythritol hexa(2-mercaptopropionate) , ethylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-indenyl) Acid ester), butanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercapto) Butyrate), ethylene glycol bis(3-mercaptoisobutyrate), diethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trishydroxyl Methylpropane tris(3-mercaptoisobutyrate), pentaerythritol tetrakis(3-mercaptoisobutyrate), dipentaerythritol hexakis(3-mercaptoisobutyrate), octanediol bis(3-mercaptobutyrate) ), octanediol bis(3-mercaptoisobutyrate), and the like. In addition, the so-called "chain" is included The concept of both linear and branched chains.

The cyclic polyfunctional thiol is not particularly limited as long as it has a cyclic structure in its molecule, and specific examples thereof include 1,4-benzenedithiol and 1,4-dimethyldecylbenzene. 2,4,6-trimethyl-s-triazine, 2-(N,N-dibutylamino)-4,6-diindenyl-s-triazine, in addition to Japanese Patent Laid-Open No. 2-153353 2-mercapto-5-substituted thiadiazole or the like described in the publication.

The polyoxo-functional thiol is not particularly limited as long as it is a polyoxyalkylene having two or more sulfur groups, and for example, hydrolyzability of a decane compound containing a sulfur group and a hydrolyzable group is exemplified. The polydecane obtained by subjecting the decane compound to hydrolysis condensation. The specific embodiment and the manufacturing method are described, for example, in JP-A-2008-242078, JP-A-2011-128239, and the like. Further, silsesquioxane having two or more sulfur groups is commercially available from Arakawa Chemical Industries Co., Ltd. as a Composeran (registered trademark) SQ series.

The fluorine-containing polyfunctional thiol is not particularly limited as long as it has a fluorine atom in its molecule, and examples thereof include a compound having a poly(perfluoroalkylene ether) chain and two or more sulfur groups. The specific embodiment and the manufacturing method are described, for example, in JP-A-2011-208046.

Among these polyfunctional thiols, an aliphatic polyfunctional thiol, a decane polyfunctional thiol, a fluorine-containing polyfunctional thiol, and a decyl polyfunctional thiol are particularly preferable in terms of further improving the desired effect. , fluorine-containing polyfunctional thiol.

In the present embodiment, the (E) polyfunctional thiol may be used singly or in combination of two or more.

In the present embodiment, the content of the (E) polyfunctional thiol is preferably 0.1 parts by mass to 30 parts by mass, particularly preferably 0.2, based on 100 parts by mass of the compound having two or more polymerizable unsaturated bonds in the above (D). Parts by mass ~ 15 parts by mass. In this case, if the content of the (E) polyfunctional thiol is too small, the desired effect may not be obtained; on the other hand, if the content of the (E) polyfunctional thiol is too large, the pattern shape may become an overhang ( Overhang).

<(F) Solvent>

The colored composition of the present embodiment contains the components (A) to (E) described above and any other components added arbitrarily, and it is preferred to prepare a liquid composition by blending a solvent (F) (hereinafter also simply referred to as a solvent). .

The solvent which can be blended in the coloring composition of the present embodiment has appropriate volatility as long as it disperses or dissolves each component or other component (A) to (E) constituting the coloring composition and does not react with these components. It can be selected and used as appropriate.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol single 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, tripropylene glycol monoethyl ether, 3-methoxy-3- (poly)alkylene glycol monoalkyl ethers such as methyl butanol; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol , (cyclo)alkyl alcohols such as tert-butanol, octanol, 2-ethylhexanol, cyclohexanol; ketone alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl 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 acid esters, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate or 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methoxy Alkoxylates such as ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Carboxylic acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate , n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxygen Other esters such as ethyl butyrate; An aromatic hydrocarbon such as toluene or xylene; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; or an indoleamine.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-3-methylbutanol, ethylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Ester, 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-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present embodiment, the (F) solvent may be used singly or in combination of two or more.

The content of the solvent (F) in the coloring composition of the present embodiment is not particularly limited, and from the viewpoints of coatability and stability of the obtained coloring composition, it is preferred that the components of the coloring composition are other than the solvent. The total concentration is 5% by mass to 50% by mass, and particularly preferably the total concentration is 10% by mass to 40% by mass.

<additive>

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

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and lanthanoid surfactants; and vinyl groups; Trimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane , N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxy Propylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Adhesion promoter such as decane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-tributyl) Antioxidant such as phenol), 2,6-di-tert-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkane UV absorbers such as oxybenzophenones; anticoagulants such as sodium polyacrylate Agent; 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 - residue improving agent such as propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(methyl)propenyloxyethyl]ester, ortho-benzene A developability improving agent such as mono[2-(methyl)acryloxyethyl)dicarboxylate or ω-carboxypolycaprolactone mono(meth)acrylate.

The colored composition of the present embodiment can be produced by an appropriate method, and as a preparation method thereof, for example, it can be prepared by using each component of (A) to (E) and (F) a solvent or any other added arbitrarily. Mix the ingredients together. Specifically, a method or the like prepared by: in (F) a solvent, in the presence of a dispersing agent, using a pearl mill, a roll mill, or the like, for coloring a lake-containing pigment The agent is pulverized together with a part of the component (B), and mixed and dispersed to prepare a pigment dispersion liquid. Preferably, each component of (B) to (E) and, if necessary, a further solvent or other component are added to the pigment dispersion liquid and mixed.

In the radiation sensitive coloring composition of the present embodiment described above, even if a lake pigment is used as the colorant, a color filter excellent in characteristics can be produced. In particular, the radiation sensitive coloring composition of the present embodiment can produce a color filter excellent in heat resistance and solvent resistance. Further, the radiation sensitive coloring composition of the present embodiment is excellent in resolution and is effective in achieving high definition of a color filter.

Therefore, the radiation sensitive coloring composition of the present embodiment can be extremely suitably used for producing a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image sensor, and a color for an organic EL display element. Various color filters typified by filters and color filters for electronic paper.

[Color filter and method of manufacturing the same]

The color filter of the present embodiment includes a coloring layer formed using the coloring composition of the present embodiment.

Fig. 1 is a cross-sectional view schematically showing a configuration of an example of a color filter of the embodiment.

The color filter of the present embodiment can have various configurations for various applications, and the color filter 1 shown in Fig. 1 is an example of the present embodiment. The color filter 1 shown in Fig. 1 is a color filter suitable for use in a color liquid crystal display element. Color filter 1 such as The transparent substrate 2 has red (R), green (G), and blue (B) pixel patterns 3, a black matrix 4, and a protective film 5 provided on the pixel pattern 3. The pixel pattern 3 is formed using the coloring composition of the present embodiment. Further, the color of the pixel pattern 3 is not limited to the above-described three colors of RGB, and other colors may be selected, or a yellow (Y) may be further added to set a color pattern of four colors.

In the present embodiment, a method of manufacturing a color filter may be exemplified by the following method.

First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to partition the portion in which the pixel pattern is formed. Then, a liquid composition such as the radiation sensitive blue composition of the present embodiment is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, post-baking is performed, thereby forming a pixel array in which blue pixel patterns are arranged in a predetermined array.

Next, using each of the green or red coloring compositions, coating, prebaking, exposing, developing, and post-baking the respective coloring compositions are carried out in the same manner as described above, and green pixel arrays are sequentially formed on the same substrate. Red pixel array. Thereby, a color filter in which pixel arrays of three primary colors of blue, green, and red are arranged on a substrate can be obtained. However, in the present embodiment, the color of the pixel array and the order in which the pixel arrays of the respective colors are formed are not limited to the order.

Further, the black matrix can be formed by using a photolithography method to form a metal film such as chromium which is formed by sputtering or vapor deposition into a desired pattern, but radiation can also be used. The black composition forms a black matrix in the same manner as the formation of the pixel pattern. The colored composition of the present embodiment can also be applied to the formation of the black matrix.

Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, for these substrates, an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum vapor deposition may be performed in advance. .

When the coloring composition is applied on the substrate, a spray method or a roll coating method may be employed. A suitable coating method such as a coating method, a spin coat method, a slit die coating method, or a bar coating method is particularly preferably a spin coating method or a slit die coating method.

The prebaking is preferably carried out by combining drying under reduced pressure with heat drying. The drying under reduced pressure is preferably carried out until it reaches 50 Pa to 200 Pa. Further, the conditions of heat drying are preferably from 70 ° C to 110 ° C for about 1 minute to 10 minutes.

The coating thickness is preferably from 0.6 μm to 8.0 μm, more preferably from 1.2 μm to 5.0 μm, in terms of the film thickness after drying.

Examples of the light source used for forming the pixel pattern and/or the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp. Or argon ion laser, Yttrium Aluminum Garnet (YAG) laser, XeCl excimer laser, nitrogen laser and other laser sources. An ultraviolet light emitting diode (LED) can also be used as the exposure light source. Preferred are radiation having a wavelength in the range of 190 nm to 450 nm.

The exposure amount of the radiation is usually preferably 10 J/m ² to 10000 J/m ² . In general, the lower the amount of exposure, the more likely the turbidity or the water stain is generated in the pixel pattern. However, when the coloring composition of the present embodiment is used, even if the exposure amount is 800 J/m ² or less and further 600 J/m ² or less, it is not easy. Produces turbidity or water marks.

Further, the alkaline developing solution is, for example, preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- eleven. An aqueous solution of an alkene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

In the alkaline developing solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkali development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, an immersion (liquid pool) development method, or the like can be applied. The developing conditions are preferably room temperature, 5 seconds to 300 seconds.

The post-baking conditions are preferably from 120 ° C to 280 ° C for about 10 minutes to 60 minutes. When the temperature of the post-baking becomes high, depending on the type of the pigment to be used, the brightness may be lowered or foreign matter may be generated in the pixel pattern. However, if the coloring composition of the present embodiment is used, the post-baking temperature is 200. The above problem can also be suppressed by ° C or more and further 220 ° C or more.

The film thickness of the pixel pattern formed in this manner is preferably 0.5 μm to 5.0 μm, and more preferably 1.0 μm to 3.0 μm.

In the second method of producing a color filter, a method of obtaining a pixel pattern of each color by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei 07-318723, and the like. In this method, first, a partition wall which also has a light blocking function is formed on the surface of the substrate. Then, a liquid composition such as the radiation sensitive blue composition of the present embodiment is ejected into the formed partition wall by an inkjet device, and then prebaked to evaporate the solvent. Next, after exposing the coating film, post-baking is performed to cure the coating film to form a blue pixel pattern.

Then, using a green or red colored composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate as described above. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on a substrate can be obtained. However, in the present embodiment, in the case of using the inkjet method, the selection of the color of the pixel pattern and the order of formation thereof are not limited to the colors and the order described above.

Further, the partition wall not only has a light-shielding function, but also has a function of not color-mixing the coloring compositions of the respective colors ejected into the block, and therefore is preferable to the black matrix used in the first method. The increase is the film thickness. Therefore, the partition wall is preferably formed using a radiation sensitive black composition.

Further, the substrate or the light source used in forming the color filter, and the method or condition of prebaking or postbaking are the same as those of the first method. As described above, the film thickness of the pixel pattern formed by the ink jet method is preferably the same as the height of the partition wall.

When the color filter of the present embodiment is formed of, for example, the blue, green, and red pixel patterns, at least one of them may be a pixel pattern formed using the coloring composition of the present embodiment. Further, in the case where a dibenzofuran-based lake pigment or a triarylmethane-based lake pigment is used as the lake pigment, it is preferred to form the blue and red pixel pattern using the coloring composition of the present embodiment. At least one of them is particularly preferable to form a blue pixel pattern using the coloring composition of the present embodiment.

The transparent conductive film can be formed by sputtering after forming a protective film as needed on the pixel pattern obtained as described above. It is also possible to form a color filter after forming a transparent conductive film and further forming a spacer. The spacer is preferably formed using a radiation sensitive composition, and a spacer having a light blocking property (black spacer) may be used. In this case, a radiation sensitive black composition is used, but the coloring composition of the present embodiment can also be applied to form the black spacer.

The color filter of the present embodiment obtained as described above has high visible light transmittance in addition to excellent properties relating to reliability such as heat resistance and solvent resistance. Therefore, the color filter of the present embodiment is suitable for providing a display element having extremely high luminance, and is extremely effective for application to a color liquid crystal display element, an organic EL display element, electronic paper, and the like. Furthermore, it is also extremely useful in terms of color image sensor elements, color sensors, and the like. Further, since the radiation sensitive coloring composition of the present embodiment has excellent resolution, the color filter of the present embodiment produced by using the radiation sensitive coloring composition can be improved in definition, in addition to being used for a large display element. In addition to its use, it is also suitable for use in display elements of portable information devices that are small and require high-definition image display.

<display element>

The display element of this embodiment has the color filter of this embodiment. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper. The display element of the present embodiment has the color filter of the present embodiment, and can realize display with high luminance and high color purity. Further, the display element of the present embodiment can also have excellent reliability.

The color liquid crystal display element having the color filter of the present embodiment can have an appropriate structure. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may be separated by a liquid crystal. The layer may be opposed to each other, and a substrate in which a color filter is formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode may be formed. The substrates are opposed to each other across the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be exceptionally increased to obtain a bright and high-definition liquid crystal display element.

The color liquid crystal display element having the color filter of the present embodiment may include a backlight unit having a white LED as a light source, in addition to a cold cathode fluorescent lamp (CCFL). The white LED may, for example, be a white LED in which a red LED, a green LED, and a blue LED are combined, and white light is obtained by color mixing; a blue LED, a red LED, and a green phosphor are combined to obtain a white color by color mixing. a white LED of light; a white LED that combines a blue LED, a red illuminating phosphor, and a green illuminating phosphor to obtain white light by color mixing; and a white color by mixing a blue LED with a YAG-based phosphor Light white LED; blue LED, orange luminescent phosphor and green luminescent phosphor In combination, a white LED that obtains white light by color mixing; a white LED that combines an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor to obtain white light by color mixing.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of an example of a liquid crystal display element of the embodiment.

The liquid crystal display element 10 shown in FIG. 2 is an example of a liquid crystal display element of the present embodiment, and is a TFT-driven twisted nematic (TN) mode color liquid crystal display element. The liquid crystal display element 10 has the configuration in which the color filter 1 of the present embodiment is sandwiched between the driving substrate 20 on which a thin film transistor (TFT) or wiring (not shown) is disposed. The liquid crystal 13 of the nematic phase of the alignment is twisted.

More specifically, as shown in FIG. 2, a TFT (not shown) and a transparent pixel electrode 7 including ITO or the like are disposed in a lattice shape on the liquid crystal 13 side of the transparent substrate 6 of the driving substrate 20. On the other hand, on the liquid crystal 13 side of the transparent substrate 2 of the color filter 1, at a position facing the pixel electrode 7, a pixel pattern 3 of, for example, red, green, and blue is disposed as described above, and further The black matrix 4 and the protective film 5 are disposed. The pixel pattern 3 is formed using the coloring composition of the present embodiment. Further, on the protective film 5 of the color filter 1, for example, a transparent common electrode 11 including ITO or the like is provided.

The alignment film 12 is provided on each of the color filter 1 and the driving substrate 20. The alignment film 12 is formed, for example, by performing an alignment treatment such as rubbing treatment on a film of polyimide or the like to achieve uniform alignment of the liquid crystal 13 .

In the color filter 1 and the driving substrate 20, a polarizing plate 14 is disposed on the side opposite to the liquid crystal 13 side. The distance between the color filter 1 and the driving substrate 20 which defines the thickness of the liquid crystal 13 is preferably 2 μm to 10 μm, and is fixed to each other by the sealing member 16 provided on the peripheral portion.

In FIG. 2, reference numeral 17 is a backlight that is irradiated to the liquid crystal 13 from a backlight unit (not shown). The backlight unit can use the unit described above.

The liquid crystal display element 10 of the configuration shown in FIG. 2 above is an example of the liquid crystal display element of the present embodiment. In the color liquid crystal display element having the color filter of the embodiment, in addition to the TN mode, a Super Twisted Nematic (STN) mode or a coplanar switching (In-Planes Switching, IPS) can be applied. Mode, fringe field A suitable liquid crystal mode such as a Fringe Field Switching (FFS) mode, a Vertical Alignment (VA) mode, or an Optically Compensated Birefringence (OCB) mode.

The organic EL display element having the color filter of the present embodiment may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

The electronic paper having the color filter of the present embodiment can have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

[Examples]

Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited to the following examples.

<Synthesis of Adhesive Resin>

Synthesis Example 1

In a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and replaced with nitrogen. Heating to 80 ° C, at this temperature, 50 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, methacrylic acid were added dropwise over 2 hours. 15 parts by mass of 2-hydroxyethyl ester, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass of an ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was allowed to stand at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour, whereby a binder resin solution (solid content concentration = 40% by mass) was obtained. The obtained adhesive resin had Mw of 11,200 and Mn of 6,000. This binder resin is referred to as "adhesive resin (B-1)".

Synthesis Example 2

In a flask equipped with a condenser and a stirrer, 25 parts by mass of 3-methacryloxymethyl-3-ethyloxetane, 18 parts by mass of methacrylic acid, and mono-2-propenyl succinate 9 parts by mass of oxyethyl ester, 10 parts by mass of N-phenylmaleimide, 24 parts by mass of benzyl methacrylate, and 14 parts by mass of hydroxyethyl methacrylate are dissolved in propylene glycol monomethyl ether acetate 300 mass Further, 6 parts by mass of 2,2'-azobisisobutyronitrile and 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were charged, followed by nitrogen purge for 15 minutes (nitrogen). Purge). After purging with nitrogen, the reaction solution was stirred and nitrogen bubbling while heating to 80 ° C to carry out polymerization for 5 hours.

Addition of isocyanic acid-2-methylpropene to 200 parts by mass of the obtained copolymer solution 13.4 parts by mass of methoxyethyl ester and 0.2 parts by mass of 4-methoxyphenol as a polymerization inhibitor were reacted at 90 ° C for 2 hours. The reaction liquid was washed twice with ion-exchanged water, and concentrated under reduced pressure to obtain a binder resin solution (solid content concentration = 40% by mass). The obtained binder resin was Mw=11000 and Mn=5800. This binder resin was referred to as "adhesive resin (B-2)".

<Synthesis of fluorine-containing polyfunctional thiols>

Synthesis Example 3

The reaction product of pentaerythritol tetrakis-mercaptopropionate and a compound represented by the following formula is obtained by the description of paragraph [0084] to paragraph [0095] of JP-A-2011-208046. This fluorine-containing polyfunctional thiol was referred to as "E-1".

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and in each molecule, there are an average of 7 perfluoromethylene groups, and an average of 8 perfluoroethylene groups, and a fluorine atom. The average number is 46)

<Preparation of Pigment Dispersion>

Preparation Example 1

A triarylmethane-based lake pigment represented by the following formula (A) as a coloring agent (wherein x=1 to 2, hereinafter also referred to as "lake pigment" is used so that the solid content concentration is 20% by mass. 1") 15 parts by mass, BYK (registered trademark)-LPN21116 (manufactured by BYK Chemical Co., Ltd.) as a dispersing agent, 1.8 parts by mass (solid content concentration = 40% by mass) and Disperbyk (registered trademark) -2164 (manufactured by BYK Chemical Co., Ltd.) 8.9 parts by mass (solid content concentration = 60% by mass), propylene glycol monomethyl ether acetate as solvent, propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent, using beads The mill was mixed and dispersed to prepare a pigment dispersion (A-1).

[Chemical 2]

Preparation Example 2

In the case where the solid content concentration is 20% by mass, 15 parts by mass of the lake pigment 1/CI Pigment Blue 15:6 = 10/5 (mass ratio) mixture as the coloring agent (A), and Biek as a dispersing agent are used ( BYK, registered trademark) - LPN21116 (manufactured by BYK Chemical Co., Ltd.) 1.8 parts by mass (solid content concentration = 40% by mass) and Disperbyk (registered trademark) - 2164 (manufactured by BYK Chemical Co., Ltd.) 8.9 parts by mass ( Solid content concentration = 60% by mass), propylene glycol monomethyl ether acetate as solvent, propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent, mixed and dispersed by a bead mill to prepare a pigment dispersion (A- 2).

Preparation Example 3

In the case where the solid content concentration is 20% by mass, 15 parts by mass of the lake pigment 1/CI pigment blue 15:6=5/10 (mass ratio) mixture as the coloring agent (A), and Biek as a dispersing agent are used ( BYK, registered trademark) - LPN21116 (manufactured by BYK Chemical Co., Ltd.) 1.8 parts by mass (solid content concentration = 40% by mass) and Disperbyk (registered trademark) - 2164 (manufactured by BYK Chemical Co., Ltd.) 8.9 parts by mass ( Solid content concentration = 60% by mass), propylene glycol monomethyl ether acetate as solvent, propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent, mixed and dispersed by a bead mill to prepare a pigment dispersion (A- 3).

Preparation Example 4

CI Pigment Red 254/CI Pigment Red 177/CI Pigment Red 81:2 ((a) colorant was used to form a dibenzopyrene which was formed by cerium molybdic acid so as to have a solid content concentration of 20% by mass. 15 parts by mass of a mixture of 10/70/20 (mass ratio) of a mixture of 10/70/20 (mass ratio), BYK (registered trademark)-LPN21116 (manufactured by BYK Chemical Co., Ltd.) as a dispersing agent, 11 parts by mass (solid content concentration = 40% by mass), propylene glycol monomethyl ether acetate as a solvent, propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent, mixed and dispersed by a bead mill to prepare a pigment dispersion (A) -4).

<Preparation and evaluation of coloring composition>

Example 1

[Preparation of coloring composition]

18.0 parts by mass of the pigment dispersion liquid (A-1), 13.6 parts by mass of the binder resin (B-1) solution as the (B) binder resin, and M-402 (II) manufactured by Toagosei Co., Ltd. as the component (D) a mixture of pentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 7.3 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1 as a photopolymerization initiator - Ketone (manufactured by BASF Corporation, trade name IRGACURE (registered trademark) 369) 1.3 parts by mass, Megafac (registered trademark) F-554 as a fluorine-based surfactant (Di Ai Sheng ( Manufactured by DIC) Co., Ltd., 0.04 parts by mass, 0.2 parts by mass of E-1 as (E) polyfunctional thiol, and propylene glycol monomethyl ether acetate as a solvent to prepare a color combination having a solid concentration of 18% by mass (CR1).

[Evaluation of heat resistance]

The colored composition (CR1) was applied onto a glass substrate using a slit die coater, and then prebaked for 4 minutes using a hot plate at 90 ° C to form a coating film having a film thickness of 2.0 μm. After cooling the substrate to room temperature, the coating film was irradiated with radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 400 J/m ² through a mask using a high-pressure mercury lamp. . Then, these substrates were subjected to shower development for 90 seconds using a 0.04% by mass aqueous potassium hydroxide solution at 23 °C. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a blue dot pattern on the substrate.

Using the color analyzer (MCPD (registered trademark) 2000 manufactured by Otsuka Electronics Co., Ltd.), the Commission International Eclairage (CIE) table was measured for the obtained dot pattern under the conditions of C light source and 2 degree field of view. The chromaticity coordinate value (x, y) and the stimulus value (Y) in the color system. Then, the chromaticity coordinate value (x, y) and the stimulating value (Y) after additional baking at 90 ° C for 90 minutes were measured, and the color change before and after the additional baking, that is, ΔE _{ab was} evaluated. As a result, the case where the value of ΔE _ab was less than 3 was evaluated as ○, the case where the value of ΔE _ab was between 3 and 5 was evaluated as Δ, and the case where the value of ΔE _ab was more than 5 was evaluated as ×. The evaluation results are shown in Table 1.

[Evaluation of solvent resistance]

Using the coloring composition (CR1), a blue dot pattern was formed on the substrate in the same manner as the "evaluation of heat resistance". The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 25° C. for 30 minutes, and ΔE _ab before and after the immersion was evaluated in the same manner as in the “evaluation of heat resistance”. As a result, the case where the value of ΔE _ab was less than 3 was evaluated as ○, the case where the value of ΔE _ab was between 3 and 5 was evaluated as Δ, and the case where the value of ΔE _ab was more than 5 was evaluated as ×. The evaluation results are shown in Table 1.

[Evaluation of resolution]

The colored composition (CR1) was applied onto a glass substrate using a slit die coater, and then prebaked for 2 minutes using a hot plate at 90 ° C to form a coating film having a film thickness of 1.7 μm. Then, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to coat at a exposure amount of 400 J/m ² through a photomask having a plurality of slits having different sizes in a range of 5 μm to 50 μm in width. The film is irradiated with radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm for exposure. Thereafter, the substrate was spray-developed for 1 minute using a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C, and then washed with ultrapure water and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C for 30 minutes to form a pixel array in which strip-shaped pixel patterns were arranged on the substrate. At this time, the substrate was observed with an optical microscope, and the minimum value of the width of the pixel pattern remaining without being peeled off as a whole was evaluated as the minimum pattern size (μm) that can be formed. The case where the minimum pattern size was less than 25 μm was evaluated as ○, the case where the minimum pattern size was 25 μm to 35 μm was evaluated as Δ, and the case where the minimum pattern size was larger than 35 μm was evaluated as ×. The evaluation results are shown in Table 1.

Example 2 to Example 10 and Comparative Example 1 to Comparative Example 3

In the same manner as in Example 1, except that the pigment dispersion liquid shown in Table 1 and (B) the binder resin were changed, the coloring composition (CR2) to the coloring composition (CR10) and coloring were prepared. Composition (CR13) ~ coloring composition (CR15). Then, in the same manner as in Example 1, except that the coloring composition (CR2) to the coloring composition (CR10) and the coloring composition (CR13) to the coloring composition (CR15) were used instead of the coloring composition (CR1). Evaluation. The evaluation results are shown in Table 1.

Example 11

36.0 parts by mass of the pigment dispersion (A-4) as the adhesive of (B) adhesive resin 9.6 parts by mass of a resin (B-2) solution, M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as component (D), 6.0 parts by mass, as photopolymerization Initiator NCI-831 (manufactured by ADEKA Co., Ltd.) 1.0 parts by mass, Megafac (registered trademark) F-554 as a fluorine-based surfactant (Di-Aisheng (DIC) Co., Ltd.) 0.04 parts by mass of the company, 0.2 parts by mass of E-1 as the (E) polyfunctional thiol, and propylene glycol monomethyl ether acetate and 3-methoxy-3-methylbutanol as a solvent to prepare a solid A coloring composition (CR11) having a component concentration of 18% by mass. Further, the content of 3-methoxy-3-methylbutanol was set to be 30% by mass in all the solvents.

Each evaluation was performed in the same manner as in Example 1 using the coloring composition (CR11). The evaluation results are shown in Table 1.

Example 12 and Comparative Example 4

A coloring composition (CR12) and a coloring composition (CR16) were prepared in the same manner as in Example 11 except that the adhesive resin was changed to (B) as shown in Table 1. In the example 12, the content of 3-methoxy-3-methylbutanol was 45% by mass in all solvents. Then, each evaluation was performed in the same manner as in Example 1 except that the coloring composition (CR12) and the coloring composition (CR16) were used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

In Table 1, each component is as follows.

E-1: the fluorine-containing polyfunctional thiol obtained in the synthesis example 3

E-2: pentaerythritol tetrakis(3-mercaptopropionate) (trade name: PEMP II-20P, manufactured by SC Organic Chemical Co., Ltd.)

E-3: 25 mass% propylene glycol monomethyl ether acetate solution of sesquioxane polyfunctional thiol (trade name: Compoceran (registered trademark) HBSQ105-9, manufactured by Arakawa Chemical Co., Ltd.)

As shown in Table 1, it was found that the coloring composition CR13 to the coloring composition CR16 of Comparative Examples 1 to 4 which do not contain the component (E) have poor resolution, and there are problems in reliability such as solvent resistance. .

On the other hand, the coloring composition CR1 to the coloring composition CR12 of Examples 1 to 12 containing the component (E) have excellent resolution, and the pattern formed by the coloring composition exhibits excellent heat resistance and resistance. Solvent-based, suitable for the production of color filters with excellent properties.

The present invention has been described above, but the present invention is not limited to the embodiments described above, and various modifications may be made without departing from the spirit and scope of the invention.

1‧‧‧Color filters

2‧‧‧Substrate

3‧‧‧ pixel pattern

4‧‧‧Black matrix

5‧‧‧Protective film

Claims (6)

A radiation sensitive coloring composition comprising: (A) a coloring agent containing a lake pigment, (B) a binder resin, (C) a photopolymerization initiator, and (D) having two or more polymerizable properties. a compound of a saturated bond and (E) a polyfunctional thiol. The radiation-sensitive coloring composition of claim 1, wherein the lake pigment contains at least one selected from the group consisting of a dibenzofuran-based lake pigment and a triarylmethane-based lake pigment. One. A radiation sensitive coloring composition according to claim 1 or 2, wherein the lake pigment is formed by coloring with a heteropoly acid. A radiation-sensitive coloring composition according to claim 1 or 2, wherein the (E) polyfunctional thiol contains a polyfunctional thiol selected from the group consisting of aliphatic polyfunctional thiols, decane, and fluorine-containing At least one of the group consisting of polyfunctional thiols. A color filter characterized by having a colored layer formed by using a radiation-sensitive coloring composition according to any one of items 1 to 4 of the patent application. A display element characterized by having a color filter as in item 5 of the patent application.