TW201319740A - Coloring composition, coloring filter and display device - Google Patents

Abstract

The present invention provides a coloring composition that can be formed a coloring layer having excellent solvent resistance when using a dye or lake pigment as a colorant. The coloring composition is characterized by containing the following components (A), (B), (C) and (D), (A) a colorant which is containing at least one selected from dyes and lake pigments, (B) a binder resin, (C) a compound having two or more unsaturated ethylene group, and (D) a photoinitiator represented by the following formula (1). [The formula (1), wherein R1 and R4 each independently represents alkyl group of 1 to 12 carbon atoms, alicyclic hydrocarbon group of 4 to 20 carbon atoms or phenyl group, etc., R2 represents alkanediyl of 1 to 20 carbon atoms, R3 represents cycloalkyl of 4 to 20 carbon atoms, phenyl group or naphthyl group, R5 represents phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, 9-fluorenyl group, 2-furyl group or 2-thienyl group, etc.]

Description

Coloring composition, color filter, and display element

The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to a transmissive or reflective type color liquid crystal display element, a solid-state image sensor element, an organic EL display element, and an electron. A coloring composition formed of a coloring layer useful for a color filter used for paper or the like, a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment-dispersed color-sensing radiation-linear composition is applied onto a substrate and dried, and then irradiated with radiation to make a dried coating film necessary. The pattern shape (hereinafter referred to as "exposure") is developed to obtain pixels of respective colors (Patent Documents 1 to 2). Further, there is a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3). There is also a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition (Patent Document 4).

In recent years, there has been a strong demand for high contrast of liquid crystal display elements and high definition of solid-state image pickup elements. In order to achieve this, it has been studied to apply dyes and lake pigments as colorants. For example, in Patent Document 5, there is a proposal to use It is an acid dye, and in patent document 6, it is proposed to use a lake pigment.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 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. 2000-310706

Patent Document 5 Japanese Patent Laid-Open Publication No. 2010-254964

Patent Document 6 Japanese Patent Laid-Open No. 2011-6602

However, if a conventional coloring composition containing a dye or a lake pigment is used, there is a problem that the solvent resistance of the pixel is remarkably inferior. For this reason, it has been strongly demanded to develop a coloring composition capable of forming a color filter having good solvent resistance.

Therefore, an object of the present invention is to provide a coloring composition capable of forming a coloring layer having good solvent resistance when a dye or a lake pigment is used as a coloring agent. Further, an object of the present invention is to provide a color filter including a coloring layer formed of the coloring composition, and a display element including the color filter.

In view of the above facts, the inventors of the present invention conducted intensive studies and found that the above problems can be solved by using a photopolymerization initiator having a specific structure, and the present invention has been accomplished.

That is, the present invention provides a coloring composition characterized by containing the following components (A), (B), (C), and (D), and (A) containing at least one coloring agent selected from the group consisting of a dye and a lake pigment. (B) binder resin, (C) A compound having two or more ethylenically unsaturated groups (hereinafter also referred to as "crosslinking agent") and (D) a photopolymerization initiator represented by the following formula (1).

[In the formula (1), R ¹ and R ⁴ each independently represent an alkyl group of carbon 1 to 12, an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a phenyl group (wherein a hydrogen atom of the above phenyl group) Some or all of them may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms), R ² represents an alkanediyl group having 1 to 20 carbon atoms, and R ³ represents a carbon atom. a 4 to 20 cycloalkyl group, a phenyl group or a naphthyl group, and R ⁵ represents a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a 2-furyl group or a 2-thiophene group. A group (wherein a part or all of the hydrogen atoms which these groups have may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms). ]

Further, the present invention provides a color filter including a coloring layer formed using the colored composition, and a display element including the color filter. Here, the "colored layer" means a color pixel, a black matrix, a black spacer, or the like used for a color filter.

By using the colored composition of the present invention, a coloring layer excellent in solvent resistance can be formed. Therefore, the coloring composition of the present invention can be suitably used for producing a color filter for a display element, a solid-state image sensor. Various color filters including color filters for color separation, color filters for organic EL display elements, and color filters for electronic paper.

Hereinafter, the present invention will be described in detail.

Coloring composition

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

- (A) colorant -

The coloring composition of the present invention contains at least one selected from the group consisting of a dye and a lake pigment as a coloring agent.

Examples of the dye include an acid dye, a basic dye, and a nonionic dye.

Here, in the present invention, the acid dye means an ionic dye in which the anion portion is a chromophore. Among them, an ionic dye which forms an intramolecular salt is also contained in an acid dye.

Examples of such acid dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI direct orange 26, CI direct green 59, CI active yellow 2, CI active red 17, CI active red 120, CI active black 5, CI medium red 7, CI medium yellow 5, CI medium black 7, CI direct green 28, etc. Azo acid dyes; triaryl methane acid dyes such as CI Acid Blue 9; lanthanide acid dyes such as CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49; CI Acid Red 52, CI Acid red 87, CI acid red 92, CI acid red 289, CI acid red 388, etc. Acid dye; CI acid yellow 3 and other quinoline acid dyes; CI acid yellow 1, CI acid orange 3 and other nitro acid dyes.

Further, in the present invention, the term "basic dye" means an ionic dye in which the cation portion is a chromophore.

Examples of such a basic dye include azo basic dyes such as CI basic blue 41 and CI basic red 18; and triarylmethane basic dyes such as CI basic blue 7; CI basic violet 11; Wait Basic dyes; CI basic blue 3, CI basic blue 9 and other quinone imine basic dyes, as well as Japanese Patent Publication No. 2007-503477, International Publication No. 10/123071, Japanese Special A basic dye described in, for example, Japanese Laid-Open Patent Publication No. 2011-145540, and Japanese Laid-Open Patent Publication No. 2011-145540.

Further, in the present invention, the nonionic dye is a dye which does not satisfy any of the above-described acid dyes and basic dyes.

Examples of such a nonionic dye include azo-based nonionic dyes such as CI-dispersed orange 5, CI-dispersed red 58, and CI-dispersed blue 165; CI-reduced blue 4, CI-dispersed red 60, and CI-dispersed blue 56. , CI disperse blue 60 and other non-ionic dyes; CI blue blue 5 (CIpad blue 5) and other phthalocyanine nonionic dyes; CI Solvent Yellow 33, CI Disperse Yellow 64 and other quinoline-based nonionic dyes; CI disperse nitro-based nonionic dye such as yellow 42; CI solvate yellow 179, disperse yellow 201 and other methine-based non-ionic dyes, and Japanese Patent Application Laid-Open No. 2010-168531 The nonionic property described in the above-mentioned Japanese Patent Application Publication No. 2010-275533, and the Japanese Patent Publication No. 2010-275533, and the Japanese Patent Publication No. 2010-275533 dye.

In the present invention, among these, from the viewpoints of solvent resistance and the like, an acid dye or a nonionic dye is preferred, and particularly preferred It is an acid dye, a triarylmethane-based acid dye, an azo-based nonionic dye, and a methine-based nonionic dye.

Further, in the present invention, a lake pigment may be contained as a colorant. Here, the lake pigment is a pigment which makes a soluble dye into an insoluble pigment by a precipitating agent. 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, katanol, and hetaluol. (tamol), homopolymeric acid, heteropoly acid, and the like. Examples of the homopolymeric acid include, for example, homopolymeric tungstic acid, homologously polymerized vanadic acid, and homologously polymerized molybdic acid. Examples of the heterogeneous polymeric acid include phosphotungstic acid, phosphomolybdic acid, and phosphotungstic acid. , 矽 tungsten molybdate, lanthanum tungstic acid, lanthanum molybdate and the like. Among these, a lake pigment which is a resin obtained by precipitating a homopolymeric acid or an isotropic polymerized acid as a precipitating agent is preferable, and a lake pigment which is a laked by using an isotropic polymeric acid as a precipitating agent is particularly preferable. The lake pigment which is formed by the use of the homopolymeric acid or the isotropic polymerized acid as a precipitating agent can be produced, for example, by the method described in JP-A-2011-186043.

In the present invention, the lake pigment is not particularly limited, but for example, It is a lake pigment, a triarylmethane lake pigment, an azo lake pigment, a phthalocyanine lake pigment, and the like.

Specific examples of the lake pigment include a pigment which is named as a color index (C.I.) as follows.

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, etc. Desiccant pigment; 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 , C.1. 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 pigments; 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 Pigment 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 Feed yellow 169, CI Pigment Yellow 183, CI Pigment Yellow 191, CI Pigment Yellow 191: 1 azo lake pigment and the like; CI Pigment Blue 17: 1, etc. phthalocyanine lake pigment.

Among these lake pigments, from the viewpoints of solvent resistance and the like, it is preferably Desiccant pigment, triarylmethane-based lake pigment, especially 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 62 , a triaryl methane-based lake pigment such as CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 27, CI Pigment Violet 39, and the like.

In the present invention, the coloring agent can be used singly or in combination of two or more.

The coloring composition of the present invention may further contain other coloring agents as the (A) coloring agent. The other coloring agent is not particularly limited, and colors and materials can be appropriately selected depending on the application.

As the other coloring agent, any of a pigment other than the lake pigment and a natural coloring matter can be used, but an organic pigment other than the lake pigment is preferable in terms of obtaining a pixel having high brightness and color purity.

Preferred examples of the organic pigment other than the above lake pigments include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, and 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.

In the present invention, when a pigment (except for the lake pigment, the same applies hereinafter) is used as the other colorant, the pigment may be recrystallized, reprecipitated, solvent washed, sublimed, vacuum heated or the like. It is used in combination and purification. Further, the pigment can be used by modifying the surface of the particles with a resin as desired. For example, a vehicle resin (vehicle resin) described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the pigment particles. For the resin coating method of the surface of the carbon black, a method described in, for example, JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed. Further, the organic pigment may be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

In the present invention, when a pigment is used as the other coloring agent, a known dispersing agent and a dispersing aid may be further contained. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkylphenyl ether dispersant, and polyethylene. A diol diester type dispersing agent, a sorbitan fatty acid ester type dispersing agent, a polyester type dispersing agent, an acryl-type dispersing agent, etc., as a dispersing adjuvant, a pigment derivative etc. are mentioned.

Such a dispersing agent can be obtained commercially, and examples thereof include, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK), as a poly A urethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above BYK), SOLSPERSE76500 (manufactured by Lubrizol Co., Ltd.); as a polyethyleneimine dispersant, SOLSPERSE 24000 (Lubrizol) In the polyester-based dispersing agent, there are AJISPER PB821, AJISPER PB822, AJISPER PB880, and AJISPER PB881 (above, Ajinomoto FINE TECHNO Co., Ltd.).

Further, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinoline yellow.

In the present invention, other coloring agents may be used singly or in combination of two or more.

The content ratio of the (A) colorant is usually 5 to 70% by mass in the solid content of the coloring composition, from the viewpoint of forming a solvent having high solvent resistance, high brightness, and excellent color purity, or a black matrix having excellent light-shielding properties. It is preferably 5 to 60% by mass. Here, the solid component is a component other than the solvent described later.

- (B) Adhesive Resin -

The (B) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer" (hereinafter referred to as "unsaturated monomer"). B1)") a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl)acryloxyloxyethyl b. Ester, ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Further, as the unsaturated monomer (b2), for example, an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; for example, styrene , α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, an aromatic vinyl compound of hydrazine; such as methyl (meth) acrylate, N-butyl methacrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, Polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2~10) (Meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [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, (meth) propyl cumylphenol Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) propylene methoxymethyl] oxetane, 3-[(methyl a (meth) acrylate of propylene methoxymethyl]-3-ethyloxetane; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 ^2,6 ] a vinyl ether of decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane; such as polystyrene, poly A macromonomer having a mono(meth)acrylinyl group at the terminal of the polymer molecular chain, such as methyl (meth)acrylate, poly(meth)acrylate, or polyoxyalkylene.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

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 to 50% by mass, further preferably from 10%. 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, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308 Copolymerization disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Things.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As a binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain can also be used as disclosed in JP-A-2008-181095.

The binder resin in the present invention is converted into polystyrene by gel permeation chromatography (hereinafter, abbreviated as GPC) (dissolving solvent: tetrahydrofuran). The weight average molecular weight (Mw) is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. When the Mw is too small, the residual film ratio of the obtained film may be lowered, or the pattern shape, heat resistance, or the like may be impaired, or electrical characteristics may be deteriorated. On the other hand, if the film thickness is too large, the resolution may be lowered or the pattern shape may be deteriorated. It is damaged or is likely to cause dry foreign matter when coated by a slit nozzle method.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mw and Mn" as used herein means a polystyrene-equivalent weight average molecular weight and a number average molecular weight measured by GPC (eluent solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871 can be used. The method disclosed therein controls its structure or Mw, Mw/Mn.

In the present invention, the content of the (B) binder resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the binder resin is too small, for example, the alkali developability may be lowered, or the storage stability of the obtained colored composition may be lowered. On the other hand, if the amount is too large, the relative colorant concentration may decrease. It is difficult to achieve the color density of the target as a film. Further, by setting the content of the (B) binder resin within the above range, solvent resistance can be improved.

In the present invention, the (B) binder resin can be used singly or in combination of two or more.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent is a compound having two or more ethylenically unsaturated groups, and preferably a compound having two or more (meth)acrylonyl groups.

Examples of the (C) crosslinking agent include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, a polyfunctional (meth) acrylate modified by caprolactone, and a ring. An oxane-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, and having a hydroxyl group A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate with an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a dihydric aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; for example, glycerin, trimethylolpropane, pentaerythritol, and An aliphatic polyhydroxy compound having 3 or more members of pentaerythritol.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth)acrylate, glycerol dimethacrylate, and the like.

Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

Examples of the acid anhydride include an acid anhydride of a dibasic acid such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and pyromellitic dianhydride. A tetrabasic acid dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, examples of the polyfunctional (meth) acrylate which is modified by the above-mentioned caprolactone include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955.

The polyfunctional (meth) acrylate which is modified by the above-mentioned alkylene oxide is exemplified by at least one selected from the group consisting of ethylene oxide of bisphenol A and propylene oxide of bisphenol A. a (meth) acrylate, a tri(meth) acrylate modified by at least one selected from the group consisting of ethylene oxide of isocyanuric acid and propylene oxide of isocyanuric acid, selected from the group consisting of Tris(meth)acrylate modified by at least one of ethylene oxide of trimethylolpropane and propylene oxide of trimethylolpropane, by ethylene oxide selected from pentaerythritol and pentaerythritol Tri (meth) acrylate modified by at least one of propylene oxide, tetrakis (methyl) modified by at least one selected from the group consisting of ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol An acrylate, a penta(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol, and ethylene oxide selected from dipentaerythritol and A hexa(meth)acrylate modified by at least one of propylene oxide of dipentaerythritol.

Among these crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, or a caprolactone-modified polyfunctional (A) is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (methyl) with carboxyl group Acrylate. It is excellent in the strength of the colored layer, the solvent resistance of the colored layer, and the surface smoothness, and it is less likely to cause floating pollution or film residue on the substrate of the unexposed portion and the light shielding layer. 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) acrylate having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferable.

In the present invention, the crosslinking agent can be used singly or in combination of two or more.

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1000 parts by mass, particularly preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. In this case, if the content of the crosslinking agent is too small, there is a concern that sufficient curing property may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and the surface of the unexposed portion or the light shielding layer is likely to be smeared. The tendency of film retention or the like. Further, by setting the content of the (C) crosslinking agent within the above range, solvent resistance can be improved.

-(D) Photopolymerization initiator -

The photopolymerization initiator of the present invention contains a photopolymerization initiator represented by the above formula (1), and can be started by exposure of radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. C) A compound of the active species of the polymerization of the crosslinking agent.

In the formula (1), the alkyl group having 1 to 12 carbon atoms in R ¹ and R ⁴ may be in a linear form or a branched form. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 2-ethylhexyl group, an octyl group, an isodecyl group, and a dodecyl group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

In addition, examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms in R ¹ and R ⁴ include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirocyclic hydrocarbon group, and a cyclic group. Olefin based and the like. More specifically, in addition to the cycloalkyl group described later, decahydro-2-naphthyl, borneol, norbornyl, adamantyl, dicyclopentenyl, tricyclopentenyl, and tricyclic [ 5.2.1.0 ^2,6 〕 decane-8-yl, pentacyclopentadecyl and the like. Among them, an alicyclic hydrocarbon group having 4 to 12 carbon atoms is preferred, and an alicyclic hydrocarbon group having 4 to 8 carbon atoms is more preferred.

Further, when R ¹ and R ⁴ are a phenyl group, part or all of the hydrogen atoms of the phenyl group may be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Specifically, the alkyl group having 1 to 12 carbon atoms is the same as the above, and among them, an alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. . Further, examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a pentyloxy group. Further, an alkoxy group having 1 to 6 carbon atoms is preferred, and an alkoxy group having 1 to 4 carbon atoms is more preferred.

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by the above R ² include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane. 1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1, 4-diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, octane-1, 8-diyl and the like. Further, an alkanediyl group having 1 to 8 carbon atoms is preferred, an alkenedialkyl group having 1 to 6 carbon atoms is more preferred, and an alkanediyl group having 1 to 4 carbon atoms is more preferred.

Examples of the cycloalkyl group having 4 to 20 carbon atoms represented by the above R ³ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and the like. . Further, a cycloalkyl group having 4 to 12 carbon atoms is preferred, and a cycloalkyl group having 4 to 8 carbon atoms is more preferred.

The above R ⁵ is a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a 2-furyl group or a 2-thienyl group, and some or all of the hydrogen atoms of the groups It may also be substituted with an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms.

In the formula (1), R ¹ and R ^{4 are} preferably an alkyl group having 1 to 12 carbon atoms or a phenyl group, and an alkyl group having 1 to 12 carbon atoms is preferably a methyl group, an ethyl group or a C group. Base, isopropyl, butyl. R ^{2 is} preferably methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6. - Diji. Further, R ^{3 is} preferably a cycloalkyl group having 4 to 20 carbon atoms, particularly preferably a cyclopentyl group or a cyclohexyl group. Further, as R ⁵ , a tolyl group or a naphthyl group is preferred.

In the present invention, the photopolymerization initiator represented by the formula (1) is preferably a compound represented by the following formulas (D-1) to (D-8).

In the present invention, a photopolymerization initiator other than the photopolymerization initiator represented by the above formula (1) (hereinafter referred to as "another photopolymerization initiator") may be used alone or in combination of two or more. Examples of such other photopolymerization initiators include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. O-mercapto fluorene-based compound, sulfonium-based compound, benzoin-based compound, benzophenone-based compound, α-diketone-based compound, and polynuclear oxime-based compound other than the compound represented by the above formula (1) A diazo compound, a quinone sulfonate compound, or the like. Among these, as another photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of the compound and the O-mercapto fluorene compound other than the compound represented by the above formula (1).

Among other photopolymerization initiators preferred in the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-iso Propyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 - Diisopropyl thioxanthone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)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, when a biimidazole-based compound is used as another photopolymerization initiator, it is preferred to use a hydrogen donor in combination for improving the sensitivity. The term "hydrogen donor" as used herein means a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine-based hydrogen donor such as a thiol-based hydrogen donor, 4,4'-bis(dimethylamino)benzophenone, or 4.4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, in terms of further improving the sensitivity, it is preferred to use one or more kinds of thiol-based hydrogen donors in combination with one or more amine-based hydrogen donors. .

Again, as the above three Specific examples of the compound can be exemplified by 2,4,6-paran (trichloromethyl). , 2-methyl-4,6-bis(trichloromethyl) are all three , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-three , 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) are all three , 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl) are all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-three Three with a halomethyl group a compound.

In addition, as a specific example of the O-mercapto fluorene-based compound other than the compound represented by the above formula (1), 1,2-octanedione-1-[4-(phenylthio)phenyl] -2-(O-benzamide), ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O -acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1- (O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Benzobenzyl}-9H-carbazol-3-yl]-1-(O-acetyl) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), etc. can also be used.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone-based compound is used, a sensitizer can also be used in combination. As Examples of the sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-diethylaminobenzene. Ethyl ketone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylamino) Benzylene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, there is a concern that the curing by the exposure is insufficient. On the other hand, if the amount is too large, the colored layer formed may be easily peeled off from the substrate during development. tendency. In addition, when the content of the (D) photopolymerization initiator is within the above range, solvent resistance can be improved.

In addition, when the photopolymerization initiator represented by the above formula (1) is used in combination with another photopolymerization initiator, the content of the photopolymerization initiator represented by the above formula (1) is in all the photopolymerization initiators. It is preferably 0.1 to 50% by mass, particularly preferably 1 to 50% by mass. Thereby, solvent resistance can be improved.

- solvent -

The colored composition of the present invention contains the above components (A) to (D) and any other components which may be added, but is usually prepared as a liquid composition in combination with a solvent. The solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (D) constituting the colored composition or other components, and does not react with these components and has appropriate volatility.

Among such 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 single positive 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, etc. (poly)oxyalkylene glycol monoalkyl ethers; lactic acid Methyl lactate such as methyl ester or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol, etc. (cyclo)alkyl alcohols; ketone 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 acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy acetate (poly)oxyalkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6 - diacetate such as hexanediol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane An alkoxycarboxylate such as ethyl acetate, ethyl ethoxyacetate or 3-methyl-3-methoxybutylpropionate; 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, ethyl 2-oxobutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; decylamine or indoleamine such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone Wait.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are preferred from the viewpoints of solubility, pigment dispersibility, and coating properties. 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, methyl 3-ethoxypropionate, 3-ethoxyl Ethyl propionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyrate B Ester, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the solvent can be used singly or in combination of two or more.

The content of the solvent is not particularly limited, but the total concentration of each component other than the solvent of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In such a manner, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.

-additive-

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

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or an anthrone-based surfactant; Vinyltrimethoxydecane, vinyltriethoxydecane, vinyl ginseng (2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy An adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-sulfuric double (4 -Methyl-6-tert-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5 - UV absorbing agents such as chlorobenzotriazole and alkoxy benzophenone; and aggregation prevention of sodium polyacrylate Stopping agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1- Residue improver such as pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(A Improvement of developability such as propylene methoxyethyl ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate Agents, etc.

The colored composition of the present invention can be produced by an appropriate method, and examples of the preparation method thereof include those disclosed in JP-A-2008-58642 and JP-A-2010-132874. When both the dye and the pigment are used as the coloring agent, the dye solution that has passed through the first filter can be used by passing the dye solution through the first filter as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874. Further, a prepared pigment dispersion or the like is mixed, and the obtained colored composition is passed through a second filter to prepare a method. Further, it is also possible to dissolve the dye and the components (B) to (D) and other additive components used as needed in a solvent, and pass the obtained solution through the first filter, and then pass the first filtration. A method in which a solution of the device is mixed with a separately prepared pigment dispersion, and the obtained colored composition is passed through a second filter. Further, by passing the dye solution through the first filter, the dye solution that has passed through the first filter can be mixed with the components (B) to (D) and other additive components used as needed. The method of preparing the solution by passing the obtained solution through the second filter, mixing the solution of the second filter with the separately prepared pigment dispersion, and passing the obtained colored composition through the third filter.

Color filter and manufacturing method thereof

The color filter of the present invention is provided with a coloring layer formed using the coloring composition of the present invention.

As a method of manufacturing a color filter, the following method can be mentioned first. First, on the surface of the substrate, a light shielding layer (black matrix) is formed as needed to form a portion of the pixel as needed. Next, on the substrate, for example, at least one red color selected from the group consisting of a dye and a lake pigment is dispersed. After the liquid composition of the color-sensing radiation composition of the present invention of the present invention, the solvent is prebaked and evaporated to form a coating film. Next, the coating film was exposed through a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which a red pixel pattern is arranged in a predetermined arrangement is formed.

Next, using the green or blue colored radiation-sensitive linear composition, the coating, prebaking, exposure, development, and post-baking of each coloring radiation composition are performed in the same manner as described above, sequentially on the same substrate. A green pixel array and a blue pixel array are formed. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, at least one of the red, green and blue pixels may be formed by the colored composition of the present invention. Further, the order in which the respective color pixels are formed is not limited to the above.

Further, 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 by photolithography, but it is also possible to use a coloring linear composition in which a black pigment is dispersed. The object is formed in the same manner as the above-described pixel formation.

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

Further, such a substrate may be subjected to an appropriate pretreatment such as a reagent treatment such as a decane coupling agent, a plasma treatment, ion plating, sputtering, a gas phase reaction method, or a vacuum vapor deposition, as necessary.

When the coloring sensitizing radiation composition is applied to a substrate, a spray coating method, a roll coating method, a spin coating method (spin coating method), or a slit die coating method may be employed. A suitable coating method such as a cloth method or a bar coating method is particularly preferably a spin coating method or a slit die coating method.

The prebaking is usually carried out by combining dry drying under reduced pressure and drying by heating. Drying under reduced pressure usually proceeds until it reaches 50 to 200 Pa. Further, the conditions for heating and drying are usually about 70 to 110 ° C for about 1 to 10 minutes.

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

Examples of the light source used for forming the pixels 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 a argon ion laser, a YAG laser, a XeCl excimer laser, a nitrogen laser or the like, preferably a radiation having a wavelength in the range of 190 to 450 nm.

The exposure amount of the radiation is generally preferably 10 to 10000 J/m ² .

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

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

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

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

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

Moreover, as a second method of producing a color filter, a method of obtaining each color pixel by an inkjet method, which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-310706, 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. Next, for example, a liquid composition of the colored thermosetting composition of the present invention in which at least one red coloring agent selected from the group consisting of a dye and a lake pigment is dispersed is spouted in the formed partition by an inkjet device. Prebaking is carried out to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a red pixel pattern.

Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above, using green or blue colored thermosetting compositions. Thereby, a color filter in which a pixel pattern of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, at least one of the red, green and blue pixels may be formed by the colored composition of the present invention. Further, the order in which the respective color pixels are formed is not limited to the above.

Further, in order to accomplish the function of not only the shading function but also the coloring composition of each color discharged in the divisional region, the partition wall is thicker than the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The method or condition for pre-baking or post-baking of the substrate or the radiation source used for spraying the color filter is the same as the first method described above. Thus, the film thickness of the pixel formed by the inkjet method is the same as the height of the partition wall.

On the thus obtained pixel pattern, a protective film is formed as needed, and a transparent conductive film is formed by sputtering. Further, after the transparent conductive film is formed, a spacer may be further formed as a color filter. The spacer is usually formed using a radiation-sensitive composition, and can also be a spacer having a light-shielding property (black spacer). In this case, a colored radiation-containing linear composition containing a black colorant is used, but the colored composition of the present invention can also be suitably used to form the black spacer.

The color filter of the present invention thus obtained is extremely useful for color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like because of extremely high brightness and color purity.

Display component

The display element of the present invention is provided with the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

A color liquid crystal display element having the color filter of the present invention may 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 a driving substrate and a substrate on which a color filter is formed may be disposed opposite to each other via a liquid crystal layer. Further, it is also possible to form a color filter on the surface of the driving substrate on which the thin film transistor (TFT) is disposed. The substrate of the sheet and the substrate on which the ITO (tin-doped indium oxide) electrode is formed are arranged to face each other with the liquid crystal layer interposed therebetween. The latter structure has an advantage that the aperture ratio can be remarkably increased, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display element including the color filter of the present invention may further 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 obtained by combining a red LED with a green LED and a blue LED to obtain white light is obtained by combining a blue LED with a red LED and a green phosphor to obtain white light. A white LED is obtained by combining a blue LED with a red-emitting phosphor and a green-emitting phosphor to obtain a white light white LED, which is obtained by mixing colors of a blue LED and a YAG-based phosphor. A white LED is obtained by combining a blue LED with an orange-emitting phosphor and a green-emitting phosphor to obtain a white LED of white light, by using an ultraviolet LED and a red-emitting phosphor and a green-emitting phosphor and blue A color light-emitting phosphor is combined with a color to obtain a white LED or the like of white light.

In the color liquid crystal display device including the color filter of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes Switching type) can be applied. A suitable liquid crystal mode such as an internal switching type, a VA (Vertical Alignment) type, or an OCB (Optically Compensated Birefringence) type.

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

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

[Examples]

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

<Synthesis of binder resin> Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added, and nitrogen was replaced. The heating was 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate 15 parts by mass and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed and maintained at this temperature for 2 hours. 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: 33% by mass) was obtained. The resulting binder resin had a Mw of 12,200 and an Mn of 6,500. This binder resin is "adhesive resin (B1)".

<Preparation of dye solution> Preparation Example 1

A dye solution (A-1) was prepared by mixing 10 parts by mass of Basic Blue 7 as a dye and 90 parts by mass of ethyl lactate as a solvent.

Preparation Example 2

In the preparation example 1, a dye solution (A-2) was prepared in the same manner as in Production Example 1 except that Acid Blue 9 was used instead of Basic Blue 7.

Preparation Example 3

In the preparation example 1, a dye solution (A-3) was prepared in the same manner as in Production Example 1, except that Basic Blue 11 was used instead of Basic Blue 7.

Preparation Example 4

In Preparation Example 1, a dye solution (A-4) was prepared in the same manner as in Production Example 1, except that Acid Red 52 was used instead of Basic Blue 7.

Preparation Example 5

In Preparation Example 1, a dye solution (A-5) was prepared in the same manner as in Production Example 1, except that Solvent Yellow 179 was used instead of Basic Blue 7.

Preparation Example 6

In the preparation example 1, a dye solution (A-6) was prepared in the same manner as in Production Example 1 except that the compound represented by the following formula (A1) was used instead of the basic blue 7.

<Preparation of lake pigment dispersion> Preparation Example 7

10 parts by mass of CI Pigment Blue 1 as a lake pigment, 18 parts by mass (solid content concentration: 33% by mass) of a binder resin (B1) solution, 64 parts by mass of propylene glycol monomethyl ether acetate, and 8 parts by mass of propylene glycol The lake pigment dispersion (A-7) was prepared by a bead mill treatment using methyl ether as a solvent.

Preparation Example 8

10 parts by mass of a triarylmethane-based lake pigment (wherein, x = 1 to 2) represented by the following formula (A2) and 5.9 parts by mass of Disperbyk as a polyurethane-based dispersant are mixed as the lake pigment. 2164 (nonvolatile content = 60%, amine price: 14 mgKOH/g, manufactured by BYK), propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether as a solvent = 90/10 (mass ratio) mixed solvent, solid content concentration The resultant was 16%, and the dispersion pigment dispersion (A-8) was prepared by bead milling and dispersion for 12 hours.

Preparation Example 9

10 parts by mass of CI Pigment Red 254/CI Pigment Red 177/CI Pigment Red 81:2 was used as a colorant (deposited by lanthanum molybdate) 色 色 颜料 = = = = = = = = = = = = = = = = = = = BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY BY Ether acetate/propylene glycol monoethyl ether = 90/10 (mass ratio) mixed solvent, the solid content concentration was 16% by mass, and a lake pigment dispersion liquid (A-9) was prepared by a bead mill treatment.

<Preparation and evaluation of coloring composition> Example 1

27.2 parts by mass of the dye solution (A-1), 21.6 parts by mass of the binder resin (B1) solution as the binder resin, and 9.2 parts by mass of the M-402 (dipentaerythritol hexaacrylate) manufactured by Toagosei Co., Ltd. as a crosslinking agent a mixture with dipentaerythritol pentaacrylate), 0.5 parts by mass of a compound represented by the following formula (D-1), and 1.7 parts by mass of 2,2'-bis(2-chlorophenyl)-4 as a photopolymerization initiator , 4',5,5'-tetraphenyl-1,2'-biimidazole (d-1), 0.4 parts by mass of 2-mercaptobenzothiazole (d-2), 0.2 mass as a fluorine-based surfactant MEGAFAC F-554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether as a solvent were prepared as a colored composition having a solid concentration of 20% by mass.

Solvent resistance evaluation

The obtained colored composition was applied onto a glass substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film having a film thickness of about 2.5 μm.

Next, after the substrate was cooled to room temperature, the coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 2000 J/m ² without using a high-pressure mercury lamp. Thus, a blue evaluation cured film was formed on the substrate.

The obtained substrate was immersed in propylene glycol monomethyl ether acetate at 25 ° C for 30 minutes. The film thickness before and after the treatment was measured by a stylus type film thickness measuring machine (IQ, KLA Tencor Co., Ltd.), and the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated. Then, when the residual film ratio is 90% or more, it is "◎", 80% or more and less than 90% is "○", and when it is less than 80%, it is "X". The evaluation results are shown in Table 1.

Examples 2 to 6 and Comparative Examples 1 to 2

In the same manner as in Example 1, except that the types of the dye solution and the photopolymerization initiator were changed as shown in Table 1, a colored composition was prepared. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7

27.2 parts by mass of the lake pigment dispersion (A-7), 16.7 parts by mass of the binder resin (B1) solution as the binder resin, and 9.2 parts by mass of M-402 (dipentaerythritol) manufactured by Toagosei Co., Ltd. as a crosslinking agent a mixture of hexaacrylate and dipentaerythritol pentaacrylate), 0.5 parts by mass of the compound represented by the above formula (D-1), and 1,7 parts by mass of 2,2'-bis(2-chloro) as a photopolymerization initiator Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (d-1), 0.4 parts by mass of 2-mercaptobenzothiazole (d-2), as a fluorine-based interface 0.2 parts by mass of the active agent, MEGAFAC F-554 (manufactured by DIC Corporation), and propylene glycol monomethyl ether as a solvent, were prepared as a coloring composition having a solid concentration of 20% by mass. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Examples 8 to 9 and Comparative Examples 3 to 5

In the same manner as in Example 7, except that the types of the lake pigment dispersion liquid and the photopolymerization initiator were changed as shown in Table 1, a colored composition was prepared. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

In Table 1, each component is as follows.

D-1: a compound represented by the above formula (D-1)

D'-1: Ethyl-1-(9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetyl) (IRGACURE) OXE02, Ciba.Specialty.Chemicals)

D-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole

D-2: 2-mercaptobenzothiazole

Claims (8)

A coloring composition characterized by containing the following components (A), (B), (C), and (D), (A) containing at least one coloring agent selected from the group consisting of a dye and a lake pigment, and (B) a binder a resin, (C) a compound having two or more ethylenically unsaturated groups, and (D) a photopolymerization initiator represented by the following formula (1), In the formula (1), R ¹ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a phenyl group (wherein the phenyl group) A part or all of a hydrogen atom may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms), R ² represents an alkanediyl group having 1 to 20 carbon atoms, and R ³ represents a cycloalkyl group having 4 to 20 carbon atoms, a phenyl group or a naphthyl group, and R ⁵ represents a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a 9-fluorenyl group, a 2-furyl group or 2 -Thienyl group (wherein a part or all of the hydrogen atoms which these groups have may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. In the coloring composition of the first aspect of the invention, the content of the photopolymerization initiator represented by the formula (1) is from 1 to 50% by mass based on the total amount of the photopolymerization initiator. The coloring composition of the first aspect of the invention, wherein the coloring agent (A) contains at least one selected from the group consisting of an acid dye and a nonionic dye. The coloring composition of claim 3, wherein the acid dye is selected from the group consisting of It is at least one of an acid dye and a triarylmethane-based acid dye. The coloring composition of the third aspect of the invention, wherein the nonionic dye contains at least one selected from the group consisting of an azo-based nonionic dye and a methine-based nonionic dye. The coloring composition of claim 1, wherein the lake pigment is selected from the group consisting of It is at least one of a lake pigment and a triarylmethane lake pigment. A color filter comprising a coloring layer formed by using the coloring composition according to any one of claims 1 to 6. A display element comprising a color filter as in claim 7 of the patent application.