JP2013195681A - Photosensitive resin composition, color filter, liquid crystal display device, and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that has an excellent image forming property, good sensitivity and adhesion, and excellent productivity.SOLUTION: A photosensitive resin composition comprises: (a) an alkylene oxide group-containing compound; (b) a photopolymerizable monomer having three or more ethylenically unsaturated bonds; (c) an alkali-soluble resin; and (d) a photopolymerization initiator; and (a) the alkylene oxide group-containing compound is represented by the following general formula (a1). Ris an alkylene group having a carbon number of 4 to 6; Aand Aare a hydrogen atom, an alkyl group having a carbon number of 1 to 10, alkyl phenyl group, or a (meth)acryloyl group. n is an integer of 2 to 50.

Description

  The present invention relates to a photosensitive resin composition, a color filter, a liquid crystal display device, and an organic EL display. More specifically, the present invention relates to a photosensitive resin composition excellent in image forming property, excellent sensitivity and adhesiveness, excellent in productivity, and its use.

  Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method and the like are known.

  In the case of producing a color filter by the pigment dispersion method, usually, a photosensitive composition obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a resin composition obtained by dispersing a pigment with a dispersant or the like. The resin composition is coated on a glass substrate, dried, exposed using a mask, and developed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.

  The photosensitive resin composition used for image formation of such a color filter is required to have characteristics such as sufficient resolution, good adhesion to a substrate, and low development residue. Furthermore, in recent years, a pixel having a high color density and a resin black matrix having a high optical density are required. For this reason, the photosensitive resin composition is required to be excellent in the above characteristics while containing a large amount of a coloring material such as a pigment or carbon black.

  In general, the photosensitive resin composition is subjected to a photolithographic process that undergoes coating, drying, exposure, and development processes. Therefore, in such a process, no residue or soiling occurs in the removed portion in the development process; There has always been a demand for the part to have sufficient solubility; to improve pixel formation such as sharpness of the pattern edge. However, when a pixel or a black matrix (hereinafter may be collectively referred to as a “pattern”) is formed using the photosensitive resin composition having a high content of the colorant as described above, a development step Residues and background stains occur on the unexposed substrate; poor solubility of the unexposed area cannot be obtained; sharpness of the pattern edge is inferior; surface curing is poor due to insufficient photocuring of the exposed area Problems are likely to occur remarkably.

  In particular, the resin black matrix contains a black color material and has a light-shielding property in a wide wavelength region, so that (1) it is extremely difficult to make a difference in crosslink density between an exposed portion and an unexposed portion, and (2) exposure is performed. The difference in cross-linking density in the film thickness direction occurs even in the part where the film is cured, that is, it is hard to cure on the base surface side even if it is sufficiently cured on the light irradiation surface side, and (3) a black color material insoluble in the developer. Since a large amount of is contained, it is difficult to obtain high developability.

  As a technique for increasing the sensitivity of the photosensitive resin composition, it is conceivable to increase the photopolymerization initiator in the composition. However, this method has a problem that the difference in crosslink density in the film thickness direction becomes larger. Moreover, it is possible to add a thiol compound as a chain transfer agent (patent document 1), but the composition containing the thiol compound has a problem in storage stability.

  In addition, there is a method of adding an alkylene oxide group-containing acrylate (Patent Documents 2 and 3), but the sensitivity is not sufficient with an ethylene oxide group or a propylene oxide group, and adhesion to glass during development is deteriorated. There was a problem and there was room for improvement.

JP-A-10-282326 Japanese Unexamined Patent Publication No. 2007-271987 JP 2010-204363 A

  An object of the present invention is to provide a photosensitive resin composition, a color filter, a liquid crystal display device, and an organic EL display, which are excellent in image forming properties, excellent in sensitivity and adhesion, and excellent in productivity.

  As a result of intensive studies by the present inventors to solve the above-mentioned problems, by adding a compound having a specific structure, high sensitivity can be realized during pattern formation, and adhesion to a substrate during development. Has been found to be satisfactory, that is, the above-mentioned problems can be solved, and the present invention has been achieved.

The first gist of the present invention is (a) an alkylene oxide group-containing compound, (b) a photopolymerizable monomer having three or more ethylenically unsaturated bonds, (c) an alkali-soluble resin, and (d) photopolymerization. A photosensitive resin composition containing an initiator,
(A) A photosensitive resin composition characterized in that the alkylene oxide group-containing compound is represented by the following general formula (a1).

(In the general formula (a1), R ¹ represents an alkylene group having 4 to 6 carbon atoms, and A ¹ and A ² are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylphenyl group, a phenyl group, or ( Represents a (meth) acryloyl group, n represents an integer of 2 to 50, and A ¹ and A ² may be the same or different.

  The second gist of the present invention resides in a cured product obtained by curing the photosensitive resin composition.

  The third gist of the present invention resides in a color filter having a pixel or a black matrix formed by using the photosensitive resin composition on a transparent substrate.

  The fourth gist of the present invention resides in a liquid crystal display device manufactured using the color filter.

  The fifth gist of the present invention resides in an organic EL display produced using the color filter.

The photosensitive resin composition of the present invention has high sensitivity, good adhesion to the substrate during development, and balances sensitivity and solubility even when containing a coloring material such as pigment or carbon black at a high concentration. Excellent, high resolution, and high-definition pixels can be formed.
According to the present invention, by using such a photosensitive resin composition, a high-quality color filter can be obtained, and further, a high-quality liquid crystal display device and an organic EL display can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”. In addition, “(acid) anhydride” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.
In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive resin composition or in the ink described later.
Moreover, in this invention, a weight average molecular weight means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is
(A) an alkylene oxide group-containing compound (b) a photopolymerizable monomer having three or more ethylenically unsaturated bonds (c) an alkali-soluble resin (d) a photopolymerization initiator as an essential component, preferably,
(E) a coloring material (f) containing a dispersant, and if necessary, an adhesion improver such as an organic solvent and a silane coupling agent, a coating property improver, a development improver, an ultraviolet absorber, an antioxidant, It contains other compounding components such as a surfactant and a pigment derivative, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.

<Alkylene oxide group-containing compound (a)>
The alkylene oxide group-containing compound (a) used in the present invention includes a compound having a structure represented by the following general formula (a1).

(In the general formula (a1), R ¹ represents an alkylene group having 4 to 6 carbon atoms, and A ¹ and A ² are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylphenyl group, a phenyl group, or ( Represents a (meth) acryloyl group, n represents an integer of 2 to 50, and A ¹ and A ² may be the same or different.

In the general formula (a1), R ¹ represents an alkylene group having 4 to 6 carbon atoms, preferably 4 carbon atoms, which may be linear or branched, but is a linear n-butylene group. , N-pentylene group and n-hexylene group are preferable, and n-butylene group is more preferable among them.

Examples of the alkyl group of the alkylphenyl group of A ¹ and A ² include an alkyl group having 1 to 10 carbon atoms. As the alkyl group of A ¹ and A ² , an alkyl group having 1 to 4 carbon atoms is preferable. Among them, as A ¹ and A ² , a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and a (meth) acryloyl group are preferable. Particularly preferred are a hydrogen atom, a methyl group, and a (meth) acryloyl group.

  n is preferably 4 to 40, and particularly preferably 6 to 30.

  Of the compounds having the structure represented by the general formula (a1), polytetramethylene glycol, polytetramethylene glycol di (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate are particularly preferable.

  In this invention, an alkylene oxide group containing compound (a) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

<Photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds>
The photosensitive resin composition of this invention contains the photopolymerizable monomer (b) which has a 3 or more ethylenically unsaturated bond in 1 molecule.

  Examples of such photopolymerizable monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and the like. And an ester obtained by an esterification reaction of an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate. , Acrylic acid esters of aliphatic polyhydroxy compounds such as dipentaerythritol hexaacrylate, methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylate, itaconic acid esters in place of itaconate, crotonic acid esters in place of clonate or Examples include maleate esters instead of maleates.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as pyrogallol triacrylate.

  The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  Other examples of the photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group. Urethane (meth) acrylates obtained by reacting a containing (meth) acrylic acid ester; Epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; Useful are acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

  Among these, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as the photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds. In particular, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are preferable.

  These photopolymerizable monomers (b) having 3 or more ethylenically unsaturated bonds may be used alone or in combination of 2 or more, but 3 or more ethylenically unsaturated Pentaerythritol tetraacrylate and / or the ratio of pentaerythritol tetraacrylate and / or dipentaerythritol hexaacrylate in the photopolymerizable monomer (b) having a bond is 40 to 100% by weight, particularly 50 to 100% by weight. It is preferable to use dipentaerythritol hexaacrylate in terms of further improving the sensitivity effect.

<Alkali-soluble resin (c)>
The alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. For example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing urethane resin, Among them, novolac resins and polyvinylphenol resins are preferable, among which epoxy (meth) acrylate resins and acrylic resins are preferable, and these can be used alone or in combination.
The alkali-soluble resin used in the present invention is particularly preferably the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). Used.

<Alkali-soluble resin (c1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.

<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol A type epoxy, etc. Epoxy obtained by reaction of alcoholic hydroxyl group of resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-740” manufactured by Kayaku Co., Ltd. (Epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg “YX-4000” manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) "EPPN-201", Yuka Shell Epoxy "EP-152", "EP-154", Dow Chemical "DEN-438"), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “E” manufactured by Nippon Kayaku Co., Ltd.) PN-503 "), cycloaliphatic epoxy resins (" Celoxide 2021P "," Celoxide EHPE "manufactured by Daicel Chemical Industries, Ltd.), epoxy resins obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, Dainippon "EXA-7200" manufactured by Ink Company, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (C1) to (C4), and the like can be suitably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (C1), and “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (C2). As an epoxy resin represented by “NC-3000” and the following general formula (C4), “ESF-300” manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned.

(In the general formula (C1), a represents an average value and represents a number of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ¹¹ present in one molecule may be the same or different.

(In the above general formula (C2), b represents an average value and represents a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ²¹ present in one molecule may be the same or different.

(In the general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2), provided that the molecular structure includes one or more adamantane structures. Represents an integer of 2 or 3.)

(In the above general formulas (C3-1) and (C3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group optionally having a substituent, a hydrogen atom, a substituent, The alkyl group having 1 to 12 carbon atoms which may have a group, or a phenyl group which may have a substituent.

(In the above general formula (C4), p and q each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ are each independently. And x and y each independently represents an integer of 0 or more.)

  Among these, it is preferable to use epoxy resins represented by general formulas (C1) to (C4).

  Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) a Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomers added with acid (anhydride) such as maleic acid, (meth) acrylic acid dimer, etc. And the like.

  Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method of adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method can be used. For example, reacting an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
In addition, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two types. You may use the above together.

  The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mg KOH / g, and further 20 It is preferable that it is a grade which becomes the range of -140 mgKOH / g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, the alkali developability tends to be poor, and when it exceeds the above range, the curing performance tends to be poor.

  In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of addition reaction of this polybasic acid and / or its anhydride.

  The carboxyl group-containing epoxy (meth) acrylate resin is usually a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group with a polybasic acid and / or Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. To the polybasic acid and / or its anhydride.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1000 or more, preferably 1500 or more, and usually 10,000 or less, preferably 8000. Below, more preferably 6000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.

  The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.

  Moreover, as long as the alkali-soluble resin (c) used in the present invention does not impair the performance of the present invention, a part of the carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (c) is preferably 50% by weight or more, particularly preferably 80% by weight or more.

As long as the performance of the present invention is not impaired, other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin are not limited, and may be selected from resins usually used for photosensitive resin compositions for color filters. . Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like.
In addition, all other binder resins may be used alone or in combination of two or more.

<Photopolymerization initiator (d)>
The photopolymerization initiator (d) is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. If necessary, additives such as accelerators and sensitizing dyes may be added and used.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is.

  Examples of the oxime ester derivatives include the following compounds (in the following, “Me” represents “methyl group”).

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Acridine derivatives such as benzyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

  Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.

  A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. Accelerators may be used alone or in combination of two or more.

  If necessary, the photopolymerization initiator can be mixed with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

  A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

<Coloring material (e)>
The photosensitive resin composition of the present invention may contain a coloring material (e) in order to color the present composition. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

  Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Moreover, when the photosensitive resin composition of this invention is the photosensitive resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material (e). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  As the carbon black, carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used.

As carbon black to be subjected to a coating treatment with a resin, the total content of Na and Ca is preferably 100 ppm or less.
That is, carbon black is usually made from raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al. , Fe and the like are contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. There is a case.

  As a method for reducing the content of ash containing these Na and Ca in carbon black, these contents are used as much as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. Examples include a method of carefully selecting a small amount and a method of minimizing the addition amount of an alkaline substance for adjusting the structure. As another method, there is a method in which Na or Ca is dissolved and removed by washing carbon black produced from a furnace with water or hydrochloric acid.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and completely separates from water. Most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The carbon black used for the resin coating is preferably so-called acidic carbon black having a pH of 6 or less. Such carbon black is suitable because it has a small dispersed diameter (agglomerated diameter) in water, and can cover even fine units. Furthermore, the carbon black used for the resin coating preferably has a particle size of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 ml / 100 g or less. If the particle size is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the coating film may not have sufficient density, and the film thickness is about 1 to 2 μm. It is because there is a possibility that it may become scarce.

  The type of resin used to coat carbon black is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure function more as amphoteric active surfactants. Is preferable from the viewpoint of dispersibility and dispersion stability.

Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfone, polyphenylene sulfone, polyarylate, and polyether ether ketone can be used.
These may be used alone or in combination of two or more.

  The coating amount of the resin on the carbon black is preferably 1 to 30% by weight with respect to the total amount of the carbon black and the resin. When the coating amount of the resin with respect to carbon black is less than 1% by weight, there is a possibility that only dispersibility and dispersion stability similar to those of untreated carbon black can be obtained. On the other hand, if it exceeds 30% by weight, the adhesiveness between the resins is strong, and it becomes a dumpling-like lump, which may prevent the dispersion from proceeding.

  The carbon black formed by coating with a resin can be used as a black matrix shading material according to a conventional method, and a color filter having this black matrix as a constituent element can be prepared by a conventional method. When such carbon black is used, a black matrix having a high light shielding rate, a low surface reflectance, and a thin film thickness can be achieved at a low cost. This is presumably because the dispersibility and dispersion stability of carbon black was significantly improved compared to the resin and solvent that make up the black matrix liquid. As a result, it is difficult to disperse to 0.1 μm or less, and even if dispersed, the stability is poor and the aggregation increases with time.) It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

  Examples of other black color materials include titanium black, aniline black, and iron oxide black pigments. Also, organic color materials of three colors of red, green, and blue can be mixed and used as a black color material. it can.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

These pigments are preferably used dispersed in such a way that the average particle size is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.
In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS. For particle size measurement, a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by weight. However, if there is a concentration recommended by the measuring instrument, its concentration And measure at 25 ° C.

<Dispersant (f)>
In the present invention, it is important to finely disperse the color material (e) and stabilize the dispersion state, so that it is important to ensure the stability of the quality. Therefore, the dispersant (f) may be included.

  The dispersant (f) is preferably a polymer dispersant having a functional group, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as a quaternary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is preferred. Of these, basic polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine, etc. are particularly preferred. .

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant include trade names of EFKA (manufactured by BASF), Disperbyk (manufactured by Big Chemie), disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (Shin-Etsu Chemical) (Manufactured by Ajinomoto Co., Inc.)
These polymer dispersants may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.

  Among these, it is particularly preferable that the dispersant (f) contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group in terms of adhesion and linearity.

  Examples of urethane and acrylic polymer dispersants include Disperbyk 160 to 166, 182 series (both urethane), Disperbyk 2000, 2001, etc. (both acrylic) (all manufactured by BYK Chemie).

  If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.

  These may be used alone or in combination of two or more.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., nitrogen-containing hetero 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  These may be used alone or in combination of two or more.

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. -200 parts by weight, preferably 20-190 parts by weight, more preferably 30-180 parts by weight, 0.2-25 parts by weight of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 -24 parts by weight.

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a class amine system, are mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.

  The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

  As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

  The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In addition to the unsaturated group-containing monomer containing the functional group, the block may contain an unsaturated group-containing monomer that does not contain the functional group. It may be contained in any form of polymerization or block copolymerization. Further, the content of the partial structure containing no functional group in the A block is usually 80% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less.

  The B block is composed of an unsaturated group-containing monomer that does not contain the above functional group. However, two or more types of monomers may be contained in one B block. It may be contained in any form of random copolymerization or block copolymerization in the block.

  The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing this acrylic polymer dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al. , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer processing, 36 , 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. can be employed.

  Whether the acrylic polymer dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer Is preferably 1/99 to 80/20, and more preferably 5/95 to 60/40 (weight ratio). Outside this range, it may not be possible to combine good heat resistance and dispersibility.

  In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mgKOH / g.

Here, the amine value of the dispersant such as these block copolymers is expressed by the weight of KOH equivalent to the base amount per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [wt%] of the dispersant sample. ]

  The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.

  Moreover, it is preferable to use a dispersing agent (f) together with the pigment derivative mentioned later from the point of a dispersion stability improvement.

<Other ingredients of the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition of the present invention includes an adhesion improver such as an organic solvent and a silane coupling agent, a coating property improver, a development improver, an ultraviolet absorber, an antioxidant, and a surfactant. In addition, pigment derivatives and the like can be appropriately blended.

(1) Organic solvent The photosensitive resin composition of the present invention usually comprises an alkylene oxide group-containing compound (a), a photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds, and an alkali-soluble resin. (C), a photopolymerization initiator (d), and a coloring material (e) used as necessary, a dispersing agent (f), and other various materials are used in a state dissolved or dispersed in an organic solvent. .

  As the organic solvent, it is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

  Examples of such organic solvents include the following.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;

  Alkyl acetates such as cyclohexanol acetate;

  Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

  Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;

  Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;

  aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

  Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

  Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;

  Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride;

  Ether ketones such as methoxymethylpentanone;

  Nitriles such as acetonitrile and benzonitrile;

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  These organic solvents may be used alone or in combination of two or more.

  When a pixel or black matrix of a color filter is formed by photolithography, the boiling point of the organic solvent is 100 to 200 ° C. (under a pressure of 101.25 [hPa]. Hereinafter, all of the boiling points are the same). It is preferable to select one. More preferably, it has a boiling point of 120 to 170 ° C.

  Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment is likely to aggregate, and the storage stability tends to decrease such as the viscosity of the resin composition obtained later increases. The proportion of glycol monoalkyl ethers in them is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

(2) Adhesion improver The photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.

  As the type of the silane coupling agent, various types such as epoxy-based, (meth) acrylic-based, and amino-based ones can be used alone or in admixture of two or more.

  Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, the silane coupling agent of epoxy silanes is mentioned.

  As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are preferable.

(In the above general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.)

  These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

(3) Surfactant As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

  Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.

  In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(4) Pigment derivatives As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketo Derivatives such as pyrrolopyrrole and dioxazine are listed, but quinophthalone is preferred.

  Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

  Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.

<Ingredient compounding amount in photosensitive resin composition>
In the photosensitive resin composition of the present invention, an alkylene oxide group-containing compound (a) (hereinafter sometimes referred to as “component (a)”) and a photopolymerizable monomer having three or more ethylenically unsaturated bonds ( The total content of b) (hereinafter sometimes referred to as “component (b)”) is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive resin composition. It is. When the total content of the component (a) and the component (b) is too large, the permeability of the developer into the exposed area becomes high, and it may be difficult to obtain a good image. In addition, the minimum of content of the sum total of a component (a) and a component (b) is 1 weight% or more normally with respect to the total solid of the photosensitive resin composition, Preferably it is 5 weight% or more.

  The content ratio of the alkylene oxide group-containing compound (a) and the photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds in the photosensitive resin composition of the present invention is usually the component (a) and the component. Component (a) is 3 to 50% by weight, preferably 5 to 40% by weight, based on 100% by weight of (b). When the component (a) is less than 3% by weight, high sensitivity may not be obtained. When the component (a) is more than 50% by weight, the solubility becomes too high, and production problems may occur.

  The content of the alkali-soluble resin (c) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably based on the total solid content of the photosensitive resin composition of the present invention. 80% by weight or less. When the content of the alkali-soluble resin (c) is extremely small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the other hand, if the content of the alkali-soluble resin (c) is too large, the permeability of the developer into the exposed area tends to be high, and the sharpness and adhesion of the pixel may be lowered.

  The content of the photopolymerization initiator (d) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.00% by weight, based on the total solid content of the photosensitive resin composition of the present invention. 7% or more, usually 30% by weight or less, preferably 20% by weight or less. When the content of the photopolymerization initiator (d) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure tends to be induced.

  When using an accelerator with a photoinitiator (d), content of an accelerator is 0 weight% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.02 weight%. In the above, it is usually 10% by weight or less, preferably 5% by weight or less, and the accelerator is usually 0.1 to 50% by weight, particularly 0.1 to 20% by weight, based on the photopolymerization initiator (d). It is preferable to use in proportion.

  If the blending ratio of the photopolymerization initiator component composed of the photopolymerization initiator (d) and the accelerator is extremely low, it may cause a decrease in sensitivity to the exposure light beam. The solubility in the liquid may be reduced, leading to poor development.

  The blending ratio of the sensitizing dye in the photosensitive resin composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably in the total solid content in the photosensitive resin composition. 0 to 10% by weight.

  The content of the coloring material (e) can be usually selected in the range of 0 to 70% by weight with respect to the total solid content in the photosensitive resin composition. When the photosensitive resin composition of the present invention contains the color material (e), the content of the color material (e) is more preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. If the content of the color material (e) is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control during liquid crystal cell formation. Conversely, if the content of the color material (e) is too large, sufficient image formability may not be obtained.

  In the photosensitive resin composition, the amount of the alkali-soluble resin (c) with respect to the coloring material (e) is usually in the range of 20 to 500% by weight, preferably 30 to 300% by weight, more preferably 40 to 200% by weight. It is. If the content ratio of the alkali-soluble resin (c) with respect to the colorant (e) is too low, the solubility of the unexposed portion in the developing solution is lowered, and it is easy to induce development failure. It becomes difficult to obtain.

  Content of a dispersing agent (f) can be normally selected in the range of 0 to 50 weight% in solid content of the photosensitive resin composition. When the photosensitive resin composition of the present invention contains the dispersant (f), the content of the dispersant (f) is more preferably 1 to 30% by weight, and particularly preferably 3 to 20% by weight. Further, the content of the dispersant (f) is usually 5% by weight or more, particularly 10% by weight or more, and usually 200% by weight or less, particularly 80% by weight or less based on the coloring material (e). preferable. If the content of the dispersant (f) is too small, sufficient dispersibility may not be obtained. If the content is too large, the proportion of other components is relatively reduced, resulting in a decrease in color density, sensitivity, film formability, and the like. Tend to.

  In particular, as the dispersant (f), it is preferable to use a polymer dispersant and a pigment derivative in combination. In this case, the blending ratio of the pigment derivative is based on the total solid content of the photosensitive resin composition of the present invention. It is usually 1% by weight or more and usually 10% by weight or less, preferably 5% by weight or less.

  When using an adhesion improving agent, the content thereof is usually 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.4%, based on the total solid content in the photosensitive resin composition. ~ 2% by weight. If the content of the adhesion improver is less than the above range, the effect of improving the adhesion may not be sufficiently obtained. If the content is too large, the sensitivity may be lowered, or the residue may remain as a defect after development. .

  Moreover, when using surfactant, the content is 0.001-10 weight% normally with respect to the total solid in the photosensitive resin composition, Preferably it is 0.005-1 weight%, More preferably, it is 0. 0.01 to 0.5 wt%, most preferably 0.03 to 0.3 wt%. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.

  In addition, the photosensitive resin composition of this invention is prepared using the above-mentioned organic solvent so that the solid content concentration may become 5 to 50 weight% normally, Preferably it becomes 10 to 30 weight%.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.

  When the color material (e) is used, it is usually preferable to disperse the color material (e) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the coloring material (e) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, when a black color material is used as the color material (e), it contributes to an improvement in light shielding ability.

  The dispersion treatment is usually preferably performed in a system in which a part of or all of the coloring material (e), the organic solvent, and, if necessary, the dispersant (f) and the alkali-soluble resin (c) are used in combination. (Hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink”.) In particular, when a polymer dispersant is used as the dispersant (f), the obtained ink and This is preferable since the thickening of the resist over time is suppressed (excellent dispersion stability).

  In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing the above-described components.

  When the color material (e) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[Color filter]
Next, a color filter using the photosensitive resin composition of the present invention will be described according to its production method.

(1) Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meta ) Thermosetting resin sheets such as acrylic resins, or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix A color matrix of the present invention can be produced by providing a black matrix on a transparent substrate, and usually forming red, green, and blue pixel images, and the photosensitive resin composition of the present invention. The product is used as at least one resist forming coating solution of black, red, green, and blue. For the black resist, on the transparent glass surface on the transparent substrate, on the resin black matrix forming surface formed on the transparent substrate for red, green, and blue, each process of coating, heat drying, image exposure, development and thermosetting is performed. The pixel image of each color is formed. A black matrix can be formed in the same manner as described below for forming red, green, and blue pixel images.

(3) Pixel formation
(3-1) Application of photosensitive resin composition After applying the photosensitive resin composition of the present invention on a transparent substrate and drying it, a photomask is superimposed on the coating film, and an image is passed through this photomask. A pixel image is formed by exposure, development, and thermosetting or photocuring as necessary to produce a black matrix. Subsequently, a color filter image can be formed by performing the same operation about the photosensitive resin composition of three colors of red, green, and blue, respectively.

  The photosensitive resin composition for the color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating film is preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.5 to 5 μm, as the film thickness after drying. It is a range.

(3-2) Drying of the coating film The drying of the coating film after applying the photosensitive resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the alkali-soluble resin (c) may be decomposed to induce thermal polymerization and cause poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The color filter according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive resin composition with the light source described above. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C. Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

(3-6) Formation of transparent electrode The color filter is used as a part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as it is. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described color filter of the present invention.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
The organic EL display of the present invention can be produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

  Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Synthesis of raw materials]
<Synthesis Example 1-1: Synthesis of carboxyl group-containing epoxy acrylate resin (c-I)>

50 g of an epoxy compound having the above structure (epoxy equivalent 247), 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine, and 0.05 g of paramethoxyphenol were attached to a thermometer, a stirrer, and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by weight of the above epoxy acrylate solution, 0.8 part by weight of trimethylolpropane (TMP), 4.1 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 2.8 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution became transparent, it was diluted with methoxybutyl acetate and prepared so as to have a solid content of 50% by weight, and the carboxyl group having an acid value of 131 mgKOH / g and a polystyrene equivalent weight average molecular weight (Mw) of 4000 measured by GPC. A contained epoxy acrylate resin (c-I) was obtained.

<Synthesis Example 2: Synthesis of Photopolymerization Initiator (d-I)>
(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to give 0.79 g of a light yellow solid photopolymerization initiator (d-I). ) The structure of the photopolymerization initiator (d-I) is shown below.

<Production Example 1: Preparation of carbon black ink (e-I)>
Color Carbon black (manufactured by Mitsubishi Chemical Corporation "MA-8", an average particle diameter of 24 [mu] m, DBP oil absorption of 57cm ^3/100 g) 25 parts by weight, Disperbyk-167 (the BYK Co.) 5 parts by weight of a dispersing agent, Further, propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content concentration was 35% by weight. The total weight of the dispersion was 181 g.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and three times the weight of the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter to prepare ink (e-I).

[Alkylene oxide group-containing compound (a)]
The following alkylene oxide group-containing compounds (a-I) to (a-V) were prepared.
a-I: Compound represented by the following structure (a11) (A-PTMG-65 (manufactured by Shin-Nakamura Chemical Co., Ltd.))
a-II: polytetramethylene oxide average molecular weight 1900-2120 (manufactured by Wako Pure Chemical Industries, Ltd.))
a-III: Compound represented by the following structure (a12) (A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.))
a-IV: Compound represented by the following structure (a13) (AM-130G (manufactured by Shin-Nakamura Chemical Co., Ltd.))
aV: Compound represented by the following structure (a14) (APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.))

[Photopolymerizable monomer having three or more ethylenically unsaturated bonds (b)]
b-I: Dipentaerythritol hexaacrylate

[Other additives]
g-I: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd., methacryloyl group-containing phosphate)
g-II: F-475 (manufactured by DIC, surfactant)

[Examples 1-2 and Comparative Examples 1-4]
(1) Preparation of resist (photosensitive resin composition) Using ink e-1 prepared in Production Example 1, each component was added so that the ratio in the solid content was the mixing ratio in Table 1-A. An organic solvent was added so that the solid content was 17% by weight, and the mixture was stirred and dissolved to prepare a black resist.

(2) Evaluation of resist The black resist prepared in (1) was applied to a glass substrate with a spin coater so that the resist film thickness after drying was 1.5 μm, and dried on a hot plate at 100 ° C. for 1 minute. did. Next, this sample was image-exposed with a high-pressure mercury lamp through a negative type mask having a linear pattern of openings 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30 μm (illuminance 30 mW). / Cm ² , time 1.7 seconds). At this time, the distance between the sample and the linear mask was 200 μm. Then, a resist pattern was obtained by spray development at a temperature of 23 ° C. using a KOH aqueous solution having a concentration of 0.04% by weight.
The time at which the unexposed area is melted and the glass surface appears is taken as the melting time. The mask opening 10 and the line width of the pattern of 30 μm when developed with a developing time 1.4 times and 1.8 times the melting time are observed with a microscope. It was measured. Further, the minimum mask size in which a pattern remained when developing with a development time twice as long as the dissolution time was confirmed. The results are shown in Table 1-B.

Tables 1-A and B show that according to the present invention, a photosensitive resin composition having high sensitivity and excellent adhesion to a substrate is provided.
On the other hand, in Comparative Example 1 which does not include an alkylene oxide group-containing compound and Comparative Examples 1 to 4 which does not include a compound having a structure represented by the general formula (a1) as an alkylene oxide group-containing compound, Example 1 , 2 has a lower sensitivity and lower adhesion to the substrate.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (14)

A photosensitive resin composition comprising (a) an alkylene oxide group-containing compound, (b) a photopolymerizable monomer having three or more ethylenically unsaturated bonds, (c) an alkali-soluble resin, and (d) a photopolymerization initiator. Because
(A) The photosensitive resin composition characterized by an alkylene oxide group containing compound being represented by the following general formula (a1).

(In the general formula (a1), R ¹ represents an alkylene group having 4 to 6 carbon atoms, and A ¹ and A ² are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylphenyl group, a phenyl group, or (meta ) Represents an acryloyl group, n represents an integer of 2 to 50, and A ¹ and A ² may be the same or different. (C) The alkali-soluble resin contains the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2), The photosensitive resin composition according to claim 1.
<Alkali-soluble resin (c1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this. (C) Alkali-soluble resin contains the following alkali-soluble resin (c1 ') and / or alkali-soluble resin (c2'), The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.
<The following alkali-soluble resin (c1 ′)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to any one of the following C1-C4 epoxy resins, and a polybasic acid and / or anhydride thereof An alkali-soluble resin obtained by reacting.
<The following alkali-soluble resin (c2 ′)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to any one of the following C1-C4 epoxy resins, and further a polyhydric alcohol, a polybasic acid and / or Or alkali-soluble resin obtained by making the anhydride react.
C1: Epoxy resin represented by the following general formula (C1)

(In the general formula (C1), a represents an average value and represents a number of 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ¹¹ present in one molecule may be the same or different.
C2: Epoxy resin represented by the following general formula (C2)

(In the above general formula (C2), b represents an average value and represents a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , A phenyl group, a naphthyl group, or a biphenyl group, wherein a plurality of R ²¹ present in one molecule may be the same or different.
C3: Epoxy resin represented by the following general formula (C3)

(In the general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2), provided that the molecular structure includes one or more adamantane structures. Represents an integer of 2 or 3.)

(In the above general formulas (C3-1) and (C3-2), R ^{31 to} R ³⁴ and R ^{35 to} R ³⁷ are each independently an adamantyl group optionally having a substituent, a hydrogen atom, a substituent, The alkyl group having 1 to 12 carbon atoms which may have a group, or a phenyl group which may have a substituent.
C4: Epoxy resin represented by the following general formula (C4)

(In the above general formula (C4), p and q each independently represent an integer of 0 to 4, R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ are each independently. And x and y each independently represents an integer of 0 or more.)   The photosensitive resin composition according to claim 1, further comprising (e) a coloring material.   The photosensitive resin composition according to claim 1, wherein (e) the color material is a black color material.   The photosensitive resin composition according to any one of claims 1 to 5, further comprising (f) a dispersant.   The photosensitive resin composition according to any one of claims 1 to 6, wherein (f) the dispersant is a basic polymer dispersant.   The content of the alkylene oxide group-containing compound (a) is 3 to 50% by weight based on 100% by weight of the total of the alkylene oxide group-containing compound (a) and the photopolymerizable monomer (b) having three or more ethylenically unsaturated bonds. The photosensitive resin composition according to claim 1, wherein the composition is%. The photosensitive resin composition according to any one of claims 1 to 8, wherein in the general formula (a1) representing the alkylene oxide group-containing compound (a), R ¹ is an alkylene group having 4 carbon atoms. object.   The alkylene oxide group-containing compound (a) is a compound selected from polytetramethylene glycol, polytetramethylene glycol di (meth) acrylate, or polytetramethylene glycol mono (meth) acrylate. The photosensitive resin composition as described in 2.   A cured product obtained by curing the photosensitive resin composition according to claim 1.   The color filter which has a pixel or black matrix formed using the photosensitive resin composition of any one of Claims 1 thru | or 10 on a transparent substrate.   A liquid crystal display device produced using the color filter according to claim 12.   An organic EL display produced using the color filter according to claim 12.

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