JP6157111B2 - Colored photosensitive resin composition, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition, a color filter, and a color liquid crystal display element.

  Color filters used for liquid crystal panels, image sensors, and the like are generally manufactured by a lithography method. In this lithography method, a black photosensitive resin composition is first applied to a glass substrate, and then exposed and developed to form a black matrix. Next, for each photosensitive resin composition to which organic pigments of green, blue, and red are added, by repeating application, exposure, and development, a pattern of each color is formed at a predetermined position to manufacture a color filter.

  At this time, if the heat resistance of the photosensitive resin composition to which the organic pigment is added is low, foreign matters are generated in the heating process, resulting in unevenness on the surface and poor contrast. Therefore, a composition having high heat resistance is desired. ing. For example, Patent Document 1 proposes using a colored composition to which a compound having a specific cyclic amidine structure is added. Since the compound having a cyclic amidine structure used here has both a cyclic amidine moiety that increases the affinity with the colorant and a characteristic group that increases the affinity with the binder component, the colored photosensitive resin composition to which this compound is added In US Pat. No. 5,637, it is reported that the dispersion stability is high, the amount of a dispersant such as a polymer dispersant can be reduced, the hue and contrast ratio are excellent, and the heat resistance is improved.

International Publication No. 2011/13318

  However, the colored photosensitive resin composition to which the compound having the cyclic amidine structure is added has a problem that the adhesion to the glass substrate is insufficient.

  The present invention has been made in view of the above problems, and is a colored photosensitive resin composition having excellent chromaticity characteristics, contrast ratio, heat resistance, and improved adhesion to a glass substrate, and the colored photosensitive resin composition. It is an object to provide a color filter formed using a color liquid crystal display element and a color liquid crystal display element including the color filter.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by containing a specific compound, and have completed the present invention.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^１及びＲ^２の少なくとも一方は有機基を示す。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^３は、単結合又は有機基を示す。Ｒ^４及びＲ^５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。ただし、Ｒ^６及びＲ^７が水酸基となることはない。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^１０は、水素原子又は有機基を示す。） A first aspect of the present invention is a colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the following formula (1), and an organic pigment. It is a thing.

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group .R ^6, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.)

  The second aspect of the present invention is a color filter comprising a colored layer formed using the colored photosensitive resin composition according to the present invention, and the third aspect of the present invention is a color filter according to the present invention. This is a color liquid crystal display element having a filter.

  According to the present invention, a colored photosensitive resin composition having excellent chromaticity and contrast ratio, excellent heat resistance, and high adhesion to a glass substrate can be obtained. Therefore, the colored photosensitive resin composition of the present invention includes various color filters for color liquid crystal display elements, color filters for solid-state image sensors, color filters for organic EL display elements, and color filters for electronic paper. It can be suitably used for the production of a color filter.

≪Colored photosensitive resin composition≫
The colored photosensitive resin composition of the present invention contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the above formula (1), and an organic pigment. First, these components will be described.

<Alkali-soluble resin>
It does not specifically limit as alkali-soluble resin which concerns on this invention, A conventionally well-known alkali-soluble resin can be used. This alkali-soluble resin may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.
In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a glass substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 2.38% by mass. When dissolved in an aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, it is dissolved in a film thickness of 0.01 μm or more.

  As the alkali-soluble resin having an ethylenically unsaturated group, for example, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

  Among these, the resin represented by the following formula (a-1) is preferable. The resin represented by the formula (a-1) itself is preferable in terms of high photocurability.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the above formula (a-2), each R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, each R ^a2 independently represents a hydrogen atom or a methyl group, W ^a represents a single bond or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

Moreover, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or a polybasic acid. (Meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine Epoxy resins, and epoxy resins such as dihydroxybenzene type epoxy resin, can also be used (meth) epoxy obtained by reacting acrylic acid (meth) acrylate resin.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate.

  On the other hand, as an alkali-soluble resin having no ethylenically unsaturated group, an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound are at least copolymerized. It is possible to use a resin obtained by the above process.

  Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl Α-alkyl acrylic acid epoxy alkyl esters such as α-ethylacrylic acid 6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; Etc. It is. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulae.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^a4 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R ^a5 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, and more preferably 5 to 25% by mass. Moreover, it is preferable that the ratio of the structural unit derived from the said epoxy-group-containing unsaturated compound is 71-95 mass%, and it is more preferable that it is 75-90 mass%. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound is 1-25 mass%, It is more preferable that it is 3-20 mass%, It is 5-15 mass%. More preferably. By setting the above range, the adhesiveness of the colored photosensitive resin composition to the glass substrate and the strength after curing of the colored photosensitive resin composition are increased while the alkali solubility of the obtained resin is moderate. Can do.

  The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  The content of the alkali-soluble resin is preferably 10 to 50% by mass and more preferably 20 to 40% by mass with respect to the solid content of the colored photosensitive resin composition. Solid content here is components other than a solvent. If the content of the alkali-soluble resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored photosensitive resin composition may be decreased. Since the organic pigment concentration decreases, it may be difficult to achieve the target color concentration as a thin film.

<Photopolymerizable monomer>
The colored photosensitive resin composition of the present invention contains a photopolymerizable monomer. Photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  The content of the photopolymerizable monomer in the present invention is preferably 10 to 50% by mass and more preferably 20 to 40% by mass with respect to the solid content of the colored photosensitive resin composition. In this case, if the content of the photopolymerizable monomer is too small, sufficient curability may not be obtained. If the content is too large, the alkali developability deteriorates and the unexposed portion on the glass substrate or light shielding. There is a tendency that dirt, film residue, etc. are likely to occur on the layer.

<Photopolymerization initiator>
The colored photosensitive resin composition of the present invention contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided. Here, the radiation is a concept including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

  The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of a photopolymerizable monomer by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray radiation.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones. Examples thereof include a compound, a polynuclear quinone compound, a diazo compound, and an imide sulfonate compound.

  In the present invention, preferred photopolymerization initiators include oxime ester compounds represented by the following formula (2).

（式中、Ｒ^ｂ１及びＲ^ｂ２は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、Ｒ^ｂ３は、水素原子、又は炭素数１〜６のアルキル基であり、ＡはＳ又はＯであり、ｎは０〜４の整数であり、ｐは０又は１であり、ｑは０〜４の整数である。）

(Wherein R ^b1 and R ^b2 are groups selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, and R ^b3 is a hydrogen atom or a carbon number of 1 -6 alkyl group, A is S or O, n is an integer of 0-4, p is 0 or 1, q is an integer of 0-4.)

In the above formula (2), when R ^b1 is a monovalent organic group, R ^b1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ^b1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Or an amino group substituted with 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like. When n is an integer of 2 to 4, R ^b1 may be the same or different. Moreover, the carbon number of the substituent does not include the carbon number of the substituent that the substituent further has.

When ^Rb1 is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Further, when R ^b1 is an alkyl group, it may be linear or branched. When R ^b1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain.

When R ^b1 is an alkoxy group, the carbon number thereof is preferably 1-20, and more preferably 1-6. Further, when R ^b1 is an alkoxy group, it may be linear or branched. When R ^b1 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain.

When R ^b1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6.

When R ^b1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7.

When R ^b1 is an alkoxycarbonyl group, the carbon number thereof is preferably 2-20, and more preferably 2-7.

When R ^b1 is a phenylalkyl group, the carbon number is preferably 7 to 20, and more preferably 7 to 10. Moreover, when ^Rb1 is a naphthyl alkyl group, the carbon number is preferably 11 to 20, and more preferably 11 to 14. When R ^b1 is a phenylalkyl group or a naphthylalkyl group, R ^b1 may further have a substituent on the phenyl group or naphthyl group.

When R ^b1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. When R ^b1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b1 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 2 carbon atoms. 20 saturated aliphatic acyl groups, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted C 7-20 phenylalkyl groups, substituents A naphthyl group that may have a substituent, a naphthoyl group that may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms that may have a substituent, a heterocyclyl group, and the like. Specific examples of these suitable organic groups are the same as those for R ^b1 .

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^b1 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Position R ^b1 is bonded to the phenyl group, the phenyl group R ^b1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

When R ^b2 in the formula (2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. As a suitable example in case ^Rb2 is an organic group in Formula (2), a C1-C6 alkyl group; a C1-C6 alkoxy group; a C2-C7 saturated aliphatic acyl group; An alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms A dialkylamino group; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group.

In R ^b2 , substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In the formula (2), q is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when q is 1, binding position of R ^b2, to the bond to the phenyl group R ^b2 are bonded is bonded to the sulfur atom is preferably in the para position.

^Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in R ^b2 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b2 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b2 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^b3 in Formula (2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When R ^b3 is a methyl group, the photopolymerization initiator composed of the compound represented by the formula (2) is particularly excellent in sensitivity.

Among the oxime ester compounds represented by formula (2), particularly preferred compounds include compounds represented by the following formula.

  As photopolymerization initiators used in the present invention, in addition to the above oxime ester compounds, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4- Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Nophenyl) -butan-1-one, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4 -Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxy Carbonyl) oxime, methyl o-benzoylbenzoate, 2,4-di Ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthio Xanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercapto Benzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) Midazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4 '-Bisdiethylaminobenzophenone (ie ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -N- Tyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylamino Benzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-a Lysinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2 -[2- (3,4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trick (Loromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) ) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-) 4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in admixture of two or more.

  In this invention, it is preferable that content of a photoinitiator is 1-20 mass% with respect to solid content of a coloring photosensitive resin composition, and it is more preferable that it is 1-10 mass%. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be peeled off from the glass substrate during development. .

<Compound represented by Formula (1)>
The colored photosensitive resin composition according to the present invention contains a compound represented by the following formula (1). This compound has good solubility in an organic solvent, and can generate a base upon irradiation or heating to improve hue, contrast ratio, heat resistance, and adhesion to a glass substrate.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

Examples of the organic group in R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. It is done. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) —, —C (═NR) —: R is A hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group of R ¹ and R ² includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond ( -N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group. , Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy Group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether Group, an amino group _{(-NH 2, -NHR, -NRR '} : R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic groups of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups. Group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Among the above, as R ¹ and R ² , at least one of them is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a heterocycloalkyl group having 2 to 20 carbon atoms bonded to each other. Alternatively, it preferably forms a heteroaryl group. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group, and examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include groups in which one hydrogen atom has been removed from an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, and the like. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified for R ¹ and R ² . Further, this organic group may be either linear or branched.

Among these, R ³ is preferably a single bond, or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group;

Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Among these, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group , Amino group is preferably a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, A sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group is shown.
Examples of the organic group for R ⁶ , R ⁷ , R ⁸ , and R ⁹ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the above formula (1), R ⁶ and R ⁷ do not become a hydroxyl group.

Two or more of R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For ^{example, R 6, R 7, R} 8, and ^{R 9} may combine two or more of ^{them, R 6, R 7, R} 8, and share an atom of the benzene ring ^{to which R 9} is attached A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. A cycloalkenyl group, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group, C1-C10 acyl group, C2-C11 ester group, C6-C20 Aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, nitro On the basis Preferably there is.

In addition, as R ⁶ , R ⁷ , R ⁸ , and R ⁹ , two or more of them are bonded to share a benzene ring atom to which R ⁶ , R ⁷ , R ⁸ , and R ⁹ are bonded. In the case where condensed rings such as naphthalene, anthracene, phenanthrene, and indene are formed, it is preferable from the viewpoint that the absorption wavelength becomes longer.

More preferably, all of R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a nitro group, and the remaining 3 One is a hydrogen atom.

In the formula ^{(1), R 10} represents a hydrogen atom or an organic group.

Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Since the compound represented by the above formula (1) has an —OR ¹⁰ group at the para-position of the benzene ring, the solubility in a solvent is good.

Among these, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

  Among the compounds represented by the above formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  In this invention, the compound represented by the said Formula (1) can be used individually or in mixture of 2 or more types.

  Moreover, it is preferable that it is 1-100 mass parts with respect to 100 mass parts of said photoinitiators, and, as for content of the compound represented by said Formula (1), it is more preferable that it is 5-50 mass parts. . By using the compound represented by the formula (1) within such a range, a colored photosensitive resin composition having excellent contrast ratio and heat resistance and high adhesion to a glass substrate can be obtained.

<Organic pigment>
The colored photosensitive resin composition of the present invention contains an organic pigment. The organic pigment is not particularly limited. For example, the organic pigment is a compound classified as “Pigment” in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color It is preferable to use an index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  In the present invention, the organic pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  The content of the organic pigment is preferably 10 to 200% by mass, preferably 50 to 150% by mass with respect to the solid content of the colored photosensitive resin composition, from the viewpoint of forming a pixel having excellent transparency and color purity. More preferably.

  In addition, it is preferable to add the organic pigment to the colored photosensitive resin composition after making the dispersion liquid dispersed at an appropriate concentration using a dispersant. As the known dispersant, a polymer dispersant is preferable, and examples thereof include an acrylic copolymer dispersant, a polyurethane dispersant, a polyester dispersant, a polyethyleneimine dispersant, and a polyallylamine dispersant. Of these, polyurethane dispersants are preferred. When these polymer dispersants are used, the dispersibility and dispersion stability of the organic pigment can be improved, and the hue, contrast ratio, and heat resistance can be improved.

<Solvent>
The colored photosensitive resin composition of the present invention can contain a solvent. As the solvent used in the present invention, the compound represented by the above formula (1), the organic pigment, and other components described later are dispersed or dissolved, and do not react with these components and have appropriate volatility. Anything is acceptable.

  Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol The Other ethers such as til ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N- Examples include amides such as dimethylformamide and N, N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

  Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone and 3-methoxybutyl acetate are represented by the above formula (1 ) Is preferable because propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferable. .

  The content of the solvent is preferably such that the total concentration of the total solid content of the colored photosensitive resin composition is 5 to 30% by mass from the viewpoint of the coating property and stability of the resulting colored photosensitive resin composition. The quantity which becomes 10-20 mass% is more preferable.

The colored photosensitive resin composition of this invention can also contain various additives as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio It can be mentioned the residue improving agents such as Le.

  In the present invention, the colored photosensitive resin composition can be prepared by an appropriate method. As a preferred method for preparing a colored photosensitive resin composition, an organic pigment is optionally dissolved in a solvent in the presence of a compound represented by the above formula (1) and other dispersant added as necessary. Along with a part of the resin, for example, a bead mill, a roll mill or the like is mixed and dispersed while being pulverized to obtain a dispersion. Next, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and the like are necessary for this dispersion. Depending on the method, an additional solvent or additive may be further added and mixed for mixing.

  According to the colored photosensitive resin composition thus prepared, it is possible to form a pixel having a good color tone, a high contrast ratio, excellent heat resistance, and improved adhesion to a glass substrate. The colored photosensitive resin composition is excellent in storage stability and alkali developability.

≪Color filter, color liquid crystal display element≫
The color filter according to the present invention comprises a colored layer formed using the colored photosensitive resin composition according to the present invention. A coating film is formed using a colored photosensitive resin composition on a glass substrate or a glass substrate on which a light-shielding layer having a desired pattern has been previously formed, and the coating film is irradiated with radiation in a predetermined pattern and developed. By doing so, pixels of the color filter can be formed.

  The color liquid crystal display element according to the present invention comprises the color filter of the present invention.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited at all by these Examples.
<Compound represented by the above formula (1)>
As a compound represented by the above formula (1), a compound 1 represented by the following formula was prepared. The synthesis method of this compound 1 is shown below.

3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), diethylamine 2.41 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 1 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

<Synthesis of alkali-soluble resin>
A flask equipped with a condenser and a stirrer was charged with 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 15 parts of styrene. Part by mass, 35 parts by mass of benzyl methacrylate, 10 parts by mass of glycerol monomethacrylate, 25 parts by mass of N-phenylmaleimide and 2.5 parts by mass of α-methylstyrene dimer as a chain transfer agent were charged and purged with nitrogen. Thereafter, the sales were gradually expanded, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution is raised to 100 ° C., 0.5 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) is added, and further polymerized for 1 hour, whereby a binder resin solution (solid) Partial concentration = 33.0%). The obtained resin was Mw = 10,000 and Mn = 6,000. This resin is referred to as “alkali-soluble resin (D1)”.

[Example 1]
<Preparation of organic pigment dispersion>
15 parts by weight of Pigment Red 254 as an organic pigment, 5 parts by weight of Compound 1, 5 parts by weight of a commercially available dispersant S76500 (manufactured by Lubrizol Corp.) (in terms of solid content), and propylene glycol monomethyl ether acetate as a solvent 75 parts by mass were treated with a bead mill to prepare an organic pigment dispersion (A-1).

<Preparation of colored photosensitive resin composition>
100 parts by mass of the obtained organic pigment dispersion (A-1), 50 parts by mass of alkali-soluble resin (D1) (in terms of solid content), 30 parts by mass of dipentaerythritol hexaacrylate as a photopolymerizable monomer, and as a photopolymerization initiator A colored photosensitive resin composition (CR1) having a solid content concentration of 15% by mass was prepared by mixing 10 parts by mass of an oxime ester compound represented by the following formula and propylene glycol monomethyl ether acetate as a solvent.

<Evaluation of chromaticity characteristics and contrast ratio>
The colored photosensitive resin composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, each coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m ² using a high-pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a cured film for evaluation.
With respect to the obtained three cured films, chromaticity coordinate values (x, y) in the CIE color system were measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view. . From the measurement results, a chromaticity coordinate value y and a stimulus value (Y) at a chromaticity coordinate value x = 0.650 were obtained. The evaluation results are shown in Table 1.
Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and a luminance meter LS-100 (Minolta) The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value x = 0.650 was obtained. The evaluation results are shown in Table 1.

<Evaluation of heat resistance>
The colored photosensitive resin composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film having a thickness of 2.5 μm.
Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to each coating film with the exposure amount of 2,000 J / m < ² > using the high pressure mercury lamp. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 270 ° C. for 60 minutes to form a cured film for evaluation.
Three different places on the obtained cured film were observed with an optical microscope (magnification: 200 times) to confirm the presence or absence of foreign matter. Table 1 shows the number of foreign objects observed in one field of view. If foreign matter adheres on the pixel, it may cause deterioration of chromaticity characteristics and a decrease in contrast, for example.

<Evaluation of storage stability>
The viscosity immediately after the preparation of the colored photosensitive resin composition (CR1) was measured using an E-type viscometer (manufactured by Tokyo Keiki). Further, the colored photosensitive resin composition (CR1) was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer. Then, the increase rate of the viscosity after storage for 14 days with respect to the viscosity immediately after the preparation is calculated. When the increase rate is less than 5%, “A”, when 5% or more and less than 10%, “B”, 10% or more The case was evaluated as “C”. The evaluation results are shown in Table 1.

<Evaluation of adhesion to glass substrate>
The adhesion of the colored photosensitive resin composition (CR1) to the glass substrate was evaluated by the size of the minimum adhesion pattern size after development. When the minimum adhesion pattern size after development is 1 μm or more and less than 5 μm, “A”, when it is 5 μm or more and less than 10 μm, “B”, when it is 10 μm or more but less than 15 μm, “C”, and when it is 15 μm or more but less than 20 μm, D ". The evaluation results are shown in Table 1.

[Comparative Example 1]
An organic pigment was prepared in the same manner as in Example 1 except that Compound 1 used in the preparation of the organic pigment dispersion in Example 1 was changed to 1,8-diazabicyclo [5.4.0] undec-7-ene. A dispersion (A-2) was prepared. Next, a colored photosensitive resin composition (CR2) was prepared in the same manner as in Example 1 except that (A-2) was used instead of the organic pigment dispersion (A-1). The colored photosensitive resin composition (CR2) was evaluated for chromaticity characteristics, contrast ratio, heat resistance, storage stability, and adhesion to a glass substrate in the same manner as (CR1). The evaluation results are shown in Table 1.

  As can be seen from Table 1, the colored photosensitive resin composition containing the compound represented by the above formula (1) is excellent in chromaticity characteristics, contrast ratio, heat resistance and storage stability, and further adhered to a glass substrate. It was a composition with high property.

Claims (3)

A colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the following formula (1), and an organic pigment, wherein the photopolymerization start The colored photosensitive resin composition whose agent is an oxime ester compound represented by the following formula (2).

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond, R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a mercapto group. , Sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group. , Sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, provided that R ⁶ and R ⁷ do not become a hydroxyl group, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ represents a hydrogen atom or an organic group.)

(Wherein R ^b1 and R ^b2 are groups selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, and R ^b3 is a hydrogen atom or a carbon number of 1 -6 alkyl group, A is S or O, n is an integer of 0-4, p is 0 or 1, q is an integer of 0-4.) A color filter provided with the colored layer formed using the colored photosensitive resin composition of Claim 1 . A color liquid crystal display device comprising the color filter according to claim 2 .