KR100928762B1 - Coloring photosensitive resin composition - Google Patents

Abstract

It provides the colored photosensitive resin composition with more ink repellency.

As a coloring photosensitive resin composition containing a photopolymerizable compound (A), ink repellent compound (B), a photoinitiator (C), and a coloring agent (D), the said ink repellent compound (B) is an epoxy-group containing acrylic monomer. After reacting an ethylenically unsaturated group containing carboxylic acid compound (b3) with the copolymer which copolymerized (b1) and the fluorine-type monomer (b2) copolymerizable with the said epoxy group containing acrylic monomer (b1) at least, polybasic acid anhydride (b4) is made to react. It is an epoxy acrylate obtained by making it react further.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to colored photosensitive resin compositions, and in particular, to colored colored photosensitive resin compositions which are very suitable for use in forming a black matrix of color filters.

Display bodies, such as a liquid crystal display, have a structure which sandwiches a liquid crystal layer between two board | substrates with which the mutually opposing electrode was formed. And inside the one board | substrate, the color filter which has the pixel area which consists of each color, such as red (R), green (G), blue (B), is formed. In this color filter, a black matrix is usually formed in a matrix so as to partition pixel areas of R, G, and B colors due to contrast enhancement, light leakage prevention, and the like.

Generally, color filters are manufactured by lithography. In this lithography method, first, a black photosensitive resin composition is applied to a substrate, followed by exposure and development to form a black matrix. Next, by repeating application | coating, exposure, and image development for each photosensitive resin composition of each of R, G, and B colors, a pattern of each color is formed in a predetermined position and a color filter is manufactured.

Moreover, in recent years, in order to improve the productivity of a color filter, the method of manufacturing a color filter by the ink jet method is examined. In this inkjet method, a black matrix is first formed by the lithography method. Next, color filters are produced by discharging ink of R, G, and B colors from the inkjet nozzles to respective regions partitioned by the black matrix, and curing the collected ink with heat or light.

By the way, in the photosensitive resin composition used to form the black matrix in this inkjet method, in order to prevent mixing of the ink between adjacent pixel regions and the like, it is necessary to use an ink solvent such as water or xylene ( (I) So-called ink repellent which is solvent property is demanded.

As a photosensitive resin composition which has such ink repellency, For example, following patent document 1 contains the C20 or less alkyl group in which at least 1 of a hydrogen atom was substituted by the fluorine atom (However, the said alkyl group contains ether-like oxygen. A negative type photosensitive resin composition containing a polymer unit having a polymerizable unit having a polymerizable unit having a polymerizable unit having an ethylene double bond and a repellent agent comprising a polymerizable unit having an ethylene double bond is disclosed. In this negative photosensitive resin composition, ink repellency is acquired by the fluoroalkyl group made from ink repellents. In addition, since the ink repellent agent has a polymerized unit having an ethylenic double bond, the ink repellent is cured by light irradiation and ink repellency is continued.

[Patent Document 1] International Publication No. 2004/042474 Pamphlet

However, in the negative photosensitive resin composition described in this patent document 1, although ink repellency can be sustained, ink repellency itself is not still satisfactory and it is desired to improve ink repellency further.

This invention is made | formed in view of the above subject, and an object of this invention is to provide the coloring photosensitive resin composition with which ink repellency was improved more.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the inventors found out that a high ink repellency is obtained by using the ink repellent compound which consists of an epoxy acrylate which has a specific structure, and this invention is found. Came to complete.

More specifically, this invention is a coloring photosensitive resin composition containing a photopolymerizable compound (A), an ink repellent compound (B), a photoinitiator (C), and a coloring agent (D), The said ink repellent compound (B) is obtained by reacting an ethylenically unsaturated group-containing carboxylic acid compound (b3) with a copolymer obtained by at least copolymerizing an epoxy group-containing acrylic monomer (b1) and a fluorine monomer (b2) copolymerizable with the epoxy group-containing acrylic monomer (b1). After that, it is an epoxy acrylate (epoxyacrylate) obtained by making the polybasic acid anhydride (b4) react further, The coloring photosensitive resin composition characterized by the above-mentioned is provided.

According to this invention, the coloring photosensitive resin composition with more ink repellency can be provided. This coloring photosensitive resin composition is suitable for use, for example, when forming the black matrix of a color filter.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In this specification, "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" refers to one or both of acrylate and methacrylate.

[Coloring Photosensitive Resin Composition]

The colored photosensitive resin composition which concerns on this invention contains a photopolymerizable compound (A), ink repellent compound (B), a photoinitiator (C), and a coloring agent (D). Hereinafter, each component is demonstrated.

[Photopolymerizable Compound (A)]

A photopolymerizable compound (A) is a substance which superposes | polymerizes and hardens | cures by irradiation of light, such as an ultraviolet-ray. As a photopolymerizable compound (A), resin or monomer which has an ethylene (ethylene) unsaturated group is preferable, and it is more preferable to combine these. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, sclerosis | hardenability can be improved and pattern formation can be made easy. In the present specification, a compound having an ethylenically unsaturated group having a mass average molecular weight of 1000 or more is referred to as "resin having an ethylenically unsaturated group", and a compound having a mass average molecular weight of less than 1000 is referred to as a "monomer having an ethylenically unsaturated group". .

≪Resin having an ethylenically unsaturated group≫

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and ethylene glycol Monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth Ta) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythrate Oligomers polymerized by lithol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc .; obtained by condensation of polyhydric alcohols with monobasic or polybasic acids Polyurethane (meth) obtained by reacting a polyester (meth) acrylate obtained by reacting (meth) acrylic acid to a polyester prepolymer, a compound having a polyol and two isocyanate groups, and then reacting (meth) acrylic acid Acrylate; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin, Bisphenol S type epoxy resin, Fe Or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene Epoxy (meth) acrylate resin etc. which are obtained by making epoxy resin, such as a type | mold epoxy resin, and (meth) acrylic acid react, etc. are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) further react with polybasic acid anhydride (a3) can be used preferably.

<Epoxy compound (a1)>

Examples of the epoxy compound (a1) include glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, and bisphenol F type. , Bisphenol S type, biphenyl type, naphthalene type, fluorene type, phenol novolak type, ortho cresol type epoxy resin, and the like. Especially, biphenyl type epoxy resin is preferable. The biphenyl type epoxy resin has one or more biphenyl skeleton represented by following formula (3) in a principal chain, and has one or more epoxy groups. Moreover, as an epoxy compound (a1), what has two or more epoxy groups is preferable. This epoxy compound (a1) can be used individually or in combination of 2 or more types.

[In Formula (3), some R <^1> represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent each independently, and l is It represents the integer of 1-4.]

Among the biphenyl epoxy resins, epoxy resins represented by the following formula (4) are preferably used, and epoxy resins represented by the following formula (5) are particularly preferably used. By using the epoxy resin of Formula (5), the coloring photosensitive resin composition which is excellent in the balance of sensitivity and solubility, and excellent in the sharpness and adhesiveness of a pixel edge can be provided.

[In formula (4), (5), some R <^2> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent, n represents the integer of 1-4. Indicates. m represents the number of 0-10 as an average value, and it is preferable that it is less than one.]

Moreover, the epoxy resin represented by following formula (6) is also preferably used among biphenyl type epoxy resins. By using the epoxy resin of Formula (6), the coloring photosensitive resin composition excellent in the balance of sensitivity and solubility, and excellent in the sharpness and adhesiveness of a pixel edge can be provided.

[In formula (6), some R <^3> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent. m represents the number of 0-10 as an average value, and it is preferable that it is less than one.]

<Ethylenic unsaturated group containing carboxylic acid compound (a2)>

As the ethylenically unsaturated group-containing carboxylic acid compound (a2), a monocarboxylic acid compound containing a reactive ethylene double bond such as an acryl group or a methacryl group in the molecule is preferable. Examples of such ethylenically unsaturated group-containing carboxylic acid compounds include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, α-cyano cinnamic acid, and cinnamic acid. Can be. This ethylenically unsaturated group containing carboxylic acid compound (a2) can be used individually or in combination of 2 or more types. In addition, as this ethylenically unsaturated group containing carboxylic acid compound (a2), the same thing as the ethylenically unsaturated group containing carboxylic acid compound (b3) mentioned later may be used, and another may be used.

A well-known method can be used as a method of making an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react. For example, an epoxy compound (a1) and an ethylenically unsaturated group-containing carboxylic acid compound (a2) are tertiary amines such as triethyl amine and benzyl ethyl amine, dodecyl trimethyl ammonium chloride, tetramethyl ammonium chloride, and tetraethyl ammonium chloride. And quaternary ammonium salts such as benzyl triethyl ammonium chloride, pyridine, triphenylphosphine, and the like as catalysts in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several ten hours. have.

The usage-amount ratio in reaction of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) is a ratio of the epoxy equivalent of an epoxy compound (a1) and the carboxylic acid equivalent of an ethylenically unsaturated group containing carboxylic acid compound (a2), Usually 1: 0.5-1: 1, Preferably it is 1: 0.8-1: 1.25, More preferably, it is 1: 1. By setting it as said range, there exists a tendency for crosslinking efficiency to improve and it is preferable.

<Polybasic acid anhydride (a3)>

Polybasic acid anhydride (a3) is an anhydride of the carboxylic acid which has two or more carboxyl groups, and the thing containing the compound which has at least two benzene rings can be used. As such polybasic acid anhydride (a3), for example, an acid anhydride having a biphenyl skeleton represented by the following formula (1), and an acid anhydride having two benzene rings represented by the following formula (2) bonded to an organic group Can be mentioned.

[In formula (2), R <^4> represents the alkylene group which may have a C1-C10 substituent.]

By using anhydrides of carboxylic acids having two or more carboxyl groups, at least two benzene rings can be introduced into the photopolymerizable compound (A).

The polybasic acid anhydride (a3) may contain other polybasic acid anhydrides in addition to the acid anhydrides having at least two benzene rings. Examples of other polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, and the like. Pyromellitic acid, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Methyl tetrahydro phthalic anhydride, 4-methyl tetrahydro phthalic anhydride, 3-ethyl tetrahydro phthalic anhydride, 4-ethyl tetrahydro phthalic anhydride is mentioned. These polybasic acid anhydrides can be used individually or in combination of 2 or more types.

A well-known method can be used as a method of making the polybasic acid anhydride (a3) further react after making an epoxy compound (a1) react with an ethylenically unsaturated group containing carboxylic acid compound (a2). In addition, the usage-amount ratio is an equivalence ratio of the number-of-moles of OH group in the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), and the acid anhydride group of polybasic acid anhydride (a3), usually 1: 1: 1: 1: 0.1, Preferably it is 1: 0.8-1: 0.2. By setting it as said range, since there exists a tendency for the solubility to a developing solution to a moderate grade, it is preferable.

The acid value of the resin obtained by further reacting the reactant of the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) with the polybasic anhydride (a3) is preferably 10 to 150 mgKOH / g in terms of resin solid content, and more preferably. Preferably 70-110 mgKOH / g. By setting the acid value of the resin to 10 mgKOH / g or more, sufficient solubility in the developer is obtained, and by setting it to 150 mgKOH / g or less, sufficient curability can be obtained and the surface property can be improved.

Moreover, it is preferable that the mass mean molecular weights of resin are 1000-30000, More preferably, it is 2000-30000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved, and by setting it to 40000 or less, sufficient solubility in a developer can be obtained.

Moreover, as resin which has an ethylenically unsaturated group, resin which has a cardo structure in a molecule | numerator can be used preferably. Since resin which has a cardo structure has high heat resistance and chemical-resistance, it can improve the heat resistance and chemical-resistance of a coloring photosensitive resin composition by using it for a photopolymerizable compound (A). For example, resin represented by following formula (7) can be used preferably.

In formula (7), X is group represented by following formula (8).

In formula (7), Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, claw anhydride It is a residue remove | excluding the carboxylic anhydride group (-CO-O-CO-) from dicarboxylic anhydrides, such as a chlorendic anhydride, methyltetrahydrophthalic anhydride, and a glutaric anhydride.

In Formula (7), Z is two or more of tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and biphenyl ether tetracarboxylic dianhydride. It is the residue remove | excluding the carboxylic anhydride group.

<< monomer having an ethylenically unsaturated group >>

As a monomer which has an ethylenically unsaturated group, there exist a monofunctional monomer and a polyfunctional monomer.

As the monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butyl acrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( Meta) 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, dimethyl Amino (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, And half (meth) acrylates of phthalic acid derivatives. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as a 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 ( Meta) acrylate, butylene glycol di (meth) acrylate, neopentylglycol 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 (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Other (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2, 2-bis (4- (meth) acryloxy diethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloxy Polyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl Ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e. tolylene Diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc., and reactants of 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene Le, there may be mentioned polyhydric alcohols and N- methylol (meth) polyfunctional monomers such as condensates of acrylamide or acrylic tree form, such as Al. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that content of the monomer which has this ethylene (ethylene) unsaturated group is 5-50 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and is preferable.

It is preferable that content of a photopolymerizable compound (A) is 5-50 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and is preferable.

[Ink repellent compound (B)]

The ink repellent compound (B) is a copolymer obtained by copolymerizing at least an epoxy group-containing acrylic monomer (b1) and a fluorine monomer (b2) copolymerizable with the epoxy group-containing acrylic monomer (b1). It is an epoxy acrylate obtained by making an ethylene unsaturated group containing carboxylic acid compound (b3) react, and then making polybasic acid anhydride (b4) react. By using such ink repellent compound (B), the coloring photosensitive resin composition excellent in ink repellency can be provided.

<Epoxy group-containing acrylic monomer (b1)>

As an epoxy-group-containing acrylic monomer (b1), glycidyl (meth) acrylate, the alicyclic epoxy compound represented by following formula (9)-(11), the carboxyl group of (meth) acrylic acid, and the epoxy group of the bifunctional or more functional epoxy compound The monomer etc. which are obtained by making the hydroxyl group or carboxyl group of the acryl-type monomer which have a hydroxyl group and a carboxyl group react with the epoxy group of the bifunctional or more than two functional epoxy compound to the monomer obtained by reaction, and a side chain are mentioned. Especially, glycidyl (meth) acrylate is preferable. These epoxy group containing acrylic monomers (b1) can be used individually or in combination of 2 or more types.

[In Formulas (10) and (11), R ⁵ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 10, and l and n each independently represent an integer of 1 to 3.

It is preferable that content of the unit guide | induced from an epoxy group containing acrylic monomer (b1) is 1-40 mass% with respect to ink repellent compound (B), More preferably, it is the range of 5-15 mass%. By setting it as said range, ink repellency tends to improve and it is preferable.

<Fluorinated monomer (b2)>

As a fluorine-type monomer (b2), what has an ethylenically unsaturated group and is copolymerizable with an epoxy group containing acrylic monomer (b1) is preferable. As such a fluorine-type monomer (b2), the compound etc. which are represented by following formula (12) are mentioned. These fluorine-type monomers (b2) can be used individually or in combination of 2 or more types.

[In Formula (12), X <^1> and X <^2> respectively independently represent a hydrogen atom or a fluorine atom, X <^3> represents a hydrogen atom, a fluorine atom, a methyl group, or a perfluoromethyl group, X <^4> and X ⁵ represents a hydrogen atom, a fluorine atom, or a perfluoromethyl group, Rf represents a fluorine-containing alkyl group having 1 to 40 carbon atoms or an ether bond having 2 to 100 carbon atoms, and a is 0 to 3 And an integer of b and c each independently represent 0 or 1.

It is preferable that content of the unit guide | induced from a fluorine-type monomer (b2) is 30-80 mass% with respect to ink repellent compound (B), More preferably, it is the range of 40-60 mass%. By setting it as said range, since there exists a tendency for compatibility with the other components of ink repellency and colored photosensitive resin composition to become favorable, it is preferable.

Further, in the fluorine-based monomer (b2), - preferably has a group represented by _{(CF 2) r F (r} = 1~10). Moreover, it is more preferable that r is 1-8, and it is more preferable that it is 2-6. By having said group, compatibility with other components of ink repellency and colored photosensitive resin composition tends to become favorable, and it is preferable.

<Other monomer>

In addition to the epoxy group-containing acrylic monomer (b1) and the fluorine monomer (b2), the copolymer may be a copolymer of other monomers as necessary. As such another monomer, the monomer which has the ethylenically unsaturated group mentioned above is mentioned. Especially, an acryl-type monomer is preferable. It is preferable that content of the unit derived from this other monomer is 0-20 mass% with respect to ink repellent compound (B).

It does not specifically limit as a synthesis | combining method of the said copolymer, A well-known method can be used.

<Ethylenic unsaturated group containing carboxylic acid compound (b3)>

As an ethylenically unsaturated group containing carboxylic acid compound (b3), the thing similar to the ethylenically unsaturated group containing carboxylic acid compound (a2) mentioned above can be used. Preferably, at least 1 sort (s) chosen from the group which consists of acrylic acid, methacrylic acid, (beta) -styryl acrylic acid, (beta) -furfuryl acrylic acid, (alpha) -cyano cinnamic acid, and cinnamic acid is used.

A well-known method can be used as a method of making an ethylenically unsaturated group containing carboxylic acid compound (b3) react with the copolymer which copolymerized the epoxy group containing acrylic monomer (b1) and the fluorine monomer (b2) at least. For example, the copolymer and the ethylenically unsaturated group-containing carboxylic acid compound (b3) may be prepared by tertiary amines such as triethyl amine and benzyl ethyl amine, dodecyl trimethyl ammonium chloride, tetramethyl ammonium chloride, tetraethyl ammonium chloride and benzyl. A quaternary ammonium salt such as triethyl ammonium chloride, pyridine, triphenylphosphine or the like is used as a catalyst, and a method of reacting for several to several ten hours at an reaction temperature of 50 to 150 ° C in an organic solvent can be mentioned.

The usage-amount ratio in reaction of the said copolymer and ethylenically unsaturated group containing carboxylic acid compound (b3) is a ratio of the epoxy equivalent in the said copolymer and the carboxylic acid equivalent of an ethylenically unsaturated group containing carboxylic acid compound (b3), and is usually 1: 0.5. -1: 2, Preferably it is 1: 0.8-1: 1.25, More preferably, it is 1: 1. By setting it as the said range, since there exists a tendency for the crosslinking efficiency in the coloring photosensitive resin composition of this application to improve, it is preferable.

<Polybasic acid anhydride (b4)>

As polybasic acid anhydride (b4), the same thing as the polybasic acid anhydride (a3) mentioned above can be used. Preferably, an acid anhydride having a biphenyl skeleton as represented by the following formula (1), or an acid anhydride having two benzene rings as represented by the following formula (2) bonded to an organic group Is used.

[In formula (2), R <^4> represents the alkylene group which may have a C1-C10 substituent.]

By using the anhydride of the carboxylic acid which has the said 2 or more carboxyl group, at least 2 benzene ring can be introduce | transduced in ink repellent compound (B).

Moreover, polybasic acid anhydride (b4) may contain other polybasic acid anhydride other than the acid anhydride which has at least two said benzene rings. Examples of other polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, and the like. Pyromellitic acid, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Methyl tetrahydro phthalic anhydride, 4-methyl tetrahydro phthalic anhydride, 3-ethyl tetrahydro phthalic anhydride, 4-ethyl tetrahydro phthalic anhydride is mentioned. These polybasic acid anhydrides can be used individually or in combination of 2 or more types.

After making an ethylenically unsaturated group containing carboxylic acid compound (b3) react with the copolymer which copolymerized the epoxy group containing acrylic monomer (b1) and the fluorine monomer (b2) at least, it is well-known as a method of making a polybasic acid anhydride (b4) react further. The method can be used. In addition, the usage-amount ratio is the ratio of the number-of-moles of OH group in the reaction material of the said copolymer and ethylenically unsaturated group containing carboxylic acid compound (b3), and the acid anhydride group of polybasic acid anhydride (b4), and is usually 1: 1-1: 0.1. And preferably 1: 0.8 to 1: 0.2. By setting it as said range, since there exists a tendency for the solubility to a developing solution to a moderate grade, it is preferable.

The acid value of the epoxy acrylate obtained by further reacting the reactant of the copolymer and the ethylenically unsaturated group-containing carboxylic acid compound (b3) with the polybasic anhydride (b4) is preferably 10 to 150 mgKOH / g in solid content, more preferably. Is 70-110 mgKOH / g. By setting the acid value of epoxy acrylate to 10 mgKOH / g or more, sufficient solubility in a developing solution is obtained, and by setting it as 150 mgKOH / g or less, sufficient hardenability can be obtained and surface quality can be made favorable.

It is preferable that the mass mean molecular weights of an ink repellent compound (B) are 2000-50000, More preferably, it is 5000-20000. By setting the mass average molecular weight to 2000 or more, heat resistance and film strength can be improved, and by setting it to 50000 or less, sufficient solubility in a developer can be obtained.

Moreover, as for content of ink repellent compound (B), it is preferable that the mass ratio of a photopolymerizable compound (A) and ink repellent compound (B) is 99.9: 0.1-70: 30. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, resolution, ink repellency, and is preferable.

[Photoinitiator (C)]

Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2. -Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropane-1-one, 2, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- 4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, ethanone- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyl oxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4 -Benzoyl-4'-methyldimethyl sulfide, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid methyl, 4- Ethyl methyl aminobenzoate, butyl 4-dimethylamino benzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-beta -methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl -1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzomonobenzoic acid methyl, 2, 4-diethyl thioxanthone, 2-chlorothioxanthone, 2, 4- dimethyl thioxane Ton, 1-chloro-4-propoxy city oxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl thioxanthene, 2-ethyl anthraquinone, octamethyl anthraquinone, 1, 2-benzanthraquinone, 2, 3-diphenyl anthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole , 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl 2 Dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4, 4 -'- bisdiethylamino benzophenone, 4, 4 -'- dichloro benzophenone, 3, 3- dimethyl-4 -Methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2 , 2-diethoxyacetophenone, p-dimethyl acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert- Butyl trichloro acetophenone, p-tert- butyl dichloro acetophenone, (alpha), (alpha)-dichloro- 4-phenoxy cetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzo water Veron, pentyl 4- dimethylamino benzoate, 9- phenyla Lidine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-meth Toxytriazine, 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 (trichloro) Romethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis ( Trichloromethyl) -s -Triazine, 2, 4-bistrichloromethyl-6- (3-bromo 4-methoxy) phenyl-s-triazine, 2, 4-bistrichloromethyl-6- (2-bromo- 4-methoxy) phenyl-s-triazine, 2,4-bistrichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bistrichloro Methyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine etc. are mentioned. These photoinitiators can be used individually or in combination of 2 or more types. Especially, it is especially preferable to use an oxime-type initiator from a viewpoint of a sensitivity.

It is preferable that content of a photoinitiator (C) is 0.5-30 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 1-20 mass%. By carrying out content in the said range, sufficient heat resistance and chemical-resistance can be obtained, and a film-forming ability can be improved and a photocurable defect can be suppressed.

[Coloring agent (D)]

As a coloring agent (D), light-shielding agents, such as carbon black and titanium black, are mentioned. Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, Al, etc. Inorganic pigments such as various metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, lamp black, can be used, but especially channel black Since it is excellent in light-shielding property, it can use it suitably. Moreover, resin coated carbon black can also be used. Specifically, the resin-coated carbon black obtained by mixing the carbon black and the resin having reactivity with a carboxyl group, a hydroxyl group, and a carbonyl group present on the carbon black surface and heating at 50 to 380 degrees, or a water-organic solvent mixture system Or resin-coated carbon black obtained by dispersing an ethylenic monomer in a water-surfactant mixed system and radical polymerization or radical copolymerization in the presence of a polymerization initiator. Since the resin-coated carbon black has lower conductivity than carbon black without a resin coating, when used as a color filter such as a liquid crystal display, leakage of current is small and a high power consumption display can be formed with high reliability.

As a coloring agent, you may add an organic pigment as an auxiliary pigment to said inorganic pigment. By appropriately selecting and adding the organic pigment which shows the complementary color of an inorganic pigment, the following effects are acquired. For example, carbon black has a reddish black color. Therefore, by adding the organic pigment which shows blue which is a red complementary color to carbon black as an auxiliary pigment, the red group of carbon black disappears and black is more preferable as a whole. It is preferable to use an organic pigment in the range of 10-80 mass% with respect to the sum total of an inorganic pigment and an organic pigment, More preferably, it is 20-60 mass%, More preferably, it is the range of 20-40 mass%.

As said inorganic pigment and organic pigment, the solution which disperse | distributed the pigment to appropriate density | concentration using a dispersing agent can be used. For example, as an inorganic pigment, the carbon dispersion CF black (containing 20% of carbon concentration) manufactured by Mikuni dye company, the carbon dispersion CF black (containing 24% of high resistance carbon) manufactured by Mikuni dye company, titanium black by Mikuni dye company. And dispersion liquid CF black (containing 20% of black titanium pigment). Moreover, as an organic pigment, the blue pigment dispersion liquid CF blue (20% of blue pigment containing) made by Mikuni dye company, the violet pigment dispersion liquid (10% containing violet pigment) made by Mikuni dye company are mentioned, for example. Moreover, as a dispersing agent, the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system is used preferably.

It is preferable that content of a coloring agent is 10-70 mass% with respect to solid content of a coloring photosensitive resin composition. By making content into 70 mass% or less, the photocuring defect can be suppressed, and by making it into 10 mass% or more, sufficient light-shielding property can be obtained. Moreover, it is preferable to adjust the density | concentration of a coloring agent so that OD (Optical Density) value per 1 micrometer of film thickness may be 1.5 or more, when forming a black matrix using the coloring photosensitive resin composition of this invention as mentioned later. When the OD value per film thickness of 1 μm is 1.5 or more, sufficient contrast can be obtained when used for the black matrix of the liquid crystal display.

[solvent]

It is preferable that the coloring photosensitive resin composition concerning this invention contains the solvent for dilution. As this solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -N-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri Propylene Glycol Monomethyl Ether, Tryp (Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol (Poly) alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy- 2-methyl ethyl propionate, 3 Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoic acid, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i- acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric i-propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethyl Formamide (N, N-dimethylfo amides such as rmamide) and N, N-dimethylacetamide (N, N-dimethylacetamide). These solvents can be used individually or in combination of 2 or more types.

It is preferable that content of a solvent is 50-500 mass parts with respect to 100 mass parts of solid content of a coloring photosensitive resin composition.

[Other ingredients]

The coloring photosensitive resin composition concerning this invention can be made to contain an additive as needed. As an additive, a thermal polymerization inhibitor, an antifoamer, surfactant, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing agent, a dispersal adjuvant, a filler, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. are mentioned.

[Preparation method of colored photosensitive resin composition]

The colored photosensitive resin composition which concerns on this invention is obtained by mixing each said component with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become uniform.

[Method for producing color filter]

First, the coloring photosensitive resin composition which concerns on this invention was made into the contact transfer type | mold coating apparatus, spinner (rotary coating apparatus), curtains, such as a roll coater, a reverse coater, and a bar coater. Coating is carried out on a substrate using a non-contact coating device such as a flow coater. As the substrate, a substrate having light transmittance is used.

Next, the applied coloring photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited, and for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C on a hot plate, and (2) water at room temperature You may use any method of the method of leaving to stand for time-several days, and (3) the method of removing a solvent in several ten minutes-several hours in a warm air heater or an infrared heater.

Next, this coating film is partially exposed by irradiating active energy rays of ultraviolet rays and excimer laser light through a negative mask. Although the energy dose to irradiate changes also with the composition of a coloring photosensitive resin composition, about 30-2000mJ / cm <^2> is preferable, for example.

Next, the film | membrane after exposure is developed with a developing solution, and patterning is carried out in a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developer include organic compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Next, the pattern after development is postbaked at about 200 ° C. At this time, it is preferable to expose the formed pattern to the whole surface. As described above, a black matrix having a predetermined pattern shape can be formed.

Next, in each of the regions partitioned by the black matrix, ink of R, G, and B colors is discharged from the inkjet nozzle, and the collected ink is cured with heat or light. Thereby, a color filter can be manufactured.

<Example 1>

As a photopolymerizable compound (A), resin (A-1) and monomer (A-3) pentaerythritol tetraacrylate were used.

[Synthesis of Resin (A-1)]

The synthesis method of resin (A-1) is as follows.

25 ml / min of the bisphenol fluorene type epoxy resin 235 g (epoxy equivalent 235), tetramethyl ammonium chloride 110 mg, 2, 6- di-tert- butyl- 4-methyl phenol 100 mg, and 72.0 g of acrylic acid It heated and melt | dissolved in 90 degreeC from 100 degreeC, blowing air into the furnace, and it heated up slowly to 120 degreeC. The acid value was measured during this time, and heating and stirring were continued for about 12 hours until it became less than 1.0 mgKOH / g. It cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate.

Next, 350 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenol fluorene type epoxy acrylate obtained above, followed by dissolving. Then, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed. It was made to react at 110 degreeC for 4 hours from 110 degreeC. After confirming the disappearance of the acid anhydride group, 38.0 g of 1, 2, 3, 6-tetrahydrophthalic anhydride (1, 2, 3, 6-tetrahydrophthalic anhydride) were mixed and reacted at 90 ° C for 6 hours to obtain a resin (A -1) was obtained. In addition, the loss | disappearance of the acid anhydride group was confirmed by IR spectrum. The obtained resin (A-1) had a mass average molecular weight of 5000 as measured by GPC, and an acid value of 80 mgKOH / g. This resin (A-1) was adjusted to 55 mass% of solid content concentration with 3-methoxybutyl acetate.

Compound (B-1) was used as the ink repellent compound (B).

[Synthesis of Compound (B-1)]

30 g of glycidyl methacrylate, 100 g of fluorine monomers (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F), and 50 g of methyl methacrylate, 7 g of n-dodecyl mercaptan as a chain transfer agent 2 g of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) was dissolved in 600 g of 3-methoxybutyl acetate and polymerized while stirring at 60 ° C. under a nitrogen atmosphere to obtain a solution of the copolymer. Got.

8 g of acrylic acid and 140 mg of triphenylphosphine are added to the solution of the copolymer and dissolved therein, followed by stirring at about 100 to 120 ° C., and an epoxy group derived from glycidyl methacrylate in the copolymer. And carboxyl group of acrylic acid were reacted. At this time, the place where it becomes less than 1.0 mgKOH / g was made into reaction end point, measuring the acid value.

Further, 38 g of 1, 2, 3, 6-tetrahydrophthalic anhydride (1, 2, 3, 6-tetrahydrophthalic anhydride) was added to the solution and reacted at 90 ° C. Compound (B-1) was obtained. The completion of the reaction was confirmed by disappearance of the acid anhydride group by the IR spectrum. The compound (B-1) had a mass average molecular weight of 15000 and an acid value of 80 mgKOH / g. In addition, this compound (B-1) was adjusted to solid content concentration 27 mass% with 3-methoxybutyl acetate.

As a photoinitiator (C), the compound (C-1) (made by Chivas Specialty Chemical Co., Ltd., IRGACURE 'OXE' 02) was used.

As the coloring agent (D), a coloring agent (D-1) (manufactured by Mikuni Color Co., Ltd., CF black: 25% by mass of carbon black, solvent: 3-methoxybutyl acetate) was used.

And each said component and a solvent (3-methoxybutyl acetate: cyclohexanone = 60: 40) are mix | blended in the ratio of Table 1, and it mixes with a stirrer for 2 hours, and is filtered by a 5 micrometer membrane filter. To prepare a colored photosensitive resin composition. In addition, the numerical value of Table 1 represents a mass part.

<Examples 2-5, Comparative Examples 1-5>

In Example 1, the coloring photosensitive resin composition is prepared like Example 1 except having prepared by the combination shown to Table 1, 2 about (A), (B), (C), (D) component. It was. About each component described in Table 1, 2, it is as follows.

[Synthesis of Compound (B-2)]

35 g glycidyl methacrylate, 100 g of fluorinated monomers (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F), and 45 g methyl methacrylate, 7 g, n-dodecyl mercaptan as a chain transfer agent 2 g of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) was dissolved in 600 g of cyclohexanone and polymerized while stirring at 60 ° C. under a nitrogen atmosphere to obtain a solution of the copolymer. .

After adding and dissolving 8 g of acrylic acid and 140 mg of triphenylphosphine to the solution of the said copolymer, it stirred at about 100-120 degreeC, and the carboxyl of the epoxy group and the acrylic acid derived from glycidyl methacrylate in the said copolymer. The group was reacted. At this time, the place where it becomes less than 1.0 mgKOH / g was made into reaction end point, measuring the acid value.

Further, 43 g of 1, 2, 3, 6-tetrahydrophthalic anhydride (1, 2, 3, 6-tetrahydrophthalic anhydride) was added to the solution, and reacted at 90 ° C to obtain a compound (B-2). The completion of the reaction was confirmed by disappearance of the acid anhydride group by the IR spectrum. The compound (B-2) had a mass average molecular weight of 13500 and an acid value of 85 MgKOH / g. In addition, this compound (B-2) was adjusted to 27 mass% of solid content concentration with cyclohexanone.

[Synthesis of Resin (A-2)]

400 g of Epicoat YX4000H (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 192), 4 g of triphenylphosphine, 153 g of acrylic acid, and 950 g of 3-methoxybutyl acetate were mixed and reacted at 90 to 100 ° C. Thereafter, 40 g of tetrahydrophthalic anhydride and 360 g of biphenyltetracarboxylic dianhydride were added as the polybasic acid anhydride, and further reacted to obtain a resin (A-2) having a biphenyl skeleton. This resin (A-2) had a mass average molecular weight of 7000 and an acid value of 90 mgKOH / g measured by GPC. In addition, this resin (A-2) was adjusted to 50 mass% of solid content concentration with 3-methoxybutyl acetate.

[Synthesis of Compound (B-3)]

100 g of fluorine-based monomers (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F), isobornyl methacrylate 50 g, 7 g of n-dodecyl mercaptan which is a chain transfer agent, 2, 2'-azobis (4 2 g of -methoxy-2 and 4-dimethylvaleronitrile) were dissolved in 384 g of 3-methoxybutyl acetate and polymerized while stirring at 60 ° C. under a nitrogen atmosphere to obtain a copolymer. The obtained resin (B-3) had a mass average molecular weight of 9800 measured by GPC. In addition, this resin (B-3) was adjusted to 30 mass% of solid content concentration with 3-methoxybutyl acetate.

[Synthesis of Compound (B-4)]

Acetone 555.0 g, fluorine monomer (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F) 72.0 g, methacrylic acid 12.0 g, 2-hydroxyethyl methacrylate 84.0 g, chain transfer agent n- After mixing 6.9 g of dodecyl mercaptan and 3.2 g of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and polymerizing at 40 ° C for 18 hours while stirring under a nitrogen atmosphere, Reprecipitation was carried out by adding water, followed by reprecipitation purification with petroleum ether, and vacuum drying to obtain Polymer 1.

100 g of polymer 1, 41.7 g of 2-methacryloyloxyethylisocyanate, 0.17 g of dibutyltin dilaurate, 2.1 g of 2,6-di-t-butyl-p-cresol, and 100 g of acetone The mixture was mixed and polymerized at 30 ° C for 18 hours with stirring, followed by reprecipitation purification by addition of water, followed by reprecipitation purification with petroleum ether, and vacuum drying to obtain compound (B-4). The obtained compound (B-4) had a mass average molecular weight of 9800 measured by GPC. In addition, this compound (B-4) was used as it is without making it a solution.

<Evaluation>

After apply | coating the coloring photosensitive resin composition prepared in the said Examples 1-5 and Comparative Examples 1-7 on the glass substrate, it dried at 90 degreeC for 2 minutes, and obtained the photosensitive layer which has a film thickness of about 2 micrometers. Subsequently, ultraviolet rays are selectively irradiated to the photosensitive layer at an exposure amount of 200 mJ / cm ² through a negative mask, and a solution of a developer "N-A3K" manufactured by Tokyo Oka Industry Co., Ltd. The pattern was formed by spray development at 25 degreeC for 60 second using. Thereafter, the formed pattern was post-baked at 22 ° C. for 30 minutes to form a grid-shaped black matrix pattern having a line width of 20 μm. Further, a black matrix pattern was formed such that the opening of the lattice was 200 m x 80 m. And developability, ink repellency, and the wettability in a pixel area were evaluated as follows.

(Developing)

The developability made (circle) and the pattern able to form what was able to form a pattern, but (triangle | delta) and the thing which could not form a pattern which made the pattern straightness bad were made into x. The results are shown in Tables 1 and 2.

(Ink repellency)

To ink castle were propylene glycol monomethyl ether or more acetate (PGMEA) measuring the contact angle, and 40 ^о of ○, 30 ^о least 40 ^о less than the △, less than 30 ^о of the phase pattern formed on a glass substrate by ×. The results are shown in Tables 1 and 2.

(Wetting in the pixel area)

The wettability in the pixel region was dropped by 20 pl of PGMEA into the formed lattice (in the pixel region), and when the PGMEA spreaded 100% of the area in the lattice. , Less than 40%. The results are shown in Tables 1 and 2.

As can be seen from Tables 1 and 2, in Examples 1 to 5 using compounds (B-1) and (B-2) which are fluorine-based epoxy acrylates (epoxyacrylate) as ink repellent compounds (B), ink repellency , All the wettability in the pixel region was excellent. In particular, since the pixel region partitioned by the black matrix has high wettability, it is considered that ink of R, G, and B colors can be uniformly collected in this pixel region. On the other hand, in Comparative Examples 1-7 which use compound (B-3) and (B-4) as ink repellent compound (B), ink repellency is inferior to Examples 1-5, and also in the pixel area | region Wetting was bad.

Claims (10)

As colored photosensitive resin composition containing a photopolymerizable compound (A), ink repellent compound (B), a photoinitiator (C), and a coloring agent (D), Said photopolymerizable compound (A) is resin represented by following formula (7),

[In Formula (7), X is group represented by following formula (8).

In formula (7), Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene anhydrous tetrahydrophthalic acid, chloric anhydride, methyltetrahydro anhydride It is the residue which removed carboxylic anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride selected from phthalic acid and glutaric anhydride. In formula (7), Z removes two carboxylic anhydride groups from tetracarboxylic dianhydride selected from pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Is a residue.] The ink repellent compound (B) is an ethylenically unsaturated group-containing carboxylic acid compound ( It is an epoxy acrylate obtained by making a polybasic acid anhydride (b4) react further after making b3) react, The content ratio (mass ratio) of the said photopolymerizable compound (A) and the said ink repellent compound (B) is 99.9-70: 0.1-30, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The ethylenically unsaturated group-containing carboxylic acid compound (b3) is at least one member selected from the group consisting of acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, α-cyano cinnamic acid, and cinnamic acid. The coloring photosensitive resin composition which makes it. The method according to claim 1 or 2, The said polybasic acid anhydride (b4) contains at least one of the compound represented by following General formula (1) or (2), The coloring photosensitive resin composition characterized by the above-mentioned.

[In formula (2), R <^4> is the alkylene group which may have a substituent of 1 to 10 carbon atoms.] The method of claim 1, Content of the unit guide | induced from the said epoxy group containing acrylic monomer (b1) in the said ink repellent compound (B) is 1-40 mass%, and content of the unit guide | induced from the said fluorine-type monomer (b2) is 30-80 mass% The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The mass average molecular weight of the said ink repellent compound (B) is 2000-50000, The coloring photosensitive resin composition characterized by the above-mentioned. delete The method of claim 1, The said photopolymerizable compound (A) contains resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react with a polybasic acid anhydride (a3) further, The coloring photosensitive resin characterized by the above-mentioned. Composition. The method of claim 1, The said photopolymerizable compound (A) contains the ethylenically unsaturated group containing monomer, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The said coloring agent (D) is a light-shielding agent, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The epoxy group-containing acrylic monomer copolymerizable with the fluorine-based monomer (b2) is - (CF _{2) r} F colored photosensitive resin composition characterized by having a group represented by (r = 1~10).