KR20040026113A - Polycarboxylic acid resin and photosensitive resin composition containing the same - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin composition which achieves high resolution, particularly a colored photosensitive resin composition which achieves high resolution even when a pigment of a small particle diameter is used at a high concentration. CONSTITUTION: The resin composition comprises a polycarboxylic acid resin obtained by reacting (a1) an epoxy compound having at least two epoxy groups per molecule with (a2) a polycarboxylic acid under such conditions as to satisfy the expression (the number of epoxy equivalents of the epoxy compound)>(the number of carboxylic acid equivalents of the polycarboxylic acid) to obtain a reaction product (a), which is brought into reaction with (b) an unsaturated group-containing monocarboxylic acid to obtain (c) a reaction product, and further reacting (c) the reaction product with (d) an acid anhydride.

Description

Polycarboxylic acid resin and photosensitive resin composition containing the same

The present invention relates to a polycarboxylic acid resin, a photosensitive resin composition containing a polycarboxylic acid resin as a binder polymer, and a cured product thereof. In particular, it relates to the photosensitive resin composition used suitably for the coloring photosensitive resin composition for color filters, the protective film for color filters, the spacer for color filters, the interlayer insulation film for color filters, etc.

The colored photosensitive resin composition containing alkali-soluble resin, a pigment, and a photoinitiator is widely used for manufacture of the color filter which is an element which comprises a color liquid crystal display device, a color solid-state imaging device, etc. As a method of manufacturing a color filter using such a colored photosensitive resin composition, the layer 1 which consists of a colored photosensitive resin composition is formed in the surface of the board | substrate 2, for example (FIG. 1 (a)), and a layer ( After 1) irradiates and exposes the light ray 4 through the photomask 3 (FIG. 1 (b)), the method of developing is known. In the colored photosensitive resin composition layer 1, the light non-irradiated region 11 to which the light ray 4 was not irradiated at the exposure is removed by development, and the light irradiation region 12 to which the light is irradiated remains black without being removed. A matrix or pixel 5 is formed (Fig. 1 (c)). In order to improve the mechanical strength of the formed black matrix or pixel, after development, heat treatment is usually performed. By repeating the above operation while changing the color of the pigment contained in the colored photosensitive resin composition, the black matrix 5BM and the pixels 5R, 5G, 5B of the colors corresponding to the three primary colors can be sequentially formed, and for the purpose of A color filter 6 can be obtained (FIG. 2).

In such a manufacturing method, in order to form a finer black matrix or a finer, higher transmittance color pixel, it is preferable to use a small particle diameter as a pigment contained in the colored photosensitive resin composition. Moreover, in order to form a thinner black matrix and color pixel, it was necessary to raise the density | concentration of the pigment contained in a coloring photosensitive resin composition.

It is an object of the present invention to provide a colored photosensitive resin composition in which high resolution is obtained even when a high resolution is used for a photosensitive resin composition, particularly a pigment having a small particle diameter.

1: A is a schematic diagram which shows the process of forming a pixel and a black matrix on a board | substrate using a coloring photosensitive resin composition.

2 is a schematic diagram partially showing an example of a color filter.

(Explanation of the sign)

1: Layer derived from colored photosensitive resin composition

2: substrate

3: mask pattern

31: glass plate

32: light shielding layer

4: rays

5: pixel, black matrix

5R, 5G, 5B: color pixels

5BM: Black Matrix

6: color filter

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to satisfy such a demand, the present inventors discovered that the said subject can be solved by using a specific polycarboxylic acid resin, and came to this invention.

That is, the present invention is a reactant (a) and an unsaturated group-containing monocarboxylic acid (b) obtained by reacting an epoxy compound (a1) having two or more epoxy groups and a polyvalent carboxylic acid compound (a2) in a molecule under the conditions of the following formula (1). ) To obtain a reactant (c), which is capable of addition polymerization of a polycarboxylic acid resin obtained by reacting the reactant (c) with an acid anhydride (d), a resin composition thereof [A], and at least one ethylenically unsaturated bond. The photosensitive resin composition containing a compound [B], a photoinitiator [C], and a solvent [D], and the hardened | cured material of such a photosensitive resin composition are provided.

The polycarboxylic acid resin (hereinafter also referred to as the present polycarboxylic acid resin) of the present invention reacts an epoxy compound (a1) and a polyvalent carboxylic acid compound (a2) having two or more epoxy groups in a molecule under the conditions of the following formula (1). Reactants (a) (hereinafter also referred to as component (a)) obtained by

The unsaturated group-containing monocarboxylic acid (b) (hereinafter also referred to as component (b)) is reacted to obtain a reactant (c) (hereinafter also referred to as component (c)) to obtain component (c) and an acid. It is obtained by reacting anhydride (d) (hereinafter also referred to as component (d)).

Equation 1

Preferred among the compounds (a1) are epoxy compounds of the general formula (1) hereinafter described as epoxy compound (1).

In Formula 1 above,

R ¹ and R ² are each independently a hydrogen atom, an alkyl group or a halogen atom,

X is a single bond or a divalent moiety that is one of Formulas 1a to 1h,

R ³ is an alkylene group,

R ⁴ is a hydrogen atom, an alkyl group or a glycidyl group,

m is an integer from 0 to 5,

n is an integer from 0 to 10,

Where, n is an integer of 2 if to 10, R ¹ to R ⁴ of the different repeating units may be the same or different.

The epoxy compound (1) can also be obtained by a known method, for example, by reacting the corresponding diol component with an appropriate amount of epichlorohydrin.

In the epoxy compound (1), the alkyl group as R ¹ and R ² is, for example, 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tertiary butyl group and the like. Alkyl group of is mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example.

Examples of the alkylene group as R ³ include an alkylene group having about 1 to 10 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. The alkylene group may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a 7 to 15 carbon atoms. An aralkyl group, an alkenyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, and the like.

Here, with a halogen atom, a chlorine atom, a bromine atom, etc. are mentioned, for example. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, and propyl group. Examples of the alkyl group when substituted with a hydroxyl group include, for example, hydroxyethyl group and hydroxypropyl. And the like.

Examples of the alkoxyl group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propyloxy group, butoxy group and the like.

Examples of the aryl group having 6 to 15 carbon atoms include a phenyl group and a naphthyl group. Examples of the aralkyl group having 7 to 15 carbon atoms include benzyl group and phenylethyl group.

As a C2-C10 alkenyl group, a vinyl group, an allyl group, etc. are mentioned, for example.

As the C2-C10 acyloxy group, an acetyloxy group, a benzoyloxy group, etc. are mentioned, for example.

The diol component for inducing the epoxy compound is a bisphenol compound of formula (3).

In Formula 3 above,

R ¹ , R ² and X are the same as defined above, respectively.

Here, as a bisphenol compound whose X is a single bond, 4,4'-biphenol, 3,3'-biphenol etc. are mentioned specifically ,.

As a bisphenol compound where X is a divalent residue of the formula (1a), specifically, for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) flu Orene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy Hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) flu Orene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, and the like. .

As a bisphenol compound where X is a divalent residue of the formula (1b), specifically, for example, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy) Hydroxy-3,5-dichlorophenyl) ketone and the like.

As bisphenol compounds in which X is a divalent residue of formula (1c), for example, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy) Hydroxy-3,5-dichlorophenyl) sulfone, etc. are mentioned.

As a bisphenol compound wherein X is a divalent residue of the formula (1d), for example, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane And bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane.

As a bisphenol compound wherein X is a divalent residue of the formula (1e), specifically, for example, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4 -Hydroxy-3,5-dichlorophenyl) dimethylsilane and the like.

As bisphenol compounds in which X is a divalent residue of formula (1f), specifically, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy) Hydroxy-3,5-dibromophenyl) methane, phenol novolak, cresol novolak and the like.

As a bisphenol compound wherein X is a divalent residue of the formula (1g), specifically, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy 3-chlorophenyl) propane etc. are mentioned.

As a bisphenol compound wherein X is a divalent residue of the formula 1h, for example, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (

4-hydroxy-3,5-dichlorophenyl) ether, etc. are mentioned.

These bisphenol compounds can be used individually or in combination of 2 types or more, respectively.

In the epoxy compound (1), X is preferably a divalent residue of the formula (1a).

Among these epoxy compounds (1), R ¹ , R ² and R ⁴ are hydrogen atoms, m = 0, and X is in position 4 with respect to the oxygen atom on the benzene ring substituted with R ¹ and R ² . Compounds which are divalent residues of; A divalent moiety of formula 1a in which R ¹ is a methyl group, R ² and R ⁴ are hydrogen atoms, m = 0, and X is in position 4 relative to the oxygen atom on the benzene ring substituted by R ¹ and R ² Phosphorus compounds; R ¹ , R ² and R ⁴ are hydrogen atoms, R ³ is an ethylene group and X is a divalent residue of formula 1a at position 4 relative to the oxygen atom on the benzene ring substituted by R ¹ and R ² ; R ¹ , R ² and R ⁴ are hydrogen atoms, R ³ is an alkylene group of the formula -C (CH ₃ ) H-CH _2- , and X is an oxygen atom on the benzene ring substituted with R ¹ and R ² A compound that is a divalent residue of Formula 1a at position 4 relative to; ² in Formula 1a wherein R ¹ is a methyl group, R ² and R ⁴ are hydrogen atoms, R ³ is an ethylene group, and X is in position 4 relative to the oxygen atom on the benzene ring substituted by R ¹ and R 2 Preferred are compounds in which is a residue.

Next, the polyhydric carboxylic acid which is compound (a2) made to react with compound (a1) is demonstrated.

Polyhydric carboxylic acid is a compound which has two or more carboxylic acid groups in one molecule, and it is preferable to have an unsaturated bond in a molecule | numerator. Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid , Chloric acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyldicarboxylic acid, biphenylethertetracarboxylic acid, and the like. Preferred examples thereof include maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and chloric acid. These can be used individually or in combination of 2 types or more, respectively.

In the reaction of compound (a1) with compound (a2), for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, di Using solvents such as ethylene glycol dimethyl ether, butyl acetate, 3-methoxy propionate methyl, 2-heptanone, ethyl methyl ketone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether acetate desirable.

In addition, in the reaction of compound (a1) and compound (a2), it is preferable to use a catalyst to promote the reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstilbin, chromium octanoate, and octanoic acid. Zirconium etc. are mentioned. The amount of the catalyst used is preferably 0.1 to 10% by mass based on the reaction raw material mixture.

When compound (a2) has an unsaturated double bond, it is preferable to use a polymerization inhibitor, in order to prevent superposition | polymerization in reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogarol and the like. Its use amount is preferably 0.01 to 1% by mass based on the reaction raw material mixture. The reaction temperature is preferably 60 to 150 ° C. In addition, the reaction time is preferably 5 to 60 hours.

In the present invention, the reaction between the compound (a1) and the compound (a2) is carried out under the condition that the (epoxy equivalent number) is larger than the (carboxylic acid equivalent number), and usually in the equivalent number ratio (epoxy) :( carboxylic acid) = 100: 1 to 100: 99. Preferably, it is 100: 20-100: 95, More preferably, it is 100: 50-100: 90. When the equivalent ratio is 100: 1 to 100: 99, the photosensitive resin composition containing the present polycarboxylic acid resin finally obtained tends to be easy to balance sensitivity, developability and resolution.

Next, an unsaturated group containing monocarboxylic acid (b) (component (b)) is demonstrated. As the component (b) in the present invention, for example, acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-flupracrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid; Semiesters which are reactants of saturated or unsaturated dibasic acid anhydrides with (meth) acrylate derivatives having one hydroxyl group in one molecule; And semiesters which are reactants of saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds. The semiesters are, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, itaconic anhydride, methylendomethylenetetrahydro Saturated and unsaturated dibasic anhydrides such as phthalic anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin Di (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, (meth) acrylate of phenylglycidyl ether, etc. (Meth) acrylate derivatives having one hydroxyl group in one molecule of Obtained semiesters or saturated or unsaturated dibasic acids (e.g., succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, fumaric acid, etc.) and monoglycidyl compounds containing unsaturated groups (E.g. glycidyl (meth) acrylate, And unsaturated group-containing monocarboxylic acids such as semiesters obtained by reacting (6) and the like in an equimolar ratio.

Component (b) can be used individually or in combination of 2 or more types.

Regarding the blending ratio of the component (a) and the component (b), the equivalent ratio of the remaining epoxy group in the component (a) and the carboxylic acid of the component (b) is usually 1: 0.5 to 1: 2, preferably 1 : 0.8 to 1: 1.25, more preferably 1: 1. When the equivalent ratio of the remaining epoxy group in component (a) and the carboxylic acid of component (b) is 1: 0.5 to 1: 2, the sensitivity is obtained when the finally obtained present polycarboxylic acid resin is used as a binder resin to form a photosensitive resin composition. Is preferable because it tends to be high.

In the reaction of component (a) and component (b), as a diluent, for example, 3-ethoxypropionate methyl, 3-ethoxypropionate, ethylcellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, di Using solvents such as ethylene glycol dimethyl ether, butyl acetate, 3-methoxy propionate methyl, 2-heptanone, ethyl methyl ketone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol methyl ether acetate desirable.

In addition, in reaction of component (a) and component (b), it is preferable to use a catalyst in order to accelerate reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstilbin, chromium octanoate and zirconium octanoate. These etc. are mentioned, Preferably, benzyl trimethyl ammonium bromide is mentioned. The usage-amount of the said catalyst is a mass fraction with respect to the total amount of reaction raw material mixture, Usually, 0.1-10 mass%, Preferably it is 0.2-5 mass%.

In reaction of component (a) and component (b), in order to prevent superposition | polymerization in reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogarol and the like. Its use amount is a mass fraction with respect to the total amount of the reaction raw material mixture, Preferably it is 0.01-1 mass%. The reaction temperature is preferably 60 to 150 ° C. In addition, the reaction time is preferably 5 to 60 hours.

The present polycarboxylic acid resin is obtained by reacting component (c) and component (d).

Examples of the component (d) include anhydrides of carboxylic acids having two or more carboxyl groups. As anhydrides of carboxylic acids having two or more carboxyl groups, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, fumaric acid, itaconic acid, citric acid, tartaric acid, phthalic acid, tetrahydro Phthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chloric acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, Anhydrides of carboxylic acids, such as biphenyl dicarboxylic acid and biphenyl ether tetracarboxylic acid, are mentioned, Preferably, tetrahydrophthalic anhydride, a benzophenone tetracarboxylic dianhydride, and a biphenyl tetracarboxylic dianhydride are mentioned.

The ratio of the amount of the component (c) to the component (d) used is the equivalent ratio of the OH group of the component (c) and the acid anhydride unit of the component (d), from 1: 1 to 1: 0.1, preferably from 1: 0.8 to 1: 0.2. If the ratio of the used amount of the component (c) and the component (d) is 1: 1 to 1: 0.1, the solubility in the developing solution tends to be appropriate, which is preferable.

The reaction is carried out by the method of reacting component (c) and component (d) in a solvent-free or solvent, but is preferably carried out in a solvent.

Examples of the solvent include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate and 3-methoxy Methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are used. Each of these solvents is used alone or in combination of two or more thereof, and the amount thereof is preferably 0.5 to 2 parts by mass based on 1 part by mass of the component (c).

In order to make a component (c) and a component (d) react, it is preferable to mix in a solvent as needed, and reaction temperature is 20 degreeC-200 degreeC normally.

The obtained polycarboxylic acid resin can be isolated from the reaction mixture and used for the colored photosensitive resin composition of the present invention. After isolation, the polycarboxylic acid resin can be further purified or used as it is without isolating the reaction mixture.

The present polycarboxylic acid resin has a polystyrene reduced weight average molecular weight of usually 1,000 to 50,000, preferably 1,500 to 20,000. When the weight average molecular weight is 1,000 to 50,000, when it is used as a binder resin to form a photosensitive resin composition, each performance of resolution, development margin, and background contamination tends to be good. The acid value is preferably 50 to 200, more preferably 70 to 170. When the acid value is within the above range, when this is used as a binder resin to form a photosensitive resin composition, the performance of resolution, development margin and ground contamination tends to be good, which is preferable.

The photosensitive resin composition (henceforth described as this photosensitive resin composition) of this invention is this polycarboxylic acid resin [A], the addition polymerization compound [B] which has at least one ethylenically unsaturated bond, the photoinitiator [C], and a solvent. It contains [D].

The content of the present polycarboxylic acid resin in the present photosensitive resin composition is usually 10 to 80% by weight, preferably 20 to 60% by weight.

Moreover, in this photosensitive resin composition, the other binder resin used for a normal photosensitive resin composition with this polycarboxylic acid resin can be contained as binder resin. As such binder resin, for example, an alkali-soluble polymer having a carboxyl group is used. Specific examples of alkali-soluble copolymers having such carboxyl groups include (meth) acrylic acid / methyl (meth) acrylate copolymers, (meth) acrylic acid / benzyl (meth) acrylate copolymers, and (meth) acrylic acid / 2-hydride. Oxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethylmeth Acrylate macro monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macro monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macro monomer copolymer, (meth) Acrylic acid / 2-hydroxyethyl

(Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethylmethacrylate macromer aerial Copolymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono succinate (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid

Mono / succinate (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / Glycerol mono (meth) acrylate copolymer, etc. are mentioned.

Next, a compound [B] capable of addition polymerization having one or more ethylenically unsaturated bonds (hereinafter also referred to as an ethylenically unsaturated compound) will be described.

Examples of the ethylenically unsaturated compound include compounds having one or more, preferably two or more polymerizable carbon-carbon unsaturated bonds, and examples thereof include esters of unsaturated carboxylic acids with aliphatic polyhydric alcohols; And amides of unsaturated carboxylic acids with aliphatic polyamines. Each of these compounds may be a monomer and may be a prepolymer, i.e., dimers, trimers, and tetramers or more oligomers. It may also be a mixture.

Here, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc. are mentioned, for example.

Specific examples of ester monomers of unsaturated carboxylic acids and aliphatic polyhydric alcohols include acrylic acid esters, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4 -Cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylic Rate, sorbitol triacrylate, Le, and the like carbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyl oxyethyl) isocyanurate, polyester acrylate oligomer.

As methacrylic acid ester, for example, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane And bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane.

As the itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol di Taconate, sorbitol tetrataconate, etc. are mentioned.

As crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. are mentioned, for example.

As isocrotonic acid ester, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. are mentioned, for example.

As maleic acid ester, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate, etc. are mentioned, for example. The mixture of such ester monomers is also mentioned.

Specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacryl Amide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

The ethylenically unsaturated compound may be a vinylurethane compound obtained by adding a vinyl monomer of the formula (2) to a polyisocyanate compound having two or more isocyanate groups in a molecule (Japanese Patent Publication No. 48-41708).

In Formula 2 above,

R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group.

Also, urethane acrylates (Japanese Patent Laid-Open No. 51-37193), polyester acrylates (Japanese Patent Laid-Open No. 48-64183, Japanese Laid-open Patent Application (Su) ) 49-43191, Japanese Patent Publication No. 52-30490], photocurable monomers (refer to the Japan Adhesion Society, Vol. 20, No. 7, pp. 300 to 308, 1984) and the like. have.

The amount of such ethylenically unsaturated compound to be used is usually 5 to 50%, preferably 10 to 40% by mass percent with respect to the solid content of the photosensitive resin composition. When the usage-amount of an ethylenically unsaturated compound is 5 to 50% on the said reference | standard, it exists in the tendency to balance the sensitivity, image development, and resolution, and is preferable. In addition, solid content of this photosensitive resin composition means the sum total of the component except a solvent.

Next, photoinitiator [C] is demonstrated. As a photoinitiator, an acetophenone type photoinitiator, a benzoin type photoinitiator, a benzophenone type photoinitiator, a thioxanthone type photoinitiator, a triazine type photoinitiator, an oxadiazole type photoinitiator, etc. can be used.

As an acetophenone type photoinitiator, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketar, 2-hydroxy-2- methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.

As a benzoin type photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type photoinitiator, a benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( Tertiary butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As a thioxanthone type photoinitiator, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned.

As a triazine type photoinitiator, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example. -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran- 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Romethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As an oxadiazole type photoinitiator, 5- (p-methoxyphenyl) -2-trichloromethyl oxadiazole, 5- (p-butoxy styryl) -2-trichloromethyl oxadiazole, etc., for example Can be mentioned.

Further, as other photopolymerization initiators, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, bispentadienyl titanium-di ( Titanocene compounds such as pentafluorophenyl)) and the like can be used.

Among these, a triazine type photoinitiator and an oxadiazole type photoinitiator are preferable.

These photoinitiators can be used individually or in combination of 2 types or more, respectively.

The amount of the photopolymerization initiator used is usually 3 to 60 parts by mass, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass per 100 parts by mass in total of the present polycarboxylic acid resin and other binder polymers added as necessary. . When the usage-amount of a photoinitiator is 3-60 mass parts, since a sensitivity does not fall and there exists a tendency for the intensity | strength of the photosensitive resin composition layer formed using this photosensitive resin composition to fall easily, it is preferable.

This photosensitive resin composition can contain a photoinitiator. The photopolymerization initiator is used to promote the photopolymerization reaction.

As photopolymerization start adjuvant, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2 -Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzo Phenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. These photopolymerization start adjuvant can be used individually or in combination of 2 or more types, respectively. When using such a photoinitiator, the usage-amount thereof is 0.01-10 mol normally with respect to 1 mol of photoinitiators.

Next, the solvent [D] will be described. As a solvent which can be used for this photosensitive resin composition, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl acetate, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxyacetic acid methyl, ethoxyacetate, 3-oxy Methyl propionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2 Propyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy Methyl propionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid Ethyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-meth Oxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate , 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate , 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate Esters such as hydrogen; Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Ethers such as glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Aromatic hydrocarbons, such as toluene, xylene, and mesitylene, etc. are mentioned.

Preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, 3-methoxybutyl acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, etc. are mentioned.

These solvents are used individually or in mixture of 2 or more types, respectively. The amount of the solvent used is an amount such that the concentration of solids is, in terms of mass percentage, usually 2 to 50%, preferably 5 to 50%, and more preferably 10 to 45% with respect to the entire photosensitive resin composition. When the usage-amount of a solvent is 2 to 50% by solid content concentration, there exists a tendency for the in-plane uniformity of coating film thickness to become favorable, and it is preferable.

Next, when using this photosensitive resin composition as a coloring photosensitive resin composition, this photosensitive resin composition further contains pigment [E]. The pigment may be an inorganic pigment or an organic pigment.

As an inorganic pigment, metal compounds, such as a metal oxide and a metal complex salt, are mentioned, for example. Examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony. The metal oxides and metal complex salts may be oxides and complex salts of such metals alone, and may be complex oxides and complex salts composed of two or more of these metals.

Examples of the organic pigments include compounds classified as pigments by Color Index (published by The Society of Dyers and Colourists).

As such an organic pigment, CI pigment yellow 1, CI pigment yellow 3, CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, CI pigment yellow 15, for example , CI pigment yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pig CIment yellow 65, CI pigment yellow 71, CI pigment yellow 73, CI pigment yellow 74, CI pigment yellow 81, CI pigment yellow 83, CI pigment yellow 93, CI pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pig CI Pigment Yellow 151, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow organic pigments, such as yellow 166, CI pigment yellow 168, CI pigment yellow 175,

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pig Orange organic pigments, such as pigment orange 51, CI pigment orange 61, CI pigment orange 63, CI pigment orange 64, CI pigment orange 71, CI pigment orange 73,

CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38, etc. Violet organic pigments,

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment CI Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI pigment red 48: 1, CI pigment red 48: 2, CI pigment red 48: 3, CI blood CI Red 48: 4, CI Red 49: 1, CI Red 49: 2, CI Red 50: 1, CI Red 52: 1, CI Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI pigment red 63: 2, CI pigment red 64: 1, CI pigment red 81: 1, CI pigment red 83, CI pigment red 88, CI pigment red 90: 1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI pigment red 112, CI pigment red 113, CI pigment red 114, CI pigment red 122, CI pigment red 123, CI pigment red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI pigment red 220, C. I. Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, Red organic pigments, such as CI pigment red 264, CI pigment red 265,

C. I. pigment blue 15, C. I. pigment blue 15: 3, C. I. pigment blue 15: 4, C. I. pigment blue 15: 6, C. I. pigment blue 60 such as blue organic pigments,

Green organic pigments, such as C. I. pigment green 7, C. I. pigment green 36,

Brown organic pigments, such as C. I. pigment brown 23, C. I. pigment brown 25,

Black organic pigments, such as C. I. pigment black 1 and C. I. pigment black 7, etc. are mentioned.

These organic pigments are used individually or in combination of 2 or more types according to the color of the pixel made into the objective.

Among these organic pigments, preferred organic pigments include, for example, CI pigment yellow 117, CI pigment yellow 128, CI pigment yellow 129, CI pigment yellow 138, and CI pigment in the yellow organic pigment. Yellow 150, CI pigment yellow 155, CI pigment yellow 185, etc. are mentioned,

Examples of the red organic pigments include C. I. pigment red 166, C. I. pigment red 178, C. I. pigment red 209, C. I. pigment red 242, C. I. pigment red 254, and the like.

CI pigment black 1, CI pigment black 7, etc. are mentioned in a black organic pigment, More preferably, CI pigment yellow 150, CI pigment red 254, CI pigment black 1, CI Pigment black 7 and the like.

Moreover, as a black pigment used for the coloring photosensitive resin composition used for manufacturing a black matrix, it is carbon black, graphite, for example. Unexamined-Japanese-Patent No. 5-311109, Unexamined-Japanese-Patent No. (Hi) 6-11613], an azo black dye (refer to Unexamined-Japanese-Patent No. 2-216102), etc. are mentioned. Moreover, organic pigments, such as said C. I. pigment black 1 and C. I. pigment black 7, can be used.

Moreover, as such a black pigment, resin as described in Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, and Unexamined-Japanese-Patent No. 2001-106938 is mentioned. Can be used carbon black coated with. Moreover, the black pigment coated with the inorganic substance as described in Unexamined-Japanese-Patent No. 2001-115043 can be used.

The average particle diameter of the pigment used is usually 0.005 to 0.2 µm, preferably 0.01 to 0.1 µm. When the average particle diameter of the pigment is in the range of about 0.01 to about 0.1, a high transmittance tends to be obtained when the color filter is formed, and the pigment particles tend to be easily dispersed in the colored photosensitive resin composition.

The pigment of such a particle diameter can be obtained by atomizing by the conventional method, such as a kneading method, a sulfuric acid method, and an alkali reduction dissolution method, for example. In addition, the pigment may be modified on the surface by a resin or the like (see Japanese Patent Laid-Open No. 8-259876).

When the present photosensitive resin composition is a colored photosensitive resin composition, the amount of pigment used is usually 20 to 60% by mass, preferably 25 to 25% by mass, based on the solids (the sum of the components except the solvent) of the colored photosensitive resin composition. 55 mass%, More preferably, it is 30-50 mass%. When the usage-amount of a pigment is 20-60 mass% on the said reference | standard, since a black matrix and a pixel can be formed in a target pattern, it is preferable.

In this invention, it is preferable that the mass ratio of the said binder resin / ethylenically unsaturated compound is 1.5-5. More preferable mass ratio is 2-4.

A small amount of thermal polymerization inhibitor may be added in order to suppress unnecessary thermal polymerization of the ethylenically unsaturated compound during the preparation or storage of other photosensitive resin compositions. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogarol, tertiary butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl- 6-tertiary butylphenol), 2,2'- methylenebis (4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, etc. are mentioned. As for the addition amount of a thermal polymerization inhibitor, about 0.01-5 mass% is preferable with respect to the mass of the whole composition.

Various additives, such as a filler, a polymer compound of that excepting the above, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. can be mix | blended with this photosensitive resin composition as needed.

Specific examples of such additives include fillers such as glass and alumina; Polymer compounds other than binder polymerizer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polychloroalkyl acrylate; Surfactants such as nonionic surfactants, cationic surfactants and anionic surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol; Ultraviolet absorbers such as 2- (tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; Agglomeration inhibitors, such as sodium polyacrylate, are mentioned.

In addition, the present photosensitive resin composition may contain a carboxylic acid, preferably a low molecular weight carboxylic acid having a molecular weight of 1000 or less, or an organic amino compound having a molecular weight of 1,000 or less having at least one amino group in a molecule.

Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl Aliphatic dicarboxylic acids such as succinic acid and citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydropinic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropinic acid, cinnamic acid, methyl cinnamic acid, benzyl cinnamic acid, cinnamilidene acetic acid, coumaric acid and umbelic acid.

Examples of the organic amino compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, secondary butyl, tertiary butylamine, n-pentylamine, n-hexylamine, n- Monoalkylamines such as heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine; Monocycloalkyl such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4-ethylcyclohexylamine Amines; Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di n-propylamine, di i-propylamine, di n-butylamine, di i-butylamine, di secondary butylamine, Dialkyl amines such as di tertiary butylamine, di n-pentylamine and di n-hexylamine; Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; Dicycloalkylamines such as dicyclohexylamine; Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi n-propylamine, ethyldi n-propylamine, tri n-propylamine, tri i-propyl Trialkylamines such as amine, tri n-butylamine, tri i-butylamine, tri secondary butylamine, tri tertiary butylamine, tri n-pentylamine and tri n-hexylamine; Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; Monoalkyldicycloalkylamines such as methyldicyclohexylamine and ethyldicyclohexylamine; Tricycloalkylamines such as tricyclohexylamine; Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol Olamines; Monocycloalkanolamines such as 4-amino-1-cyclohexanol; Dialkanolamines such as diethanolamine, di n-propanolamine, di i-propanolamine, di n-butanolamine, di i-butanolamine, di n-pentanolamine, and di n-hexanolamine; Dicycloalkanolamines such as di (4-cyclohexanol) amine; Trialkanolamines such as triethanolamine, tri n-propanolamine, tri i-propanolamine, tri n-butanolamine, tri i-butanolamine, tri n-pentanolamine, and tri n-hexanolamine; Tricycloalkanolamines such as tri (4-cyclohexanol) amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2 Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol and 2-diethylamino-1,3-propanediol; Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol; Amino group-containing cycloalkanethanols such as 1-aminocyclopentanmethanol and 4-aminocyclopentanmethanol; Amino such as 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol Group-containing cycloalkanethanols; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1 Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid; Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, p-tert-butylaniline, 1-naphthylamine, Aromatic amines such as 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and p-methyl-N, N-dimethylaniline; aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol; and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

In the present invention, the carboxylic acid and the organic amino compound may be used alone or in combination of two or more thereof. The usage-amount of the carboxylic acid and the organic amino compound in this photosensitive resin composition is 0.001-15 mass% of the whole composition normally, Preferably they are 0.01-10 mass% of the whole composition.

The layer derived from the photosensitive resin composition is formed by applying and drying this photosensitive resin composition to a board | substrate by application | coating methods, such as rotational coating, casting | flow_spread coating, roll coating, etc., exposing through a predetermined | prescribed mask pattern, and developing with a developing solution, and pattern Is formed. When a pigment is contained in this photosensitive resin composition, it becomes a coloring photosensitive resin composition and a coloring pattern (color filter?) Is formed. As radiation used for exposure, especially ultraviolet rays, such as g line | wire, h line | wire, and i line | wire, are used preferably. The coating thickness is the thickness of the film after drying, which is usually 0.1 to 10 µm, preferably 0.2 to 5.0 µm, particularly preferably 0.2 to 3.0 µm.

As a board | substrate used when forming this color filter in case this photosensitive resin composition is a coloring photosensitive resin composition, glass, silicone, a polycarbonate, polyester, aromatic polyamide, polyamideimide, a polyimide, etc. are mentioned, for example. Can be. Such a substrate can be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as desired.

As the developing solution, any developing solution can be used as long as it dissolves the present photosensitive resin composition and does not dissolve the exposed portion. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As an organic solvent, the above-mentioned solvent used when manufacturing this photosensitive resin composition is mentioned.

For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole And alkaline compounds such as piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene are dissolved in a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. The alkaline aqueous solution which was made is mentioned. A suitable amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution, for example.

The developing conditions can apply various conditions. For example, as the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid dipping) developing method, or the like can be applied. Developing temperature can generally be set in the range of 10-40 degreeC. The developing time is generally set to 10 to 300 seconds. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes with water after image development.

As mentioned above, although embodiment of this invention was described, embodiment of this invention described above is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the present invention is set forth in the claims, and also includes all modifications within the meaning and range equivalent to the description of the claims. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Example 1

46.3 g of bisphenol fluorenediglycidyl ether, 8.7 g of itaconic acid, 0.09 g of triethylbenzylammonium chloride, 0.18 g of tetraethylammonium bromide, 0.02 g of metoquinone and 55 g of propylene glycol monomethyl ether acetate in a 300 mL four-necked flask Was injected and reacted for 4 hours at 120 DEG C while heating and stirring to obtain a clear pale yellow viscous liquid. 4.8 g of propylene glycol monomethyl ether acetate and 4.8 g of acrylic acid were further added to the obtained viscous liquid and reacted at 120 ° C. for 8 hours. This is called Compound A.

Next, 55 g of Compound A, 10.2 g of tetrahydrophthalic anhydride, and 10.2 g of propylene glycol monomethyl ether acetate were injected and reacted at 120 ° C. under heating and stirring for 2 hours to obtain a pale yellow transparent resin solution A1. The weight average molecular weight (Mw) of the obtained resin was 8200, and the acid value was 100.

Example 2

[Production of Colored Photosensitive Resin Composition]

[E] 52 parts by mass of a mixture [pigment] of 40 parts by mass of a black pigment (C. I. pigment black 7) having an average particle diameter of 0.03 μm and a dispersant of 12 parts by mass;

[A] 33 parts by mass (in terms of solid content) of the resin solution A1 [binder polymer] obtained in Synthesis Example 1,

[B] 10 parts by mass of dipentaerythritol [a compound capable of addition polymerization having a hexaacrylate ethylenically unsaturated bond],

[C] 5.0 parts by mass of 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine [photopolymerization initiator] and

[D] 374 parts by mass of propylene glycol monomethyl ether acetate [solvent] was mixed to obtain a colored photosensitive resin composition (black).

[Formation of Colored Photosensitive Resin Composition Layer]

The layer obtained by applying the coloring photosensitive resin composition obtained above to the surface of a glass substrate (refer to "# 7059" Corning Corporation make) by the spin coating method, heating and drying at 100 degreeC for 3 minutes, and originating in a coloring photosensitive resin composition. Is formed on the substrate. The thickness of the layer derived from the coloring photosensitive resin composition after such drying was 1.2 micrometers.

[Formation of Colored Pattern (Evaluation of Resolution)]

The ultraviolet-ray is irradiated with an ultrahigh pressure mercury lamp (the irradiation amount is 200mJ / cm <2>) through the photomask which has a 5 micrometers L / S (line and space) pattern to the board | substrate with which the layer derived from the coloring photosensitive resin composition was formed above. The colored photosensitive resin composition layer after exposure is immersed in a developing solution (aqueous solution containing potassium hydroxide at 0.01% by mass and containing a nonionic surfactant) and developed for 50 seconds until the unexposed portion is eluted.

After development, it was washed with water and heated at 230 ° C. for 20 minutes to form a black colored pattern (black matrix) on the substrate 2. As a result of observing such a black matrix with an optical microscope, the 5 micrometers L / S pattern had favorable reproducibility, and the linearity of the pattern was also favorable.

[Evaluation of Development Margin]

A black matrix was formed in the same manner as above except that the immersion time (development time) in the developer was set to 70 seconds. As a result of observing with an optical microscope similar to the above, the 5 micrometers L / S pattern is formed with favorable reproducibility.

[Evaluation of sensitivity]

As a mask pattern, it operates similarly to the above except exposing using the mask pattern which the light transmittance of a light shielding layer is changing in steps, and since the pattern is formed, the minimum required amount of light irradiation (sensitivity) is calculated | required.

The sensitivity obtained was very high at 100 mJ / cm 2.

Comparative Example 1

Copolymer of benzyl methacrylate with methacrylic acid instead of the binder polymer used in Example 2 [benzyl methacrylate unit content is 65% in mol fraction, methacrylic acid unit content is 35% in mol fraction, polystyrene equivalent weight Average molecular weight is 13,000] The same procedure as in Example 2 was repeated except that 30 parts by mass of dipentaerythritol hexaacrylate was used, thereby obtaining a colored photosensitive resin composition (black) to give a colored photosensitive The layer (thickness: 1.2 micrometers) derived from a resin composition is formed.

[evaluation]

Evaluation was carried out in the same manner as in Example 2, except that a substrate having a layer derived from the colored photosensitive resin composition obtained above was used in place of the substrate having the layer derived from the colored photosensitive resin composition obtained in Example 2. As a result, the unexposed part to be eluted was not completely eluted by the phenomenon for 50 seconds. Further, as a result of the same development time of 70 seconds, the unexposed portion to be eluted is eluted, but all the colored patterns having a thickness of 5 mu m disappear and are not formed at all.

The sensitivity was 300 mJ / cm 2 as determined in the same manner as in Example 2.

The polycarboxylic acid resin of the present invention is suitably used as a binder polymer of the photosensitive resin composition, and particularly when used in a colored photosensitive resin composition containing a pigment, high resolution is obtained with high sensitivity, and development margin is also excellent. Even when a pigment having a small particle diameter is used at a high concentration, a high sensitivity, a high resolution, and a wide development margin are similarly obtained.

Especially the photosensitive resin composition of this invention is used suitably for the coloring photosensitive resin composition for color filters, the protective film for color filters, the spacer for color filters, the interlayer cutting film for color filters, etc.

Claims (10)

Reactant (a) obtained by reacting an epoxy compound (a1) having two or more epoxy groups and a polyvalent carboxylic acid compound (a2) in a molecule under the conditions of the following Equation 1 Reacting the unsaturated group-containing monocarboxylic acid (b) to give a reactant (c), Polycarboxylic acid resin obtained by reacting reactant (c) with acid anhydride (d). Equation 1 The polycarboxylic acid resin according to claim 1, wherein compound (a1) is a compound of formula (1). Formula 1 In Formula 1 above, R ¹ and R ² are each independently a hydrogen atom, an alkyl group or a halogen atom, X is a single bond or a divalent moiety that is one of Formulas 1a to 1h, R ³ is an alkylene group, R ⁴ is a hydrogen atom, an alkyl group or a glycidyl group, m is an integer from 0 to 5, n is an integer from 0 to 10, However, may be the same or different, each n is 2 if an integer of 1 to 10, R ¹ to R ⁴ in the different repeating unit. Formula 1a Formula 1b Formula 1c Formula 1d Formula 1e Formula 1f Formula 1g Formula 1h The polycarboxylic acid resin according to claim 1 or 2, wherein the compound (a2) is a polyvalent carboxylic acid having an unsaturated double bond. The polycarboxylic acid resin according to any one of claims 1 to 3, wherein the compound (a2) is at least one compound selected from the group consisting of maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid and chloric acid. The polycarboxylic acid resin according to any one of claims 1 to 4, wherein the unsaturated group-containing monocarboxylic acid (b) is at least one member selected from the group consisting of acrylic acid, methacrylic acid and crotonic acid. The polycarboxylic acid resin according to any one of claims 1 to 5, wherein the acid anhydride (d) is at least one member selected from the group consisting of tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride and biphenyltetracarboxylic dianhydride. . The photosensitive composition containing the polycarboxylic acid resin [A] as described in any one of Claims 1-6, the addition-polymerizable compound [B] which has at least one ethylenically unsaturated bond, the photoinitiator [C], and the solvent [D]. Resin composition. The photosensitive resin composition of Claim 7 which further contains pigment [E]. The photosensitive resin composition of Claim 8 whose pigment [E] is a black pigment containing carbon black. Hardened | cured material of the photosensitive resin composition of any one of Claims 7-9.