TWI857067B - Black photosensitive resin composition, black pattern, color filter, and liquid crystal display device - Google Patents

Abstract

A photosensitive resin composition, a black pattern, a color filter, and a liquid crystal display device are provided. The developed black pattern has good developability and good adhesion. The photosensitive resin composition includes an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) which has a structure represented by formula (G-1).

Description

Black photosensitive resin composition, black pattern, color filter, and liquid crystal display device

The present invention relates to a black photosensitive resin composition, and more particularly to a black pattern having the advantages of good developability and good adhesion formed by the black photosensitive resin composition after exposure, development and hardening.

In recent years, with the rapid development of various technologies of liquid crystal display devices, and in order to improve the contrast and display quality of liquid crystal display devices, black patterns, such as black matrix, are usually set between the stripes and dots of the color filter in the liquid crystal display device. The black matrix can prevent defects such as the decrease of contrast ratio and the decrease of color purity caused by light leakage between pixels.

Japanese Patent Publication No. 2008-268854 discloses a black photosensitive resin composition. The photosensitive resin composition comprises an alkali-soluble resin having a carboxylic acid group and an unsaturated group for polymerization, a photopolymerizable monomer containing an ethylenic unsaturated group, a photopolymerization initiator, and a black pigment. The patent improves the resolution of a black pattern formed by a photosensitive resin composition with a high content of black pigment by using a specific alkali-soluble resin. In addition, Japanese Patent Publication No. 2009-145432 discloses a black photosensitive resin composition. The photosensitive resin composition comprises a monomer containing an ethylenic unsaturated group, a photopolymerization initiator, a black pigment, and a resin. The resin is selected from thermosetting resin, photosensitive resin, thermoplastic resin, or a combination thereof. The patent improves the problem of low photosensitivity and poor developing performance of a photosensitive resin composition with a high content of black pigment in a photolithography process by adjusting the content of black pigment in the solid content of the photosensitive resin composition.

However, as the industry now has higher and higher requirements for the light-shielding property of black patterns, the solution is to increase the content of black pigment to improve the light-shielding property of the black pattern. However, the black pattern made of the photosensitive resin composition of the prior art has the problems of poor developing property and adhesion.

Therefore, how to overcome the problems of poor developing performance and poor adhesion to meet the current industry requirements is the goal of research in the technical field to which the present invention belongs.

In view of this, the present invention provides a black photosensitive resin composition, which can improve the above-mentioned problems of poor developing property and poor adhesion.

The present invention provides a black photosensitive resin composition, comprising: an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) having a structure represented by formula (G-1). Formula (G-1) In formula (G-1), ^R12 , ^R22 and ^R32 each independently represent a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonylalkoxy group, and at least one of ^R12 , ^R22 and ^R32 is a hydroxyl group. ^R13 , ^R23 and ^R33 each independently represent a hydrogen atom or an alkyl group. ^R14 , ^R24 and ^R34 each independently represent a hydroxyl group, an alkoxy group, an alkyl group, a hydroxyalkoxy group, an alkoxycarbonylalkoxy group, a 3-alkoxy-2-hydroxy-propoxy group or an alkylcarbonyloxy group.

In one embodiment of the present invention, the alkali-soluble resin (A) includes an alkali-soluble resin (A-1), and the alkali-soluble resin (A-1) has a branched alkyl group, an acid group, and a polymerizable unsaturated bond.

In one embodiment of the present invention, the alkali-soluble resin (A) includes an alkali-soluble resin (A-2), and the alkali-soluble resin (A-2) has an aromatic group, an acid group and a polymerizable unsaturated bond.

In one embodiment of the present invention, the alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed by a first mixture with a polymerizable unsaturated monobasic acid (a5) and then reacting with a polyacid or its anhydride (a6). The first mixture includes an acrylate compound (a1) having a branched alkyl group, an acrylic compound (a2) having an epoxy group, and other unsaturated compounds (a3).

In one embodiment of the present invention, the alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed by a second mixture with a polymerizable unsaturated monobasic acid (a5) and then reacting with a polyacid or its anhydride (a6). The second mixture includes an unsaturated compound (a4) having an aromatic group, an acrylic compound (a2) having an epoxy group, and other unsaturated compounds (a3).

In one embodiment of the present invention, the polycarbonate diol (F) is a compound represented by formula (F-1), Formula (F-1): In formula (F-1), a plurality of R ^1s each independently represents a divalent organic group; and m represents an integer of 1 to 20.

In one embodiment of the present invention, the number average molecular weight of the polycarbonate diol (F) is 500-3000.

In one embodiment of the present invention, based on the total usage of the alkali-soluble resin (A) being 100 parts by weight, the usage of the compound (B) having an ethylenically unsaturated group is 20 to 180 parts by weight, the usage of the photoinitiator (C) is 7 to 70 parts by weight, the total usage of the solvent (D) is 400 to 3000 parts by weight, the usage of the black pigment (E) is 150 to 900 parts by weight, the usage of the polycarbonate diol (F) is 4 to 40 parts by weight, and the usage of the compound (G) is 5 to 45 parts by weight.

In one embodiment of the present invention, based on the total usage of the alkali-soluble resin (A) being 100 parts by weight, the usage of the alkali-soluble resin (A-1) is 10 parts by weight to 60 parts by weight.

In one embodiment of the present invention, based on the total usage of the alkali-soluble resin (A) being 100 parts by weight, the usage of the alkali-soluble resin (A-2) is 40 parts by weight to 90 parts by weight.

The present invention further provides a black pattern formed by subjecting the above-mentioned black photosensitive resin composition to pre-baking, exposure, development and post-baking.

The present invention further provides a color filter including the black pattern as described above.

The present invention further provides a liquid crystal display device, comprising the color filter as described above.

Based on the above, the black photosensitive resin composition of the present invention uses polycarbonate diol (F) and contains a compound (G) with a specific structure. Therefore, the black photosensitive resin composition can improve the technical problems of poor developing property and poor adhesion in the prior art.

In order to make the above features and advantages of the present invention more clearly understood, embodiments are specifically described below in detail.

< Black photosensitive resin composition > The present invention provides a black photosensitive resin composition, comprising an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F) and a compound (G), and optionally an additive (H). The following will describe in detail the various components of the black photosensitive resin composition used in the present invention. Alkali-soluble resin ( A )

The alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2). In addition, the alkali-soluble resin (A) may further include another alkali-soluble resin (A-3). Alkali-soluble resin ( A-1 )

The alkali-soluble resin (A-1) has a branched alkyl group, an acid group and a polymerizable unsaturated bond. The alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed by the first mixture with a polymerizable unsaturated monobasic acid (a5) and then reacting with a polyacid or its anhydride (a6). The first mixture includes an acrylate compound (a1) having a branched alkyl group, an acrylic compound (a2) having an epoxy group and other unsaturated compounds (a3).

When the black photosensitive resin composition includes an alkali-soluble resin (A-1), the developability of the black pattern formed by the black photosensitive resin composition can be further improved. Acrylate compound having a branched alkyl group ( a1 )

Specific examples of the acrylate compound (a1) having a branched alkyl group include (meth)acrylate compounds such as isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, isotetradecyl (meth)acrylate, and isooctadecyl (meth)acrylate.

Based on the total molar number of the compounds in the first mixture being 1.0 mole, the amount of the acrylate compound (a1) having a branched alkyl group is 0.05 to 0.4 mole, preferably 0.07 to 0.38 mole, and more preferably 0.1 to 0.35 mole. The acrylic compound ( a2 ) having an epoxy group

Specific examples of the acrylic compound (a2) having an epoxy group include glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and lactone adducts thereof (e.g., Cyclomer A200 and M100 manufactured by DAICEL Chemical Industries, Ltd.), mono(meth)acrylate of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxy compounds of dicyclopentenyl (meth)acrylate, and epoxy compounds of dicyclopentenyloxyethyl (meth)acrylate.

Based on the total molar number of the compounds in the first mixture being 1.0 mole, the amount of the acrylic compound (a2) having an epoxy group is 0.3 to 0.85 mole, preferably 0.35 to 0.83 mole, and more preferably 0.4 to 0.8 mole. Other unsaturated compounds ( a3 )

Other unsaturated compounds (a3) are unsaturated compounds that do not belong to the above-mentioned acrylate compounds (a1) having a branched alkyl group, the acrylic compounds (a2) having an epoxy group, and the unsaturated compounds (a4) having an aromatic group described below. Other unsaturated compounds (a3) include unsaturated compounds (a3-1) and unsaturated compounds (a3-2). Unsaturated compound ( a3-1 )

The unsaturated compound (a3-1) is at least one selected from the group consisting of an acrylate compound having a structure represented by the following formula (a3-1-1) and formula (a3-1-2), and a compound represented by the following formula (a3-1-3): Formula (a3-1-1) Formula (a3-1-2) Formula (a3-1-3) In formula (a3-1-3), X and Y each independently represent a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a alkyl group having 1 to 20 carbon atoms, or a carboxylic acid group having 1 to 20 carbon atoms, wherein the alkyl group and the carboxylic acid group are unsubstituted or substituted with a substituent; or R ¹ and R ² are bonded to each other to form a ring structure.

Specific examples of the acrylate compound having the structure represented by formula (a3-1-1) include acrylate compounds having a tricyclodecane skeleton such as dicyclopentyl (meth)acrylate (trade names FA-513A, FA-513M, manufactured by Hitachi Chemical Co., Ltd.). Specific examples of the acrylate compound having the structure represented by formula (a3-1-2) include acrylate compounds having a dicyclopentadiene skeleton, such as tricyclo[5.2.1.0 ^2,6 ]dec-8-yl acrylate (trade name FA-511A, manufactured by Hitachi Chemical Co., Ltd.), 2-(tricyclo[5.2.1.0 ^2,6 ]dec-3-ene-8(9)-oxy)ethyl (meth)acrylate (dicyclopentenyloxyethyl (meth)acrylate, trade names FA-512A and FA-512M, manufactured by Hitachi Chemical Co., Ltd.). Specific examples of the compound represented by the formula (a3-1-3) include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, tricyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, tricyclo[4.4.0.1 2,5 .1 ^7,12 ]dodec-3-ene, tricyclo[6.2.1.0 ^1,8 ]undec-9-ene, tricyclo[6.2.1.0 ^1,8 ]undec-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 7,10 .0 ^1,6 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^{1,6 ]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 2,5 .1 7,12} ]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadeca-4-ene, pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] pentadeca-3-ene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dianhydride. The above-mentioned compounds may be used alone or in combination of two or more.

Based on the total molar amount of the compounds in the first mixture being 1.0 mole, the amount of the unsaturated compound (a3-1) used is 0.01 to 0.09 mole, preferably 0.012 to 0.08 mole, and more preferably 0.015 to 0.07 mole. Unsaturated compound ( a3-2 )

Specific examples of the unsaturated compound (a3-2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, n-octadecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: A M-90G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, butanetriol mono(meth)acrylate, pentatriol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, furanyl (meth)acrylate, furanmethyl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, pyranyl (meth)acrylate, 3-(N,N-dimethyl)-(meth)acrylate (meth)acrylates having no aromatic ring, such as (meth)acrylic acid esters having 10 to 20 carbon atoms ... (Meth)acrylic amides such as anthracenylamide and (meth)acrylic acid; vinyl compounds such as (meth)acrylic aniline, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, and vinyl acetate; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; unsaturated dicarboxylic acid diester compounds such as diethyl hexaconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; N-(meth)acryloyl o-phthalimide, etc. These monomers may be used alone or in combination of two or more monomers.

Based on the total molar amount of the compounds in the first mixture being 1.0 mole, the amount of the other unsaturated compound (a3) used is 0 to 0.6 mole, preferably 0 to 0.5 mole, and more preferably 0 to 0.4 mole. Polymerizable unsaturated monobasic acid ( a5 )

The polymerizable unsaturated monobasic acid (a5) used for reacting with the addition copolymer formed from the first mixture or the second mixture described below may be any one having a polymerizable unsaturated bond and an acid group, and examples thereof include unsaturated carboxylic acids, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples of the polymerizable unsaturated monobasic acid (a5) include unsaturated carboxylic acids such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, and 2-methacryloylethoxysuccinate; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. These unsaturated monobasic acids may be used alone or in combination of two or more.

Based on the total molar amount of the compounds in the first mixture being 1.0 mole, the amount of the polymerizable unsaturated monobasic acid (a5) used is 0.25 to 0.85 mole, preferably 0.3 to 0.83 mole, and more preferably 0.35 to 0.8 mole. Polybasic acid or its anhydride ( a6 )

The polyacid or its anhydride (a6) used for reacting with the addition copolymer formed by the first mixture or the second mixture described below may be any of saturated or unsaturated polyacids or their anhydrides, and specific examples thereof include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride. , maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, liconic acid, liconic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, dibasic acid or anhydride thereof such as phthalic anhydride, tribasic acid or anhydride thereof such as trimellitic acid and trimellitic anhydride, tetrabasic acid or anhydride thereof such as pyromellitic acid and pyromellitic anhydride, etc. Among these, dibasic acid anhydrides are preferably used.

Based on the total molar amount of the compounds in the first mixture being 1.0 mole, the amount of the polyacid or its anhydride (a6) used is 0.01 to 0.75 mole, preferably 0.03 to 0.7 mole, and more preferably 0.05 to 0.65 mole. Alkaline soluble resin ( A-2 )

The alkali-soluble resin (A-2) has an aromatic group, an acid group and a polymerizable unsaturated bond. The alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed by the second mixture with a polymerizable unsaturated monobasic acid (a5) and then reacting with a polybasic acid or its anhydride (a6). The second mixture includes an unsaturated compound (a4) having an aromatic group, an acrylic compound (a2) having an epoxy group and other unsaturated compounds (a3).

If the black photosensitive resin composition includes an alkali-soluble resin (A-2), the adhesion of the black pattern formed by the black photosensitive resin composition can be further improved.

Specific examples of the acrylic compound (a2) having an epoxy group, other unsaturated compounds (a3), polymerizable unsaturated monobasic acids (a5), and polybasic acids or their anhydrides (a6) used in the production process of the alkali-soluble resin (A-2) are the same as those of the acrylic compound (a2) having an epoxy group, other unsaturated compounds (a3), polymerizable unsaturated monobasic acids (a5), and polybasic acids or their anhydrides (a6) used in the production process of the alkali-soluble resin (A-1), and thus are not described in detail here.

The amount of the acrylic compound (a2) having an epoxy group is 0.3 to 0.85 mol, preferably 0.35 to 0.83 mol, and more preferably 0.4 to 0.8 mol, based on the total mole of the compounds in the second mixture being 1.0 mol.

Based on the total molar amount of the compounds in the second mixture being 1.0 mole, the amount of the other unsaturated compound (a3) used is 0 to 0.6 mole, preferably 0 to 0.5 mole, and more preferably 0 to 0.4 mole. Unsaturated compound ( a4 ) having an aromatic group

Specific examples of the unsaturated compound (a4) having an aromatic group include styrene-based unsaturated compounds such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, 4-nitrostyrene, 4-cyanostyrene, 4-acetylaminostyrene or indene; benzyl (meth)acrylate (Meth)acrylates having an aromatic ring such as phenethyl (meth)acrylate, methyl (meth)acrylate, cumyl (meth)acrylate, piperine (meth)acrylate, salicyclic alcohol (meth)acrylate, triphenylmethyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: tetraacrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, and p-phenoxybenzyl acrylate.

The unsaturated compound (a4) having an aromatic group is used in an amount of 0.03 to 0.45 mol, preferably 0.05 to 0.43 mol, and more preferably 0.08 to 0.4 mol, based on 1.0 mol of the total mole of the compounds in the second mixture.

Based on the total molar amount of the compounds in the second mixture being 1.0 mole, the amount of the polymerizable unsaturated monobasic acid (a5) used is 0.25 to 0.85 mole, preferably 0.3 to 0.83 mole, and more preferably 0.35 to 0.8 mole.

Based on the total molar number of the compounds in the second mixture being 1.0 mole, the amount of the polyacid or its anhydride (a6) used is 0.01 to 0.75 mole, preferably 0.03 to 0.7 mole, and more preferably 0.05 to 0.65 mole. Alkali-soluble resin ( A-1 ) and method for producing alkali-soluble resin ( A-2 )

The alkali-soluble resin (A-1) (or alkali-soluble resin (A-2)) is obtained by reacting an addition copolymer formed by the first mixture (or the second mixture) with a polymerizable unsaturated monobasic acid (a5), and then reacting with a polybasic acid or its anhydride (a6). The production method thereof will be described in detail below.

The copolymerization reaction of the addition copolymer formed from the first mixture (or the second mixture) can be carried out in the presence or absence of a polymerization solvent according to a free radical polymerization method known in the art. For example, the first mixture (or the second mixture) can be dissolved in a solvent as desired, a polymerization initiator can be added to the solution, and the copolymerization reaction can be carried out at 50-130° C. for 1-20 hours.

The solvent that can be used for the copolymerization reaction is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, ... (Poly) alkyl glycol monoalkyl ether compounds such as propylene glycol monoethyl ether, tripropylene glycol monoethyl ether, etc.; (Poly) alkyl glycol monoalkyl ether acetate compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate Ester compounds such as propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbon compounds such as toluene and xylene; carboxylic acid amide compounds such as N-methyldipyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. The above solvents may be used alone or in combination of two or more.

Among these, preferred are (poly)alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, that is, glycol ether solvents.

The amount of the polymerization solvent used is not particularly limited, and is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of the first mixture (or the second mixture) is 100 parts by mass. In particular, by making the amount of the solvent used less than 1,000 parts by mass, the molecular weight reduction of the copolymer caused by chain transfer can be suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. In addition, by making the amount of the solvent more than 30 parts by mass, abnormal polymerization reaction can be prevented, the polymerization reaction can be carried out stably, and coloring or gelation of the copolymer can also be prevented.

In addition, the polymerization initiator that can be used for this copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, etc. These can be used alone or in combination of two or more. When the total amount of the first mixture (or the second mixture) added is 100 parts by weight, the amount of the polymerization initiator used is generally 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight.

Then, by using the epoxy groups contained in the addition copolymer thus produced to carry out the following modification reaction, an alkali-soluble resin having an acid group and a polymerizable unsaturated bond in the side chain, a glass transition temperature of 20°C or less, and a weight average molecular weight of 1,000 to 50,000 in terms of polystyrene can be obtained.

The modification reaction comprises the following steps: Step 1: All epoxy groups contained in the addition copolymer are subjected to a ring-opening reaction by using a polymerizable unsaturated monobasic acid (a5). Step 2: The hydroxyl group generated by the ring-opening reaction is reacted with a polyacid or its anhydride (a6).

The amount of the polymerizable unsaturated monoacid (a5) used in step 1 can be appropriately selected according to the desired unsaturated group equivalent value of the hardening polymer. Generally, based on the total molar number of epoxy groups contained in the addition copolymer being 1.0 mole, the amount of the polymerizable unsaturated monoacid (a5) used is 0.90 to 1 mole, preferably 0.95 to 1 mole. If the amount of the polymerizable unsaturated monoacid (a5) used is too small, there is a risk of side reactions occurring in the subsequent reactions.

Step 1 can be carried out according to a common method. For example, after adding the addition copolymer and the polymerizable unsaturated monobasic acid to the reaction solvent, a catalyst can be further added, and the reaction can be carried out at, for example, 50-150° C., preferably 80-130° C. In addition, in step 1, even if a solvent for copolymerization is included, there is no particular problem, so step 1 can be carried out without removing the solvent after the copolymerization reaction is completed.

Furthermore, in order to prevent gelation during step 1, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methyl hydroquinone, and hydroquinone monomethyl ether. Furthermore, the catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds.

In the above step 1, the epoxy group in the addition copolymer is introduced into the side chain of the polymer by a ring-opening reaction, and an unsaturated bond from the polymerizable unsaturated monobasic acid (a5) is simultaneously generated, and a hydroxyl group from the epoxy group is simultaneously generated. In the present invention, an acid group is introduced into the polymer by a step 2 of reacting the hydroxyl group with a polyacid or its anhydride (a6).

The amount of the hydroxyl group and the polyacid or its anhydride (a6) used in step 2 can be appropriately selected according to the acid value of the desired curable polymer. Usually, based on the total molar number of the hydroxyl group generated in step 1 being 1.0 mol, the amount of the polyacid or its anhydride (a6) used is 0.01 to 0.9 mol, preferably 0.02 to 0.85 mol. If the amount of the hydroxyl group and the polyacid or its anhydride (a6) used is too small, there is a risk of insufficient developing properties, and conversely, if it is too large, there is a risk of reduced sensitivity.

Step 2 can also be carried out according to a common method. For example, after step 1, a polyacid or anhydride thereof (a6) can be added to the reaction system, and the reaction can be carried out at 50-150° C., preferably 80-130° C. The reaction time can be appropriately selected, and is usually 0.05-10 hours, preferably 0.1-7 hours.

The alkali-soluble resin (A-1) has a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene.

The alkali-soluble resin (A-2) has a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the alkali-soluble resin (A-1) is 10 to 60 parts by weight, preferably 15 to 55 parts by weight, and more preferably 20 to 50 parts by weight.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the alkali-soluble resin (A-2) is 40 to 90 parts by weight, preferably 45 to 85 parts by weight, and more preferably 50 to 80 parts by weight. Other alkali-soluble resins ( A-3 )

Other alkali-soluble resins (A-3) are resins other than alkali-soluble resins (A-1) and alkali-soluble resins (A-2). Other alkali-soluble resins (A-3) are, for example, resins having carboxylic acid groups or hydroxyl groups, but are not limited to resins having carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins (A-3) include acrylic resins, fluorene resins, urethane resins, novolac resins and the like. Compounds having ethylenically unsaturated groups ( B )

The compound (B) having an ethylenically unsaturated group may be selected from compounds having one ethylenically unsaturated group or compounds having two or more (including two) ethylenically unsaturated groups.

The aforementioned compound having an ethylenically unsaturated group may include but is not limited to (meth)acrylamide, (meth)acryloyl morpholine, (meth)acrylate-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, (meth)acrylate isobornyloxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate-2-ethylhexyl ester, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylate dimethylaminoethyl ester, (meth)acrylate dodecyl ester, (meth)acrylate dicyclopentenyloxyethyl ester, (meth)acrylate dicyclopentenyl ester, N,N-dimethyl (meth)acrylamide, (meth)acrylate Compounds such as tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, ethyl 2-hydroxy (meth)acrylate, propyl 2-hydroxy (meth)acrylate, vinyl caprolactam, N-vinyl pyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene mono(meth)acrylate, propylene mono(meth)acrylate, or bornyl (meth)acrylate may be used. The compounds having one ethylenically unsaturated group may be used alone or in combination of a plurality of them.

The aforementioned compound having two or more (including two) ethylenically unsaturated groups may include but is not limited to ethylene glycol di(meth)acrylate, dicyclopentene di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tri(2-hydroxyethyl)isocyanate di(meth)acrylate, tri(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified tri( 2-hydroxyethyl) isocyanate tri(meth)acrylate, tri(meth)acrylate trihydroxymethylpropyl, ethylene oxide (EO) modified tri(meth)acrylate trihydroxymethylpropyl, propylene oxide (PO) modified tri(meth)acrylate tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, tetra(meth)acrylate dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra ... Hydroxymethyl propyl ester, bisphenol A di(meth)acrylate modified with ethylene oxide, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with propylene oxide, bisphenol F di(meth)acrylate modified with ethylene oxide, or novolac polyglycidyl ether (meth)acrylate. The above-mentioned compound having two or more (including two) ethylenically unsaturated groups can be used alone or in combination of two or more.

Specific examples of the compound (B) having an ethylenically unsaturated group may include, but are not limited to, trihydroxymethylpropyl triacrylate, trihydroxymethylpropyl triacrylate modified with ethylene oxide, trihydroxymethylpropyl triacrylate modified with propylene oxide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate modified with caprolactone, ditrihydroxymethylpropyl tetraacrylate, glycerol triacrylate modified with propylene oxide, or any combination thereof.

The compound (B) having an ethylenically unsaturated group may preferably be trihydroxymethylpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or any combination thereof.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the compound (B) having an ethylenically unsaturated group is 20 to 180 parts by weight, preferably 25 to 170 parts by weight, and more preferably 30 to 160 parts by weight. Photoinitiator ( C )

The photoinitiator (C) includes a first photoinitiator (C-1) represented by formula (CI), and a second photoinitiator (C-2). First photoinitiator ( C-1 )

The first photoinitiator (C-1) is a compound represented by the following formula (CI). Formula (CI) wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, an alkyl group having 1 to 20 carbon atoms, COR ₁₆ , a group represented by formula (C-II), Formula (C-II); or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ are independently and collectively a group represented by Formula (C-III); Formula (C-III); provided that at least one pair of _R1 and _R2 , _R2 and _R3 , _R3 and _R4 , _R5 and _R6 , _R6 and _R7 or _R7 and _R8 is a group represented by Formula (C-III), _R9 , _R10 , _R11 and _R12 are independently hydrogen, an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted by one or more of the following groups: halogen, phenyl; or _R9 , _R10 , _R11 and _R12 are independently phenyl, unsubstituted or phenyl substituted by one or more of the following groups: an alkyl group having 1 to 6 carbon atoms, halogen; X represents CO or a direct bond; R _{R 13} represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted by one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ ; or R ₁₃ represents an alkyl group having 2 to 20 carbon atoms, which is doped with one or more O or CO, wherein the doped alkyl group having 2 to 20 carbon atoms is unsubstituted or substituted by one or more halogens; or R ₁₃ represents a phenyl group or a naphthyl group, each of which is unsubstituted or substituted by one or more of the following groups: an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms; R ₁₄ represents hydrogen, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms; R _{R 15} is an aryl group having 6 to 20 carbon atoms, each of which is unsubstituted or substituted by one or more of the following groups: halogen, halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ , alkyl group having 2 to 20 carbon atoms doped with one or more O; or each of which is substituted by an alkyl group having 1 to 20 carbon atoms, said alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted by one or more of the following groups: halogen, COOR ₁₇ , phenyl, OR ₁₇ ; or R ₁₅ represents hydrogen, cycloalkyl group having 3 to 8 carbon atoms; or R ₁₅ is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted by one or more of the following groups: halogen, cycloalkyl group having 3 to 8 carbon atoms; R _{R 16} represents an aryl group having 6 to 20 carbon atoms, each of which is unsubstituted or substituted by one or more of the following groups: halogen, halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ ; or each of which is substituted by one or more alkyl groups having 1 to 20 carbon atoms, said alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted by one or more of the following groups: halogen, OR ₁₇ ; R ₁₇ represents hydrogen, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted by one or more of the following groups: halogen or cycloalkyl group having 3 to 20 carbon atoms doped with one or more O; or R ₁₇ represents an alkyl group having 2 to 20 carbon atoms doped with one or more O; or R ₁₇ represents a phenyl group, each of which is unsubstituted or substituted by one or more of the following groups: a halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms; provided that at least one group represented by the formula (C-II) is present in the formula (CI).

The compound of formula (CI) is characterized in that it contains one or more annelated unsaturated rings on the carbazole portion. In other words, at least one pair of _R1 and _R2 , _R2 and _R3 , R3 and _R4 , _R5 and _{R6 , R6} and _R7 , or _R7 and _R8 is a group represented by formula (C-III), Formula (C-III).

The alkyl group having 1 to 20 carbon atoms is linear or branched, and examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl.

Halogenated alkyl radicals having 1 to 4 carbon atoms are alkyl radicals having 1 to 4 carbon atoms as defined above which are substituted with halogen as defined below. The alkyl radical is, for example, mono- or _{polyhalogenated} , up to all H atoms being replaced by halogen. It is, for example, _CzHxHaly , where x+ _y =2z+1 and Hal is a halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, in particular trifluoromethyl or trichloromethyl.

The alkyl group with a carbon number of 2 to 20, which is doped with one or more O, is doped with O, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times. Two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). The alkyl groups are straight or branched. For example, the following structural units are present: _-CH2 - _{CH2 - O-CH2CH3 ,} -[ _CH2CH2O ] _y - _CH3 (wherein y=1 to 9), -( _CH2 - _CH2O ) _{7 - CH2CH3} , _-CH2 -CH( _CH3 )-O- _{CH2 - CH2CH3} , _-CH2- CH( _CH3 )-O- _CH2 - _CH3 .

The alkoxy group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms substituted with one O atom.

The aryl group having 6 to 20 carbon atoms is, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysyl, tetraphenyl, triphenyl, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

Substituted aryl (phenyl, naphthyl, aryl with 6 to 20 carbon atoms) is substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, in particular 1 time, 2 times or 3 times, respectively. Obviously, an aryl group by definition cannot have more substituents than the free positions at the aryl ring.

The substituents on the phenyl ring are preferably in position 4 or in a 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6- configuration on the phenyl ring.

An interrupted or multiply doped group is doped, for example, 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times (obviously, the number of intervening atoms depends on the number of C atoms to be doped). An interrupted or multiply substituted group has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

A radical substituted with one or more defined substituents is intended to have one substituent or multiple substituents which are the same or different as defined. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If _R1 and _R2 , _R2 and _R3 , R3 and _R4 or _R5 and _R6 , _R6 and _{R7 , R7} and _R8 are independently and collectively a radical represented by formula (C-III), Formula (C-III) forms a structure such as the following formula (C-Ia) to formula (C-Ii): Formula (C-Ia), Formula (C-Ib), Formula (C-Ic), Formula (C-Id), Formula (C-Ie), Formula (C-If), Formula (C-Ig), Formula (C-Ih), Formula (C-Ii).

Examples of the compounds of the present invention are preferably formula (C-Ia), formula (C-Ib), formula (C-Ic), more preferably formula (C-Ia) or formula (C-Ic), or formula (C-Ia), formula (C-Ic) or formula (C-Id), and particularly preferably formula (C-Ia).

In the formula, R ₁₅ represents, for example, hydrogen, phenyl, naphthyl, each of which is unsubstituted or substituted with an alkyl group having 1 to 8 carbon atoms, or OR ₁₇ ; or R ₁₅ represents an alkyl group having 1 to 20 carbon atoms; or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, in which one or more Os are mixed.

R ₁₆ represents, for example, an aryl group having 6 to 20 carbon atoms (especially phenyl or naphthyl, especially phenyl), each of which is unsubstituted or substituted by one or more of the following groups: halogen, halogenated alkyl group having 1 to 4 carbon atoms, OR ₁₇ ; or each of which is substituted by one or more alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted by one or more of the following groups: halogen, OR ₁₇ .

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, in particular phenyl or carbazole, each of which is unsubstituted or substituted by one or more of the following groups: halogen, halogenated alkyl having 1 to 4 carbon atoms, OR ₁₇ or alkyl having 1 to 20 carbon atoms.

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, in particular phenyl, each of which is unsubstituted or substituted by one or more of the following groups: halogen, OR ₁₇ or alkyl having 1 to 20 carbon atoms.

R ₁₆ is in particular, for example, phenyl, which is unsubstituted or substituted by one or more of the following groups: OR ₁₇ or alkyl having 1 to 20 carbon atoms.

Preferably, R ₁₆ is a phenyl group substituted with one or more alkyl groups having 1 to 20 carbon atoms.

R ₁₇ represents, for example, hydrogen, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted by one or more of the following groups: a halogen or a cycloalkyl group having 3 to 20 carbon atoms doped with one or more O; or R ₁₇ represents a phenyl group, each of which is unsubstituted or substituted by one or more of the following groups: a halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms.

Examples of the compounds of the invention formula (1) include the following compounds represented by formula (C-1-1) to formula (C-1-23): Formula (C-1-1) Formula (C-1-2) Formula (C-1-3) Formula (C-1-4) Formula (C-1-5) Formula (C-1-6) Formula (C-1-7) Formula (C-1-8) Formula (C-1-9) Formula (C-1-10) Formula (C-1-11) Formula (C-1-12) Formula (C-1-13) Formula (C-1-14) Formula (C-1-15) Formula (C-1-16) Formula (C-1-17) Formula (C-1-18) Formula (C-1-19) Formula (C-1-20) Formula (C-1-21) Formula (C-1-22) Formula (C-1-23)

Based on 100 parts by weight of the alkali-soluble resin (A), the first photoinitiator (C-1) is used in an amount of 7 to 60 parts by weight, preferably 8 to 55 parts by weight, and more preferably 9 to 50 parts by weight. The second photoinitiator ( C-2 )

The second photoinitiator (C-2) is, for example, an acetophenone compound, a biimidazole compound, or a combination of the above compounds.

Specific examples of acetophenone compounds include p-dimethylaminoacetophenone, α,α'-dimethoxyazoacetophenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone or a combination of the above compounds.

Specific examples of the diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methyl ... -Bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or a combination of the above compounds.

The second photoinitiator (C-2) is preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or a combination of the above compounds.

The second photoinitiator (C-2) may further contain the following compounds as needed: benzophenone compounds such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone; α-diketones such as benzil and acetyl; acyloins such as benzoin; acyloins such as benzoin methylether, benzoin ethylether, benzoin isopropyl ether; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; -phosphineoxide), bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide, etc.; quinones such as anthraquinone and 1,4-naphthoquinone; halides such as phenacyl chloride, tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine; peroxides such as di-tertbutylperoxide; or combinations thereof. The compound added to the photoinitiator (C) is preferably a benzophenone compound, and more preferably 4,4'-bis(diethylamino)benzophenone.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C) is 7 to 70 parts by weight, preferably 8 to 65 parts by weight, and more preferably 9 to 60 parts by weight. Solvent ( D )

The solvent (D) is a solvent that can dissolve the alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the black pigment (E) described below, the polycarbonate diol (F) and the additive (G) but does not react with the above components, and preferably has appropriate volatility.

Specific examples of the solvent (D) include alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ether, other ether compounds, ketone compounds, lactic acid alkyl ester compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amide compounds or combinations thereof.

Specific examples of alkyl glycol monoalkyl ether compounds include: ethylene glycol monomethyl ether, ethylene glycol monoethyl 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or their analogs, or combinations thereof.

Specific examples of alkyl glycol monoalkyl ether acetate compounds include ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, or the like, or a combination of the above compounds.

Specific examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like, or a combination thereof.

Specific examples of other ether compounds include tetrahydrofuran or its analogs.

Specific examples of ketone compounds include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like, or a combination of the above compounds.

Specific examples of lactic acid alkyl ester compounds include methyl lactate, ethyl lactate or their analogs, or a combination of the above compounds.

Specific examples of other ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-eth ... Oxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl 2-oxybutyrate or the like, or a combination of the foregoing compounds.

Specific examples of aromatic hydrocarbon compounds include toluene, xylene or the like, or a combination of the above compounds.

The carboxylic acid amide compound is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or the like, or a combination of the above compounds.

The solvent (D) may be used alone or in combination of two or more.

The solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the solvent (D) is 400 to 3000 parts by weight, preferably 500 to 2800 parts by weight, and more preferably 600 to 2500 parts by weight. Black pigment ( E )

The black pigment (E) is preferably a black pigment having heat resistance, light resistance, and solvent resistance.

Specific examples of black pigments (E) include black organic pigments such as perylene black, cyanine black or aniline black; mixed organic pigments that are close to black by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine or magenta; light-shielding materials such as carbon black, chromium oxide, iron oxide, titanium black or graphite, wherein specific examples of the above-mentioned carbon black include C.I.pigment black 7 or commercial products manufactured by Mitsubishi Chemical (trade names MA100, MA230, MA8, #970, #1000, #2350 or #2650). The above-mentioned black pigments (E) can be used alone or in combination.

The black pigment (E) is preferably carbon black, and carbon black is, for example, commercially available products MA100 or MA230 manufactured by Mitsubishi Chemical.

Based on the usage of the alkali-soluble resin (A) being 100 parts by weight, the usage of the black pigment (E) is 150 to 900 parts by weight, preferably 170 to 850 parts by weight, and more preferably 200 to 800 parts by weight. Polycarbonate diol ( F )

Polycarbonate diol (F) is a compound represented by formula (F-1), Formula (F-1)

In formula (F-1), a plurality of R ^1's each independently represent a divalent organic group; and m represents an integer of 1 to 20.

If the black photosensitive resin composition does not include the polycarbonate diol (F), the black pattern formed by the black photosensitive resin composition has poor developability.

When the black photosensitive resin composition contains the polycarbonate diol (F) represented by the formula (F-1), the developing property is better.

Specific examples of the polycarbonate diol (F) represented by the formula (F-1) include PCDL T-4671, T-4672, T-4691, T-4692, T-5650E, T-5650J, T-5651, T-5652, T-6001, T-6002 (all trade names) manufactured by Asahi Kasei Co., Ltd.; Placcel CD (registered trademark) CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL manufactured by Daicel Co., Ltd.; Kuraray polyol (Kuraray Polyol) C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090; and Nippollan 963, 965, 968, 976, 981, 980R, 982R and the like manufactured by Tosoh Corporation. The above polycarbonate diols (F) may be used alone or in combination of two or more.

The polycarbonate diol (F) has a styrene-equivalent number average molecular weight (Mn) of 500 to 3000, preferably 650 to 2500, and more preferably 800 to 2000. When the number average molecular weight of the polycarbonate diol (F) is within the above range, the developing property is better.

Based on the usage of the alkali-soluble resin (A) being 100 parts by weight, the usage of the polycarbonate diol (F) is 4 to 40 parts by weight, preferably 5 to 35 parts by weight, and more preferably 6 to 30 parts by weight. Compound ( G )

The compound (G) has a structure represented by the following formula (G-1): Formula (G-1) In formula (G-1), ^R12 , ^R22 and ^R32 each independently represent a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonylalkoxy group, and at least one of ^R12 , ^R22 and ^R32 is a hydroxyl group. ^R13 , ^R23 and ^R33 each independently represent a hydrogen atom or an alkyl group. ^R14 , ^R24 and ^R34 each independently represent a hydroxyl group, an alkoxy group, an alkyl group, a hydroxyalkoxy group, an alkoxycarbonylalkoxy group, a 3-alkoxy-2-hydroxy-propoxy group or an alkylcarbonyloxy group.

Specific examples of compound (G) include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4 -bis(hydroxyphenyl)triazine compounds such as bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine.

Specific examples of compound (G) include compounds represented by formulae (G-1-1) to (G-1-5). Formula (G-1-1) Formula (G-1-2) Formula (G-1-3) Formula (G-1-4) Formula (G-1-5)

Based on 100 parts by weight of the alkali-soluble resin (A), the compound (G) is used in an amount of 5 to 45 parts by weight, preferably 6 to 40 parts by weight, and more preferably 7 to 35 parts by weight.

If the black photosensitive resin composition does not include the compound (G), the adhesion of the black pattern formed by the black photosensitive resin composition is poor. Additive ( H )

Under the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may further selectively add an additive (H). Specific examples of the additive (H) include surfactants, fillers, polymers (referring to polymers other than the above-mentioned alkali-soluble resin (A)), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents or other coloring agents.

Surfactants help improve the coating properties of photosensitive resin compositions. Specific examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants, or a combination of the above surfactants.

Specifically, the surfactant is, for example, polyoxyethylene alkyl ethers such as polyethoxy dodecyl ether, polyethoxy stearyl ether, and polyethoxy oleyl ether; polyethoxy alkyl phenyl ethers such as polyethoxy octyl phenyl ether and polyethoxy nonyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; or tertiary amine-modified polyurethanes. The above-mentioned surfactants can be used alone or in combination.

Specific examples of surfactants include KP products manufactured by Shin-Etsu Chemical Co., Ltd., SF-8427 products manufactured by Dow Corning Toray Co., Ltd., Polyflow products manufactured by Kyoeisha Oil & Fat Chemical Co., Ltd., F-Top products manufactured by Tochem Products Co., Ltd., Megafac products manufactured by Dainippon Ink Chemical Co., Ltd., Fluorade products manufactured by Sumitomo 3M, Asahi Guard products manufactured by Asahi Glass Co., Ltd., or Surflon products manufactured by Asahi Glass Co., Ltd.

Specific examples of fillers include glass, aluminum, and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or a combination of the above polymers.

Specific examples of adhesion promoters include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidyltrimethoxysilane, propylmethyldiethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane, 3-butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane or a combination thereof.

Specific examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or a combination of the above compounds.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenylhydrazine, alkoxyphenone, or a combination of the above compounds.

Specific examples of anti-agglomeration agents include sodium polyacrylate and the like.

Other colorants include inorganic pigments, organic pigments, or a combination of the two.

Specific examples of inorganic pigments include metal oxides, metal compounds of metal salts, etc. (e.g., metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, etc.) or composite oxides of the above-mentioned metals.

Specific examples of organic pigments include C.I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; C. I. Orange pigment 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 103 4, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190 , 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38, 39; C. I. Pigment blue 1, 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 66; C. I. Pigment green 7, 36, 37; C. I. Pigment brown 23, 25, 28 or a combination of the above pigments.

< Method for preparing black photosensitive resin composition > For example, a method for preparing a black photosensitive resin composition includes placing an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F) and a compound (G) in a stirrer and stirring them to uniformly mix them into a solution state. If necessary, an additive (H) may be added. After uniformly mixing, a black photosensitive resin composition in a solution state can be obtained.

In addition, the method for preparing the black photosensitive resin composition is not particularly limited. The method for preparing the black photosensitive resin composition is, for example, to first disperse a portion of the alkali-soluble resin (A) and the compound (B) having an ethylenically unsaturated group in a portion of the solvent (D) to form a dispersed solution; and then mix the remaining alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F) and a compound (G) to prepare the black photosensitive resin composition.

Alternatively, the black photosensitive resin composition may be prepared by dispersing a portion of the black pigment (E) in a mixture of a portion of the alkali-soluble resin (A) and a portion of the solvent (D) to form a black pigment dispersion, and then adding the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D), the black pigment (E), the polycarbonate diol (F) and the compound (G). Furthermore, the dispersion of the black pigment (E) may be carried out by mixing with a mixer such as a beads mill or a roll mill.

< Method for producing black pattern > The black pattern is produced by sequentially applying pre-baking, exposure, development and post-baking treatments to the above-mentioned black photosensitive resin composition on the substrate. Moreover, when the film thickness of the obtained black pattern is 1 μm, the optical density range can be above 3.0, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The following is a detailed description of the method for producing the black pattern.

First, a black photosensitive resin composition in a solution state is uniformly coated on the substrate by a coating method such as spin coating or cast coating to form a coating film. Specific examples of the above-mentioned substrate include: alkali-free glass, sodium calcium glass, hard glass (Pyles glass), quartz glass and a transparent conductive film attached to the glass used in liquid crystal display devices, etc.; or a photoelectric conversion device substrate (such as a silicon substrate) used in solid-state imaging devices, etc.

After the coating is formed, most of the solvent is removed by reduced pressure drying, and then the remaining solvent is completely removed by pre-baking to form a pre-baked coating. It is worth noting that the conditions of reduced pressure drying and pre-baking vary depending on the type and ratio of each component. Generally speaking, reduced pressure drying is carried out at a pressure of less than 200 mmHg for 1 second to 20 seconds, and pre-baking is a heating treatment of the coating at a temperature of 70℃ to 110℃ for 1 minute to 15 minutes.

Then, the pre-baked coating is exposed to light using a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device can be a (super) high-pressure mercury lamp and a metal halogen lamp.

Then, the exposed pre-baked coating is immersed in a developing solution at a temperature of 23±2° C. to remove the unexposed portion of the pre-baked coating, thereby forming a specific pattern on the substrate.

The developer is, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene. The concentration of the developer is generally 0.001 wt% to 10 wt%, preferably 0.005 wt% to 5 wt%, and more preferably 0.01 wt% to 1 wt%.

After the pre-baked coating is developed, the substrate with the specific pattern is washed with water, and then the specific pattern is air-dried with compressed air or compressed nitrogen. Then, a post-bake treatment is performed using a heating device such as a hot plate or an oven. The post-bake temperature is usually 150 to 250°C, wherein the heating time using a hot plate is 5 minutes to 60 minutes, and the heating time using an oven is 15 minutes to 150 minutes. After the above processing steps, a black pattern can be formed on the substrate.

< Method for manufacturing color filters > The method for manufacturing color filters is similar to the method for manufacturing black patterns. Specifically, a color filter is coated with a photosensitive composition on a substrate on which a black pattern has been formed, and then pre-baking, exposure, development and post-baking are sequentially performed to obtain the color filter. However, under the conditions of reduced pressure drying, the reduced pressure drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds. After the above-mentioned processing steps, a specific pattern can be fixed to form a pixel layer. Furthermore, the above-mentioned steps are repeated to sequentially form red, green, blue and other pixel layers on the substrate, and a substrate with a black pattern and a pixel layer formed thereon (i.e., a color filter with a pixel layer) can be obtained.

< Liquid crystal display device > First, the color filter formed by the above-mentioned color filter manufacturing method and the substrate provided with a thin film transistor (TFT) are arranged opposite to each other, and a gap (cell gap) is set between the two. Then, the color filter and the surrounding part of the above-mentioned substrate are bonded with an adhesive and an injection hole is left. Then, liquid crystal is injected into the gap separated by the substrate surface and the adhesive through the injection hole, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display element is produced by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer. The liquid crystal used above, that is, the liquid crystal compound or liquid crystal composition, is not particularly limited here, and any liquid crystal compound and liquid crystal composition can be used.

In addition, the liquid crystal alignment film used in the manufacture of the color filter is used to limit the alignment of the liquid crystal molecules, and there is no particular limitation, for example, any inorganic or organic material can be used, and the present invention is not limited thereto.

The present invention is described in detail below with reference to the following examples , but the present invention is not limited to the contents disclosed in these examples .

The following are the synthesis examples A-1-1 to A-1-7 of the alkali-soluble resin (A-1): Synthesis example A-1-1

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 262.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the temperature was raised to 120° C. while stirring while replacing the atmosphere with nitrogen.

Next, 19.0 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) was added to a monomer mixture consisting of 5.70 g (0.05 mol) of isopropyl acrylate, 121 g (0.85 mol) of glycidyl methacrylate, 13.2 g (0.06 mol) of dicyclopentyl methacrylate, and 4.00 g (0.04 mol) of methyl methacrylate, and the mixture was dripped from a dropping funnel into the aforementioned flask over 2 hours. After the dripping was completed, the mixture was stirred at 120° C. for 2 hours to perform a copolymerization reaction, thereby generating an addition copolymer. Then, the atmosphere in the flask was replaced with air, and 73.2 g (0.85 mol) of methacrylic acid, 0.6 g of triphenylphosphine (catalyst) and 0.2 g of methyl hydroquinone were added to the above addition copolymer solution. The reaction was continued at 110°C with stirring for 10 hours. The epoxy group from glycidyl methacrylate was ring-opened by the ring-opening reaction with methacrylic acid, and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Then, 114 g (0.75 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued at 110°C with stirring for 3 hours, so that the hydroxyl group produced by the ring-opening reaction of the epoxy group reacted with the anhydride of tetrahydrophthalic anhydride to introduce a carboxyl group into the side chain, thereby obtaining an alkali-soluble resin (A-1-1). Synthesis Examples A-1-2 to A-1-7

The alkali-soluble resins of Synthesis Examples A-1-2 to A-1-7 were prepared by the same steps as Synthesis Example A-1-1, and the difference was that the monomer components and their usage amounts were changed (as shown in Table 1). Synthesis Example of Alkali-soluble Resin ( A-2 )

The following are the synthesis examples A-2-1 to A-2-7 of the alkali-soluble resin (A-2): Synthesis example A-2-1

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 262.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the temperature was raised to 120° C. while stirring while replacing the atmosphere with nitrogen.

Next, 19.0 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) was added to a monomer mixture consisting of 45.8 g (0.16 mol) of α-methylstyrene, 107 g (0.75 mol) of glycidyl methacrylate, 18.5 g (0.07 mol) of dicyclopentenyloxyethyl methacrylate, and 1.88 g (0.02 mol) of norbornene, and the mixture was dripped from a dropping funnel into the aforementioned flask over 2 hours. After the dripping was completed, the mixture was stirred at 120° C. for 2 hours to perform a copolymerization reaction, thereby generating an addition copolymer. Then, the atmosphere in the flask was replaced with air, and 50.4 g (0.7 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst) and 0.2 g of methyl hydroquinone were added to the above addition copolymer solution. The mixture was stirred at 110°C for 10 hours to continue the reaction. The epoxy group from glycidyl methacrylate was ring-opened by the ring-opening reaction with acrylic acid, and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Then, 63.0 g (0.63 mol) of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C with stirring for 3 hours, so that the hydroxyl group produced by the ring-opening reaction of the epoxy group reacted with the anhydride of succinic anhydride to introduce a carboxyl group into the side chain, thereby obtaining an alkali-soluble resin (A-2-1). Synthesis Examples A-2-2 to A-2-7

The alkali-soluble resins of Synthesis Examples A-2-2 to A-1-7 were prepared by the same steps as Synthesis Example A-2-1, and the difference was that the monomer component types and usage amounts were changed (as shown in Table 2).

In addition, the compounds corresponding to the abbreviations in Tables 1 and 2 are as follows. Abbreviation Chinese name IPA Isopropyl acrylate IBMA Isobutyl methacrylate EHA 2-ethylhexyl acrylate IOA Isooctyl acrylate IDMA Isodecyl methacrylate GMA Glycidyl methacrylate EBA 3,4-epoxy butyl acrylate EC-MAA 3,4-epoxycyclohexylmethyl methacrylate GOEA 2-glycidyloxyethyl acrylate EHMA 6,7-epoxy heptyl methacrylate FA-513M Dicyclopentanyl methacrylate FA-512M Dicyclopentenyloxyethyl methacrylate NBHE Norbornene (bicyclo[2.2.1]hept-2-ene) MA Methyl acrylate MMA Methyl methacrylate SM Styrene α-MS α-methyl styrene p-MS 4-methoxy styrene p-AS 4-amino styrene BYZGR Benzyl methacrylate MAA Methacrylic acid AA Acrylic acid HOMS 2-Methacryloyloxyethyl succinate monoester THPA Tetrahydrophthalic anhydride SA Succinic anhydride MA Maleic acid

[Table 1] Composition (molar number) Synthesis Example A-1-1 A-1-2 A-1-3 A-1-4 A-1-5 A-1-6 A-1-7 Acrylate compound having a branched alkyl group (a1) IPA 0.05 - - 0.12 - - - IBMA - 0.16 - - 0.10 - - EHA - - 0.27 - 0.25 - - IOA - - - - - 0.40 - IDMA - - - - - - 0.33 Acrylic compound (a2) having an epoxy group GMA 0.85 - - - 0.63 - - EBA - 0.75 - - - - 0.30 EC-MAA - - 0.48 - - - 0.10 GOEA - - - 0.35 - - - EHMA - - - - - 0.30 - Other unsaturated compounds (a3) (a3-1) FA-513M 0.06 - - - 0.02 - - FA-512M - 0.07 - 0.03 - - - NBHE - 0.02 0.01 - - - - (a3-2) MA - - 0.24 0.20 - 0.30 - MMA 0.04 - - 0.30 - - 0.27 Polymerizable unsaturated monoacid (a5) MAA 0.85 - - - 0.56 - - AA - 0.70 - 0.35 - - - HOMS - - 0.48 - - 0.25 0.40 Polybasic acid or its anhydride (a6) THPA 0.75 - - - - - 0.20 SA - 0.63 - 0.12 - 0.01 - MA - - 0.36 - 0.50 - -

[Table 2] Composition (molar number) Synthesis Example A-2-1 A-2-2 A-2-3 A-2-4 A-2-5 A-2-6 A-2-7 Unsaturated compound having an aromatic group (a4) SM - 0.03 - - - - - α-MS 0.16 - - 0.10 - 0.45 - p-MS - - 0.27 0.25 - - - p-AS - - - - 0.12 - - BYZGR - - - - - - 0.33 Acrylic compound (a2) having an epoxy group GMA 0.75 - - 0.63 - - - EBA - 0.85 - - - - 0.30 EC-MAA - - 0.48 - - 0.30 - GOEA - - - - 0.35 - - EHMA - - - - - - 0.10 Other unsaturated compounds (a3) (a3-1) FA-513M - 0.06 - 0.02 - - - FA-512M 0.07 - - - 0.03 - - NBHE 0.02 - 0.01 - - - - (a3-2) MA - - 0.24 - 0.20 0.25 - MMA - 0.06 - - 0.30 - 0.27 Polymerizable unsaturated monoacid (a5) MAA - 0.85 - 0.56 - - - AA 0.70 - - - 0.35 - - HOMS - - 0.48 - - 0.25 0.40 Polybasic acid or its anhydride (a6) THPA - 0.75 - - - - 0.20 SA 0.63 - - - 0.12 0.01 - MA - - 0.36 0.50 - - - Synthesis Examples of Other Alkaline Soluble Resins ( A-3 ) Synthesis Example A-3-1

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 267.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the temperature was raised to 120°C while stirring while replacing the atmosphere with nitrogen.

Next, 19.2 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) was added to a monomer mixture consisting of 55.3 g (0.3 mol) of 2-ethylhexyl acrylate, 17.2 g (0.2 mol) of methacrylic acid, 11.0 g (0.05 mol) of dicyclopentyl methacrylate, 25.0 g (0.25 mol) of methyl methacrylate, and 35.2 g (0.2 mol) of benzyl methacrylate. The mixture was dripped from a dropping funnel into the aforementioned flask over a period of 2 hours. After the dripping was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, thereby obtaining another alkali-soluble resin (A-3-1). Example of black photosensitive resin composition

The following describes Examples 1 to 12 and Comparative Examples 1 to 3 of the black negative photosensitive resin composition: Example 1

10 parts by weight of alkali-soluble resin (A-1-1), 90 parts by weight of alkali-soluble resin (A-2-1), 30 parts by weight of trihydroxymethylpropyl triacrylate (B-1), 7 parts by weight of the compound represented by formula (C-1-1) (C-1-1), 150 parts by weight of black pigment MA100 (E-1), 13 parts by weight of polycarbonate diol Nippollan 976 (F-1), and 5 parts by weight of the compound represented by formula (G-1-1) (G-1) are added to 400 parts by weight of propylene glycol monomethyl ether acetate (D-1), and the mixture is stirred evenly with a shaking stirrer to obtain the black photosensitive resin composition of Example 1. Examples 2 to 12

The black photosensitive resin compositions of Examples 2 to 12 are prepared in the same steps as Example 1, and the difference is that the types of components and the amounts used of the black photosensitive resin compositions are changed (as shown in Tables 3 and 4). Comparative Examples 1 to 3

The photosensitive resin compositions of Comparative Examples 1 to 3 were prepared in the same steps as Example 1, and the difference was that the types of components and the amounts used of the photosensitive resin compositions were changed (as shown in Table 4).

The compounds corresponding to the numbers in Table 3 and Table 4 are shown below. Abbreviation Chinese name A-1-1 Alkali-soluble resin of Synthesis Example A-1-1 (A-1-1) A-1-2 Alkali-soluble resin of Synthesis Example A-1-2 (A-1-2) A-1-3 Alkali-soluble resin of Synthesis Example A-1-3 (A-1-3) A-1-4 Alkali-soluble resin of Synthesis Example A-1-4 (A-1-4) A-1-5 Alkali-soluble resin of Synthesis Example A-1-5 (A-1-5) A-1-6 Alkali-soluble resin of Synthesis Example A-1-6 (A-1-6) A-1-7 Alkali-soluble resin of Synthesis Example A-1-7 (A-1-7) A-2-1 Alkali-soluble resin of Synthesis Example A-2-1 (A-2-1) A-2-2 Alkali-soluble resin of Synthesis Example A-2-2 (A-2-2) A-2-3 Alkali-soluble resin of Synthesis Example A-2-3 (A-2-3) A-2-4 Alkali-soluble resin of Synthesis Example A-2-4 (A-2-4) A-2-5 Alkali-soluble resin of Synthesis Example A-2-5 (A-2-5) A-2-6 Alkali-soluble resin of Synthesis Example A-2-6 (A-2-6) A-2-7 Alkali-soluble resin of Synthesis Example A-2-7 (A-2-7) A-3-1 Other alkali-soluble resins of Synthesis Example A-3-1 (A-3-1) A-3-2 PGMEA solution of epoxy acrylate acid adduct having a fluorene skeleton (resin solid content concentration = 55.5 mass %, trade name: V259ME, manufactured by Nippon Steel Chemical Co., Ltd.) B-1 Trimethylolpropane triacrylate B-2 Dipentaerythritol hexacrylate B-3 Pentaerythritol triacrylate, esterified with phthalic acid C-1-1 The compound represented by formula (C-1-1) C-1-2 The compound represented by formula (C-1-9) C-1-3 The compound represented by formula (C-1-23) C-2-1 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone-1-(O-acetyloxime) Trade name: OXE-02, manufactured by Ciba Specialty Chemicals C-2-2 2-Methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone Trade name: IRGACURE 907, manufactured by Ciba Specialty Chemicals D-1 Propylene glycol monomethyl ether acetate (PGMEA) D-2 Ethyl 3-ethoxypropionate (EEP) E-1 MA100 (Mitsubishi Chemical) E-2 MA230 (Mitsubishi Chemical) F-1 Nippollan 976 (Mn=500, manufactured by Tosoh Corporation) F-2 Nippollan 965 (Mn=1000, manufactured by Tosoh Corporation) F-3 Nippollan 963 (Mn=200, manufactured by Tosoh Corporation) F-4 Nippollan 968 (Mn=3000, manufactured by Tosoh Corporation) F-5 Nippollan 981 (Mn=1000, manufactured by Tosoh Corporation) F-6 Nippollan 980R (Mn=2000, manufactured by Tosoh Corporation) F-7 PCDL T-5650E (Mn=500, manufactured by Asahi Kasei) F-8 PCDL T-5650J (Mn=800, manufactured by Asahi Kasei) F-9 PCDL T-5651 (Mn=1000, manufactured by Asahi Kasei) F-10 PCDL T-5652 (Mn=2000, manufactured by Asahi Kasei) G-1 The compound represented by formula (G-1-1) G-2 The compound represented by formula (G-1-2) G-3 The compound represented by formula (G-1-3) G-4 The compound represented by formula (G-1-4) G-5 The compound represented by formula (G-1-5) G-6 2-[4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine G-7 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine G-8 2,4-Bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine G-9 2,4-Bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine G-10 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine

[Table 3] Ingredients (parts by weight) Embodiment 1 2 3 4 5 6 7 Alkaline soluble resin (A) A-1 A-1-1 10 - - - - - - A-1-2 - 20 - - - - - A-1-3 - - 30 - - - - A-1-4 - - - 40 - - - A-1-5 - - - - 50 - - A-1-6 - - - - - 60 - A-1-7 - - - - - - 25 A-2 A-2-1 90 - - - - - - A-2-2 - 80 - - - - - A-2-3 - - 70 - - - - A-2-4 - - - 60 - - - A-2-5 - - - - 50 - - A-2-6 - - - - - 40 - A-2-7 - - - - - - 75 A-3 A-3-1 - - - - - - - A-3-2 - - - - - - - Compound having ethylenically unsaturated groups (B) B-1 30 - - 80 - - 90 B-2 - 40 - - 80 - - B-3 - - 50 - 25 65 - Photoinitiator (C) C-1 C-1-1 7 - - 20 - - 50 C-1-2 - 10 - - 30 - - C-1-3 - - 15 - - 40 - C-2 C-2-1 - - - 10 - - - C-2-2 - - - - - - 20 Solvent (D) D-1 400 - 1100 - 1600 1000 2500 D-2 - 600 - 1300 - 1000 - Black pigment (E) E-1 150 - 350 - 450 600 750 E-2 - 200 - 300 - - - Polycarbonate diol (F) F-1 13 - - - - - - F-2 - 10 - - - - - F-3 - - 4 - - - - F-4 - - - 8 - - - F-5 - - - - 17 - - F-6 - - - - - 20 - F-7 - - - - - - 25 F-8 - - - - - - - F-9 - - - - - - - F-10 - - - - - - - Compound (G) G-1 5 - - - 10 - - G-2 - 10 - - - - - G-3 - - 15 - - - - G-4 - - - 20 - - - G-5 - - - - 15 - - G-6 - - - - - 30 - G-7 - - - - - - 35 G-8 - - - - - - - G-9 - - - - - - - G-10 - - - - - - - Visibility evaluation ◎ ◎ ◎ ◎ ◎ ◎ ◎ Adhesion evaluation ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 4] Ingredients (parts by weight) Embodiment Comparison Example 8 9 10 11 12 1 2 3 Alkaline soluble resin (A) A-1 A-1-1 35 - - - - - - - A-1-2 - - - - - - - - A-1-3 - - - - - - - - A-1-4 - - - - - - - - A-1-5 - - - - - - - - A-1-6 - - - - - - - - A-1-7 - - - - - - - - A-2 A-2-1 - - - - - - - - A-2-2 - - - - - - - - A-2-3 - 45 - - - - - - A-2-4 - - - - - - - - A-2-5 - - - - - - - - A-2-6 - - - - - - - - A-2-7 - - - - - - - - A-3 A-3-1 65 10 100 - 50 100 - 100 A-3-2 - 45 - 100 50 - 100 - Compound having ethylenically unsaturated groups (B) B-1 - - 130 - - 80 - - B-2 45 - - 180 - - 100 - B-3 - 150 - - 60 - - 150 Photoinitiator (C) C-1 C-1-1 60 - - 27 - - - - C-1-2 - 25 - - 35 - - - C-1-3 - - 13 - - - - - C-2 C-2-1 - - - 3 - 25 20 - C-2-2 - - - - - - - 15 Solvent (D) D-1 - 800 - 2200 1000 1000 - - D-2 3000 - 1800 - - - 1500 800 Black pigment (E) E-1 - 900 - 50 500 250 200 - E-2 800 - 250 600 - - - 300 Polycarbonate diol (F) F-1 - 20 - 28 - - 15 - F-2 - - - - twenty three - - - F-3 - - - - - - - - F-4 - - - - - - - - F-5 - - - - - - - - F-6 - - - - - - - - F-7 - - - - - - - - F-8 33 - - - - - - - F-9 - 20 - - - - - - F-10 - - 6 - - - - - Compound (G) G-1 - - - 12 twenty three 10 - - G-2 - - - - - - - - G-3 - - - - - - - - G-4 - - - - - - - - G-5 - - - - - - - - G-6 - - - - - - - - G-7 - - - - - - - - G-8 40 - - - - - - - G-9 - 45 - - - - - - G-10 - - 8 - - - - - Visibility evaluation ◎ ○ ○ ○ ○ X ○ X Adhesion evaluation ○ ◎ ○ ○ ○ ○ X X Evaluation method

Development property The black photosensitive resin composition prepared in the above-mentioned embodiments and comparative examples was applied on a 100 mm×100 mm glass substrate by spin coating, and then dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 100°C for 2 minutes to form a pre-baked coating with a film thickness of 3.0 μm. Next, the pre-baked coating was developed with a 0.045% potassium hydroxide aqueous solution at 23°C, and the time t required for the pre-baked coating to dissolve was measured, which was equivalent to the developing time, and evaluated according to the following standards: ◎: t≦40 seconds; ○: 40 seconds < t≦50 seconds; △: 50 seconds < t≦60 seconds; ╳: 60 seconds < t.

Adhesion The black photosensitive resin composition prepared in the above-mentioned embodiments and comparative examples was coated on a glass substrate with an average length and width of 100 mm by a coating machine (model MS-A150, purchased from Shin Kong Trading) by a rotary coating method. Then, the above-mentioned glass substrate was pre-baked at 100°C for 2 minutes to form a pre-baked coating film with a film thickness of 3.0 μm. Then, the above-mentioned pre-baked coating film was exposed to ultraviolet light of 80 mJ/ ^cm2 (exposure machine model AG500-4N; manufactured by M&R Nano Technology). Next, develop with 0.045% potassium hydroxide aqueous solution at 23°C for 1 minute, then wash with water and post-bake the pre-baked coating at 235°C for 30 minutes to form a black cured film on the glass substrate. After further irradiating the black cured film with 830 mJ/ ^cm2 of ultraviolet light, cut the black cured film into 100 cross-hatched grids with a knife according to the cross-hatched measurement method of 8.5.2 in JIS.K5400 (1900) 8.5 Adhesion Test Method. Then, stick with tape (3M396) and tear it off, observe the grid residue, and evaluate according to the following criteria. Among them, the higher the residue ratio, the better the adhesion. ◎: 99% ≦ cross-hatched residue. ○: 97% ≦ Mesh residue < 99%. △: 95% ≦ Mesh residue < 97%. ╳: Mesh residue < 95%. Evaluation results

As shown in Tables 3 and 4, compared with the black patterns prepared by the black photosensitive resin composition containing both the specific polycarbonate diol (F) and the compound (G) having a specific structure (Examples 1 to 12), the black patterns of Comparative Examples 1 and 3 not containing the specific polycarbonate diol (F) have poor developability; and the black patterns of Comparative Examples 2 and 3 not containing the compound (G) having a specific structure have poor adhesion.

In addition, when the black photosensitive resin composition further contains an alkali-soluble resin (A-1) (Examples 1 to 8), the developability of the black pattern can be further improved.

In addition, when the black photosensitive resin composition further contains an alkali-soluble resin (A-2) (Examples 1 to 7, 9), the adhesion of the black pattern can be further improved.

In summary, the black photosensitive resin composition of the present invention contains polycarbonate diol (F) and a compound (G) having a specific structure. Therefore, the black photosensitive resin composition can improve the technical problems of poor developing property and poor adhesion resistance in the prior art.

In addition, when the black photosensitive resin composition further contains an alkali-soluble resin (A-1), the developability of the black pattern can be further improved, and when the black photosensitive resin composition further contains an alkali-soluble resin (A-2), the adhesion of the black pattern can be further improved.

Although the present invention has been disclosed as above by the embodiments, they are not intended to limit the present invention. Any person with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be defined by the scope of the attached patent application.

Claims (12)

A black photosensitive resin composition comprises: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); a solvent (D); a black pigment (E); a polycarbonate diol (F); and a compound (G) having a structure represented by formula (G-1), wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), and the alkali-soluble resin (A-1) has a branched alkyl group, an acid group and a polymerizable unsaturated bond.

In formula (G-1), R ¹² , R ²² and R ³² each independently represent a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonylalkoxy group, and at least one of R ¹² , R ²² and R ³² is a hydroxyl group; R ¹³ , R ²³ and R ³³ each independently represent a hydrogen atom or an alkyl group; and R ¹⁴ , R ²⁴ and R ³⁴ each independently represent a hydroxyl group, an alkoxy group, an alkyl group, a hydroxyalkoxy group, an alkoxycarbonylalkoxy group, a 3-alkoxy-2-hydroxy-propoxy group or an alkylcarbonyloxy group. A black photosensitive resin composition as described in claim 1, wherein the alkali-soluble resin (A) includes an alkali-soluble resin (A-2), and the alkali-soluble resin (A-2) has an aromatic group, an acid group, and a polymerizable unsaturated bond. The black photosensitive resin composition as described in claim 1, wherein the alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed by a first mixture with a polymerizable unsaturated monobasic acid (a5) and then reacting with a polyacid or its anhydride (a6); the first mixture includes an acrylate compound (a1) having a branched alkyl group, an acrylic compound (a2) having an epoxy group, and other unsaturated compounds (a3). A black photosensitive resin composition as described in claim 2, wherein the alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed by a second mixture with a polymerizable unsaturated monobasic acid (a5) and then with a polyacid or its anhydride (a6); the second mixture includes an unsaturated compound (a4) having an aromatic group, an acrylic compound (a2) having an epoxy group, and other unsaturated compounds (a3). The black photosensitive resin composition as described in claim 1, wherein the polycarbonate diol (F) is a compound represented by formula (F-1),

In formula (F-1), a plurality of R ^1's each independently represent a divalent organic group; and m represents an integer of 1 to 20. The black photosensitive resin composition as described in claim 1, wherein the number average molecular weight of the polycarbonate diol (F) is 500-3000. The black photosensitive resin composition as described in claim 1, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, the amount of the compound (B) having an ethylenically unsaturated group used is 20 parts by weight to 180 parts by weight, the amount of the photoinitiator (C) used is 7 parts by weight to 70 parts by weight, the total amount of the solvent (D) used is 400 parts by weight to 3000 parts by weight, the amount of the black pigment (E) used is 150 parts by weight to 900 parts by weight, the amount of the polycarbonate diol (F) used is 4 parts by weight to 40 parts by weight, and the amount of the compound (G) used is 5 parts by weight to 45 parts by weight. The black photosensitive resin composition as described in claim 1, wherein the amount of the alkali-soluble resin (A-1) used is 10 to 60 parts by weight based on the total amount of the alkali-soluble resin (A) used being 100 parts by weight. The black photosensitive resin composition as described in claim 2, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the alkali-soluble resin (A-2) used is 40 parts by weight to 90 parts by weight. A black pattern is formed by subjecting the black photosensitive resin composition as described in any one of claims 1 to 9 to pre-baking, exposure, development and post-baking. A color filter comprising a black pattern as described in claim 10. A liquid crystal display device, comprising a color filter as described in claim 11.