TW202144441A - 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 in particular, to a black pattern with the advantages of good developability and good adhesion formed by exposure, development and hardening of the black photosensitive resin composition.

In recent years, with the vigorous development of various technologies of liquid crystal display devices, and in order to improve the contrast ratio and display quality of liquid crystal display devices, the color filter stripes and dots in the liquid crystal display devices are usually divided between stripes and dots. A black pattern, such as a black matrix, is provided between the gaps. The black matrix can prevent defects such as a decrease in contrast ratio and a decrease in color purity caused by light leakage between pixels.

Japanese Patent Laid-Open No. 2008-268854 discloses a black photosensitive resin composition. The photosensitive resin composition includes an alkali-soluble resin having a carboxylic acid group and an unsaturated group for polymerization, an ethylenically unsaturated group-containing photopolymerizable monomer, a photopolymerization initiator, and a black pigment. This patent improves the resolution of the black pattern formed by the photosensitive resin composition with a high content of black pigment by using a specific alkali-soluble resin. In addition, Japanese Patent Laid-Open No. 2009-145432 discloses a black photosensitive resin composition. The photosensitive resin composition contains an ethylenically unsaturated group-containing monomer, a photopolymerization initiator, a black pigment, and a resin. The resin is selected from thermosetting resin, photosensitive resin, thermoplastic resin, or a combination thereof. This patent improves the problems of low sensitivity and poor developability of photosensitive resin compositions with high content of black pigments in the photolithography process by regulating the content of black pigments in the solid content of the photosensitive resin compositions.

However, due to the increasing demand for the light-shielding properties of black patterns in the industry, the solution is to increase the content of black pigments to improve the light-shielding properties of black patterns. However, the photosensitive resin composition of the prior art is obtained The black pattern has problems of poor developability and adhesion.

Therefore, how to overcome the problems of poor developability and adhesion in order to meet the requirements of the current industry is the goal of hard work in the technical field to which the present invention pertains.

In view of this, the present invention provides a black photosensitive resin composition capable of improving the above-mentioned problems of poor developability and adhesion.

式(G-1) 式(G-1)中，R¹² 、R²² 及R³² 分別獨立地表示羥基、烷基、烷氧基或烷氧基羰基烷氧基，且R¹² 、R²² 及R³² 中至少一個為羥基。R¹³ 、R²³ 及R³³ 分別獨立地表示氫原子或烷基。R¹⁴ 、R²⁴ 及R³⁴ 分別獨立地表示羥基、烷氧基、烷基、羥基烷氧基、烷氧基羰基烷氧基、3-烷氧基-2-羥基-丙氧基或烷基羰氧基。The present invention provides a black photosensitive resin composition, comprising: an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and 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), R ¹² , R ²² and R ³² each independently represent a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonylalkoxy group, and R ¹² , R ²² and At least one of R ^{32 is hydroxy.} R ¹³ , R ²³ and R ³³ each independently represent a hydrogen atom or an alkyl group. R ¹⁴ , R ²⁴ and R ³⁴ each independently represent hydroxy, alkoxy, alkyl, hydroxyalkoxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy or alkyl Carbonyloxy.

In an embodiment of the present invention, the above-mentioned 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 an embodiment of the present invention, the above-mentioned 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 an embodiment of the present invention, the above-mentioned alkali-soluble resin (A-1) is the addition copolymer formed by the first mixture and the polymerizable unsaturated monobasic acid (a5) after the reaction, and then with the polybasic acid or its Anhydride (a6) derived from the reaction. 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 an embodiment of the present invention, the above-mentioned alkali-soluble resin (A-2) is formed by reacting the addition copolymer formed by the second mixture with the polymerizable unsaturated monobasic acid (a5), and then reacting with the polybasic acid or its Anhydride (a6) derived from the reaction. 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).

式(F-1) 式(F-1)中，多個R¹ 分別獨立地表示2價有機基；m表示1~20的整數。In an embodiment of the present invention, the above-mentioned polycarbonate diol (F) is a compound represented by formula (F-1),

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

In an embodiment of the present invention, the above-mentioned polycarbonate diol (F) has a number average molecular weight of 500-3000.

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

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

In an embodiment of the present invention, based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount 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, which is formed by subjecting the above black photosensitive resin composition to pre-baking treatment, exposure treatment, development treatment and post-baking treatment.

The present invention further provides a color filter comprising the above-mentioned black pattern.

The present invention further provides a liquid crystal display device comprising the above-mentioned color filter.

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

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following specific examples are given for detailed description as follows.

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

The alkali-soluble resin (A) includes the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). In addition, the alkali-soluble resin (A) may further include other alkali-soluble resins (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 the addition copolymer formed from the first mixture with the polymerizable unsaturated monobasic acid (a5), and then reacting with the polybasic acid 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 the alkali-soluble resin (A-1), the developability of the black pattern formed by the black photosensitive resin composition can be further improved. Acrylate compounds with branched alkyl groups ( a1 )

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

The total mol of the compounds based on the first mixture is 1.0 mol, and the acrylate compound (a1) having a branched alkyl group is used in an amount of 0.05 to 0.4 mol, preferably 0.07 to 0.38 mol, more preferably 0.1 to 0.35 moles. Acrylic compound with epoxy group ( a2 )

Specific examples of the acrylic compound (a2) having an epoxy group include glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and (meth)acrylate- 3,4-Epoxybutyl ester, (meth)acrylate-6,7-epoxyheptyl ester, (meth)acrylate-3,4-epoxycyclohexylmethyl ester and their lactone adducts (such as DAICEL Chemical Industry Co., Ltd. Cyclomer A200, M100), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate mono(meth)acrylate, ( Epoxy compound of dicyclopentenyl meth)acrylate, epoxy compound of dicyclopentenyloxyethyl (meth)acrylate, etc.

The total moles of the compounds based on the first mixture are 1.0 moles, and the acrylic compound (a2) having an epoxy group is used in an amount of 0.3 to 0.85 moles, preferably 0.35 to 0.83 moles, more preferably 0.4 to 0.4 moles. 0.8 moles. Other unsaturated compounds ( a3 )

The other unsaturated compound (a3) refers to an unsaturated compound that does not belong to the above-mentioned branched alkyl group-containing acrylate compound (a1), epoxy group-containing acrylic compound (a2), and the following aromatic group-containing unsaturated compound (a4). Saturated compounds. Other unsaturated compounds (a3) include unsaturated compounds (a3-1) and unsaturated compounds (a3-2). Unsaturated compound ( a3-1 )

式(a3-1-1)

式(a3-1-2)

式(a3-1-3) 式(a3-1-3)中，X、Y各自獨立表示氫原子、碳數為1至4的直鏈狀烴基或者碳數為1至4的分支狀烴基；R¹ 、R² 各自獨立表示氫原子、碳數為1至20的烴基或者碳數為1至20的羧酸基，所述烴基及所述羧酸基為未經取代或經取代基取代；或者所述R¹ 、R² 彼此相互鍵結形成環狀結構。The unsaturated compound (a3-1) is selected from the group consisting of acrylate compounds including the structures represented by the following formula (a3-1-1) and formula (a3-1-2), and those represented by the following formula (a3-1-3) At least one of the compounds shown:

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 hydrocarbon group having 1 to 4 carbon atoms, or a branched hydrocarbon group having 1 to 4 carbon atoms; R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a carboxylic acid group with 1 to 20 carbon atoms, and the hydrocarbon group and the carboxylic acid group are unsubstituted or substituted with a substituent; Alternatively, the R ¹ and R ² are bonded to each other to form a cyclic structure.

Specific examples of the acrylate compound having the structure represented by the formula (a3-1-1) include dicyclopentyl (meth)acrylate (trade names FA-513A and FA-513M, manufactured by Hitachi Chemical Co., Ltd.) Such as acrylate compounds having a tricyclodecane skeleton. Specific examples of the acrylate compound having the structure represented by the formula (a3-1-2) include tricyclo[5.2.1.0 ^2,6 ]dec-8-yl acrylate (trade name FA-511A, available from Hitachi Chemical Industries, Ltd.) Co., Ltd.), 2-(tricyclo[5.2.1.0 ^2,6 ]dec-3-ene-8(9)-oxy)ethyl (meth)acrylate (dicyclopentenyloxyethyl) Meth)acrylates, trade names FA-512A, FA-512M, manufactured by Hitachi Chemical Co., Ltd.) and acrylate compounds having a dicyclopentadiene skeleton. 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-ethyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] twelve-3-ene, 8-methyl-tetracyclo [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, Tricyclic [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 ]undec-3-ene, tricyclo[4.4.0.1 2,5]undec-3-ene 6.2.1.0 ^1,8] eleven-9-ene, tricyclo [6.2.1.0 ^1,8] eleven-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6] twelve-3-ene, 8-ethylidene tetracyclo [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 ] Dodec-3-ene, Pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] Pentadec-4-ene, pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ]pentadec-3- alkene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid and 5-norbornene-2,3-dianhydride and other compounds. Only one of the compounds listed above may be used, or two or more of them may be used simultaneously.

The total moles of the compounds based on the first mixture is 1.0 moles, and the unsaturated compound (a3-1) is used in an amount of 0.01 to 0.09 moles, preferably 0.012 to 0.08 moles, more preferably 0.015 to 0.07 moles Ear. Unsaturated compounds ( 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-Amyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, n-(meth)acrylate Octadecyl, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, methoxy-triethyl Glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, Shin Nakamura Chemical Industry Co., Ltd. (meth)acrylate), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, butanetriol mono(meth)acrylate, pentanetriol mono(meth)acrylate, 1,4 -Cyclohexanedimethanol mono(meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, (meth)acrylate base) perfluoroethyl acrylate, perfluoron-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, furyl (meth)acrylate, furanmethyl (meth)acrylate, ( (Meth)acrylates that do not have an aromatic ring, such as tetrahydrofuryl meth)acrylate, pyranyl (meth)acrylate, and 3-(N,N-dimethylamino)propyl (meth)acrylate ; Dicyclopentenyl (meth)acrylate, dicyclohexyl (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5 (meth)acrylate -(meth)acrylic acid having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, such as ethyl norbornyl ester, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and rosin (meth)acrylate Esters; (meth)acrylate amide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-diethylamide Propyl amide, (meth) acrylic acid N,N-diisopropyl amide, (meth) acrylate anthryl amide and other (meth) acrylate amide; (meth) acrylate aniline, (meth) acrylate ) vinyl compounds such as acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; butadiene, 2,3 - Dimethyl butadiene, isoprene, chloroprene and other diene compounds; diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid Etc. unsaturated dicarboxylic acid diester compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl) Monomaleimide compounds such as maleimide; N-(meth)acryloyl phthalimide, etc. These monomers may be used alone, or two or more kinds of monomers may be used in combination.

The total moles of the compounds based on the first mixture is 1.0 moles, and the other unsaturated compounds (a3) are used in an amount of 0 to 0.6 moles, preferably 0 to 0.5 moles, more preferably 0 to 0.4 moles . Polymerizable unsaturated monobasic acid ( a5 )

The polymerizable unsaturated monobasic acid (a5) used for the reaction with the addition copolymer formed from the first mixture or the following second mixture may be any one having a polymerizable unsaturated bond and an acid group, for example, An unsaturated carboxylic acid, an unsaturated sulfonic acid, an unsaturated phosphonic acid, etc. are illustrated. Specific examples of the polymerizable unsaturated monobasic acid (a5) include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propyolic acid, and cinnamon Acid, α-Cyanocinnamic Acid, Monomethyl Maleate, Monoethyl Maleate, Monoisopropyl Maleate, Monomethyl Fumarate, Monoethyl Iconate, 2-Methpropene Unsaturated carboxylic acids such as acyl ethoxysuccinate; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, p-styrenesulfonic acid, etc. ; Unsaturated phosphonic acid such as vinylphosphonic acid, etc. These unsaturated monobasic acids may be used alone or in combination of two or more.

The total moles of the compounds based on the first mixture is 1.0 moles, and the polymerizable unsaturated monobasic acid (a5) is used in an amount of 0.25 to 0.85 moles, preferably 0.3 to 0.83 moles, more preferably 0.35 to 0.8 moles Moore. Polyacid or its anhydride ( a6 )

The polybasic acid or its anhydride (a6) used to react with the addition copolymer formed from the first mixture or the following second mixture may be either a saturated or unsaturated polybasic acid or an anhydride thereof, and a specific example may be Malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexa Hydrophthalic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, 5-norbornene-2,3- Dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, phthalic anhydride and other dibasic acids or their anhydrides, trimene Tribasic acids such as triacids, trimellitic anhydride or their anhydrides, and tetrabasic acids such as pyromellitic acid and pyromellitic anhydride or their anhydrides. Among these, dibasic acid anhydrides are preferably used.

The total mol of the compound based on the first mixture is 1.0 mol, and the polybasic acid or its anhydride (a6) is used in an amount of 0.01 to 0.75 mol, preferably 0.03 to 0.7 mol, more preferably 0.05 to 0.65 mol Ear. Alkali 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 the addition copolymer formed from the second mixture with the polymerizable unsaturated monobasic acid (a5), and then reacting with the 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).

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

Moreover, the acrylic compound (a2) which has an epoxy group, other unsaturated compound (a3), polymerizable unsaturated monobasic acid (a5), and polybasic acid or Specific examples of its anhydride (a6) and epoxy group-containing acrylic compound (a2), other unsaturated compound (a3), and polymerizable unsaturated monobasic acid used in the production process of alkali-soluble resin (A-1) (a5) and the polybasic acid or its anhydride (a6) are the same, so they will not be repeated here.

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

The total number of moles of the compounds based on the second mixture is 1.0 moles, and the other unsaturated compound (a3) is used in an amount of 0 to 0.6 moles, preferably 0 to 0.5 moles, more preferably 0 to 0.4 moles . Unsaturated compounds with aromatic groups ( a4 )

Specific examples of the unsaturated compound (a4) having an aromatic group include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 2-methylstyrene. Chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-aminostyrene, 3-amine Styrenic unsaturated compounds such as styrene, 4-aminostyrene, 4-nitrostyrene, 4-cyanostyrene, 4-acetylaminostyrene or indene; benzyl (meth)acrylate ester, phenethyl (meth)acrylate, phenmethyl (meth)acrylate, cumyl (meth)acrylate, piperonyl (meth)acrylate, salicylyl (meth)acrylate, ( Trityl 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.), (meth)acrylates having an aromatic ring such as o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, and p-phenoxybenzyl acrylate.

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

The total moles of the compounds based on the second mixture is 1.0 moles, and the polymerizable unsaturated monobasic acid (a5) is used in an amount of 0.25 to 0.85 moles, preferably 0.3 to 0.83 moles, more preferably 0.35 to 0.8 moles Moore.

The total mol of the compound based on the second mixture is 1.0 mol, and the polyacid or its anhydride (a6) is used in an amount of 0.01 to 0.75 mol, preferably 0.03 to 0.7 mol, more preferably 0.05 to 0.65 mol Ear. Alkali-soluble resin ( A-1 ) and alkali-soluble resin ( A-2 ) manufacturing method

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

The copolymerization 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 free radical polymerization methods well known in the art. For example, after dissolving the first mixture (or the second mixture) in a solvent as desired, a polymerization initiator may be added to the solution, and a copolymerization reaction may be performed at 50 to 130° C. for 1 to 20 hours.

The solvent that can be used in the copolymerization reaction is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Ethyl 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 mono Ethyl 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, tripropylene glycol monoethyl ether, etc. ( Poly) Alkylene Glycol Monoalkyl Ether Compounds; Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate (poly)alkanediol monoalkyl ether acetate compounds; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Compounds; ketone compounds of methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxy propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3 - methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, acetic acid Isoamyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl pyruvate Ester compounds of methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbon compounds such as toluene, xylene, etc.; N-methyldipyrrolidone, N,N-dimethylene Carboxylic acid amide compounds such as carboxamide, N,N-dimethylacetamide, etc. The above-mentioned solvents may be used alone or in combination of two or more.

Among them, (poly)alkanediol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly)alkanediol monoalkyl ether ethyl esters such as propylene glycol monomethyl ether acetate are preferred. Ester-based solvent, that is, glycol ether-based solvent.

The usage-amount of a polymerization solvent is not specifically limited, When the total of the 1st mixture (or 2nd mixture) is 100 mass parts, it is generally 30-1,000 mass parts, Preferably it is 50-800 mass parts. In particular, by setting the amount of the solvent used to be 1,000 parts by mass or less, the molecular weight of the copolymer can be suppressed from being lowered due to chain transfer, and the viscosity of the copolymer can be controlled within an appropriate range. Moreover, by making the compounding quantity of a solvent into 30 mass parts or more, an abnormal polymerization reaction can be prevented, a polymerization reaction can be performed stably, and the coloring and gelation of a copolymer can also be prevented.

In addition, the polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzyl peroxide, and tert-butyl peroxide. Oxy-2-ethylhexanoate, etc. These systems can be used individually or in combination of 2 or more types. When the total added amount of the first mixture (or the second mixture) is 100 parts by mass, the usage amount of the polymerization initiator is generally 0.5-20 parts by mass, preferably 1-10 parts by mass.

Next, by carrying out the following modification reaction using the epoxy group contained in the addition copolymer thus produced, it is possible to obtain an acid group and a polymerizable unsaturated bond in the side chain, and the glass transition temperature is 20°C or lower, And it is an alkali-soluble resin whose weight average molecular weight in terms of polystyrene is 1,000 to 50,000.

Above-mentioned modification reaction comprises the steps: Step 1: Ring-opening reaction is performed on all epoxy groups contained in the addition copolymer by means of the polymerizable unsaturated monobasic acid (a5). Step 2: The hydroxyl group generated through the above-mentioned ring-opening reaction is reacted with the polybasic acid or its anhydride (a6).

The amount of the polymerizable unsaturated monobasic acid (a5) used in the first step can be appropriately selected according to the value of the unsaturated group equivalent of the desired curable polymer. Usually, based on the total number of moles of epoxy groups contained in the addition copolymer, the total number of moles is 1.0 moles, and the amount of the polymerizable unsaturated monobasic acid (a5) used is 0.90 to 1 moles, preferably 0.95 to 1 moles. . When the usage-amount of a polymerizable unsaturated monobasic acid (a5) is too small, there exists a possibility that a side reaction may generate|occur|produce in the subsequent reaction.

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

Moreover, when performing step 1, in order to prevent gelation, a polymerization inhibitor may be added as needed. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. Further, 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, chromium chelating compounds, etc.

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

The usage-amount of the hydroxyl group and the polybasic acid or its anhydride (a6) used in the second step can be appropriately selected according to the acid value of the intended curable polymer. Usually based on the total number of moles of hydroxyl groups generated in step 1 is 1.0 moles, the usage amount of the polybasic acid or its anhydride (a6) is 0.01-0.9 moles, preferably 0.02-0.85 moles. When the usage-amount of a hydroxyl group, a polybasic acid, or its anhydride (a6) is too small, there exists a possibility that the developability may become inadequate, and conversely, if it is too large, there exists a possibility that a sensitivity may fall.

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

The weight average molecular weight of the alkali-soluble resin (A-1) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is 1,000 to 50,000, preferably 3,000 to 40,000.

The weight average molecular weight of the alkali-soluble resin (A-2) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is 1,000 to 50,000, preferably 3,000 to 40,000.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the alkali-soluble resin (A-1) used is 10 to 60 parts by weight, preferably 15 to 55 parts by weight, 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) used is 40 to 90 parts by weight, preferably 45 to 85 parts by weight, more preferably 50 to 80 parts by weight . Other alkali-soluble resins ( A-3 )

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

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

The aforementioned compounds with one ethylenically unsaturated group may include, but are not limited to, (meth)acrylamido, (meth)acrylomorpholine, (meth)acrylic acid-7-amino-3,7-dimethyl Octyl ester, isobutoxymethyl(meth)acrylamide, isobornyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, 2-ethylhexyl(meth)acrylate , ethyl diethylene glycol (meth)acrylate, third octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, ( Dodecyl meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, Tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, (meth)acrylate 2-Tetrabromophenoxyethyl acrylate, 2-Trichlorophenoxyethyl (meth)acrylate, Tribromophenyl (meth)acrylate, 2-Tribromophenoxy (meth)acrylate Ethyl 2-hydroxy-(meth)acrylate, 2-hydroxy-(meth)acrylate, 2-hydroxy-(meth)acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate ester, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene mono(meth)acrylate, polypropylene mono(meth)acrylate or bornol (meth)acrylate compounds such as esters. The compound having one ethylenically unsaturated group may be used alone or in combination.

The aforementioned compounds with two or more (including two) ethylenically unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate (Meth)acrylate, Tetraethylene glycol di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate (Meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, ethylene oxide ( Referred to as EO) modified trimethylolpropyl acrylate, propylene oxide modified (referred to as PO) trimethylolpropyl acrylate, tripropylene glycol di(meth)acrylic acid ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate ) acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified Substantially dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, tetra(meth)acrylate ditrimethylolpropyl, modified with ethylene oxide Bisphenol A di(meth)acrylate, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, Propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate or novolac polyglycidyl ether (meth)acrylate, etc. the compound. The compound having two or more (including two) ethylenically unsaturated groups may 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: trimethylolpropyl triacrylate, ethylene oxide modified trimethylolpropyl triacrylate, propylene oxide Modified trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate ester, ditrimethylolpropyl tetraacrylate, propylene oxide modified glycerol triacrylate, or any combination of the above.

The compound (B) having an ethylenically unsaturated group can preferably be trimethylolpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or any combination of the above compounds.

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

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

式(C-I) 其中R₁ 、R₂ 、R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 彼此獨立地為氫、碳數為1至20的烷基、COR₁₆ 、由式(C-II)所表示的基團、

式(C-II)； 或R₁ 及R₂ 、R₂ 及R₃ 、R₃ 及R₄ 、R₅ 及R₆ 、R₆ 及R₇ 或R₇ 及R₈ 彼此獨立地共同為式(C-III)所表示的基團；

式(C-III)； 但條件為R₁ 及R₂ 、R₂ 及R₃ 、R₃ 及R₄ 、R₅ 及R₆ 、R₆ 及R₇ 或R₇ 及R₈ 中之至少一對是由式(C-III)所表示的基團， R₉ 、R₁₀ 、R₁₁ 及R₁₂ 彼此獨立地為氫、碳數為1至20的烷基，該碳數為1至20的烷基是未經取代或經一或多個以下基團取代：鹵素、苯基； 或R₉ 、R₁₀ 、R₁₁ 及R₁₂ 彼此獨立地為未經取代之苯基或經一或多個以下基團取代之苯基：碳數為1至6的烷基、鹵素； X表示CO或直接鍵； R₁₃ 表示碳數為1至20的烷基，其未經取代或經一或多個以下基團取代：鹵素、R₁₇ 、COOR₁₇ 、OR₁₇ ； 或R₁₃ 表示碳數為2至20的烷基，其間雜有一或多個O或CO，其中該經間雜之碳數為2至20的烷基是未經取代或經一或多個鹵素取代； 或R₁₃ 表示苯基或萘基，其各為未經取代或經一或多個以下基團取代：碳數為1至20的烷基、碳數為1至4的鹵代烷基； R₁₄ 表示氫、碳數為1至20的烷氧基或碳數為1至20的烷基； R₁₅ 是碳數為6至20的芳基，其各是未經取代或經一或多個以下基團取代：鹵素、碳數為1至4的鹵代烷基、OR₁₇ 、間雜有一或多個O之碳數為2至20的烷基；或其各經碳數為1至20的烷基取代，該碳數為1至20的烷基是未經取代或經一或多個以下基團取代：鹵素、COOR₁₇ 、苯基、OR₁₇ ； 或R₁₅ 表示氫、碳數為3至8的環烷基；或R₁₅ 是碳數為1至20的烷基，其是未經取代或經一或多個以下基團取代：鹵素、碳數為3至8的環烷基； R₁₆ 表示碳數為6至20的芳基，其各是未經取代或經一或多個以下基團取代：鹵素、碳數為1至4的鹵代烷基、OR₁₇ ；或其各經一或多個碳數為1至20的烷基取代，該碳數為1至20的烷基是未經取代或經一或多個以下基團取代：鹵素、OR₁₇ ； R₁₇ 表示氫、碳數為1至20的烷基，其是未經取代或經一或多個以下基團取代：鹵素或間雜有一或多個O之碳數為3至20的環烷基； 或R₁₇ 表示碳數為2至20的烷基，其間雜有一或多個O； 或R₁₇ 表示苯基，其各是未經取代或經一或多個以下基團取代：鹵素、碳數為1至12的烷基、碳數為1至12的烷氧基； 但條件為在式(C-I)中存在至少一個由式(C-II)所表示的基團。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 of each other hydrogen, alkyl having a carbon number of 1 to 20, COR ₁₆ , represented by the formula ( C-II) represents the group,

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 independently of each other and together are the formula ( A group represented by C-III);

Formula (C-III); provided that at least one pair _{of 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 is a group represented by the formula (C-III), R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently hydrogen, an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms group is unsubstituted or substituted with one or more of the following groups: halogen, phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are unsubstituted phenyl or substituted with one or more of the following Group-substituted phenyl: alkyl with 1 to 6 carbons, halogen; X represents CO or a direct bond; R ₁₃ represents alkyl with 1 to 20 carbons, which is unsubstituted or substituted by one or more of the following Group substitution: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ ; or R ₁₃ represents an alkyl group with a carbon number of 2 to 20, intermixed with one or more O or CO, wherein the intervening carbon number is 2 to 20 The alkyl group is unsubstituted or substituted with one or more halogens; or R ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: carbon number 1 to 20 Alkyl, haloalkyl with 1 to 4 carbons; R ₁₄ represents hydrogen, alkoxy with 1 to 20 carbons or alkyl with 1 to 20 carbons; R ₁₅ is aryl with 6 to 20 carbons groups, each of which is unsubstituted or substituted with one or more of the following groups: halogen, haloalkyl with 1 to 4 carbons, OR ₁₇ , alkyl with 2 to 20 carbons interspersed with one or more O ; or each substituted by an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted by one or more of the following groups: halogen, COOR ₁₇ , phenyl, OR ₁₇ ; or R ₁₅ represents hydrogen, a cycloalkyl having a carbon number of 3 to 8; or R ₁₅ is an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with one or more of the following groups: halogen , cycloalkyl with a carbon number of 3 to 8; R ₁₆ represents an aryl group with a carbon number of 6 to 20, each of which is unsubstituted or substituted with one or more of the following groups: halogen, carbon number 1 to 4 haloalkyl, OR ₁₇ ; or each substituted with one or more alkyl groups with 1 to 20 carbon atoms, which are unsubstituted or substituted with one or more of the following groups : halogen, OR ₁₇ ; R ₁₇ represents hydrogen, an alkyl group with a carbon number of 1 to 20, which is unsubstituted or substituted by one or more of the following groups: halogen or interspersed with one or more O and the carbon number is 3 cycloalkyl to 20; or R ₁₇ represents an alkyl group with a carbon number of 2 to 20, interspersed 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 Group substitution: halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons; provided that at least one group represented by formula (C-II) is present in formula (CI) .

式(C-III)。Compounds of formula (CI) are characterized in that they contain one or more annlated unsaturated rings on the carbazole moiety. In other words, _{at least one pair of 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 is represented by formula (C-III) represents the group,

Formula (C-III).

Alkyl having a carbon number from 1 to 20 is straight or branched, examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl base, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, Eighteen bases and twenty bases.

A haloalkyl group having a carbon number of 1 to 4 is an alkyl group having a carbon number of 1 to 4 as defined above substituted with halogen as defined below. Alkyl groups are, for example, mono- or polyhalogenated until all H-atoms are replaced by halogen. Which is (e.g.) C _z H _x Hal _y, wherein x + y = 2z + 1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

An alkyl group having 2 to 20 carbon atoms interspersed with one or more Os is interspersed with O, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylene groups). The alkyl groups are straight or branched. For example, the presence of the following structural _{units: -CH 2 -CH 2 -O-CH} 2 CH 3, - [CH 2 CH 2 O] y -CH 3 ( wherein y = l to 9), - (CH ₂ - CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ .

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

Aryl having a carbon number of 6 to 20 is, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, enyl, naphthyl, triphenyl, etc., especially phenyl or naphthyl, Preferred is phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

Substituted aryl groups (phenyl, naphthyl, aryl having 6 to 20 carbon atoms) are respectively substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 time, 2 times or 3 times, respectively . Obviously, an aryl group as defined cannot have more substituents than there are free positions at the aryl ring.

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

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 4 times, 1 to 3 times or 1 time or 2 times (obviously, the number of interstitial atoms depends on the number of C atoms to be interspersed). A substituted group that is substituted one or more times has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 identical or different substituents.

式(C-III)，則形成例如以下述式(C-Ia)-式(C-Ii)所示的結構:

式(C-Ia)、

式(C-Ib)、

式(C-Ic)、

式(C-Id)、

式(C-Ie)、

式(C-If)、

式(C-Ig)、

式(C-Ih)、

式(C-Ii)。A group substituted with one or more of the defined substituents is intended to have one substituent or more substituents with the same or different definitions as given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ independently of each other and together are represented by formula (C-III) the group,

Formula (C-III), then form for example the structure shown in following formula (C-Ia)-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 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-Ic) -Ia), formula (C-Ic) or formula (C-Id), particularly preferably formula (C-Ia).

Formula R ₁₅ represents, for example, hydrogen, phenyl, naphthyl, each of which is unsubstituted or substituted with an alkyl group having a carbon number of 1 to 8, OR ₁₇ ; or R ₁₅ represents an alkyl group having a carbon number of 1 to 20; Or R ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and one or more Os are mixed therebetween.

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

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

Furthermore, R ₁₆ represents, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OR ₁₇ or alkyl having 1 to 20 carbons.

R _{16 is} especially, for example, phenyl, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ or alkyl having 1 to 20 carbons.

Preferably R ₁₆ is phenyl substituted with one or more alkyl groups having 1 to 20 carbons.

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

式(C-1-1)

式(C-1-2)

式(C-1-3)

式(C-1-4)

式(C-1-5)

式(C-1-6)

式(C-1-7)

式(C-1-8)

式(C-1-9)

式(C-1-10)

式(C-1-11)

式(C-1-12)

式(C-1-13)

式(C-1-14)

式(C-1-15)

式(C-1-16)

式(C-1-17)

式(C-1-18)

式(C-1-19)

式(C-1-20)

式(C-1-21)

式(C-1-22)

式(C-1-23)Examples of the inventive compound of 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 amount of the first photoinitiator (C-1) used is 7 to 60 parts by weight, preferably 8 to 55 parts by weight, more preferably 9 to 60 parts by weight 50 parts by weight. Second photoinitiator ( C-2 )

The second photoinitiator (C-2) is, for example, an acetophenone-based compound (acetophenone), a biimidazole-based compound (biimidazole), or a combination thereof.

Specific examples of the acetophenone-based compound 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, nitrogen-dimethylamine -1-(4-Morpholinophenyl)-1-butanone or a combination of the above compounds.

Specific examples of the diimidazole-based compound 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(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 , Nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl diimidazole or a combination of the above compounds.

The second photoinitiator (C-2) may further add the following compounds as needed: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxan, benzophenone , 4,4'-bis (dimethylamine) benzophenone, 4,4'-bis (diethylamine) benzophenone and other benzophenone (benzophenone) compounds; benzil (benzil), Alpha-diketones such as acetyl; acyloin such as benzoin; benzoin methylether, benzoin methylether Keto alcohol ethers such as benzoin ethylether and benzoin isopropyl ether; 2,4,6-trimethylbenzodiphenylphosphine oxide (2,4,6-trimethyl-benzoyl -diphenyl-phosphineoxide), bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphineoxide [bis-(2,6-dimethoxy-benzoyl)-2, 4,4-trimethyl-benzyl-phosphineoxide] and other phosphine oxides; anthraquinone (anthraquinone), 1,4-naphthoquinone (1,4-naphthoquinone) and other quinones; phenacyl chloride (phenacyl chloride), Halides such as tribromomethyl-phenylsulfone and tris(trichloromethyl)-s-triazine; di-tert-butyl peroxide (di- tertbutylperoxide) and other peroxides; or a combination of the above. The compound added to the photoinitiator (C) is preferably a benzophenone-based compound, and more preferably 4,4'-bis(diethylamine)benzophenone.

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

The solvent (D) means that the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the following black pigment (E), the polycarbonate diol ( F) and the additive (G) dissolve, but do not react with the above-mentioned components, and are preferably those with suitable volatility.

Specific examples of the solvent (D) include: alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ethers, other ether compounds, ketone compounds, alkane lactate Esters, other esters, aromatic hydrocarbons, carboxylic acid amines, or a combination of the foregoing.

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 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 analogs thereof, or a combination of the above compounds.

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

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

Specific examples of other ether compounds include tetrahydrofuran or the like.

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

Specific examples of the alkyl lactate compound include methyl lactate, ethyl lactate or the like, 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, 3-methoxypropionate ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3 -Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Isobutyl, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvic acid ethyl ester, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate, or the like, or a combination of the foregoing.

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

Carboxylic amine compounds 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.

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

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

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

Specific examples of the black pigment (E) include black organic pigments such as perylene black, cyanine black, or aniline black; , cyanine (cyanine) or magenta (magenta) and other pigments, select two or more pigments to be mixed to form a color-mixing organic pigment that is close to black; carbon black (carbon black), chromium oxide, oxidized Light-shielding materials such as iron, titanium black (titanium black), graphite, etc., wherein specific examples of the above-mentioned carbon black include CIpigment black 7 or commercial products (trade names MA100, MA230, MA8, #970, #1000) manufactured by Mitsubishi Chemical , #2350 or #2650). The above-mentioned black pigment (E) can be used alone or in combination of two or more.

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

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

式(F-1)The polycarbonate diol (F) is a compound represented by the formula (F-1),

Formula (F-1)

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

If the polycarbonate diol (F) is not included in the black photosensitive resin composition, the developability of the black pattern formed by the black photosensitive resin composition is not good.

When the black photosensitive resin composition contains the polycarbonate diol (F) represented by the formula (F-1), the developability 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 of the above are trade names); Placcel CD (registered trademark) manufactured by Daicel CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL; 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 other commercial products manufactured by Tosoh Corporation. The above-mentioned polycarbonate diols (F) may be used alone or in combination of two or more.

The number average molecular weight (Mn) of the polycarbonate diol (F) in terms of styrene is 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 in the above range, the developability is better.

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

式(G-1) 式(G-1)中，R¹² 、R²² 及R³² 分別獨立地表示羥基、烷基、烷氧基或烷氧基羰基烷氧基，且R¹² 、R²² 及R³² 中至少一個為羥基。R¹³ 、R²³ 及R³³ 分別獨立地表示氫原子或烷基。R¹⁴ 、R²⁴ 及R³⁴ 分別獨立地表示羥基、烷氧基、烷基、羥基烷氧基、烷氧基羰基烷氧基、3-烷氧基-2-羥基-丙氧基或烷基羰氧基。Compound (G) has a structure represented by the following formula (G-1):

Formula (G-1) 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 R ¹² , R ²² and At least one of R ^{32 is hydroxy.} R ¹³ , R ²³ and R ³³ each independently represent a hydrogen atom or an alkyl group. R ¹⁴ , R ²⁴ and R ³⁴ each independently represent hydroxy, alkoxy, alkyl, hydroxyalkoxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy or alkyl Carbonyloxy.

Specific examples of the compound (G) include 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, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl) phenyl)-1,3,5-triazine and other mono(hydroxyphenyl)triazine compounds; such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4- Dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl) -1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1, Bis(hydroxyphenyl)triazine compounds such as 3,5-triazine; and 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, 2,4,6-tri[2- Tris(hydroxyphenyl)triazine compounds such as hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine.

式(G-1-1)

式(G-1-2)

式(G-1-3)

式(G-1-4)

式(G-1-5)Specific examples of the 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 above-mentioned alkali-soluble resin (A), the amount of compound (G) used is 5 to 45 parts by weight; preferably 6 to 40 parts by weight, more preferably 7 to 35 parts by weight.

When the compound (G) is not included in the black photosensitive resin composition, the black pattern formed by the black photosensitive resin composition has poor adhesion. Additives (H)

On the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may further optionally add an additive (H). Specific examples of the additive (H) include surfactants, fillers, polymers (refer to polymers other than the above-mentioned alkali-soluble resin (A)), adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and others Colorant.

The surfactant contributes to improving the coatability of the photosensitive resin composition. Specific examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or the above-mentioned interfacial active agents combination of agents.

Specifically, the surfactant is, for example, polyoxyethylene alkyl ethers such as polyethoxy lauryl ether, polyethoxy stearyl ether, and polyethoxy oleyl ether; Polyethoxyalkyl phenyl ethers such as ethoxy octyl phenyl ether and polyethoxy nonyl phenyl ether; polyethylene glycol such as polyethylene glycol dilaurate and polyethylene glycol distearate Diesters; 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 Industry, SF-8427 products manufactured by Dow Corning Toray Co., Ltd., and general products manufactured by Kyeisha Oil Chemical Industry. Polyflow products, F-Top products manufactured by Tochem Products Co., Ltd., Mekafco manufactured by Dainippon Ink Chemical Industry Co., Ltd. (Megafac) products, Fluorade products made by Sumitomo 3M, Asahi Guard products made by Asahi Glass, or Surflon products made by Asahi Glass.

Specific examples of the filler 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 foregoing polymers.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxy Propanolpropyltrimethoxysilane, 3-glycidolpropylmethyldiethoxysilane, 3-glycidolpropylmethyldimethoxysilane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a combination of the foregoing.

Specific examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or combinations thereof.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxy phenone, or compounds of the above-mentioned compounds. combination.

Specific examples of the anti-aggregation agent 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 such as metal zirconium salts (for example, metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, etc.) or the above A composite oxide of a metal is exemplified.

Specific examples of organic pigments include CI 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; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI 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, 104, 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; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; CI Pigment Blue 1, 2, 15, 15:3, 15:4 , 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37; CI Pigment Brown 23, 25, 28 or a combination of the above.

< Manufacturing method of black photosensitive resin composition > The method that can be used to prepare the black photosensitive resin composition is, for example: alkali-soluble resin (A), compound (B) having an ethylenically unsaturated group, photoinitiator (C) ), solvent (D), black pigment (E), polycarbonate diol (F) and compound (G) are placed in a stirrer and stirred to make them evenly mixed into a solution state, and additives (H) can also be added if necessary. ) and uniformly mixed to obtain a black photosensitive resin composition in a solution state.

Moreover, the preparation method of a black photosensitive resin composition is not specifically limited. The preparation method of the black photosensitive resin composition is, for example, firstly dispersing a part of the alkali-soluble resin (A) and the compound (B) having an ethylenically unsaturated group in a part of the solvent (D) to form a dispersion solution; and then Mix the rest of the alkali-soluble resin (A), compound having an ethylenically unsaturated group (B), photoinitiator (C), solvent (D), black pigment (E), polycarbonate diol (F) and compound (G) to prepare.

Alternatively, the black photosensitive resin composition may be formed by first dispersing a part of the black pigment (E) in a mixture consisting of a part of the alkali-soluble resin (A) and a part of the solvent (D) to form a black pigment dispersion; And add alkali-soluble resin (A), compound (B) having ethylenically unsaturated group, photoinitiator (C), solvent (D), black pigment (E), polycarbonate diol (F) and Compound (G) is prepared. In addition, the dispersing step of the above-mentioned black pigment (E) can be performed by mixing with a mixer such as a bead mill or a roll mill.

<Method of producing a black pattern> black pattern are sequentially administered by the black photosensitive resin composition on a substrate, prebaking, exposure, development and post-baking treatment system. Moreover, when the film thickness of the obtained black pattern is 1 μm, the optical density can be in the range of 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The preparation method of the black pattern is described in detail below.

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

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by a pre-bake method to form a pre-bake coating film. It is worth noting that the conditions for drying under reduced pressure and pre-baking vary according to the type and ratio of each component. In general, drying under reduced pressure is performed under a pressure of less than 200 mmHg for 1 second to 20 seconds, and prebaking is a heat treatment of the coating film at a temperature of 70°C to 110°C for 1 minute to 15 minutes.

Next, the above-mentioned pre-baked coating film is exposed to light with a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device can be (ultra) high pressure mercury lamp and metal halide lamp.

Then, at a temperature of 23±2° C., the above-mentioned exposed pre-baking coating film is immersed in a developing solution to remove the pre-baking coating film of the above-mentioned unexposed part, whereby the pre-baking coating film on the substrate can be removed. form a specific pattern.

The developer is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, Basic compounds such as tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo-[5,4,0]-7-undecene, etc. 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 film 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, post-bake treatment is performed with a heating device such as a hot plate or an oven. The post-baking 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-mentioned processing steps, a black pattern can be formed on the substrate.

<Method of producing a color filter> The method for producing a color filter manufacturing method is similar to a black pattern. Specifically, the photosensitive composition for a color filter is coated on a substrate on which a black pattern has been formed, and then pre-baking, exposure, development, and post-baking treatments are sequentially applied to prepare it. However, in the condition of drying under reduced pressure, drying under reduced pressure is carried out under the 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, thereby forming a pixel layer. And, repeating the above steps to sequentially form red, green, blue and other pixel layers on the substrate to obtain a substrate (ie, a color filter with a pixel layer) on which black patterns and pixel layers are formed.

< Liquid crystal display device > First, the color filter formed by the above-mentioned method for producing a color filter and the substrate provided with a thin film transistor (TFT) are arranged to face each other, and the A gap (cell gap) is set between them. Next, the color filter and the peripheral portion of the above-mentioned substrate are bonded together with an adhesive and an injection hole is left. Then, the liquid crystal is injected through the injection hole on the surface of the substrate and the gap separated by the adhesive, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display element was fabricated by providing polarizers on the other side of the color filter contacting the liquid crystal layer and the other side of the substrate contacting the liquid crystal layer. The liquid crystal used above, that is, a liquid crystal compound or a 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 production of the color filter is used to limit the alignment of liquid crystal molecules, and there is no particular limitation, either inorganic or organic matter can be used, and the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to the contents disclosed by these examples. < Example> Synthesis example of alkali-soluble resin ( A-1 )

Synthesis Example A-1-1 to Synthesis Example A-1-7 of the alkali-soluble resin (A-1) will be described below: Synthesis Example A-1-1

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

Next, 5.70 g (0.05 moles) of isopropyl acrylate, 121 g (0.85 moles) of glycidyl methacrylate, 13.2 g (0.06 moles) of dicyclopentyl methacrylate and methyl methacrylate To the monomer mixture consisting of 4.00 g (0.04 mol), 19.0 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) was added, and the obtained It was added dropwise to the aforementioned flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the copolymerization reaction was performed by stirring at 120° C. for 2 hours to generate an addition copolymer. Then, the inside of the flask was replaced with air, and 73.2 g (0.85 moles) of methacrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.2 g of methylhydroquinone were added to the above-mentioned addition copolymer solution, and the solution was heated at 110° C. The reaction was continued under stirring for 10 hours, and a polymerizable unsaturated bond was introduced into the side chain of the polymer while the epoxy group was ring-opened by the ring-opening reaction of the epoxy group derived from glycidyl methacrylate and methacrylic acid. Next, 114 g (0.75 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued by stirring at 110° C. for 3 hours, so that the hydroxyl group generated by the ring-opening reaction of the epoxy group was reacted with tetrahydrophthalic acid. An alkali-soluble resin (A-1-1) can be obtained by introducing a carboxyl group into a side chain by reacting an acid anhydride of dimethyl anhydride. Synthesis Example A-1-2 to Synthesis Example A-1-7

The alkali-soluble resins of Synthesis Example A-1-2 to Synthesis Example A-1-7 were prepared in the same steps as those of Synthesis Example A-1-1, except that the kinds of components of the monomers and their use were changed. amount (as shown in Table 1). Synthesis example of alkali-soluble resin ( A-2)

Synthesis Example A-2-1 to Synthesis Example A-2-7 of the alkali-soluble resin (A-2) will be described below: Synthesis Example A-2-1

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

Next, 45.8 g (0.16 moles) of α-methylstyrene, 107 g (0.75 moles) of glycidyl methacrylate, 18.5 g (0.07 moles of dicyclopentenyloxyethyl methacrylate) ear) and 1.88 g (0.02 mol) of norbornene in the monomer mixture, 19.0 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O), the resultant was added dropwise to the aforementioned flask from a dropping funnel over 2 hours. After completion of the dropwise addition, the copolymerization reaction was performed by stirring at 120° C. for 2 hours to generate an addition copolymer. Then, the inside of 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 methylhydroquinone were added to the above-mentioned addition copolymer solution, followed by stirring at 110° C. The reaction was continued for 10 hours, and the epoxy group was ring-opened by the ring-opening reaction of the epoxy group derived from glycidyl methacrylate and acrylic acid, and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 63.0 g (0.63 mol) of succinic anhydride was added to the reaction system, and the reaction was continued by stirring at 110° C. for 3 hours, and the hydroxyl group generated by the ring-opening reaction of the epoxy group was reacted with the acid anhydride of succinic anhydride to react in the reaction system. By introducing a carboxyl group into a side chain, an alkali-soluble resin (A-2-1) can be obtained. Synthesis Example A-2-2 to Synthesis Example A-2-7

The alkali-soluble resins of Synthesis Example A-2-2 to Synthesis Example A-1-7 were prepared in the same steps as those of Synthesis Example A-2-1, except that the kinds of components of the monomers and their use were changed. amount (as shown in Table 2).

In addition, the compounds corresponding to the abbreviations in Table 1 and Table 2 are shown below. short name 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 (α-methyl styrene) p-MS 4-methoxy styrene p-AS 4-amino styrene BzMA 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 (a1) having branched alkyl group 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 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 monobasic acid (a5) MAA 0.85 - - - 0.56 - - AA - 0.70 - 0.35 - - - HOMS - - 0.48 - - 0.25 0.40 Polyacid 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 (a4) having aromatic group SM - 0.03 - - - - - α-MS 0.16 - - 0.10 - 0.45 - p-MS - - 0.27 0.25 - - - p-AS - - - - 0.12 - - BzMA - - - - - - 0.33 Acrylic compound (a2) having 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 monobasic acid (a5) MAA - 0.85 - 0.56 - - - AA 0.70 - - - 0.35 - - HOMS - - 0.48 - - 0.25 0.40 Polyacid or its anhydride (a6) THPA - 0.75 - - - - 0.20 SA 0.63 - - - 0.12 0.01 - MA - - 0.36 0.50 - - - Synthesis example of other alkali-soluble resin ( A-3 ) Synthesis example A-3-1

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

Next, 55.3 g (0.3 moles) of 2-ethylhexyl acrylate, 17.2 g (0.2 moles) of methacrylic acid, 11.0 g (0.05 moles) of dicyclopentyl methacrylate, methyl methacrylate To the monomer mixture consisting of 25.0 g (0.25 mol) and 35.2 g (0.2 mol) of benzyl methacrylate, 19.2 g of tert-butylperoxy-2-ethylhexanoate (polymerization start) was added. A solvent, NOF Corporation make, Perbutyl O), the resultant was added dropwise to the aforementioned flask from a dropping funnel over 2 hours. After completion of the dropwise addition, the copolymerization reaction was performed by stirring at 120° C. for 2 hours to obtain another alkali-soluble resin (A-3-1). Examples of black photosensitive resin compositions

Examples 1 to 12 and Comparative Examples 1 to 3 of the black negative photosensitive resin composition will be described below: 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 trimethylol propyl triacrylate (abbreviated as B-1) , 7 parts by weight of the compound represented by formula (C-1-1) (abbreviated as C-1-1), 150 parts by weight of black pigment MA100 (abbreviated as E-1), 13 parts by weight of polycarbonate Diol Nippollan 976 (abbreviated as F-1) and 5 parts by weight of the compound represented by formula (G-1-1) (abbreviated as G-1) were added to 400 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as G-1). The black photosensitive resin composition of Example 1 can be obtained after it is in D-1) and stirred uniformly with a shaking stirrer. Example 2 to Example 12

The black photosensitive resin compositions of Examples 2 to 12 were prepared in the same steps as those of Example 1, and the difference was that the types of components of the black photosensitive resin compositions and their usage amounts (as shown in Table 3) were changed. , as shown in Table 4). Comparative Example 1 to Comparative Example 3

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

C-1-2 由式(C-1-9)所示的化合物

C-1-3 由式(C-1-23)所示的化合物

C-2-1 1-[9-乙基-6-(2-甲基苯醯基)-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙醯基肟) (l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone-1-(O-acetyloxime)) 商品名：OXE-02，汽巴精化有限公司(Ciba Specialty Chemicals)製造 C-2-2 2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮 (2-Methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone) 商品名：IRGACURE 907，汽巴精化有限公司製造 D-1 丙二醇單甲醚醋酸酯(Propylene glycol monomethyl ether acetate，PGMEA) D-2 3-乙氧基丙酸乙酯(Ethyl 3-ethoxypropionate，EEP) E-1 MA100(三菱化學製) E-2 MA230(三菱化學製) F-1 Nippollan 976(Mn=500，東曹公司製) F-2 Nippollan 965(Mn=1000，東曹公司製) F-3 Nippollan 963(Mn=200，東曹公司製) F-4 Nippollan 968(Mn=3000，東曹公司製) F-5 Nippollan 981(Mn=1000，東曹公司製) F-6 Nippollan 980R(Mn=2000，東曹公司製) F-7 PCDL T-5650E(Mn=500，旭化成製) F-8 PCDL T-5650J(Mn=800，旭化成製) F-9 PCDL T-5651(Mn=1000，旭化成製) F-10 PCDL T-5652(Mn=2000，旭化成製) G-1 由式(G-1-1)所示的化合物

G-2 由式(G-1-2)所示的化合物

G-3 由式(G-1-3)所示的化合物

G-4 由式(G-1-4)所示的化合物

G-5 由式(G-1-5)所示的化合物

G-6 2-[4-[(2-羥基-3-十二烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪 G-7 2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪 G-8 2,4-雙(2-羥基-3-甲基-4-丙氧基苯基)-6-(4-甲基苯基)-1,3,5-三嗪 G-9 2,4-雙(2-羥基-4丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三嗪 G-10 2,4,6-三(2-羥基-4-辛氧基苯基)-1,3,5-三嗪 The compounds corresponding to the symbols in Tables 3 and 4 are shown below. short name Chinese name A-1-1 Alkali-Soluble Resin (A-1-1) of Synthesis Example A-1-1 A-1-2 Alkali-Soluble Resin (A-1-2) of Synthesis Example A-1-2 A-1-3 Alkali-Soluble Resin (A-1-3) of Synthesis Example A-1-3 A-1-4 Alkali-Soluble Resin (A-1-4) of Synthesis Example A-1-4 A-1-5 Alkali-Soluble Resin (A-1-5) of Synthesis Example A-1-5 A-1-6 Alkali-Soluble Resin (A-1-6) of Synthesis Example A-1-6 A-1-7 Alkali-Soluble Resin (A-1-7) of Synthesis Example A-1-7 A-2-1 Alkali-Soluble Resin (A-2-1) of Synthesis Example A-2-1 A-2-2 Alkali-Soluble Resin (A-2-2) of Synthesis Example A-2-2 A-2-3 Alkali-Soluble Resin (A-2-3) of Synthesis Example A-2-3 A-2-4 Alkali-Soluble Resin (A-2-4) of Synthesis Example A-2-4 A-2-5 Alkali-Soluble Resin (A-2-5) of Synthesis Example A-2-5 A-2-6 Alkali-Soluble Resin (A-2-6) of Synthesis Example A-2-6 A-2-7 Alkali-Soluble Resin (A-2-7) of Synthesis Example A-2-7 A-3-1 Other Alkali-Soluble Resins (A-3-1) of Synthesis Example 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 Ester product of pentaerythritol triacrylate and phthalic acid C-1-1 Compound represented by formula (C-1-1)

C-1-2 Compound represented by formula (C-1-9)

C-1-3 Compound represented by formula (C-1-23)

C-2-1 1-[9-Ethyl-6-(2-methylbenzyl)-9H-carbazole-3-substituent]-ethanone-1-(O-acetyloxime) (l-[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-morpholino-1-propanone (2-Methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone) : IRGACURE 907, manufactured by Ciba Refinery Co., Ltd. D-1 Propylene glycol monomethyl ether acetate (PGMEA) D-2 Ethyl 3-ethoxypropionate (EEP) E-1 MA100 (manufactured by Mitsubishi Chemical) E-2 MA230 (made by 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 Compound represented by formula (G-1-1)

G-2 Compound represented by formula (G-1-2)

G-3 Compound represented by formula (G-1-3)

G-4 Compound represented by formula (G-1-4)

G-5 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) Example 1 2 3 4 5 6 7 Alkali 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 (B) having ethylenically unsaturated group 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 - - - - - - - developability evaluation ◎ ◎ ◎ ◎ ◎ ◎ ◎ Adhesion evaluation ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 4] Ingredients (parts by weight) Example Comparative example 8 9 10 11 12 1 2 3 Alkali 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 (B) having ethylenically unsaturated group 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 - - - - - developability evaluation ◎ ○ ○ ○ ○ X ○ X Adhesion evaluation ○ ◎ ○ ○ ○ ○ X X Evaluation method

Developability The black photosensitive resin compositions prepared in the above examples and comparative examples were coated on a glass substrate of 100 mm × 100 mm by spin coating, and then dried under reduced pressure at a pressure of 100 mmHg and a time of 100 mmHg. 30 seconds, and then pre-bake at 100°C for 2 minutes to form a pre-bake coating with a thickness of 3.0 μm. Next, develop with 0.045% potassium hydroxide aqueous solution at 23°C, measure the time t required for the pre-baking coating film to dissolve, which is equivalent to the development time, and evaluate according to the following criteria: ◎: t≦40 seconds; ○ : 40 seconds < t≦50 seconds; △: 50 seconds < t≦60 seconds; ╳: 60 seconds < t.

Adhesion The black photosensitive resin compositions prepared in the above-mentioned examples and comparative examples were coated with a coating machine (model MS-A150, purchased from Shin Kong Trading) by spin coating on an average length and width. on a 100 mm glass substrate. 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 with ultraviolet light of 80 mJ/cm 2} (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-bake coating film at 235° C. for 30 minutes to form a black cured film on the glass substrate. This black cured film was further irradiated with ultraviolet light of 830 mJ/cm ² , and then the cross-hatched measurement method of 8.5.2 in JIS.K5400 (1900) 8.5 Adhesion Test Method was used. The above-mentioned black cured film was cut into 100 meshes with a knife. Then, after sticking with a tape (3M396), it was peeled off, and the remaining state of the mesh was observed and evaluated according to the following criteria. Among them, the higher the residual ratio, the better the adhesion. ◎: 99%≦Mesh residue. ○: 97%≦residual mesh grid <99%. △: 95%≦residue of mesh grid <97%. ╳: Residual mesh grid <95%. Evaluation results

From Table 3 and Table 4, the black pattern (Example 1 to 12) In contrast, the black patterns of Comparative Examples 1 and 3 that did not contain the specific polycarbonate diol (F) had poor developability; the black patterns of Comparative Examples 2 and 3 that did not contain the compound (G) having a specific structure Adhesion of the black pattern is poor.

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

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

To sum up, because the black photosensitive resin composition of the present invention contains polycarbonate diol (F) and a compound (G) having a specific structure, the black photosensitive resin composition can improve the existence of the prior art. The technical problem of poor developability and adhesion resistance.

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

Although the present invention has been disclosed above by the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the 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 determined by the scope of the appended patent application.

Claims (13)

A black photosensitive resin composition, comprising: 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 Ester diol (F); and compound (G), having the structure represented by formula (G-1),

Formula (G-1) 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 R ¹² , R ²² and At least one of 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, and a hydroxyalkane oxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy or alkylcarbonyloxy. The black photosensitive resin composition according to claim 1, wherein The alkali-soluble resin (A) includes the 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. The black photosensitive resin composition according to 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 according to claim 2, wherein The alkali-soluble resin (A-1) is obtained by reacting the addition copolymer formed by the first mixture with the polymerizable unsaturated monobasic acid (a5), and then reacting with the polybasic acid 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). The black photosensitive resin composition according to claim 3, wherein The alkali-soluble resin (A-2) is obtained by reacting the addition copolymer formed by the second mixture with the polymerizable unsaturated monobasic acid (a5), and then reacting with the 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). The black photosensitive resin composition according to claim 1, wherein the polycarbonate diol (F) is a compound represented by the formula (F-1),

Formula (F-1) In formula (F-1), a plurality of R ¹ each independently represents a divalent organic group; m represents an integer of 1 to 20. The black photosensitive resin composition according to claim 1, wherein The number average molecular weight of the polycarbonate diol (F) is 500-3000. The black photosensitive resin composition according to claim 1, wherein the total usage amount based on the alkali-soluble resin (A) is 100 parts by weight, The use amount of the compound (B) with an ethylenically unsaturated group is 20 to 180 parts by weight, The usage amount of the photoinitiator (C) is 7 parts by weight to 70 parts by weight, The total usage amount of the solvent (D) is 400 to 3000 parts by weight, The black pigment (E) is used in an amount of 150 to 900 parts by weight, The usage amount of the polycarbonate diol (F) is 4 to 40 parts by weight, And the compound (G) is used in an amount of 5 parts by weight to 45 parts by weight. The black photosensitive resin composition according to claim 2, wherein based on the total usage of the alkali-soluble resin (A) is 100 parts by weight, the usage of the alkali-soluble resin (A-1) is 10 parts by weight to 60 parts by weight. The black photosensitive resin composition according to claim 3, wherein based on the total usage of the alkali-soluble resin (A) is 100 parts by weight, the usage of the alkali-soluble resin (A-2) is 40 parts by weight to 90 parts by weight. A black pattern is formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 10 to pre-baking treatment, exposure treatment, development treatment and post-baking treatment. A color filter comprising the black pattern of claim 11. A liquid crystal display device, comprising the color filter according to claim 12.