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

Abstract

This invention provides a black photosensitive resin composition, a black pattern, a color filter, and a liquid crystal display device. The resulting black pattern exhibits excellent developability and adhesion. The black photosensitive resin composition comprises an alkali-soluble resin (A), a compound having an ethylene unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) having the structure shown in formula (G-1).

Description

Technical Field

[0001] This invention relates to a black photosensitive resin composition, and more particularly to a black pattern, color filter, and liquid crystal display device formed by the black photosensitive resin composition after exposure, development, and curing treatment, which has the advantages of good developability and good adhesion. Background Technology

[0002] In recent years, with the rapid development of various technologies for liquid crystal display devices, and in order to improve the contrast and display quality of liquid crystal display devices, black patterns, such as black matrices, are usually set between the stripes and dots of the color filters in liquid crystal display devices. These black matrices can prevent defects such as decreased contrast ratio and decreased color purity caused by light leakage between pixels.

[0003] Japanese Patent Application Publication No. 2008-268854 discloses a black photosensitive resin composition. This photosensitive resin composition comprises an alkali-soluble resin having a carboxylic acid group and a polymerization-supporting unsaturated group, a photopolymerizable monomer containing an ethylene unsaturated group, a photopolymerization initiator, and a black pigment. This patent improves the resolution of black patterns formed by photosensitive resin compositions with high black pigment content by using a specific alkali-soluble resin. Furthermore, Japanese Patent Application Publication No. 2009-145432 discloses a black photosensitive resin composition. This photosensitive resin composition comprises a monomer containing an ethylene unsaturated group, a photopolymerization initiator, a black pigment, and a resin. The resin is selected from thermosetting resins, photosensitive resins, thermoplastic resins, or combinations thereof. This patent improves the problems of low photosensitivity and poor developability in photolithography processes for photosensitive resin compositions with high black pigment content by controlling the black pigment content in the solid portion of the photosensitive resin composition.

[0004] However, as the industry now demands increasingly higher levels of light-blocking properties for black patterns, the solution is to increase the content of black pigment to improve the light-blocking properties of black patterns. However, black patterns made from existing photosensitive resin compositions suffer from poor developability and adhesion.

[0005] Therefore, overcoming the problems of poor developability and adhesion to meet the current industry requirements is the goal of research in the technical field to which this invention pertains. Summary of the Invention

[0006] In view of this, the present invention provides a black photosensitive resin composition that can improve the aforementioned problems of poor developability and adhesion.

[0007] The present invention provides a black photosensitive resin composition comprising: an alkali-soluble resin (A), a compound having an ethylene unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) having the structure shown in formula (G-1).

[0008]

[0009] In equation (G-1), R 12 R 22 and R 32 Each independently represents a hydroxyl, alkyl, alkoxy, or alkoxycarbonylalkoxy group, and R 12 R 22 and R 32 At least one of them is a hydroxyl group. R 13 R 23 and R 33 Each can be used independently to represent a hydrogen atom or an alkyl group. R 14 R 24 and R 34 Each can be independently represented as hydroxyl, alkoxy, alkyl, hydroxyalkoxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy, or alkylcarbonyloxy.

[0010] In one embodiment of the present invention, the alkali-soluble resin (A) includes alkali-soluble resin (A-1), and the alkali-soluble resin (A-1) has branched alkyl groups, acid groups and polymerizable unsaturated bonds.

[0011] In one embodiment of the present invention, the alkali-soluble resin (A) includes alkali-soluble resin (A-2), and alkali-soluble resin (A-2) has aromatic groups, acid groups and polymerizable unsaturated bonds.

[0012] In one embodiment of the present invention, the alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed from a first mixture with a polymerizable unsaturated monocarboxylic acid (a5), followed by a reaction with a polycarboxylic acid or its anhydride (a6). The first mixture includes an acrylate compound (a1) having branched alkyl groups, an acrylic compound (a2) having epoxy groups, and other unsaturated compounds (a3).

[0013] In one embodiment of the present invention, the alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed from the second mixture with a polymerizable unsaturated monocarboxylic acid (a5), followed by a reaction with a polycarboxylic acid or its anhydride (a6). The second mixture includes an aromatic unsaturated compound (a4), an epoxy-containing acrylic compound (a2), and other unsaturated compounds (a3).

[0014] In one embodiment of the present invention, the above-mentioned polycarbonate diol (F) is a compound represented by formula (F-1).

[0015]

[0016] In equation (F-1), multiple R 1 Each of the two groups represents a divalent organic group independently; m represents an integer from 1 to 20.

[0017] In one embodiment of the present invention, the average molecular weight of the polycarbonate diol (F) is 500 to 3000.

[0018] In one embodiment of the present invention, the total amount of alkali-soluble resin (A) used is 100 parts by weight, the amount of compound (B) having an ethylene unsaturated group used is 20 to 180 parts by weight, the amount of photoinitiator (C) used is 7 to 70 parts by weight, the total amount of solvent (D) used is 400 to 3000 parts by weight, the amount of black pigment (E) used is 150 to 900 parts by weight, the amount of polycarbonate diol (F) used is 4 to 40 parts by weight, and the amount of compound (G) used is 5 to 45 parts by weight.

[0019] In one embodiment of the present invention, the total amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of alkali-soluble resin (A-1) used is 10 to 60 parts by weight.

[0020] In one embodiment of the present invention, the total amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of alkali-soluble resin (A-2) used is 40 to 90 parts by weight.

[0021] The present invention further provides a black pattern formed by pre-baking, exposure, development and post-baking of a black photosensitive resin composition as described above.

[0022] The present invention further provides a color filter, including the black pattern as described above.

[0023] The present invention further provides a liquid crystal display device, including the color filter as described above.

[0024] Based on the above, the black photosensitive resin composition of the present invention uses polycarbonate diol (F) and contains a compound (G) having a specific structure. Therefore, the black photosensitive resin composition can improve the technical problems of poor developability and adhesion in the prior art.

[0025] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described in detail below. Detailed Implementation

[0026] <Black Photosensitive Resin Composition>

[0027] This invention provides a black photosensitive resin composition comprising an alkali-soluble resin (A), a compound having an ethylene unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G), and optionally an additive (H). The various components of the black photosensitive resin composition used in this invention will be described in detail below.

[0028] Alkali-soluble resin (A)

[0029] Alkali-soluble resin (A) includes alkali-soluble resin (A-1) and alkali-soluble resin (A-2). Furthermore, alkali-soluble resin (A) may also include other alkali-soluble resins (A-3).

[0030] Alkali-soluble resin (A-1)

[0031] The alkali-soluble resin (A-1) has branched alkyl groups, acid groups, and polymerizable unsaturated bonds. The alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed from the first mixture with a polymerizable unsaturated monobasic acid (a5), followed by a reaction with a polybasic acid or its anhydride (a6). The first mixture includes an acrylate compound (a1) having branched alkyl groups, an acrylic compound (a2) having epoxy groups, and other unsaturated compounds (a3).

[0032] If the black photosensitive resin composition includes an alkali-soluble resin (A-1), the developability of the black pattern formed by the black photosensitive resin composition can be further improved.

[0033] Acrylate compounds with branched alkyl groups (a1)

[0034] Specific examples of acrylate compounds (a1) having branched alkyl groups include isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, isodecanyl methacrylate, isotetradecyl methacrylate, isotetradecyl methacrylate, isooctadecyl methacrylate, etc.

[0035] The total molar amount of the compounds in the first mixture is 1.0 molar, and the amount of the branched alkyl acrylate compound (a1) used is 0.05 to 0.4 molar, preferably 0.07 to 0.38 molar, more preferably 0.1 to 0.35 molar.

[0036] Acrylic acid compounds with epoxy groups (a2)

[0037] Specific examples of acrylic compounds (a2) having epoxy groups include glycidyl (meth)acrylate, 2-epoxypropyloxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate and its lactone adducts (e.g., Cyclomer A200, M100 manufactured by DAICL Chemical Industries, Ltd.), mono(meth)acrylates of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epoxy compounds of dicyclopentenyl (meth)acrylate, and epoxy compounds of dicyclopentenyloxyethyl (meth)acrylate.

[0038] The total molar amount of the compounds in the first mixture is 1.0 molar, and the amount of the epoxy-based acrylic compound (a2) used is 0.3 to 0.85 molar, preferably 0.35 to 0.83 molar, more preferably 0.4 to 0.8 molar.

[0039] Other unsaturated compounds (a3)

[0040] Other unsaturated compounds (a3) ​​refer to unsaturated compounds that do not belong to the above-mentioned branched alkyl acrylate compounds (a1), epoxy acrylate compounds (a2), and aromatic unsaturated compounds (a4) described below. Other unsaturated compounds (a3) ​​include unsaturated compounds (a3-1) and unsaturated compounds (a3-2).

[0041] Unsaturated compound (a3-1)

[0042] The unsaturated compound (a3-1) is selected from at least one of the following: acrylate compounds comprising the structures shown in formula (a3-1-1), formula (a3-1-2), and compounds represented by formula (a3-1-3).

[0043]

[0044] In formula (a3-1-3), X and Y each independently represent a hydrogen atom, a straight-chain hydrocarbon group with 1 to 4 carbon atoms, or a branched hydrocarbon group with 1 to 4 carbon atoms; R 1 R 2 Each of the following groups independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carboxylic acid group having 1 to 20 carbon atoms, wherein the hydrocarbon group and the carboxylic acid group are unsubstituted or substituted; or the R group... 1 R 2 They are bonded together to form a ring structure.

[0045] Specific examples of acrylate compounds including those with the structure shown in formula (a3-1-1) include acrylate compounds having a tricyclic decane skeleton, such as (meth)acrylate dicyclopentyl ester (trade names FA-513A, FA-513M, manufactured by Hitachi Chemical Co., Ltd.). Specific examples of acrylate compounds including those with the structure shown in formula (a3-1-2) include tricyclic acrylate [5.2.1.0] 2,6 ] Dec-8-yl ester (trade name FA-511A, manufactured by Hitachi Chemical Co., Ltd.), (meth)acrylate 2-(tricyclo[5.2.1.0] 2,6 Acrylates with a dicyclopentadiene skeleton, such as dec-3-en-8(9)-oxy)ethyl ester (dicyclopentenyloxyethyl (meth)acrylate, trade names FA-512A, FA-512M, manufactured by Hitachi Chemical Co., Ltd.). Specific examples of compounds represented by formula (a3-1-3) include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1]hept-2-ene, etc. 2，5 .1 7，10 Dodecyl-3-ene, 8-methyltetracyclo[4.4.0.1] 2，5 .1 7，10 Dodecyl-3-ene, 8-ethyltetracyclo[4.4.0.1] 2，5 .1 7，10 Dodecyl-3-ene, dicyclopentadiene, tricyclo[5.2.1.0] 2,6 ] Dec-8-ene, tricyclic [5.2.1.0 2,6 ] Dec-3-ene, tricyclic [4.4.0.1 2，5 Undecylene, tricyclic [6.2.1.0] 1,8 Undecyl-9-ene, tricyclic [6.2.1.0] 1,8 Undecyl-4-ene, tetracyclo[4.4.0.1] 2，5 .1 7，10 .0 1,6 Dodecyl-3-ene, 8-methyltetracyclo[4.4.0.1] 2，5 .1 7，10 .0 1,6 Dodecyl-3-ene, 8-ethylidene tetracyclo[4.4.0.1] 2，5 .1 7，12 Dodecyl-3-ene, 8-ethylidene tetracyclo[4.4.0.1] 2，5 .1 7，10 .0 1,6 Dodecyl-3-ene, pentacyclic [6.5.1.1] 3,6 .0 2,7 .0 9,13Pentadecanene, pentacyclic [7.4.0.1] 2,5 .1 9，12 .0 8,13 Compounds such as pentabornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dianhydride. Only one of the listed compounds may be used, or two or more may be used simultaneously.

[0046] The total number of moles of the compounds in the first mixture is 1.0 mole, and the amount of unsaturated compound (a3-1) used is 0.01 to 0.09 moles, preferably 0.012 to 0.08 moles, more preferably 0.015 to 0.07 moles.

[0047] Unsaturated compound (a3-2)

[0048] Specific examples of unsaturated compounds (a3-2) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate, n-octadecyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, ethylcyclohexyl methacrylate, methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy-polyethylene glycol methacrylate, and methoxy-polyethylene glycol acrylate (trade name: A). M-90G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycerol mono(meth)acrylate, glycerol mono(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, allyl methacrylate, propyne methacrylate, 1,1,1-trifluoroethyl methacrylate, perfluoroethyl methacrylate, perfluoropropyl methacrylate, perfluoroisopropyl methacrylate, furanyl methacrylate, methyl furanyl methacrylate, tetrahydrofuranyl methacrylate, pyranyl methacrylate, 3-(N,N-dimethyl)methacrylate (Meth)acrylates without aromatic rings, such as aminopropyl esters; (meth)acrylates with bridged cyclic hydrocarbon groups having 10-20 carbon atoms, such as dicyclopentenyl (meth)acrylate, dicyclohexyl (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, isobornyl (meth)acrylate, adamantane (meth)acrylate, and rosin ester (meth)acrylate; (meth)acrylamide, N,N-dimethylamide (meth)acrylate, N,N-diethylamide (meth)acrylate, N,N-dipropylamide (meth)acrylate, N,N-diisopropylamide (meth)acrylate, and methpropylene. (Methacrylamides) such as anthraquinones; vinyl compounds such as (meth)acrylanilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide, etc. These monomers can be used alone or in combination of two or more monomers.

[0049] The total moles of the compounds in the first mixture are 1.0 moles, and the amount of other unsaturated compounds (a3) ​​used is 0 to 0.6 moles, preferably 0 to 0.5 moles, more preferably 0 to 0.4 moles.

[0050] Polymerizable unsaturated monocarboxylic acids (a5)

[0051] Polymerizable unsaturated monocarboxylic acids (a5) used for reacting with addition copolymers formed from the first mixture or the second mixture described below are acceptable as long as they possess polymerizable unsaturated bonds and acid groups. Examples include unsaturated carboxylic acids, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples of polymerizable unsaturated monocarboxylic acids (a5) include unsaturated carboxylic acids such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl isocyanate, and 2-methacryloylethoxysuccinate; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, and p-styrene sulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. These unsaturated monocarboxylic acids can be used alone or in combination of two or more.

[0052] The total molar amount of the compounds in the first mixture is 1.0 molar, and the amount of polymerizable unsaturated monocarboxylic acid (a5) used is 0.25 to 0.85 molar, preferably 0.3 to 0.83 molar, more preferably 0.35 to 0.8 molar.

[0053] Polybasic acids or their anhydrides (a6)

[0054] The polybasic acid or its anhydride (a6) used for reacting with the addition copolymer formed from the first mixture or the second mixture described below can be any of the saturated or unsaturated polybasic acids or their anhydrides. Specific examples include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, etc., dibasic acids or their anhydrides, trimellitic acid, trimellitic anhydride, etc., tribasic acids or their anhydrides, benzopyrene, benzopyrene anhydride, etc., tetrabasic acids or their anhydrides, etc. Of these, dicarboxylic anhydrides are more suitable.

[0055] The total moles of the compounds in the first mixture are 1.0 moles, and the amount of the polybasic acid or its anhydride (a6) used is 0.01 to 0.75 moles, preferably 0.03 to 0.7 moles, more preferably 0.05 to 0.65 moles.

[0056] Alkali-soluble resin (A-2)

[0057] The alkali-soluble resin (A-2) possesses aromatic groups, acid groups, and polymerizable unsaturated bonds. Alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed from a second mixture with a polymerizable unsaturated monobasic acid (a5), followed by a reaction with a polybasic acid or its anhydride (a6). The second mixture includes an unsaturated compound with aromatic groups (a4), an acrylic compound with epoxy groups (a2), and other unsaturated compounds (a3).

[0058] If the black photosensitive resin composition includes an alkali-soluble resin (A-2), the adhesion of the black pattern formed by the black photosensitive resin composition can be further improved.

[0059] Furthermore, the specific examples of the epoxy-containing acrylic compound (a2), other unsaturated compound (a3), polymerizable unsaturated monocarboxylic acid (a5), and polybasic acid or its anhydride (a6) used in the manufacture of alkali-soluble resin (A-2) are the same as those used in the manufacture of alkali-soluble resin (A-1), and therefore will not be repeated here.

[0060] The total molar amount of the compounds in the second mixture is 1.0 molar, and the amount of the epoxy-based acrylic compound (a2) used is 0.3 to 0.85 molar, preferably 0.35 to 0.83 molar, more preferably 0.4 to 0.8 molar.

[0061] The total molar amount of the compounds in the second mixture is 1.0 molar, and the amount of other unsaturated compounds (a3) ​​used is 0 to 0.6 molar, preferably 0 to 0.5 molar, more preferably 0 to 0.4 molar.

[0062] Unsaturated compounds with aromatic groups (a4)

[0063] Specific examples of styrene-based unsaturated compounds (a4) with aromatic groups include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, 4-nitrostyrene, 4-cyanostrene, 4-acetylaminostyrene, or indene; benzyl (meth)acrylate. Phthalate, methyl methacrylate, isopropyl methacrylate, piperine methacrylate, salicyl methacrylate, triphenyl methacrylate, naphthyl methacrylate, anthracene methacrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate (trade name: tetraacrylate P-200A, manufactured by Kyorei Chemicals), o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, p-phenoxybenzyl acrylate, and other (meth)acrylates with aromatic rings.

[0064] The total molar amount of the compounds in the second mixture is 1.0 molar, and the amount of the unsaturated compound (a4) having an aromatic group is 0.03 to 0.45 molar, preferably 0.05 to 0.43 molar, more preferably 0.08 to 0.4 molar.

[0065] The total molar amount of the compounds in the second mixture is 1.0 molar, and the amount of polymerizable unsaturated monocarboxylic acid (a5) used is 0.25 to 0.85 molar, preferably 0.3 to 0.83 molar, more preferably 0.35 to 0.8 molar.

[0066] The total molar amount of the compounds in the second mixture is 1.0 molar, and the amount of the polybasic acid or its anhydride (a6) used is 0.01 to 0.75 molar, preferably 0.03 to 0.7 molar, more preferably 0.05 to 0.65 molar.

[0067] Methods for manufacturing alkali-soluble resin (A-1) and alkali-soluble resin (A-2)

[0068] Alkali-soluble resin (A-1) (or alkali-soluble resin (A-2)) is obtained by reacting an addition copolymer formed from a first mixture (or a second mixture) with a polymerizable unsaturated monobasic acid (a5), and then with a polybasic acid or its anhydride (a6). The manufacturing method will be described in detail below.

[0069] The copolymerization reaction of the addition copolymer formed from the first mixture (or the second mixture) can be carried out in the presence or absence of a polymerization solvent, according to free radical polymerization methods well known in the art. For example, the first mixture (or the second mixture) can be dissolved in a solvent as desired, and a polymerization initiator can be added to the solution, followed by a copolymerization reaction at 50–130°C for 1–20 hours.

[0070] There are no particular limitations on the solvents that can be used in this copolymerization reaction. Examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl 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 monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether. (Poly)alkyl glycol monoalkyl ether compounds such as alkyl ethers and tripropylene glycol monoethyl ether; (Poly)alkyl glycol monoalkyl ether acetate compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methyl-3-methoxybutylacetate, methyl 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isoethyl acetate Ester compounds such as propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbon compounds such as toluene and xylene; carboxylic acid amide compounds such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. The above solvents may be used alone or in combination of two or more.

[0071] Among these, solvents such as (poly)alkyl glycol monoalkyl ethers, such as propylene glycol monomethyl ether, and solvents such as (poly)alkyl glycol monoalkyl ether acetate, such as propylene glycol monomethyl ether acetate, are preferred, i.e., glycol ether solvents.

[0072] There is no particular limitation on the amount of polymerization solvent used. When the total amount of the first mixture (or the second mixture) is 100 parts by mass, it is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass. In particular, by using less than 1,000 parts by mass of solvent, the decrease in molecular weight of the copolymer due to chain transfer can be suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. Furthermore, by using more than 30 parts by mass of solvent, abnormal polymerization reactions can be prevented, the polymerization reaction can be carried out stably, and the coloring or gelation of the copolymer can also be prevented.

[0073] Furthermore, there are no particular limitations on the polymerization initiator that can be used in this copolymerization reaction; examples include azobisisobutyronitrile, azobisisovalerate, benzoyl peroxide, and tert-butylperoxy-2-ethylhexanoate. These can be used alone or in combination of two or more. When the total amount of the first mixture (or the second mixture) added is 100 parts by mass, the amount of polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass.

[0074] Next, by using the epoxy groups contained in the addition copolymer thus manufactured to carry out the following modification reaction, an alkali-soluble resin with acid groups and polymerizable unsaturated bonds in the side chains, a glass transition temperature of 20°C or less, and a polystyrene equivalent weight average molecular weight of 1,000 to 50,000 can be obtained.

[0075] The above-mentioned modification reaction includes the following steps:

[0076] Step 1: The ring-opening reaction of all the epoxy groups contained in the addition copolymer is carried out by a polymerizable unsaturated monobasic acid (a5).

[0077] Step 2: React the hydroxyl group generated by the above ring-opening reaction with a polybasic acid or its anhydride (a6).

[0078] The amount of polymerizable unsaturated monocarboxylic acid (a5) used in step one can be appropriately selected according to the required equivalent value of unsaturated groups in the curing polymer. Generally, based on a total of 1.0 moles of epoxy groups in the addition copolymer, the amount of polymerizable unsaturated monocarboxylic acid (a5) used is 0.90 to 1 mole, preferably 0.95 to 1 mole. If the amount of polymerizable unsaturated monocarboxylic acid (a5) used is too small, there is a risk of side reactions occurring in subsequent reactions.

[0079] Step one can be carried out using common methods. For example, an addition copolymer and a polymerizable unsaturated monocarboxylic acid can be added to the reaction solvent, followed by the addition of a catalyst, and the reaction can be carried out at, for example, 50–150°C, preferably 80–130°C. Furthermore, even if the solvent used for the copolymerization reaction is included in step one, there are no particular problems, so step one can be carried out without removing the solvent after the copolymerization reaction is completed.

[0080] Furthermore, during step one, polymerization inhibitors may be added as needed to prevent gelation. There are no particular limitations on polymerization inhibitors; examples include hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether. Similarly, there are no particular limitations on catalysts; examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelating compounds of chromium.

[0081] Through step one described above, the epoxy groups in the addition copolymer undergo a ring-opening reaction, introducing unsaturated bonds from a polymeric unsaturated monocarboxylic acid (a5) into the side chain of the polymer, while simultaneously generating hydroxyl groups from the epoxy groups. In this invention, an acid group is introduced into the polymer through step two, which involves reacting this hydroxyl group with a polycarboxylic acid or its anhydride (a6).

[0082] The amount of hydroxyl groups and polybasic acids or their anhydrides (a6) used in step two can be appropriately selected according to the acid value of the desired curable polymer. Typically, based on a total molar number of hydroxyl groups generated in step one of 1.0 molars, the amount of polybasic acid or its anhydride (a6) used is 0.01 to 0.9 molars, preferably 0.02 to 0.85 molars. If the amount of hydroxyl groups and polybasic acids or their anhydrides (a6) used is too small, there is a risk of insufficient development; conversely, if the amount is too large, there is a risk of reduced sensitivity.

[0083] Step two can also be carried out using common methods. For example, after step one, a polybasic acid or its anhydride (a6) can be added to the reaction system, and the reaction can be carried out at 50–150°C, preferably 80–130°C. The reaction time can be appropriately selected, typically 0.05–10 hours, preferably 0.1–7 hours.

[0084] The alkali-soluble resin (A-1) has a weight-average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as determined by gel permeation chromatography (GPC).

[0085] The alkali-soluble resin (A-2) has a weight-average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as determined by gel permeation chromatography (GPC).

[0086] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of 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.

[0087] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of 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.

[0088] Other alkali-soluble resins (A-3)

[0089] Other alkali-soluble resins (A-3) are resins other than alkali-soluble resins (A-1) and alkali-soluble resins (A-2). Other alkali-soluble resins (A-3) are, for example, resins containing carboxylic acid groups or hydroxyl groups, but are not limited to resins containing carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins (A-3) include acrylic resins, fluorene resins, urethane resins, phenolic varnish resins, and the like.

[0090] Compound (B) containing an ethylene-unsaturated group.

[0091] The compound (B) having an ethylene unsaturated group can be selected from compounds having one ethylene unsaturated group or compounds having two or more ethylene unsaturated groups.

[0092] The aforementioned compounds having an ethylene unsaturated group may include, but are not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylate-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl(meth)acrylamide, (meth)acrylate isobornyloxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate-2-ethylhexyl ester, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylate dimethylaminoethyl ester, (meth)acrylate dodecyl ester, (meth)acrylate dicyclopentenoxyethyl ester, (meth)acrylate dicyclopentenyl ester, N,N-dimethyl (meth)acrylamide, (meth)propylene Compounds of tetrachlorophenyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl methacrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl methacrylate, ethyl 2-hydroxy-(meth)acrylate, propyl 2-hydroxy-(meth)acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate, polyethylene mono(meth)acrylate, propylene mono(meth)acrylate, or borneol methacrylate, etc. The compounds having an ethylene unsaturated group may be used alone or in combination.

[0093] The aforementioned compounds having two or more (including two) vinyl unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tri(2-hydroxyethyl) isocyanate di(meth)acrylate, tri(2-hydroxyethyl) isocyanate tri(meth)acrylate, caprolactone-modified tri(2-hydroxyethyl) isocyanate tri(meth)acrylate, trimethylolpropene tri(meth)acrylate tri(meth)acrylate tri(meth)acrylate tri(meth)acrylate tri(meth)acrylate tri(meth)acrylate modified with ethylene oxide (EO), trimethylolpropene tri(meth)acrylate tri(meth)acrylate modified with propylene oxide (PO), tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, Compounds of 6-hexanediol di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, di(trimethylolpropionic acid)tetra(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, or phenolic varnish polyglycidyl ether (meth)acrylate, etc. The compound having two or more (including two) ethylene unsaturated groups may be used alone or in combination.

[0094] Specific examples of compounds (B) having an ethylene unsaturated group may include, but are not limited to: trimethylolpropene triacrylate, ethylene oxide-modified trimethylolpropene triacrylate, propylene oxide-modified trimethylolpropene triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropene tetraacrylate, propylene oxide-modified glycerol triacrylate, or any combination of the above compounds.

[0095] The compound (B) having an ethylene unsaturated group is preferably trimethylolpropionic acid triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or any combination thereof.

[0096] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of compound (B) having an ethylene unsaturated group used is 20 to 180 parts by weight, preferably 25 to 170 parts by weight, more preferably 30 to 160 parts by weight.

[0097] Photoinitiator (C)

[0098] The photoinitiator (C) includes a first photoinitiator (C-1) as shown in formula (CI) and a second photoinitiator (C-2).

[0099] First photoinitiator (C-1)

[0100] The first photoinitiator (C-1) is a compound represented by the following formula (CI).

[0101]

[0102] R1, R2, R3, R4, R5, R6, R7, and R8 are independently hydrogen, alkyl groups having 1 to 20 carbon atoms, or COR. 16 The group represented by formula (C-II),

[0103]

[0104] Or R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7 or R7 and R8 are independently and collectively groups represented by formula (C-III);

[0105]

[0106] However, the condition is that at least one pair of R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 are groups represented by formula (C-III).

[0107] R9, R 10 R 11 and R 12 Each of the above is an alkyl group consisting of hydrogen atoms and having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: halogen, phenyl;

[0108] Or R9, R 10 R 11 and R 12 Each is an unsubstituted phenyl or a phenyl substituted with one or more of the following groups: alkyl groups having 1 to 6 carbon atoms, halogens;

[0109] X represents CO or a direct bond;

[0110] R 13This refers to an alkyl group having 1 to 20 carbon atoms, which is either unsubstituted or substituted with one or more of the following groups: halogen, R 17 COOR 17 , OR 17 ;

[0111] Or R 13 It refers to an alkyl group having 2 to 20 carbon atoms, intercalated with one or more O or CO atoms, wherein the intercalated alkyl group having 2 to 20 carbon atoms is unsubstituted or substituted with one or more halogens;

[0112] Or R 13 It represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: alkyl with 1 to 20 carbon atoms, haloalkyl with 1 to 4 carbon atoms;

[0113] R 14 It indicates hydrogen, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms;

[0114] R 15 It is an aryl group having 6 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: halogen, haloalkyl group having 1 to 4 carbon atoms, OR 17 Alkyl groups having 2 to 20 carbon atoms interspersed with one or more O atoms; or each of which is substituted with an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , phenyl, OR 17 ;

[0115] Or R 15 Indicates a cycloalkyl group with 3 to 8 carbon atoms; or R 15 It is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted by one or more of the following groups: halogen, cycloalkyl group having 3 to 8 carbon atoms;

[0116] R 16 This refers to aryl groups having 6 to 20 carbon atoms, each of which is unsubstituted or substituted with one or more of the following groups: halogen, haloalkyl group having 1 to 4 carbon atoms, OR 17 ; or each of them is substituted with one or more alkyl groups having 1 to 20 carbon atoms, wherein the alkyl groups having 1 to 20 carbon atoms are unsubstituted or substituted with one or more of the following groups: halogen, OR 17 ;

[0117] R 17 The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with one or more of the following groups: halogen or intercalated with one or more O atoms, having 3 to 20 carbon atoms;

[0118] Or R 17This refers to an alkyl group having 2 to 20 carbon atoms, interspersed with one or more oxygen atoms;

[0119] Or R 17 The phenyl group represents a phenyl group that is unsubstituted or substituted with one or more of the following groups: halogen, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms;

[0120] However, the condition is that at least one group represented by formula (C-II) exists in formula (CI).

[0121] Compounds of formula (CI) are characterized by containing one or more annealed unsaturated rings on the carbazole moiety. In other words, at least one pair of R1 and R2, R2 and R3, R3 and R4, R5 and R6, R6 and R7, or R7 and R8 are groups represented by formula (C-III).

[0122]

[0123] Alkyl groups having 1 to 20 carbon atoms are either straight-chain or branched, examples of which are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and icosyl.

[0124] A halogenated alkyl group having 1 to 4 carbon atoms is a halogen-substituted alkyl group having 1 to 4 carbon atoms as defined below. The alkyl group is, for example, mono- or polyhalogenated until all H atoms are replaced with halogens. It is, for example, C10. z H x Hal y Where x+y=2z+1 and Hal is a halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

[0125] Alkyl groups with 2 to 20 carbon atoms intercalated with one or more oxygen atoms are intercalated with oxygen atoms (e.g., 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times). The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene). These alkyl groups are straight-chain or branched. For example, the following structural units will be present: -CH2-CH2-O-CH2CH3, -[CH2CH2O] y -CH3 (where y = 1 to 9), -(CH2-CH2O)7-CH2CH3, -CH2-CH(CH3)-O-CH2-CH2CH3, -CH2-CH(CH3)-O-CH2-CH3.

[0126] An alkoxy group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms that has been substituted with one O atom.

[0127] Aryl groups with 6 to 20 carbon atoms are, for example, phenyl, naphthyl, anthraceneyl, phenanthryl, pyrene, The group may contain phenyl, naphthyl, or triphenylene, especially phenyl or naphthyl, with phenyl being preferred. The naphthyl group may be 1-naphthyl or 2-naphthyl.

[0128] The substituted aryl group (phenyl, naphthyl, aryl with 6 to 20 carbon atoms) is substituted 1 to 7 times, 1 to 6 times, or 1 to 4 times, especially 1 time, 2 times, or 3 times. Obviously, the defined aryl group cannot have more substituents than the number of free positions at the aryl ring.

[0129] The substituents on the phenyl ring are preferably in position 4 on the phenyl ring or in a configuration of 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-.

[0130] Intercalated once or more, the intercalated group is intercalated (e.g.) 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times, or 1 or 2 times (obviously, the number of intercalated atoms depends on the number of carbon atoms in the pseudo-intercalation). The substituted group is substituted once or more, having (e.g.) 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 identical or different substituents.

[0131] A group substituted with one or more defined substituents is intended to have one or more substituents as defined in the same or different ways. Halogens are fluorine, chlorine, bromine, and iodine, especially fluorine, chlorine, and bromine, preferably fluorine and chlorine. If R1 and R2, R2 and R3, R3 and R4 or R5 and R6, R6 and R7, R7 and R8 are independently and collectively groups represented by formula (C-III),

[0132] This results in a structure, for example, as shown in the following formulas (C-Ia) to (C-Ii):

[0133]

[0134] Examples of the compounds of the present invention are preferably of formula (C-Ia), formula (C-Ib), or formula (C-Ic), more preferably of formula (C-Ia) or formula (C-Ic), or formula (C-Ia), formula (C-Ic), or formula (C-Id), and especially preferably of formula (C-Ia).

[0135] R 15 Represents (for example) hydrogen, phenyl, naphthyl, each unsubstituted or via an alkyl group having 1 to 8 carbon atoms, OR 17 Replace; or R 15Indicates an alkyl group having 1 to 20 carbon atoms; or R 15 It refers to an alkyl group having 2 to 20 carbon atoms, interspersed with one or more O atoms.

[0136] R 16 This refers to, for example, aryl groups (especially phenyl or naphthyl, especially phenyl) having 6 to 20 carbon atoms, each unsubstituted or substituted with one or more of the following groups: halogen, haloalkyl having 1 to 4 carbon atoms, OR 17 ; or each of them is substituted with one or more alkyl groups having 1 to 20 carbon atoms, wherein the alkyl groups having 1 to 20 carbon atoms are unsubstituted or substituted with one or more of the following groups: halogen, OR 17 .

[0137] In addition, R 16 This indicates, for example, phenyl or naphthyl, especially phenyl or carbazole, each unsubstituted or substituted with one or more of the following groups: halogen, haloalkyl having 1 to 4 carbon atoms, OR 17 Or alkyl groups having 1 to 20 carbon atoms.

[0138] In addition, R 16 This indicates, 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 groups having 1 to 20 carbon atoms.

[0139] R 16 Especially phenyl, which is unsubstituted or substituted with one or more of the following groups: OR 17 Or alkyl groups having 1 to 20 carbon atoms.

[0140] better location R 16 It is a phenyl group, which is substituted with one or more alkyl groups having 1 to 20 carbon atoms.

[0141] R 17 This refers to, for example, hydrogen, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more of the following groups: halogen or cycloalkyl group having 3 to 20 carbon atoms intercalated with one or more O atoms; or R 17 The symbol represents a phenyl group, which is either unsubstituted or substituted with one or more of the following groups: halogen, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms.

[0142] Examples of compounds of inventive formula (1) include the following compounds represented by formulas (C-1-1) to (C-1-23):

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of first photoinitiator (C-1) used is 7 to 60 parts by weight, preferably 8 to 55 parts by weight, more preferably 9 to 50 parts by weight.

[0151] Second photoinitiator (C-2)

[0152] The second photoinitiator (C-2) is, for example, an acetophenone compound, a biimidazole compound, or a combination of the above compounds.

[0153] Specific examples of acetophenone compounds include p-dimethylamine acetophenone, α,α'-dimethoxyazoacetophenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-aza,aza-dimethylamine-1-(4-morpholinophenyl)-1-butanone, or combinations thereof.

[0154] Specific examples of diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, and 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 combinations of the above compounds.

[0155] The second photoinitiator (C-2) is preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-aza-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, or a combination of the above compounds.

[0156] The second photoinitiator (C-2) may be further supplemented with the following compounds as needed: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4,4'-bis(diethylamine)benzophenone, and other benzophenone-based compounds; α-diketones such as benzil and acetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Ketone alcohol ethers such as isopropylether; acylphosphine oxides such as 2,4,6-trimethyl-benzoyl-diphenyl-phosphine oxide and bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; halides such as phenacyl chloride, tribromomethyl-phenylsulfone, and tris(trichloromethyl)-s-triazine; peroxides such as di-tert-butylperoxide; or combinations of the above compounds. The compound added to the photoinitiator (C) is preferably a benzophenone-based compound, and more preferably 4,4'-bis(diethylamine)benzophenone.

[0157] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of 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.

[0158] Solvent (D)

[0159] The solvent (D) refers to a solvent that can dissolve the alkali-soluble resin (A), the compound (B) having an ethylene unsaturated group, the photoinitiator (C), the black pigment (E), the polycarbonate diol (F), and the additive (G) without reacting with the above components, and is preferably a solvent with appropriate volatility.

[0160] Specific examples of solvent (D) include: alkyl diol monoalkyl ethers, alkyl diol monoalkyl ether acetates, diethylene glycol alkyl ethers, other ethers, ketones, lactic acid alkyl esters, other esters, aromatic hydrocarbons, carboxylic acid amines, or combinations thereof.

[0161] Specific examples of alkyl glycol monoalkyl ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or the like, or combinations thereof.

[0162] Specific examples of alkyl diol 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 similar compounds, or combinations thereof.

[0163] Specific examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like, or combinations thereof.

[0164] Other specific examples of ether compounds include tetrahydrofuran or its analogues.

[0165] Specific examples of ketone compounds include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or their analogues, or combinations thereof.

[0166] Specific examples of lactic acid alkyl esters include methyl lactate, ethyl lactate, or their analogues, or combinations thereof.

[0167] Other specific examples of ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxybutyl acetate, methyl 3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate or their analogues, or combinations thereof.

[0168] Specific examples of aromatic hydrocarbon compounds include toluene, xylene or their analogues, or combinations thereof.

[0169] Carboxylic acid amine compounds N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or their analogues, or combinations thereof.

[0170] Solvent (D) can be used alone or in combination.

[0171] The solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone, or ethyl 3-ethoxypropionate.

[0172] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of solvent (D) used is 400 to 3000 parts by weight, preferably 500 to 2800 parts by weight, more preferably 600 to 2500 parts by weight.

[0173] Black pigment (E)

[0174] The black pigment (E) is preferably a black pigment that has heat resistance, light resistance and solvent resistance.

[0175] Specific examples of black pigments (E) include: black organic pigments such as perylene black, cyanine black, or aniline black; mixed organic pigments formed by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, or magenta to create a near-black color; and light-blocking materials such as carbon black, chromium oxide, iron oxide, titanium black, or graphite, with specific examples of carbon black including CIpigment black 7 or commercially available products manufactured by Mitsubishi Chemical (trade names MA100, MA230, MA8, #970, #1000, #2350, or #2650). The aforementioned black pigments (E) can be used alone or in combination.

[0176] The black pigment (E) is preferably carbon black, and the carbon black is, for example, commercially available MA100 or MA230 manufactured by Mitsubishi Chemical.

[0177] Based on the above-mentioned use of 100 parts by weight of alkali-soluble resin (A) and the use of black pigment (E) of 150 to 900 parts by weight, preferably 170 to 850 parts by weight, more preferably 200 to 800 parts by weight.

[0178] Polycarbonate diol (F)

[0179] Polycarbonate diol (F) is a compound represented by formula (F-1).

[0180]

[0181] In equation (F-1), multiple R 1 Each of the two groups represents a divalent organic group independently; m represents an integer from 1 to 20.

[0182] If the black photosensitive resin composition does not contain polycarbonate diol (F), the black pattern formed by the black photosensitive resin composition has poor developability.

[0183] When the black photosensitive resin composition contains polycarbonate diol (F) as shown in formula (F-1), the developability is better.

[0184] Specific examples of polycarbonate diols (F) represented by formula (F-1) include: PCDLT-4671, T-4672, T-4691, T-4692, T-5650E, T-5650J, T-5651, T-5652, T-6001, and T-6002 (all trade names) manufactured by Asahi Kasei Corporation; PlaccelCD (registered trademark) CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, and CD220HL manufactured by Daicel Corporation; and Kuraray polyols (Kuraray...) manufactured by Kuraray Corporation. Polycarbonate diols include C-1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, and C-2090; and commercially available products from Tosoh Corporation such as Nippollan 963, 965, 968, 976, 981, 980R, and 982R. These polycarbonate diols (F) can be used alone or in combination.

[0185] The number average molecular weight (Mn) of the polycarbonate diol (F) converted from 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 within the above range, the developability is better.

[0186] Based on the above-mentioned alkali-soluble resin (A) being used in an amount of 100 parts by weight, and polycarbonate diol (F) being used in an amount of 4 to 40 parts by weight, preferably 5 to 35 parts by weight, more preferably 6 to 30 parts by weight.

[0187] Compound (G)

[0188] Compound (G) has the structure shown in the following formula (G-1):

[0189]

[0190] In equation (G-1), R 12 R 22 and R 32 Each independently represents a hydroxyl, alkyl, alkoxy, or alkoxycarbonylalkoxy group, and R 12 R 22 and R 32 At least one of them is a hydroxyl group. R 13 R 23 and R 33 Each can be used independently to represent a hydrogen atom or an alkyl group. R 14 R 24 and R34 Each can be independently represented as hydroxyl, alkoxy, alkyl, hydroxyalkoxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy, or alkylcarbonyloxy.

[0191] Specific examples of compound (G) include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tetrazoloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; for example, 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)-1,3,5-triazine and other bis(hydroxyphenyl)triazine compounds; and 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and other tri(hydroxyphenyl)triazine compounds.

[0192] Specific examples of compound (G) can be listed as compounds represented by formulas (G-1-1) to (G-1-5).

[0193]

[0194]

[0195] The amount of the alkali-soluble resin (A) used is 100 parts by weight, and 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.

[0196] If the black photosensitive resin composition does not contain compound (G), the adhesion of the black pattern formed by the black photosensitive resin composition is poor.

[0197] Additive (H)

[0198] Without affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may be further selectively supplemented with additives (H). Specific examples of additives (H) include surfactants, fillers, polymers (referring to polymers other than the alkali-soluble resin (A) mentioned above), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, or other colorants.

[0199] Surfactants help improve the coatability of photosensitive resin compositions. Specific examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorinated surfactants, or combinations of the above surfactants.

[0200] Specifically, surfactants include, for example, polyoxyethylene alkyl ethers such as polyethoxylated dodecyl ether, polyethoxylated stearyl ether, and polyethoxylated oil ether; polyethoxylated alkylphenyl ethers such as polyethoxylated octylphenyl ether and polyethoxylated nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; or tertiary amine-modified polyurethanes. These surfactants can be used alone or in combination.

[0201] Specific examples of surfactants include KP products manufactured by Shin-Etsu Chemical Industry Co., Ltd., SF-8427 products manufactured by Dow Corning Toray Co., Ltd., Polyflow products manufactured by Kyoeisha Oil & Fat Chemical Co., Ltd., F-Top products manufactured by Tochem Products Co., Ltd., Megafac products manufactured by Dai Nippon Inmo Chemical Co., Ltd., Fluorade products manufactured by Sumitomo 3M, Asahi Guard products manufactured by Asahi Glass Co., Ltd., and Surflon products manufactured by Asahi Glass Co., Ltd.

[0202] Specific examples of fillers include glass and aluminum.

[0203] Specific examples of polymers include polyvinyl alcohol, polyethylene glycol monoalkyl ethers, polyfluoroacrylates, or combinations thereof.

[0204] Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropanolpropyltrimethoxysilane, 3-epoxypropanolpropylmethyldiethoxysilane, 3-epoxypropanolpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxypropionyloxypropyltrimethoxysilane, or combinations of the above compounds.

[0205] Specific examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or combinations thereof.

[0206] Specific examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azido, alkoxy phenone, or combinations thereof.

[0207] Specific examples of anti-agglomerating agents include sodium polyacrylate.

[0208] Other colorants include inorganic pigments, organic pigments, or combinations of both.

[0209] Specific examples of inorganic pigments include metal compounds such as metal oxides and metal salts (e.g., metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc.) or composite oxides of the metals listed above.

[0210] 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 combinations of the above pigments.

[0211] <Method for manufacturing black photosensitive resin composition>

[0212] A method for preparing a black photosensitive resin composition is as follows: placing an alkali-soluble resin (A), a compound having an ethylene unsaturated group (B), a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) in a stirrer and stirring them to mix them uniformly into a solution. If necessary, an additive (H) may also be added. After uniform mixing, a black photosensitive resin composition in solution state can be obtained.

[0213] Furthermore, there are no particular limitations on the preparation method of the black photosensitive resin composition. For example, the preparation method of the black photosensitive resin composition involves first dispersing a portion of an alkali-soluble resin (A) and a compound (B) having an ethylene unsaturated group in a portion of a solvent (D) to form a dispersion solution; and then mixing the remaining alkali-soluble resin (A), the compound (B) having an ethylene unsaturated group, a photoinitiator (C), a solvent (D), a black pigment (E), a polycarbonate diol (F), and a compound (G) to prepare the composition.

[0214] Alternatively, the black photosensitive resin composition can be prepared by first dispersing a portion of black pigment (E) in a mixture consisting of a portion of alkali-soluble resin (A) and a portion of solvent (D) to form a black pigment dispersion; and then adding the alkali-soluble resin (A), a compound (B) having an ethylene unsaturated group, a photoinitiator (C), solvent (D), black pigment (E), polycarbonate diol (F), and compound (G). Furthermore, the dispersion step of the black pigment (E) can be performed by mixing using a mixer such as a bead mill or a roll mill.

[0215] <Method for creating black patterns>

[0216] The black pattern is obtained by sequentially applying the aforementioned black photosensitive resin composition to a substrate through pre-baking, exposure, development, and post-baking processes. Furthermore, when the thickness of the resulting black pattern is 1 μm, the optical density can be 3.0 or higher, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The method for preparing the black pattern is described in detail below.

[0217] First, a black photosensitive resin composition in solution is uniformly coated onto a substrate using a coating method such as spin coating or cast coating to form a coating film. Specific examples of the aforementioned substrates include: alkali-free glass, soda-lime glass, hard glass (Pelles glass), quartz glass, and glass with a transparent conductive film attached thereto for use in liquid crystal display devices; or substrates for photoelectric conversion devices (such as silicon substrates) for use in solid-state imaging devices, etc.

[0218] After the coating film is formed, most of the solvent is removed by vacuum drying, and then the remaining solvent is completely removed by pre-bake to form a pre-baked coating film. It is worth noting that the conditions for vacuum drying and pre-baking vary depending on the type and ratio of each component. Generally, vacuum drying is carried out at a pressure of less than 200 mmHg for 1 to 20 seconds, and pre-baking involves heat treatment of the coating film at a temperature of 70°C to 110°C for 1 to 15 minutes.

[0219] Next, the pre-baked coating is exposed to light using a photomask with a specific pattern. The light used during exposure is preferably ultraviolet light, such as g-rays, h-rays, or i-rays, and the ultraviolet irradiation device can be a (ultra) high-pressure mercury lamp or a metal halide lamp.

[0220] Then, at a temperature of 23±2℃, the exposed pre-baked coating is immersed in a developing solution to remove the unexposed portions of the pre-baked coating, thereby forming a specific pattern on the substrate.

[0221] The developer may be, for example, a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo-[5,4,0]-7-undecene. The concentration of the developer is generally from 0.001 wt% to 10 wt%, preferably from 0.005 wt% to 5 wt%, and more preferably from 0.01 wt% to 1 wt%.

[0222] After the pre-baked coating is developed, the substrate with the specific pattern is washed with water and then air-dried with compressed air or compressed nitrogen. Next, a post-bake process is performed using a heating device such as a hot plate or oven. The post-bake temperature is typically 150 to 250°C, with the hot plate heating time ranging from 5 to 60 minutes and the oven heating time from 15 to 150 minutes. After these processing steps, a black pattern is formed on the substrate.

[0223] <Manufacturing Method of Color Filters>

[0224] The manufacturing method of the color filter is similar to that of the black pattern. Specifically, the color filter is coated onto a substrate with a pre-formed black pattern using a photosensitive composition, followed by pre-baking, exposure, development, and post-baking processes. However, in the vacuum drying condition, the vacuum drying is performed for 1 to 60 seconds at a pressure of 0 mmHg to 200 mmHg. After the above processing steps, a specific pattern can be fixed, thereby forming a pixel layer. Furthermore, by repeating the above process, red, green, and blue pixel layers are sequentially formed on the substrate to obtain a substrate with a black pattern and pixel layers (i.e., a color filter with pixel layers).

[0225] Liquid crystal display device

[0226] First, a color filter formed by the above-described color filter manufacturing method and a substrate in which a thin-film transistor (TFT) is disposed are arranged facing each other, with a gap (cell gap) between them. Next, an adhesive is used to bond the color filter to the periphery of the substrate, leaving injection holes. Then, liquid crystal is injected through the injection holes into the substrate surface and the gap separated by the adhesive, and finally, the injection holes are sealed to form a liquid crystal layer. Subsequently, a liquid crystal display element is fabricated by providing polarizing plates on the other side of the color filter that contacts the liquid crystal layer and on the other side of the substrate that contacts the liquid crystal layer. The liquid crystal used above, i.e., a liquid crystal compound or liquid crystal composition, is not particularly limited here, and any liquid crystal compound or liquid crystal composition can be used.

[0227] Furthermore, the liquid crystal alignment film used in the fabrication of color filters is used to restrict the alignment of liquid crystal molecules, and there are no particular limitations; any inorganic or organic material can be used, and the present invention is not limited thereto.

[0228] The present invention will be described in detail below with examples, but the present invention is not limited to the contents disclosed in these examples.

[0229] <Example>

[0230] Synthesis example of alkali-soluble resin (A-1)

[0231] The following describes the synthesis examples A-1-1 to A-1-7 of the alkali-soluble resin (A-1):

[0232] Synthesis Example A-1-1

[0233] Add 262.0 g of propylene glycol monomethyl ether acetate (PGMEA) to a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube, stir while purging with nitrogen, and heat to 120°C.

[0234] Next, 19.0 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl O) was added to a monomer mixture consisting of 5.70 g (0.05 mol) of isopropyl acrylate, 121 g (0.85 mol) of glycidyl methacrylate, 13.2 g (0.06 mol) of dicyclopentyl methacrylate, and 4.00 g (0.04 mol) of methyl methacrylate. The resulting mixture was added dropwise from a dropping funnel to the aforementioned flask over a period of 2 hours. After the addition was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, generating an addition copolymer. Then, the flask was purged with air, and 73.2 g (0.85 mol) of methacrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.2 g of methylhydroquinone were added to the above addition copolymer solution. The reaction was continued by stirring at 110°C for 10 hours. The epoxy groups from glycidyl methacrylate undergo ring-opening reactions with methacrylic acid, resulting in the introduction of polymerically unsaturated bonds into the side chains of the polymer. 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. The hydroxyl groups generated by the ring-opening reaction of the epoxy groups react with the anhydride of tetrahydrophthalic anhydride, introducing carboxyl groups into the side chains. Thus, an alkali-soluble resin (A-1-1) was prepared.

[0235] Synthetic Examples A-1-2 to A-1-7

[0236] The alkali-soluble resins of Synthetic Examples A-1-2 to A-1-7 were prepared using the same process as those of Synthetic Example A-1-1, except that the types and amounts of monomers used were changed (as shown in Table 1).

[0237] Synthesis example of alkali-soluble resin (A-2)

[0238] The following describes the synthesis examples A-2-1 to A-2-7 of the alkali-soluble resin (A-2):

[0239] Synthesis Example A-2-1

[0240] Add 262.0 g of propylene glycol monomethyl ether acetate (PGMEA) to a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube, stir while purging with nitrogen, and heat to 120°C.

[0241] Next, 19.0 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl O) was added to a monomer mixture consisting of 45.8 g (0.16 mol) of α-methylstyrene, 107 g (0.75 mol) of glycidyl methacrylate, 18.5 g (0.07 mol) of dicyclopentenyloxyethyl methacrylate, and 1.88 g (0.02 mol) of norbornene. The resulting mixture was added dropwise from a dropping funnel to the aforementioned flask over a period of 2 hours. After the addition was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, generating an addition copolymer. Then, the flask was purged 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 addition copolymer solution. The reaction was continued by stirring at 110°C for 10 hours. The epoxy groups from glycidyl methacrylate undergo ring-opening reactions with acrylic acid, resulting in the introduction of polymerically unsaturated bonds into the side chains 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. The hydroxyl groups generated by the ring-opening reaction of the epoxy groups react with the anhydride of the succinic anhydride, introducing carboxyl groups into the side chains. Thus, an alkali-soluble resin (A-2-1) was prepared.

[0242] Synthetic Examples A-2-2 to A-2-7

[0243] The alkali-soluble resins of Synthetic Examples A-2-2 to A-1-7 were prepared using the same process as those of Synthetic Example A-2-1, except that the types and amounts of monomers used were changed (as shown in Table 2).

[0244] In addition, the compounds corresponding to the abbreviations in Tables 1 and 2 are shown below.

[0245]

[0246]

[0247] [Table 1]

[0248]

[0249] [Table 2]

[0250]

[0251] Synthesis examples of other alkali-soluble resins (A-3)

[0252] Synthesis Example A-3-1

[0253] Add 267.5 g of propylene glycol monomethyl ether acetate (PGMEA) to a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube, and stir while purging with nitrogen, and heat to 120°C.

[0254] Next, 19.2 g of tert-butylperoxy-2-ethylhexyl acrylate (a polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl O) was added to a monomer mixture consisting of 55.3 g (0.3 mol) of 2-ethylhexyl acrylate, 17.2 g (0.2 mol) of methacrylic acid, 11.0 g (0.05 mol) of dicyclopentyl methacrylate, 25.0 g (0.25 mol) of methyl methacrylate, and 35.2 g (0.2 mol) of benzyl methacrylate. The resulting mixture was added dropwise from a dropping funnel to the aforementioned flask over a period of 2 hours. After the addition was completed, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, yielding another alkali-soluble resin (A-3-1).

[0255] Examples of black photosensitive resin compositions

[0256] Examples 1 to 12 and Comparative Examples 1 to 3 of the black negative photosensitive resin composition are described below:

[0257] Example 1

[0258] 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 trimethylolpropionic acid 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 Nippollan976 (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 D-1), and stirred evenly with a shaking stirrer to obtain the black photosensitive resin composition of Example 1.

[0259] Examples 2 to 12

[0260] The black photosensitive resin compositions of Examples 2 to 12 were prepared using the same procedures as those of Example 1, except that the types and amounts of the components in the black photosensitive resin compositions were changed (as shown in Tables 3 and 4).

[0261] Comparative Examples 1 to 3

[0262] The photosensitive resin compositions of Comparative Examples 1 to 3 were prepared in the same process as that of Example 1, and the difference was that the types and amounts of the components of the photosensitive resin composition were changed (as shown in Table 4).

[0263] The compounds corresponding to the reference numerals in Tables 3 and 4 are as follows.

[0264]

[0265]

[0266]

[0267]

[0268] [Table 3]

[0269]

[0270] [Table 4]

[0271]

[0272] Evaluation method

[0273] Developability

[0274] The black photosensitive resin compositions obtained in the above Examples and Comparative Examples were spin-coated on a 100 mm × 100 mm glass substrate, first dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 100 °C for 2 minutes to form a pre-baked coating film with a film thickness of 3.0 μm.

[0275] Then, it was developed with a 0.045% potassium hydroxide aqueous solution at 23 °C, and the time t required for the pre-baked coating film to dissolve was measured, which was equivalent to the development time, and evaluated according to the following criteria:

[0276] ◎: t ≤ 40 seconds;

[0277] ο: 40 seconds < t ≤ 50 seconds;

[0278] △: 50 seconds < t ≤ 60 seconds;

[0279] ×: 60 seconds < t.

[0280] Adhesion

[0281] The black photosensitive resin compositions obtained in the above embodiments and comparative examples were coated onto a glass substrate with dimensions of 100 mm using a spin coater (model MS-A150, purchased from Shin Kong Trading Co., Ltd.). The glass substrate was then pre-baked at 100°C for 2 minutes to form a pre-baked coating film with a thickness of 3.0 μm. The pre-baked coating film was then subjected to 80 mJ / cm² heat treatment. 2 Exposure was performed using ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology). Next, development was performed with a 0.045% potassium hydroxide aqueous solution at 23°C for 1 minute. Then, the film was washed with water and post-baked at 235°C for 30 minutes to form a black hardened film on the glass substrate.

[0282] This black hardened film is then further subjected to ultraviolet light at 830 mJ / cm 2 After irradiation with light, the black hardened film was cut into 100 cross-hatched sections using a knife according to the cross-hatched test method in JIS.K5400(1900) 8.5. Then, the cross-hatched sections were adhered to the film with adhesive tape (3M396) and then peeled off. The extent of any remaining cross-hatched sections was observed and evaluated according to the following criteria. A higher percentage of remaining cross-hatched sections indicates better adhesion.

[0283] ◎: 99% ≤ Residual mesh.

[0284] ○: 97% ≤ Reticulated grid residue < 99%.

[0285] △: 95% ≤ Reticulated grid residue < 97%.

[0286] ×: Residual mesh <95%.

[0287] Evaluation results

[0288] As shown in Tables 3 and 4, compared with the black patterns (Examples 1 to 12) prepared by the black photosensitive resin composition containing both a specific polycarbonate diol (F) and a compound (G) with a specific structure, the black patterns of Comparative Examples 1 and 3, which do not contain the specific polycarbonate diol (F), have poor developability; and the black patterns of Comparative Examples 2 and 3, which do not contain the compound (G) with a specific structure, have poor adhesion.

[0289] Furthermore, when the black photosensitive resin composition contains more alkali-soluble resin (A-1) (Examples 1 to 8), the developability of black patterns can be further improved.

[0290] Furthermore, when the black photosensitive resin composition contains more alkali-soluble resin (A-2) (Examples 1 to 7, 9), the adhesion of the black pattern can be further improved.

[0291] In summary, the black photosensitive resin composition of the present invention uses polycarbonate diol (F) and a compound (G) having a specific structure, thus improving the technical problems of poor developability and adhesion resistance in the prior art.

[0292] Furthermore, when the black photosensitive resin composition contains an alkali-soluble resin (A-1), the developability of the black pattern will be further improved, and when the black photosensitive resin composition contains an alkali-soluble resin (A-2), the adhesion of the black pattern will be further improved.

[0293] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Any person skilled in the art may make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A black photosensitive resin composition, characterized in that, include: Alkali-soluble resin (A); Compound (B) containing an ethylene-unsaturated group; Photoinitiator (C); Solvent (D); Black pigment (E); Polycarbonate diol (F) having the structure shown in formula (F-1) and having a number-average molecular weight of 500 to 3000; and Compound (G) has the structure shown in formula (G-1). In equation (F-1), Multiple R 1 Each of these groups independently represents a divalent organogroup; m represents an integer from 1 to 20. In equation (G-1), R 12 R 22 and R 32 Each independently represents a hydroxyl, alkyl, alkoxy, or alkoxycarbonylalkoxy group, and R 12 R 22 and R 32 At least one of them is a hydroxyl group; R 13 R 23 and R 33 Each independently represents a hydrogen atom or an alkyl group; and R 14 R 24 and R 34 Each can be independently represented as hydroxyl, alkoxy, alkyl, hydroxyalkoxy, alkoxycarbonylalkoxy, 3-alkoxy-2-hydroxy-propoxy, or alkylcarbonyloxy.

2. The black photosensitive resin composition according to claim 1, wherein... The alkali-soluble resin (A) includes an alkali-soluble resin (A-1), and the alkali-soluble resin (A-1) has branched alkyl groups, acid groups, and polymerizable unsaturated bonds.

3. The black photosensitive resin composition according to claim 1, wherein... The alkali-soluble resin (A) includes alkali-soluble resin (A-2), and the alkali-soluble resin (A-2) has aromatic groups, acid groups and polymerizable unsaturated bonds.

4. The black photosensitive resin composition according to claim 2, wherein... The alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed from the first mixture with a polymerizable unsaturated monobasic acid (a5), and then reacting it with a polybasic acid or its anhydride (a6). The first mixture includes an acrylate compound having branched alkyl groups (a1), an acrylic compound having epoxy groups (a2), and other unsaturated compounds (a3).

5. The black photosensitive resin composition according to claim 3, wherein... The alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed from the second mixture with a polymerizable unsaturated monobasic acid (a5), and then with a polybasic acid or its anhydride (a6). The second mixture includes an aromatic unsaturated compound (a4), an epoxy acrylic compound (a2), and other unsaturated compounds (a3).

6. The black photosensitive resin composition according to claim 1, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight. The compound (B) having an ethylene unsaturated group is used in an amount of 20 parts by weight to 180 parts by weight. The amount of the photoinitiator (C) used is from 7 parts by weight to 70 parts by weight. The total amount of solvent (D) used is from 400 parts by weight to 3000 parts by weight. The amount of the black pigment (E) used is from 150 parts by weight to 900 parts by weight. The amount of polycarbonate diol (F) used is from 4 parts by weight to 40 parts by weight. The amount of compound (G) used is from 5 parts by weight to 45 parts by weight.

7. The black photosensitive resin composition according to claim 2, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight. The amount of the alkali-soluble resin (A-1) used is from 10 parts by weight to 60 parts by weight.

8. The black photosensitive resin composition according to claim 3, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight. The amount of the alkali-soluble resin (A-2) used is from 40 parts by weight to 90 parts by weight.

9. A color filter comprising a black pattern, The black pattern is formed by pre-baking, exposure, development and post-baking of the black photosensitive resin composition as described in any one of claims 1 to 8.

10. A liquid crystal display device, comprising the color filter as described in claim 9.

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