Negative photosensitive resin composition, black matrix, color filter, and display

Abstract

The present application relates to a negative photosensitive resin composition, black matrix, color filter and display. The negative photosensitive resin composition comprises alkali-soluble resin (A), ethylenically unsaturated group-containing compound (B), photoinitiator (C), black pigment (D), solvent (E) and phosphate compound (F). The black matrix prepared by the negative photosensitive resin composition has good adhesion and solvent resistance.

Description

Technical Field

[0001] This invention relates to a negative photosensitive resin composition, and more particularly to a negative photosensitive resin composition having good adhesion and solvent resistance, and the black matrix obtained therefrom. Background Technology

[0002] In recent years, to improve the contrast and display quality of current displays, a black matrix is ​​generally placed between the stripes and dots of a color filter. This black matrix prevents light leakage between pixels, which can cause a decrease in contrast and color purity. However, the materials used for black matrices in the past have primarily been vapor-deposited films containing chromium or chromium oxide. Using these vapor-deposited films as the material for black matrices has drawbacks such as complex manufacturing processes and high material costs. To address this issue, a technique for forming black matrices from photosensitive resin compositions using photolithography has been proposed.

[0003] Japanese Patent Application Publication No. 2008-268854 discloses a photosensitive resin composition for black matrix applications. 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 pattern resolution of black matrices 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 photosensitive resin composition for black matrix applications. 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, the black matrix produced by these photosensitive resin compositions has the drawbacks of poor adhesion and solvent resistance.

[0005] In view of this, there is an urgent need to develop a photosensitive resin composition for black matrices with good adhesion and solvent resistance in order to overcome the above-mentioned problems of existing black matrices. Summary of the Invention

[0006] Therefore, one aspect of the present invention is to provide a negative photosensitive resin composition comprising an alkali-soluble resin (A), a compound containing an vinyl unsaturated group (B), a photoinitiator (C), a black pigment (D), a solvent (E), and a phosphate ester compound (F), and this negative photosensitive resin composition exhibits good adhesion and solvent resistance. Furthermore, the negative photosensitive resin composition of the present invention may selectively include a thiol compound (G).

[0007] Another aspect of the present invention is to provide a black matrix, which is formed by sequentially pre-baking, exposure, development and post-baking of the aforementioned negative photosensitive resin composition.

[0008] Another aspect of the present invention is to provide a color filter comprising the aforementioned black matrix.

[0009] Another aspect of the present invention is to provide a display comprising the aforementioned color filter.

[0010] According to the above-described form of the present invention, a negative photosensitive resin composition is provided, which comprises an alkali-soluble resin (A), a compound containing an ethylene unsaturated group (B), a photoinitiator (C), a black pigment (D), a solvent (E), and a phosphate ester compound (F), and may selectively include a thiol compound (G), as described below.

[0011] Alkali-soluble resin (A)

[0012] The alkali-soluble resin (A) of the present invention may comprise a resin (A-1) having unsaturated groups, and may selectively comprise other alkali-soluble resins (A-2).

[0013] Resin with unsaturated groups (A-1)

[0014] The resin (A-1) with unsaturated groups is obtained by polymerizing a mixture, which includes a diol compound (a-1-1) containing polymerizable unsaturated groups, a tetracarboxylic acid or its dianhydride (a-1-2), and a dicarboxylic acid or its dianhydride (a-1-3).

[0015] Diol compounds containing polymerizable unsaturated groups (a-1-1)

[0016] The diol compound containing polymerizable unsaturated groups (a-1-1) is obtained by reacting an epoxy compound having at least two epoxy groups with a compound having at least one carboxylic acid group and at least one vinyl unsaturated group. The epoxy compound having at least two epoxy groups has the structures shown in formulas (II-1) to (II-3).

[0017] Specifically, the structure represented by equation (II-1) is as follows:

[0018]

[0019] In equation (II-1), W 1 W 2 W 3 and W 4 Each of the following can independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0020] Epoxy compounds having at least two epoxy groups and a structure as shown in formula (II-1) may include bisphenol A compounds having epoxy groups obtained by reacting bisphenol A compounds with halogenated propylene oxide.

[0021] Specific examples of the aforementioned bisphenol A compounds may include 9,9-bis(4-hydroxyphenyl)fucose, 9,9-bis(4-hydroxy-3-methylphenyl)fucose, 9,9-bis(4-hydroxy-3-chlorophenyl)fucose, 9,9-bis(4-hydroxy-3-bromophenyl)fucose, 9,9-bis(4-hydroxy-3-fluorophenyl)fucose, 9,9-bis(4-hydroxy-3-methoxyphenyl)fucose, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fucose, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fucose, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fucose, or analogues thereof, or any combination thereof.

[0022] Specific examples of halogenated propylene oxides may include 3-chloro-1,2-epoxypropane or 3-bromo-1,2-epoxypropane or their analogues, or any combination thereof.

[0023] Specific examples of bisphenol A compounds containing an epoxy group as shown in formula (II-1) may include, but are not limited to, (1) products manufactured by Nippon Steel Chemicals: for example, the product with model number ESF-300 or similar; (2) products manufactured by Osaka Gas: for example, the product with model number PG-100 or EG-210, or similar; and (3) products manufactured by SMS Technology Co.: for example, the product with model number SMS-F9PhPG, SMS-F9CrG or SMS-F914PG, or similar.

[0024] Specifically, the structure represented by equation (II-2) is as follows:

[0025]

[0026] In equation (II-2), W5 To W 18 Each of the following can be independently represented: a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; and s represents an integer from 0 to 10.

[0027] An epoxy compound having at least two epoxy groups and containing a structure as shown in formula (II-2) may be obtained by reacting a compound having a structure of formula (II-2-I) with a halopropane in the presence of an alkali metal hydroxide.

[0028]

[0029] In equation (II-2-1), W 5 To W 18 The definitions of s and s have been described above and will not be repeated here.

[0030] A method for synthesizing an epoxy compound having at least two epoxy groups with a structure as shown in formula (II-2) can be found in Taiwan Patent Publication No. TW 201508418.

[0031] Specific examples of epoxy compounds containing at least two epoxy groups as shown in formula (II-2) may include, but are not limited to, products manufactured by Nippon Kayaku under trade names such as NC-3000, NC-3000H, NC-3000S and NC-3000P.

[0032] Specifically, the structure represented by equation (II-3) is as follows:

[0033]

[0034] In formula (II-3), Ar3 represents the naphthalene ring, W 19 Represents cyano, halogen, or hydrocarbon groups; W 20 Represents hydrocarbon groups, alkoxy groups, cycloalkoxy groups, aryloxy groups, arylalkoxy groups, alkylthio groups, cycloalkoxy groups, arylthio groups, arylalkoxy groups, acyl groups, halogen groups, nitro groups, cyano groups, or substituted amino groups; W 21 denoted as alkyl; a represents an integer from 0 to 4; b represents an integer from 0 to 6; and c represents an integer equal to or greater than 0.

[0035] Specific examples of epoxy compounds having at least two epoxy groups and having the structure shown in formula (II-3) may include, but are not limited to, 9,9-bis(glycidoxynaphthyl)fluorene, and may specifically be, for example, 9,9-bis(6-glycidoxy-2-naphthyl)fluorene or 9,9-bis(5-glycidoxy-1-naphthyl)fluorene and similar compounds.

[0036] The aforementioned compounds having at least one carboxylic acid group and at least one vinyl unsaturated group are selected from one of the following groups (1) to (3):

[0037] (1) Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxybutyl succinic acid, 2-methacryloyloxyethyl adipic acid, 2-methacryloyloxybutyl adipic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxypropyl maleic acid, 2-methacryloyloxybutyl maleic acid, 2-methacryloyloxypropyl succinic acid, 2-methacryloyloxypropyl adipic acid, 2-methacryloyloxypropyl tetrahydrophthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-methacryloyloxybutyl phthalic acid, 2-methacryloyloxybutyl hydrogen phthalic acid or analogues thereof;

[0038] (2) A compound obtained by reacting a (meth)acrylate having a hydroxyl group with a dicarboxylic acid compound. Specific examples of the dicarboxylic acid compound may include adipic acid, succinic acid, maleic acid, phthalic acid, or analogs thereof; and

[0039] (3) A half-ester compound obtained by reacting a hydroxyl-containing (meth)acrylate with a carboxylic anhydride compound. Specific examples of hydroxyl-containing (meth)acrylates may include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate, or analogs thereof. The carboxylic anhydride compound described herein is the same as the tetracarboxylic dianhydride or dicarboxylic anhydride described later, and will not be further elaborated here.

[0040] Tetracarboxylic acids or their dianhydrides (a-1-2)

[0041] Tetracarboxylic acids or their dianhydrides (a-1-2) comprise tetracarboxylic acids or their dianhydrides having a fluorine atom, other tetracarboxylic acids or their dianhydrides besides the tetracarboxylic acids or their dianhydrides having a fluorine atom, or a combination of both.

[0042] The tetracarboxylic acid or its dianhydride containing a fluorine atom can be selected from the group consisting of the tetracarboxylic acid compound with a fluorine atom shown in formula (V-1) and the tetracarboxylic acid dianhydride compound containing a fluorine atom shown in formula (V-2). Specifically, the tetracarboxylic acid compound with a fluorine atom shown in formula (V-1) and the tetracarboxylic acid dianhydride compound containing a fluorine atom shown in formula (V-2) are respectively as follows.

[0043]

[0044] In formulas (V-1) and (V-2), Z is a tetravalent aromatic group having fluorine, and preferably a group having a benzene ring. Specifically, Z is preferably selected from one of the groups shown in formulas (V-3) to (V-8).

[0045]

[0046] In formulas (V-3) to (V-8), E independently represents a fluorine atom or a trifluoromethyl group, and "*" represents the position of the bond between Z and a carbon atom.

[0047] In detail, specific examples of tetracarboxylic acids or their dianhydrides containing fluorine atoms may include fluorine-containing aromatic tetracarboxylic acids such as 4,4'-hexafluoroisopropylidene phthalic acid, 1,4-difluoropyromellitic acid, 1-monofluoropyromellitic acid, and 1,4-di(trifluoromethyl)pyromellitic acid, or dianhydride compounds of the above tetracarboxylic acid compounds, or any combination of the above compounds.

[0048] Specific examples of tetracarboxylic acids or their dianhydrides containing fluorine atoms may also include fluorine-containing tetracarboxylic acid compounds such as 3,3'-hexafluoroisopropylidene phthalic acid, 5,5'-[2,2,2-trifluoro-1-[3-(trifluoromethyl)phenyl]ethylidene] phthalic acid, 5,5'-[2,2,3,3,3-pentafluoro-1-(trifluoromethyl)propylidene] phthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl)pyromellitic acid, 4-(trifluoromethyl)pyromellitic acid, 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or dianhydride compounds of the above tetracarboxylic acid compounds, or any combination of the above compounds.

[0049] Other tetracarboxylic acids or their dianhydrides may include saturated straight-chain tetracarboxylic acids, alicyclic tetracarboxylic acids, aromatic tetracarboxylic acids, or dianhydride compounds of the above tetracarboxylic acid compounds, or combinations thereof.

[0050] Specific examples of the aforementioned saturated straight-chain tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or any combination thereof. Saturated straight-chain tetracarboxylic acids may also have substituents.

[0051] Specific examples of the aforementioned alicyclic tetracarboxylic acids may include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornenetetracarboxylic acid, or any combination thereof. The alicyclic tetracarboxylic acids may also have substituents.

[0052] Specific examples of the aforementioned aromatic tetracarboxylic acids may include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, or any combination of the above compounds. The aromatic tetracarboxylic acids may also have substituents.

[0053] Dicarboxylic acids or their anhydrides (a-1-3)

[0054] Dicarboxylic acids or their anhydrides (a-1-3) may include dicarboxylic acids or their anhydrides having a fluorine atom, other dicarboxylic acids or their anhydrides besides the dicarboxylic acids or their anhydrides having a fluorine atom, or a combination of both.

[0055] The dicarboxylic acid or its anhydride containing a fluorine atom can be selected from the group consisting of dicarboxylic acid compounds containing fluorine atoms represented by formula (VI-1) and dicarboxylic acid anhydride compounds containing fluorine atoms represented by formula (VI-2). Specifically, the dicarboxylic acid compounds containing fluorine atoms represented by formula (VI-1) and the dicarboxylic acid anhydride compounds containing fluorine atoms represented by formula (VI-2) are shown below, respectively.

[0056]

[0057] In formulas (VI-1) and (VI-2), X represents an organic group with 1 to 100 carbon atoms and fluorine atoms.

[0058] Specific examples of dicarboxylic acids or their anhydrides containing fluorine atoms may include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, tetrafluorosuccinic acid, or anhydride compounds of the above dicarboxylic acid compounds, or any combination of the above compounds.

[0059] Other examples of dicarboxylic acids or their anhydrides may include, but are not limited to, saturated straight-chain hydrocarbon dicarboxylic acids, saturated cyclic hydrocarbon dicarboxylic acids, unsaturated dicarboxylic acids, or anhydrides of the above dicarboxylic acid compounds, or any combination of the above compounds.

[0060] Specific examples of the aforementioned saturated straight-chain dicarboxylic acids may include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, octanoic acid, diethylene glycol, or any combination of the above compounds. The hydrocarbon group in the saturated straight-chain dicarboxylic acid may also be substituted.

[0061] Specific examples of the aforementioned saturated cyclic hydrocarbon dicarboxylic acids may include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotriphenyl benzoic acid, or any combination of the above compounds. The saturated cyclic hydrocarbon dicarboxylic acid may also be an alicyclic dicarboxylic acid derived from a substituted saturated hydrocarbon.

[0062] Specific examples of the aforementioned unsaturated dicarboxylic acids may include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl-bridged methylenetetrahydrophthalic acid, chlorogenic acid, trimellitic acid, or any combination of the above compounds.

[0063] In some specific examples, other dicarboxylic acids or their anhydrides may include, but are not limited to, trimethoxysilylpropylsuccinic anhydride, triethoxysilylpropylsuccinic anhydride, methyldimethoxysilylpropylsuccinic anhydride, methyldiethoxysilylpropylsuccinic anhydride, trimethoxysilylbutylsuccinic anhydride, triethoxysilylbutylsuccinic anhydride, methyldiethoxysilylbutylsuccinic anhydride, p-(trimethoxysilyl)phenylsuccinic anhydride, p-(triethoxysilyl)phenylsuccinic anhydride, p-(methyldimethoxysilyl)phenylsuccinic anhydride, p-(methyldiethoxysilyl)phenylsuccinic anhydride, m-(trimethoxysilyl)phenylsuccinic anhydride, m-(triethoxysilyl)phenylsuccinic anhydride, m-(methyldiethoxysilyl)phenylsuccinic anhydride, etc., or dicarboxylic acid compounds of the above dicarboxylic acid anhydrides, or any combination of the above compounds.

[0064] The aforementioned resin (A-1) with unsaturated groups can be used alone or in combination.

[0065] The method for synthesizing the resin (A-1) with unsaturated groups of the present invention is not particularly limited. It can be obtained by reacting the aforementioned diol compound (a-1-1) containing polymerizable unsaturated groups, tetracarboxylic acid or its dianhydride (a-1-2), and dicarboxylic acid or its dianhydride (a-1-3). The synthesis can be carried out with reference to the patent published by Taiwan Patent No. TW 201508418.

[0066] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of resin (A-1) having unsaturated groups used being 30 to 100 parts by weight, preferably 50 to 100 parts by weight, and even more preferably 70 to 100 parts by weight.

[0067] If the alkali-soluble resin (A) contains a resin (A-1) with unsaturated groups, the resulting black matrix can have better solvent resistance.

[0068] Other alkali-soluble resins (A-2)

[0069] The alkali-soluble resin (A) may optionally include other alkali-soluble resins (A-2). Other alkali-soluble resins (A-2) are resins other than those having unsaturated groups (A-1). Other alkali-soluble resins (A-2) may be, for example, resins having carboxylic acid groups or hydroxyl groups, but are not limited to resins having carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins (A-2) may include acrylic resins, polysiloxanes, urethane resins, or phenolic varnish resins, etc.

[0070] The aforementioned acrylic resins are obtained by copolymerizing unsaturated carboxylic acids or unsaturated carboxylic anhydride compounds, and other unsaturated compounds in a solvent in the presence of a suitable polymerization initiator.

[0071] The aforementioned polysiloxane is prepared by polycondensation reaction of silane monomers, or by polycondensation reaction of silane monomers and other polymerizable compounds. The silane monomers may include monofunctional, difunctional, trifunctional, and tetrafunctional silane monomers, and the other polymerizable compounds may include siloxane prepolymers, silica particles, or combinations thereof.

[0072] The aforementioned other alkali-soluble resins (A-2) can be used alone or in combination.

[0073] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of other alkali-soluble resin (A-2) used may be 0 to 70 parts by weight, preferably 0 to 50 parts by weight, and even more preferably 0 to 30 parts by weight.

[0074] Compounds containing vinyl unsaturated groups (B)

[0075] The compound (B) containing an ethylene unsaturated group may be selected from compounds having one ethylene unsaturated group or compounds having two or more ethylene unsaturated groups.

[0076] Compounds having an ethylene unsaturated group may include, but are not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylate-7-amino-3,7-dimethyloctyl acrylate, 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. Compounds such as N,N-dimethyl(meth)acrylamide, tetrachlorophenyl(meth)acrylate, 2-tetrachlorophenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, tetrabromophenyl(meth)acrylate, 2-tetrabromophenoxyethyl(meth)acrylate, 2-trichlorophenoxyethyl(meth)acrylate, tribromophenyl(meth)acrylate, 2-tribromophenoxyethyl(meth)acrylate, ethyl(2-hydroxy(meth)acrylate), propyl(2-hydroxy(meth)acrylate), vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl(meth)acrylate, pentachlorophenyl(meth)acrylate, pentabromophenyl(meth)acrylate, polyethylene(meth)acrylate, propylene(meth)acrylate, or borneol(meth)acrylate, etc. The aforementioned compounds having an ethylene unsaturated group can be used alone or in combination.

[0077] 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 tri(meth)acrylate tri(meth)acrylate tri(meth)acrylate modified with ethylene oxide (EO), propylene oxide (PO), tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and polyester di(meth)acrylate. Compounds including acrylates, 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 aforementioned compounds having two or more (including two) vinyl unsaturated groups can be used alone or in combination.

[0078] Specific examples of the compound (B) containing an ethylene unsaturated group in this invention 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.

[0079] Preferably, the compound (B) containing an vinyl unsaturated group can be trimethylolpropionic acid triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or any combination of the above compounds.

[0080] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of compound (B) containing vinyl unsaturated groups used being 10 to 150 parts by weight, preferably 12 to 135 parts by weight, and even more preferably 15 to 120 parts by weight.

[0081] Photoinitiator (C)

[0082] The photoinitiator (C) of the present invention may comprise an oxo-acyl oxime or a non-oxo-acyl oxime photoinitiator.

[0083] Oxy-acyloxime compounds

[0084] Specific examples of oxy-acyl oxime compounds may include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime), or any combination thereof. The aforementioned 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime) may, for example, be a commercial product manufactured by Ciba Specialty Chemicals Ltd., and marketed under the model number IRGACURE OXE-01.

[0085] Furthermore, specific examples of oxy-acyl oxime compounds may include, but are not limited to, 1-[4-(benzoyl)phenyl]-heptane-1,2-dione-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituted]-ethanephenone-1-(O-acetyl oxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazole-3-substituted]-ethanephenone-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-substituted]-ethanephenone-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl- [4-Tetrahydrofuranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethaneketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethaneketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethaneketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethaneketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)]-1-(O-acetyl oxime), ethaneketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)]-1-(O-acetyl oxime) [-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanephenone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime] ... [H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanecone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanecone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxapentyl)benzoyl}-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanecone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxapentyl)methoxybenzoyl}-9H-carbazole-3-substituent]-1-(O-acetyl oxime), or any combination of the above compounds. The aforementioned 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanecone-1-(O-acetyl oxime) can be, for example, a product manufactured by Ciba Specialty Chemicals Ltd., and marketed under the model name IRGACURE OXE-02.

[0086] The aforementioned oxo-acyl oxime compounds can be used alone or in combination.

[0087] Non-oxy-acyl oxime photoinitiators

[0088] Specific examples of non-oxy-acyl oxime photoinitiators may include, but are not limited to, triazabenzene compounds, phenylethane ketone compounds, diimidazole compounds, benzophenone compounds, α-diketone compounds, alcohol ketone compounds, alcohol ketone ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or any combination of the above compounds.

[0089] Specific examples of the aforementioned triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituent)-4,6-bis(halomethyl)-s-triazabenzene compounds, 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compounds, or any combination of the above compounds.

[0090] Specific examples of vinyl-halomethyl-s-triazabenzene compounds may include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene, or any combination of the above compounds.

[0091] Specific examples of 2-(naphtho-1-substituted)-4,6-bis(halomethyl)-s-triazabenzene compounds may include 2-(naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-butoxy-naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-substituted]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1-substituent]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1-substituent]-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(2-methoxy-naphtho-1-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(6-methoxy-naphtho-2-substituent)-4,6-bis(trichloromethyl)-s-triazabenzene 2-(5-methoxy-naphtho-1-substitute)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substitute)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(6-ethoxy-naphtho-2-substitute)-4,6-di(trichloromethyl)-s-triazabenzene, 2-(4,5-dimethoxy-naphtho-1-substitute)-4,6-di(trichloromethyl)-s-triazabenzene, or any combination of the above compounds.

[0092] Specific examples of 4-(p-aminophenyl)-2,6-di(halomethyl)-s-triazabenzene compounds may include 4-[p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-(p-N- 4-(p-N-ethoxycarbonylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di(phenyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene Triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di(ethoxy) [o-[o-chloro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s- Triazabenzene, 4-[m-bromo-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,[N-Di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N- 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene Triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 2,4-di(trichloromethyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, or any combination of the above compounds. The aforementioned triazabenzene compounds may be used alone or in combination.

[0093] Preferably, the triazabenzene compound comprises 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 2,4-di(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, or any combination of the above compounds.

[0094] Specific examples of the aforementioned phenylethane ketone compounds may include, but are not limited to, p-dimethylamine phenylethane ketone, α,α'-dimethoxyazophenylethane ketone, 2,2'-dimethyl-2-phenylphenylethane ketone, p-methoxyphenylethane ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, or any combination of the above compounds.

[0095] Phenylacetone compounds can be used alone or in combination.

[0096] 2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone may be, for example, a product manufactured by Ciba Specialty Chemicals Ltd., and marketed under the model name IRGACURE 907. 2-Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone may be, for example, a product manufactured by Ciba Specialty Chemicals Ltd., and marketed under the model name IRGACURE 369.

[0097] Preferably, the phenylethane ketone compound comprises 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, or any combination of the above compounds.

[0098] Specific examples of the aforementioned diimidazole compounds may include, but are not limited to, 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, and 2,2'-bis(p-) 2,2'-bis(2,2',4,4'-tetraphenyldiimidazole), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, or any combination of the above compounds.

[0099] Diimidazole compounds can be used alone or in combination.

[0100] Preferably, the diimidazole compound may be 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

[0101] Specific examples of the aforementioned benzophenone compounds may include, but are not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4,4'-bis(diethylamine)benzophenone, or any combination of the above compounds. Benzophenone compounds may be used alone or in combination. 4,4'-bis(diethylamine)benzophenone is preferred as a benzophenone compound.

[0102] Specific examples of the aforementioned α-diketone compounds may include, but are not limited to, benzoyl, diacetyl, or any combination thereof. α-diketone compounds may be used alone or in combination.

[0103] Specific examples of the aforementioned ketol compounds may include, but are not limited to, diphenylethanol ketone. Ketone alcohol compounds may be used alone or in combination.

[0104] Specific examples of the aforementioned ketol ether compounds may include, but are not limited to, diphenylethanol ketone methyl ether, diphenylethanol ketone ethyl ether, diphenylethanol ketone isopropyl ether, or any combination thereof. Ketool ether compounds may be used alone or in combination.

[0105] Specific examples of the aforementioned acylphosphine oxide compounds may include, but are not limited to, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide, or any combination thereof. Acylphosphine oxide compounds may be used alone or in combination with other related compounds.

[0106] Specific examples of the aforementioned quinone compounds may include, but are not limited to, anthraquinones, 1,4-naphthoquinones, or any combination thereof. Quinone compounds may be used alone or in combination.

[0107] Specific examples of the aforementioned halogen-containing compounds may include, but are not limited to, benzoylmethyl chloride, tribromomethyl sulfone, tris(trichloromethyl)-s-triazabenzene, or any combination thereof. Halogen-containing compounds may be used alone or in combination.

[0108] Specific examples of the aforementioned peroxides may include, but are not limited to, di-tert-butylperoxide. Peroxides may be used alone or in combination.

[0109] The amount of alkali-soluble resin (A) used is 100 parts by weight, and the amount of photoinitiator (C) used is 1 to 30 parts by weight, preferably 2 to 28 parts by weight, and even more preferably 3 to 25 parts by weight.

[0110] Black pigment (D)

[0111] The black pigment (D) of the present invention may comprise a first black pigment (D-1), and the black pigment (D) may optionally comprise a second black pigment (D-2).

[0112] First Black Pigment (D-1)

[0113] The first black pigment (D-1) may contain a compound having a structure as shown in formula (III) or a geometrical isomer thereof, its salts or salts of its geometrical isomers thereof.

[0114]

[0115] In formula (III), D1 and D6 independently represent a hydrogen atom, -CH3, -CF3, a fluorine atom, or a chlorine atom, respectively; D2, D3, D4, D5, D7, D8, D9, and D 10 Each of the following independently represents a hydrogen atom, a halogen atom, and a D atom. 11 -COOH, -COOD 11 COO-, -CONH2, -CONHD 11 -COND 11 D 12 -CN, -OH, -OD 11 -COCD 11 -OOCNH2, -OOCNHD 11 -OOCND 11 D 12 -NO2, -NH2, -NHD 11 -ND 11 D 12 -NHCOD 12 -ND 11 COD 12 -N=CH2, -N=CHD 11 -N=CD 11 D 12 -SH, -SD 11 -SOD 11 -SO2D 11 -SO3D 11 , -SO3H, SO3-, -SO2NH2, -SO2NHD 11 or -SO2ND 11 D 12 And freely choose D2 and D3, D3 and D4, D4 and D5, D7 and D8, D8 and D9, and D9 and D 10 At least one combination of the groups consists of direct bonds between each other, or bonds formed by oxygen atoms, sulfur atoms, NH or ND atoms. 11 Bridged and mutually bonded; D 11 and D 12 Each of these can independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0116] Geometric isomers of the compounds shown in formula (III) above may have the core structure shown below (but substituents are omitted in the structural formula), and the trans-trans isomers may be the most stable.

[0117]

[0118] When the compound represented by formula (III) above is anionic, it is preferably a salt formed by compensating for its charge with any known suitable cation, such as a metal, organic, inorganic, or organometallic cation, specifically an alkali metal, an alkaline earth metal, a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as a trialkylammonium, a quaternary ammonium such as a tetraalkylammonium, or an organometallic complex. Secondly, when the geometric isomers of the compound represented by formula (III) above are anionic, it is preferably the same salt.

[0119] Regarding the substituents in formula (III) above and the definitions therein, the following are preferred in terms of their tendency to increase the hiding power. This is because the following substituents can be considered to have no absorption and therefore do not affect the hue of the pigment: D2, D4, D5, D7, D9, and D... 10 They are independent of each other, preferably hydrogen, fluorine, or chlorine atoms, and more preferably hydrogen atoms. D3 and D8 are independent of each other, preferably hydrogen atoms, NO2, OCH3, OC2H5, bromine atoms, chlorine atoms, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3 - It is preferable to use hydrogen atoms or SO3H.

[0120] D1 and D6 are independent of each other, preferably hydrogen atoms, CH3 or CF3, and more preferably hydrogen atoms. They are preferably selected from D1 and D6, D2 and D7, D3 and D8, D4 and D9, and D5 and D6. 10 The groups formed must contain at least one identical combination, preferably D1 and D6 are identical, D2 and D7 are identical, D3 and D8 are identical, D4 and D9 are identical, and D5 and D... 10 same.

[0121] The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, tributyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, or dodecyl.

[0122] The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, and terpenoid. base, Norcaryl, caryl It can be alkyl, norpinyl, pinyl, 1-adamantyl, or 2-adamantyl.

[0123] The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2- 1-Buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, or dodecenyl.

[0124] The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-para-cyclohexadien-1-yl, etc. En-8-yl, 4(10)-thujen-10-yl, 2-decyl alken-1-yl, 2,5-decyl Dien-1-yl, 7,7-dimethyl-2,4-norcaredien-3-yl, or camphenyl (camphenyl).

[0125] The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-dodecyn-12-yl.

[0126] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0127] In one preferred embodiment of the present invention, D2, D4, D5, D7, D9 and D of formula (III) 10 Each atom is independently hydrogen, fluorine, or chlorine. D3 and D8 are independently hydrogen, NO2, OCH3, OC2H5, bromine, chlorine, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H, or SO3-. D1 is the same as D6, D2 is the same as D7, D3 is the same as D8, D4 is the same as D9, and D5 is the same as D... 10 same.

[0128] The first black pigment (D-1) is preferably a compound represented by the following formula (III-1).

[0129]

[0130] Based on the amount of alkali-soluble resin used being 100 parts by weight, the amount of the first black pigment (D-1) used can be from 50 parts by weight to 500 parts by weight, more preferably from 60 parts by weight to 450 parts by weight, and even more preferably from 70 parts by weight to 400 parts by weight.

[0131] If the black pigment (D) contains the first black pigment (D-1), the resulting black matrix can have better solvent resistance.

[0132] Second Black Pigment (D-2)

[0133] The second black pigment (D-2) may include, but is not limited to: (1) black organic pigments: perylene black, cyanine black, aniline black, etc.; (2) mixed organic pigments made by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc., to make them nearly black; (3) light-blocking materials: carbon black, chromium oxide, iron oxide, titanium black, graphite, etc.

[0134] Specific examples of the aforementioned carbon black may include, but are not limited to, CIPigment black 7, or products manufactured by Mitsubishi Chemical Corporation, with model numbers MA100, MA220, MA230, MA8, #970, #1000, #2350, or #2650. This second black pigment (D-2) may be used alone or in combination with other pigments.

[0135] Preferably, the second black pigment (D-2) may be carbon black, or a product of the aforementioned type MA100 or MA230.

[0136] The aforementioned black pigment (D) can be used alone or in combination with other pigments.

[0137] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of black pigment (D) used being 50 to 600 parts by weight, preferably 60 to 550 parts by weight, and even more preferably 70 to 500 parts by weight.

[0138] Solvent (E)

[0139] The solvent (E) of the present invention refers to a solvent that can dissolve the alkali-soluble resin (A), the compound containing an ethylene unsaturated group (B), the photoinitiator (C), the black pigment (D), and the phosphate ester compound (F) described later, without reacting with the above components, and preferably has appropriate volatility.

[0140] Specific examples of solvent (E) may include, but are not limited to: alkyl glycol monoalkyl ethers, alkyl glycol monoalkyl ether acetates, diethylene glycol alkyl ethers, other ethers, ketones, lactic acid alkyl esters, other esters, aromatic hydrocarbons, carboxylic acid amines, or any combination of the above compounds.

[0141] 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 any combination thereof.

[0142] 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 the like, or any combination thereof.

[0143] 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 any combination of the above compounds.

[0144] Other specific examples of ether compounds include tetrahydrofuran or its analogues.

[0145] Specific examples of ketone compounds include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or their analogues, or any combination thereof.

[0146] Specific examples of lactic acid alkyl esters include methyl lactate, ethyl lactate, or their analogues, or any combination thereof.

[0147] 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 any combination thereof.

[0148] Specific examples of aromatic hydrocarbon compounds include toluene, xylene or their analogues, or any combination thereof.

[0149] Specific examples of carboxylic acid amine compounds include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, or their analogues, or any combination thereof. The aforementioned solvent (E) may be used alone or in combination.

[0150] Preferably, the solvent (E) of the present invention may be propylene glycol methyl ether acetate, cyclohexanone, or ethyl 3-ethoxypropionate.

[0151] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of solvent (E) used can be from 500 parts by weight to 5000 parts by weight, preferably from 600 parts by weight to 4500 parts by weight, and even more preferably from 700 parts by weight to 4000 parts by weight.

[0152] Phosphate compounds (F)

[0153] The phosphate compound (F) of the present invention may have the structure shown in formula (I):

[0154]

[0155] In formula (I), R1, R2 and R3 independently represent straight-chain alkyl with 1 to 20 carbon atoms, branched alkyl with 3 to 20 carbon atoms, cycloalkyl or aromatic with 3 to 20 carbon atoms, and R1, R2 and R3 may be the same or different.

[0156] In formula (I), R1, R2, and R3 can be, but are not limited to, the following specific examples: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, phenyl, tolyl, xylyl, ethylphenyl, isopropylphenyl, or beryl, etc. To reduce changes in color, viscosity, and molecular weight after storage, the upper limit of the number of carbon atoms in R1, R2, and R3 is preferably 15, more preferably 10, even more preferably 5, and more preferably 3.

[0157] There are no particular limitations on the phosphate ester compound (F), which can be a triester of phosphoric acid and alcohol or phenolic compounds, and can be aliphatic phosphate triester, alicyclic phosphate triester, aromatic phosphate triester or aliphatic-aromatic phosphate triester, etc.

[0158] Specific examples of aliphatic triphosphates may include, but are not limited to, the following compounds: trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-n-pentyl phosphate, tri-n-hexyl phosphate, or tri(2-ethylhexyl) phosphate. Preferably, based on the viewpoint of reducing changes in color, viscosity, and molecular weight after storage, the aliphatic triphosphate is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, and tri-n-pentyl phosphate. More preferably, the aliphatic triphosphate is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, and triisobutyl phosphate. Even more preferably, the aliphatic triphosphate is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, and triisopropyl phosphate.

[0159] Specific examples of alicyclic phosphate triesters include, but are not limited to, the following compounds: tricyclohexyl phosphate, etc.

[0160] Specific examples of aromatic triphosphates may include, but are not limited to, the following compounds: triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene(diphenyl) phosphate, or tri(isopropylphenyl) phosphate, etc.

[0161] Specific examples of aliphatic-aromatic triphosphates may include, but are not limited to, the following compounds: methyl (diphenyl) phosphate, dimethyl (phenyl) phosphate, ethyl (diphenyl) phosphate, or diethyl (phenyl) phosphate, etc.

[0162] The phosphate compound (F) is preferably an aliphatic triphosphate or an aliphatic-aromatic triphosphate, and more preferably an aliphatic triphosphate.

[0163] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of phosphate compound (F) used can be from 1 part by weight to 25 parts by weight, preferably from 1.5 parts by weight to 22 parts by weight, and even more preferably from 2 parts by weight to 20 parts by weight.

[0164] If the negative photosensitive resin composition of the present invention does not contain phosphate ester compound (F), the resulting black matrix has defects such as poor solvent resistance and adhesion.

[0165] Thiol compounds (G)

[0166] The negative photosensitive resin composition of the present invention may selectively include a thiol compound (G). The thiol compound (G) has the structure shown in formula (IV):

[0167]

[0168] In formula (IV), G1 and G2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; G3 represents a single bond or an alkyl group having 1 to 10 carbon atoms; G4 represents an organic group with a u valence, where u represents an integer from 2 to 6.

[0169] When G1 and G2 are alkyl groups, the alkyl group can be straight-chain or branched-chain, preferably straight-chain. When G1 and G2 are alkyl groups, the number of carbon atoms in the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As a combination of G1 and G2, it is preferred that one of them is a hydrogen atom and the other is an alkyl group, particularly preferably that one of them is a hydrogen atom and the other is a methyl group.

[0170] When G3 is an alkyl group, the alkyl group may be linear or branched, preferably linear. When G3 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0171] The u-valent organic group defined by G4 specifically refers to aliphatic groups with 2 to 6 valents that may contain atoms other than carbon. Examples of atoms other than carbon that can be included in G4 include nitrogen, oxygen, sulfur, fluorine, chlorine, bromine, and iodine atoms. The structure of the aliphatic group to which G4 belongs can be linear, branched, or cyclic, or it can be a combination of these structures.

[0172] Of the thiol compound (G) represented by formula (IV), the compound represented by formula (IV-1) is more preferably preferred:

[0173]

[0174] In formula (IV-1), G4 and u are defined in the same way as in formula (IV), and G5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0175] Specific examples of thiol compounds (G) can be listed below in formulas (IV-2) to (IV-15), but are not limited to these specific examples.

[0176]

[0177]

[0178]

[0179] Based on the amount of alkali-soluble resin (A) used being 100 parts by weight, the amount of thiol compound (G) used being 1 to 10 parts by weight, preferably 1.2 to 9.5 parts by weight, and even more preferably 1.3 to 9 parts by weight.

[0180] When the negative photosensitive resin composition of the present invention contains a thiol compound (G), the resulting black matrix can have better adhesion and solvent resistance.

[0181] The weight ratio ((F) / (G)) of the aforementioned phosphate ester compound (F) to thiol compound (G) can be 0.5 to 4, preferably 0.6 to 3.7, and even more preferably 0.7 to 3.5.

[0182] When the weight ratio of phosphate compound (F) to thiol compound (G) ((F) / (G)) is within the aforementioned range, the resulting black matrix can have better adhesion and solvent resistance.

[0183] Additive (H)

[0184] Without affecting the efficacy of the present invention, the negative photosensitive resin composition of the present invention may selectively add additives (H), and specific examples of additives (H) may include, but are not limited to, surfactants, fillers, polymers (referring to polymers other than the aforementioned alkali-soluble resin (A)), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents and / or other colorants.

[0185] The aforementioned surfactants help improve the coatability of the negative photosensitive resin composition of the present invention. Specific examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorinated surfactants, or any combination of the above surfactants.

[0186] Specifically, surfactants can be, 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 polyurethane esters. The above-mentioned surfactants can be used alone or in combination with other surfactants.

[0187] Specific examples of surfactants include products manufactured by Shin-Etsu Chemical Industry Co., Ltd. and designated as KP; products manufactured by Dow Corning Toray Co., Ltd. and designated as SF-8427; products manufactured by Kyoeisha Oil & Fat Chemical Co., Ltd. and designated as Polyflow; products manufactured by Tochem Products Co., Ltd. and designated as F-Top; products manufactured by Dai Nippon Insoh Chemical Co., Ltd. and designated as Megafac; products manufactured by Sumitomo 3M and designated as Fluorade; and products manufactured by Asahi Glass and designated as Asahi Guard or Surflon.

[0188] Specific examples of fillers include glass and aluminum.

[0189] Specific examples of polymers include polyvinyl alcohol, polyethylene glycol monoalkyl ethers, polyfluoroacrylates, or any combination of the above polymers.

[0190] 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 any combination of the above compounds.

[0191] Specific examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination of the above compounds.

[0192] Specific examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azido, alkoxy phenone, or any combination of the above compounds.

[0193] Specific examples of anti-agglomerating agents include sodium polyacrylate.

[0194] Other colorants include inorganic pigments, organic pigments, or any combination of the two.

[0195] Specific examples of inorganic pigments include metal oxides, metal salts and other metal compounds (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.

[0196] Specific examples of organic pigments include CI pigments 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 pigments 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 any combination of the above pigments.

[0197] Preparation method of negative photosensitive resin composition

[0198] The method for preparing the negative photosensitive resin composition of the present invention can be, for example, by placing an alkali-soluble resin (A), a compound containing an ethylene unsaturated group (B), a photoinitiator (C), a black pigment (D), a solvent (E), and a phosphate ester compound (F) in a stirrer and stirring them to make them uniformly mixed into a solution. If necessary, a thiol compound (G) and an additive (H) can also be added. After uniform mixing, a photosensitive resin composition in solution state can be obtained.

[0199] Furthermore, there are no particular limitations on the preparation method of the negative photosensitive resin composition. For example, the preparation method of the negative photosensitive resin composition involves first dispersing a portion of an alkali-soluble resin (A) and a compound containing an ethylene unsaturated group (B) in a portion of a solvent (E) to form a dispersion solution; and then mixing the remaining alkali-soluble resin (A), the compound containing an ethylene unsaturated group (B), a photoinitiator (C), a black pigment (D), a solvent (E), and a phosphate ester compound (F) to prepare the composition.

[0200] Alternatively, the photosensitive resin composition can be prepared by first dispersing a portion of black pigment (D) in a mixture consisting of a portion of alkali-soluble resin (A) and a portion of solvent (E) to form a black pigment dispersion; and then adding alkali-soluble resin (A), a compound containing vinyl unsaturated groups (B), a photoinitiator (C), black pigment (D), solvent (E), and a phosphate ester compound (F). Furthermore, the dispersion step of the black pigment (D) can be performed using a mixer such as a bead mill or a roll mill.

[0201] Method for creating a black matrix

[0202] The black matrix is ​​prepared by sequentially applying the aforementioned negative photosensitive resin composition to a substrate through pre-baking, exposure, development, and post-exposure baking. Furthermore, when the thickness of the resulting black matrix is ​​1 μm, the optical density can be 3.0 or higher, preferably 3.2 to 5.5, and even more preferably 3.5 to 5.5. The preparation method of the black matrix is ​​described in detail below.

[0203] First, a photosensitive resin composition for a black matrix 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 substrate may include: alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, and glass with a transparent conductive film attached thereto for displays, etc.; or photoelectric conversion device substrates (such as silicon substrates) for solid-state imaging devices, etc.

[0204] After the coating film is formed, most of the solvent is removed by vacuum drying, and 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, while pre-baking involves heat treatment of the coating film at a temperature of 70°C to 110°C for 1 to 15 minutes.

[0205] 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.

[0206] Then, at a temperature of 21°C to 25°C, 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.

[0207] 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 even more preferably from 0.01 wt% to 1 wt%.

[0208] 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 between 150°C and 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 matrix is ​​formed on the substrate.

[0209] Methods for preparing pixel layers and color filters

[0210] The manufacturing method of the pixel layer is similar to that of the black matrix. Specifically, a color filter is coated with a photosensitive composition onto a substrate on which a black matrix has been formed. Then, pre-baking, exposure, development, and post-baking processes are sequentially applied to obtain the pixel layer. However, in the vacuum drying conditions, vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 to 60 seconds. After the above processing steps, a specific pattern is fixed, thereby forming the pixel layer. Furthermore, by repeating the above steps, red, green, and blue pixel layers are sequentially formed on the substrate to obtain a substrate with a black matrix and pixel layer (i.e., a color filter with a pixel layer).

[0211] Display manufacturing method

[0212] 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 display 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. However, any liquid crystal compound and liquid crystal composition can be used.

[0213] 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.

[0214] The following describes the application of the present invention using several embodiments, but these are not intended to limit the present invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the present invention. Detailed Implementation

[0215] Preparation of diol compounds containing polymerizable unsaturated groups (a-1-1)

[0216] The following describes the preparation examples 1 to 3 of diol compounds (a-1-1) containing polymerizable unsaturated groups.

[0217] Preparation Example 1

[0218] First, 100 parts by weight of a fumonisin epoxy compound (model ESF-300, manufactured by Nippon Steel Chemicals; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol, and 130 parts by weight of propylene glycol monomethyl ether acetate were added continuously to a 500 mL four-necked flask. The feed rate was controlled at 25 parts by weight / min, and the reaction temperature was maintained at 100°C to 110°C. After reacting for 15 hours, a pale yellow transparent mixture with a solid content of 50% by weight was obtained. Next, the pale yellow transparent mixture was subjected to extraction, filtration, and heating and drying to obtain the diol compound (a-1-1-a) containing polymerizable unsaturated groups of Preparation Example 1 with a solid content of 99.9% by weight.

[0219] Preparation Example 2

[0220] First, 100 parts by weight of a fumonisin epoxy compound (model PG-100, manufactured by Osaka Gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol, and 135 parts by weight of propylene glycol monomethyl ether acetate were added continuously to a 500 mL four-necked flask. The feed rate was controlled at 25 parts by weight / min, and the reaction temperature was maintained at 100°C to 110°C. After reacting for 15 hours, a pale yellow transparent mixture with a solid content of 50% by weight was obtained. The pale yellow transparent mixture was then subjected to extraction, filtration, and heating and drying to obtain the diol compound (a-1-1-b) containing polymerizable unsaturated groups of Preparation Example 2 with a solid content of 99.9% by weight.

[0221] Preparation Example 3

[0222] 100 parts by weight of a fumonisin epoxy compound (model ESF-300, manufactured by Nippon Steel Chemicals; epoxy equivalent 231), 100 parts by weight of 2-methacryloylethoxysuccinate, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol, and 200 parts by weight of propylene glycol monomethyl ether acetate were added continuously to a 500 mL four-necked flask. The feed rate was controlled at 25 parts by weight / min, and the reaction temperature was maintained at 100°C to 110°C. After reacting for 15 hours, a pale yellow transparent mixture with a solid content of 50% by weight was obtained. The pale yellow transparent mixture was subjected to extraction, filtration, and heating and drying to obtain the diol compound (a-1-1-c) containing polymerizable unsaturated groups of Preparation Example 3 with a solid content of 99.9% by weight.

[0223] Preparation of resin with unsaturated groups (A-1)

[0224] The following are resins (A-1) with unsaturated groups prepared according to Table 1, from Synthesis Example A-1-1 to Preparation Example A-1-6.

[0225] Synthesis Example A-1-1

[0226] First, 1.0 mole of the diol compound with polymerizable unsaturated groups from Preparation Example 1 (a-1-1-a), 0.3 mole of biphenyl tetracarboxylic acid (a-1-2-b), 1.4 mole of succinic acid (a-1-3-d), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-tert-butyl-p-cresol, 700 g of propylene glycol monomethyl ether acetate (PGMEA), and 100 g of ethyl 3-ethoxypropionate (EEP) were simultaneously added to a 500 mL four-necked flask to form a reaction solution. Here, "simultaneous addition" means adding the tetracarboxylic acid or its dianhydride (a-1-2) and the dicarboxylic acid or its anhydride (a-1-3) at the same reaction time. Next, the reaction solution was heated to 110°C and reacted for 2 hours to obtain the resin with unsaturated groups (A-1-1) of Synthesis Example A-1-1.

[0227] Synthesis Example A-1-2

[0228] 1.0 mol of the diol compound with polymerizable unsaturated groups from Preparation Example 2 (a-1-1-b), 2.9 g of benzyltriethylammonium chloride, and 950 g of propylene glycol methyl ether acetate were added to a 500 mL four-necked flask to form a reaction solution. Next, 0.6 mol of benzophenone tetracarboxylic acid dianhydride (a-1-2-c) was added, and the reaction was carried out at 90 °C for 2 hours. Then, 0.8 mol of maleic acid (a-1-3-b) was added, and the reaction was carried out at 90 °C for 4 hours. Here, "segmented addition" means that tetracarboxylic acid or its dianhydride (a-1-2) and dicarboxylic acid or its dianhydride (a-1-3) were added at different reaction times; that is, tetracarboxylic acid or its dianhydride (a-1-2) was added first, followed by dicarboxylic acid or its dianhydride (a-1-3). Through the above synthetic steps, the resin with unsaturated groups of Synthetic Example A-1-2 (A-1-2) was obtained.

[0229] Synthetic Examples A-1-3, A-1-5 and A-1-6

[0230] Synthetic Examples A-1-3, A-1-5, and A-1-6 are prepared using the same method as the resin with unsaturated groups in Synthetic Example A-1-2. The difference lies in the type and amount of raw materials and reaction conditions in Synthetic Examples A-1-3, A-1-5, and A-1-6. Their formulations and reaction parameters are shown in Table 1, and will not be described further here.

[0231] Synthesis Example A-1-4

[0232] Synthesis Example A-1-4 uses the same preparation method as the synthesis method of the resin with unsaturated groups in Synthesis Example A-1-1. The difference is that Synthesis Example A-1-4 changes the type and amount of raw materials used and the reaction conditions in the resin with unsaturated groups. Its formulation and reaction parameters are shown in Table 1, and will not be described again here.

[0233] Table 1

[0234]

[0235] a-1-1-a Preparation Example 1: Diol compound containing polymerizable unsaturated groups

[0236] a-1-1-b Preparation Example 2: Diol compound containing polymerizable unsaturated groups

[0237] a-1-1-c Preparation Example 3: Diol compound containing polymerizable unsaturated groups

[0238] a-1-2-a 4,4′-hexafluoroisopropylidene diphthalic dianhydride (6FDA)

[0239] a-1-2-b Biphenyl tetracarboxylic acid

[0240] α-1-2-c Benzophenone tetracarboxylic dianhydride

[0241] α-1-2-d Pyromellitic dianhydride

[0242] α-1-3-α-3-fluorophthalic anhydride

[0243] α-1-3-b Maleic acid

[0244] α-1-3-c Tetrahydrophthalic anhydride

[0245] α-1-3-d Succinic acid

[0246] PGMEA (Propylene glycol monomethyl ether acetate)

[0247] Ethyl 3-ethoxypropionate (EEP)

[0248] Preparation of other alkali-soluble resins (A-2)

[0249] The following describes the synthesis example A-2-1 and preparation example A-2-2 of other alkali-soluble resins (A-2).

[0250] Synthesis Example A-2-1

[0251] A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a 1000 mL four-necked conical flask. After introducing nitrogen, 15 parts by weight of acrylic acid, 15 parts by weight of glycidyl methacrylate, 70 parts by weight of paraben methacrylate, 3 parts by weight of 2,2'-azobis(2-methylbutyronitrile), and 300 parts by weight of diethylene glycol dimethyl ether were added. The mixture was then slowly stirred and the solution was heated to 80°C, where it underwent polycondensation for 6 hours. After solvent evaporation, the other alkali-soluble resin (A-2-1) of Synthetic Example A-2-1 was obtained.

[0252] Synthesis Example A-2-2

[0253] In a 500 mL three-necked flask, 0.1 mol of 3-(triethoxysilyl)propylsuccinic anhydride, 0.1 mol of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 0.50 mol of methyltrimethoxysilane, 0.30 mol of diphenyldimethoxysilane, and 200 g of 4-hydroxy-4-methyl-2-pentanone were added. An aqueous solution of oxalic acid (0.35 g oxalic acid / 75 g water) was added over 30 minutes with stirring at room temperature. The flask was then immersed in an oil bath at 30 °C and stirred for 30 minutes. The oil bath temperature was then increased to 120 °C over 30 minutes. When the solution temperature dropped to 110 °C (the reaction temperature), polymerization was continued with heating and stirring for 5 hours (the polycondensation time). The solvent was then removed by distillation to obtain the other alkali-soluble resin (A-2-2) of synthetic example A-2-2.

[0254] Preparation of negative photosensitive resin composition

[0255] The following are the negative photosensitive resin compositions prepared according to Table 2 for Examples 1 to 18 and Comparative Examples 1 to 3.

[0256] Example 1

[0257] 100 parts by weight of the alkali-soluble resin (A-1-1) prepared in Synthesis Example A-1-1, 10 parts by weight of ethylene glycol dimethacrylate (B-1), 2 parts by weight of ethanecone, 1-[9-ethyl-6-(2-methylbenzoyl)-9-hydro-carbazole-3-substitute]-1-(oxoacetyl oxime) (C-1), 200 parts by weight of the second black pigment (D-2-1) (manufactured by Mitsubishi Chemical, model MA100), and 2.0 parts by weight of trimethyl phosphate (F-1) were added to 700 parts by weight of propylene glycol monomethyl ether acetate (E-1), and stirred evenly with a shaker to obtain the negative photosensitive resin composition of Example 1. The obtained negative photosensitive resin composition was evaluated using the following methods for evaluating adhesion and solvent resistance, and the results are shown in Table 2, which will not be repeated here.

[0258] Examples 2 to 18 and Comparative Examples 1 to 3

[0259] Examples 2 to 18 and Comparative Examples 1 to 3 were prepared using the same method as the negative photosensitive resin composition of Example 1. The difference was that the types and amounts of raw materials in the negative photosensitive resin composition were changed. The formulations and evaluation results are shown in Table 2, and will not be repeated here.

[0260]

[0261] Abbreviated Chinese name

[0262] B-1 Ethylene glycol dimethacrylate

[0263] B-2 Trimethylolpropionic acid

[0264] B-3 Dipentaerythritol Hexaacrylate

[0265] C-1 Ethylene, 1-[9-ethyl-6-(2-methylbenzoyl)-9-hydro-carbazole-3-substituent]-1-(oxoacetyl oxime) [Trade name OXE-02; manufactured by Ciba Specialty Chemicals]

[0266] C-2 2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (trade name IRGACURE 907; manufactured by Ciba Specialty Chemicals Ltd.)

[0267] D-1-1

[0268] D-1-2

[0269] D-1-3

[0270] D-2-1 Black pigment manufactured by Mitsubishi Chemical, model MA100

[0271] D-2-2 Black pigment manufactured by Mitsubishi Chemical, model MA230

[0272] E-1 Propylene Glycol Monomethyl Ether Acetate

[0273] E-2 3-ethoxypropionate ethyl ester

[0274] F-1 Trimethyl Phosphate

[0275] F-2 Triisopropyl Phosphate

[0276] F-3 Triisobutyl Phosphate

[0277] F-4 Tri-n-hexyl phosphate

[0278] F-5 Tris(2-ethylhexyl) phosphate

[0279] F-6 Tricyclohexyl phosphate

[0280] F-7 Triphenyl Phosphate

[0281] F-8 Toluene diphenyl phosphate

[0282] F-9 dimethyl phenyl phosphate

[0283] F-10 Ethyl diphenyl phosphate

[0284] G-1 Thiol compounds as shown in formula (IV-2)

[0285] G-2 Thiol compounds as shown in formula (IV-3)

[0286] G-3 Thiol compounds as shown in formula (IV-5)

[0287] G-4 Thiol compounds as shown in formula (IV-8)

[0288] G-5 Thiol compounds as shown in formula (IV-9)

[0289] G-6 Thiol compounds as shown in formula (IV-11)

[0290] G-7 Thiol compounds as shown in formula (IV-12)

[0291] G-8 Thiol compounds as shown in formula (IV-13)

[0292] G-9 Thiol compounds as shown in formula (IV-14)

[0293] G-10 is a thiol compound as shown in formula (IV-15).

[0294] Evaluation method

[0295] 1. Adhesion

[0296] The negative 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 90°C for 2 minutes to form a pre-baked coating with a thickness of 2.0 μm. Next, the pre-baked coating was subjected to a 60 mJ / cm² spray test. 2 Exposure to ultraviolet light (exposure machine model AG500-4N; manufactured by M&R NanoTechnology) is performed. Afterwards, it is baked at 120°C for 30 minutes to form a black hardened film.

[0297] According to the cross-hatched test method in JIS.K5400(1900)8.5, the above-mentioned black hardened film was cut into 100 cross-hatched sections using a knife. Then, it was adhered to with adhesive tape (3M396) and then peeled off. The extent of cross-hatched residue was observed and evaluated according to the following criteria. A higher residue ratio indicates better adhesion.

[0298] ◎: 99% ≦ Residual mesh.

[0299] ○: 97% ≤ reticular cell residue < 99%.

[0300] △: 95% ≤ reticular cell residue < 97%.

[0301] X: Residual mesh <95%.

[0302] 2. Solvent resistance

[0303] A small amount of ethanol (95 vol%) was added to lens paper made by Kimberly-Clark, and the black hardened film on the glass substrate was repeatedly wiped with the ethanol-soaked lens paper. The number of wipings when the black hardened film peeled off was recorded.

[0304] ◎: 100 times ≦ number of wipes.

[0305] ○: 80 times ≦ Number of wipes < 100 times.

[0306] △: 60 times ≦ Number of wipes < 80 times.

[0307] ╳: Number of wipes < 60 times.

[0308] As can be seen from the results in Table 2, when the negative photosensitive resin composition of the present invention does not contain phosphate ester compound (F), the resulting black matrix has defects such as poor adhesion and solvent resistance.

[0309] When the negative photosensitive resin composition of the present invention contains a phosphate ester compound (F) and is used in the aforementioned range, it has better solvent resistance.

[0310] When the black pigment (D) contains the first black pigment (D-1), the resulting black matrix can have better solvent resistance.

[0311] Furthermore, when the negative photosensitive resin composition of the present invention contains a thiol compound (G), the resulting black matrix can exhibit better adhesion and solvent resistance. Specifically, if the weight ratio ((F) / (G)) of the phosphate ester compound (F) to the thiol compound (G) is within the aforementioned range, the resulting black matrix can exhibit even better adhesion and solvent resistance.

[0312] It should be added that although the present invention uses specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments as examples to illustrate the negative photosensitive resin composition of the present invention and its applications, it is clear to anyone with ordinary knowledge in the art that the present invention is not limited thereto. Without departing from the spirit and scope of the present invention, the negative photosensitive resin composition of the present invention and its applications can also be carried out using other compounds, compositions, reaction conditions, processes, analytical methods, or instruments.

[0313] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which this invention pertains may make various 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 scope of the claims.

Claims

1. A negative photosensitive resin composition, characterized in that, This negative photosensitive resin composition includes: Alkali-soluble resin (A); Compounds containing ethylene unsaturated groups (B); Photoinitiator (C); Black pigment (D), wherein the black pigment (D) comprises a first black pigment (D-1), and the first black pigment (D-1) comprises a compound having a structure as shown in formula (III) or a geometrical isomer thereof, a salt thereof, or a salt of a geometrical isomer thereof: In formula (III), D1 and D6 independently represent a hydrogen atom, -CH3, -CF3, a fluorine atom, or a chlorine atom, respectively; D2, D3, D4, D5, D7, D8, D9, and D 10 Each of the following independently represents a hydrogen atom, a halogen atom, and a D atom. 11 -COOH, -COOD 11 COO-, -CONH2, -CONHD 11 -COND 11 D 12 -CN, -OH, -OD 11 -COCD 11 -OOCNH2, -OOCNHD 11 -OOCND 11 D 12 -NO2, -NH2, -NHD 11 -ND 11 D 12 -NHCOD 12 -ND 11 COD 12 -N=CH2, -N=CHD 11 -N=CD 11 D 12 -SH, -SD 11 -SOD 11 -SO2D 11 -SO3D 11 , -SO3H, SO3-, -SO2NH2, -SO2NHD 11 or -SO2ND 11 D 12 And freely choose D2 and D3, D3 and D4, D4 and D5, D7 and D8, D8 and D9, and D9 and D 10 At least one combination in the group is directly bonded to each other, or is formed by oxygen atoms, sulfur atoms, NH or ND atoms. 11 Bridged and mutually bonded; D 11 and D 12 Each of these can independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms; Solvent (E); A phosphate ester compound (F), wherein the phosphate ester compound (F) has the structure shown in formula (I): In formula (I), R1, R2, and R3 independently represent a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group, and R1, R2, and R3 may be the same or different; and The thiol compound (G) has the structure shown in formula (IV): In formula (IV), G1 and G2 independently represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms; G3 represents a single bond or an alkyl group having 1 to 10 carbon atoms; G4 represents an organic group with a valence of u, where u represents an integer from 2 to 6. The weight ratio ((F) / (G)) of the phosphate compound (F) and the thiol compound (G) is 0.6 to 3.

7.

2. The negative photosensitive resin composition according to claim 1, characterized in that, The alkali-soluble resin (A) comprises a resin (A-1) having unsaturated groups, which is obtained by polymerizing a mixture comprising: Diol compounds containing polymerizable unsaturated groups (a-1-1); Tetracarboxylic acids or their dianhydrides (a-1-2); and dicarboxylic acids or their anhydrides (a-1-3), and The diol compound (a-1-1) containing polymerizable unsaturated groups is obtained by reacting an epoxy compound having at least two epoxy groups with a compound having at least one carboxylic acid group and at least one vinyl unsaturated group, and the epoxy compound having at least two epoxy groups has the structures shown in formulas (II-1) to (II-3) below: In equation (II-1), W 1 W 2 W 3 and W 4 Each of the following can independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. In equation (II-2), W 5 To W 18 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms; and s represents an integer from 0 to 10; In formula (II-3), Ar3 represents the naphthalene ring, W 19 Represents cyano, halogen, or hydrocarbon groups; W 20 Represents hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, arylalkoxy group, alkylthio group, cycloalkoxy group, arylthio group, arylalkoxy group, acyl group, halogen group, nitro group, cyano group, or substituted amino group; W 21 denoted as alkyl; a represents an integer from 0 to 4; b represents an integer from 0 to 6; and c represents an integer equal to or greater than 0.

3. The negative photosensitive resin composition according to claim 1, characterized in that, The amount of the alkali-soluble resin (A) used is 100 parts by weight, the amount of the compound (B) containing an ethylene unsaturated group used is 10 to 150 parts by weight, the amount of the photoinitiator (C) used is 1 to 30 parts by weight, the amount of the black pigment (D) used is 50 to 600 parts by weight, the amount of the solvent (E) used is 500 to 5000 parts by weight, and the amount of the phosphate compound (F) used is 1 to 25 parts by weight.

4. The negative photosensitive resin composition according to claim 2, characterized in that, Based on the amount of the alkali-soluble resin (A) used being 100 parts by weight, the amount of the resin (A-1) having unsaturated groups used being 30 to 100 parts by weight.

5. The negative photosensitive resin composition according to claim 1, characterized in that, Based on the amount of the alkali-soluble resin (A) used being 100 parts by weight, the amount of the first black pigment (D-1) used being 50 to 500 parts by weight.

6. The negative photosensitive resin composition according to claim 1, characterized in that, Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the thiol compound (G) used is from 1 to 10 parts by weight.

7. A black matrix, characterized in that, The black matrix is ​​formed by pre-baking, exposure, development and post-baking of the negative photosensitive resin composition as described in any one of claims 1 to 6.

8. A color filter, characterized in that, The color filter contains the black matrix as described in claim 7.

9. A display, characterized in that, The display includes the color filter as described in claim 8.

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