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

Abstract

The present invention provides a black photosensitive resin composition, a black pattern, a color filter, and a liquid crystal display element. The black pattern produced can improve the technical problem of poor taper angle and drying. The black photosensitive resin composition includes an alkali-soluble resin (A), a compound having an ethylenic unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E). The alkali-soluble resin (A) includes a first alkali-soluble resin (A-1). The first alkali-soluble resin (A-1) is obtained by polymerization of a first mixture including a diol compound (a-1-1) represented by formula (A-I). The photoinitiator (C) includes a first photoinitiator (C-1) having a group represented by formula (C-II).

Description

TECHNICAL FIELD

[0001] The present application relates to a black photosensitive resin composition, in particular to a black photosensitive resin composition which forms a black pattern having a taper angle and a good development adhesion after hardening, a color filter and a liquid crystal display device. BACKGROUND

[0002] In recent years, with the vigorous development of various technologies of liquid crystal display devices, and in order to improve the contrast ratio and display quality of the liquid crystal display device, a black pattern, such as a black matrix, is usually arranged in the gap between the stripes and dots of the color filter in the liquid crystal display device. The black matrix can prevent the defects such as contrast ratio reduction and color purity reduction caused by light leakage between pixels.

[0003] Japanese Patent Application Publication No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition comprises an alkali-soluble resin having a carboxylic acid group and an unsaturated group for polymerization, a photopolymerizable monomer containing an ethylenic unsaturated group, a photopolymerization initiator, and a black pigment. This patent improves the pattern resolution of the black matrix formed by the photosensitive resin composition with a high content of black pigment by using a specific alkali-soluble resin. In addition, Japanese Patent Application Publication No. 2009-145432 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition comprises a monomer containing an ethylenic unsaturated group, a photopolymerization initiator, a black pigment, and a resin. The resin is selected from a thermally hardening resin, a photosensitive resin, a thermoplastic resin, or a combination thereof. This patent improves the problems of photosensitivity and development failure of the photosensitive resin composition with a high content of black pigment in the photolithography process by adjusting the content of black pigment in the solid content of the photosensitive resin composition.

[0004] However, as the industry requires higher and higher light shielding properties of the black matrix, the solution is to increase the content of black pigment to improve the light shielding properties of the black matrix. However, the taper angle and development adhesion of the black pattern formed by the aforementioned black photosensitive resin composition are poor. When the taper angle is poor, it is difficult to control the shape of the color photoresist in the subsequent process; and when the development adhesion is poor, small line width patterns cannot be generated.

[0005] In summary, how to make the black pattern, such as the black matrix, formed by the black photosensitive resin composition have good taper angle and development adhesion to meet the requirements of the industry is the goal of the present application in the technical field. SUMMARY

[0006] In view of the above, the present application provides a black photosensitive resin composition capable of improving the problems of the taper angle and poor development adhesion.

[0007] The present application provides a black photosensitive resin composition comprising: an alkali-soluble resin (A), a compound having an ethylenic unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E).

[0008] The alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1). The first alkali-soluble resin (A-1) is obtained by polymerization of a first mixture. The first mixture comprises a diol compound (a-1-1) represented by Formula (A-I), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3).

[0009] The photoinitiator (C) comprises a first photoinitiator (C-1) represented by Formula (C-I),

[0010]

[0011] In Formula (A-I), each of A1 and A1' is R a SR b , the R a is a single bond, an alkylene group having a carbon number of 1 to 10, or an arylene group having a carbon number of 6 to 15, and the R b is an alkyl group having a carbon number of 1 to 10 or an aryl group having a carbon number of 6 to 15; n is an integer of 1 to 6; each of A2 and A2' is hydrogen, a hydroxyl group, a thiol group, an amine group, a nitro group, or a halogen substituent,

[0012]

[0013] In Formula (C-I), each of X1 and X2 independently represents a group represented by Formula (C-II); k represents 0 or 1; when k = 0, G represents a monovalent aromatic phosphine oxide group having a carbon number of 12 to 19; when k = 1, G represents a single bond or an alkylene group having a carbon number of 1 to 6;

[0014]

[0015] In Formula (C-II), each of R1 and R2 independently represents a hydrogen atom, a halogen atom, or an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aromatic group having a carbon number of 1 to 12; m represents 1 or 2; each of R3 independently represents a single bond or an organic group having a carbon number of 1 to 24; and R4 represents NO2, an aroyl group having a carbon number of 7 to 11, or an aromatic group having a carbon number of 7 to 12 formed with R1;

[0016] M1 represents a single bond or is absent; when M1 represents a single bond, M2 represents NR5, and R5 represents a single bond or an alkyl group having a carbon number of 1 to 6; when M1 is absent, M2 represents a sulfur atom;

[0017] C-M3 represents C=O, C=N-OH, C-OH, or C=N-OCOR6, R6 represents an organic group having a carbon number of 1 to 11, and at least one group represented by C=N-OCOR6 is present in the compound represented by formula (C-I);

[0018] In formula (C-II), R3 or R5 is bonded to the group G.

[0019] In one embodiment of the present application, the above-mentioned compound (B) having an ethylenically unsaturated group includes a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.

[0020] In one embodiment of the present application, the above-mentioned compound (B) having an ethylenically unsaturated group includes a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.

[0021]

[0022] In formula (F-I),

[0023] Each of a plurality of Z independently represents a halogen atom or an alkyl group having a carbon number of 1 to 5;

[0024] Each of a plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 to 10;

[0025] Each of a plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 to 10;

[0026] Each of a plurality of Y3 independently represents a hydrogen atom or a group represented by formula (F-II) or formula (F-III), wherein at least one of Y3 is a group represented by formula (F-II) or formula (F-III);

[0027] Each of a plurality of L1 independently represents a hydrogen atom or a methyl group;

[0028] Each of i independently represents an integer of 0 to 4;

[0029] i represents an integer of 0 to 2,

[0030]

[0031] In formula (F-II) and formula (F-III),

[0032] Each of a plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 5;

[0033] L3 represents a single bond or an alkylene group having a carbon number of 1 to 10; * represents a bonding site,

[0034] In the alkylene group having said carbon number of 1 to 10 in Y1, Y2, and L3, any -CH2- can be replaced with -O-, -CH=CH-, or -C≡C-, and any hydrogen atom can be replaced with a halogen atom.

[0035] In one embodiment of the present application, based on the total amount of use of the alkali-soluble resin (A) being 100 parts by weight, the amount of use of the alkali-soluble resin (A-1) is 10 parts by weight to 100 parts by weight, the amount of use of the compound (B) having an ethylenic unsaturated group is 20 parts by weight to 200 parts by weight, the amount of use of the photoinitiator (C) is 10 parts by weight to 70 parts by weight, the amount of use of the first photoinitiator (C-1) is 10 parts by weight to 60 parts by weight, the total amount of use of the solvent (D) is 600 parts by weight to 5000 parts by weight, and the amount of use of the black pigment (E) is 50 parts by weight to 450 parts by weight.

[0036] In one embodiment of the present application, based on the total amount of use of the alkali-soluble resin (A) being 100 parts by weight, the amount of use of the compound (B-1) having an acid group and at least three ethylenic unsaturated groups is 20 parts by weight to 180 parts by weight.

[0037] In one embodiment of the present application, based on the total amount of use of the alkali-soluble resin (A) being 100 parts by weight, the amount of use of the compound (F) having an epoxy group structure is 30 parts by weight to 250 parts by weight.

[0038] In one embodiment of the present application, the above-mentioned first photoinitiator (C-1) includes at least one selected from the group consisting of compounds represented by the following formulae (C-I-1) to (C-I-17),

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] The present application also provides a black pattern formed by the above-mentioned black photosensitive resin composition through a pre-baking process, an exposure process, a development process, and a post-baking process.

[0046] The present application also provides a color filter including the above-mentioned black pattern.

[0047] The present application also provides a liquid crystal display device comprising the color filter as described above.

[0048] Based on the above, the black photosensitive resin composition of the present application can improve the technical problems of poor taper angle and drying property in the prior art due to the use of the alkali-soluble resin (A-1) containing a base-soluble resin having a specific structure and the first photoinitiator (C-1).

[0049] In order to make the above features and advantages of the present application more apparent and understandable, specific examples are described below in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is a schematic view of measuring the taper angle of a photoresist pattern.

[0051] BRIEF DESCRIPTION OF DRAWINGS

[0052] 701: glass substrate

[0053] 703: black pattern

[0054] θ: taper angle DETAILED DESCRIPTION

[0055] <Black photosensitive resin composition>

[0056] The present application provides a black photosensitive resin composition comprising an alkali-soluble resin (A), a compound having an ethylenic unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E), and optionally a compound having an epoxy group structure (F) and an additive (G). The alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1). The first alkali-soluble resin (A-1) is obtained by polymerization of a first mixture. The first mixture comprises a diol compound (a-1-1) represented by formula (A-I), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3). The photoinitiator (C) comprises a first photoinitiator (C-1) represented by formula (C-I). Each component of the black photosensitive resin composition for use in the present application will be described in detail below.

[0057] Alkali-soluble resin (A)

[0058] The alkali-soluble resin (A) comprises the alkali-soluble resin (A-1) and an alkali-soluble resin (A-2).

[0059] Alkali-soluble resin (A-1)

[0060] The alkali-soluble resin (A-1) is obtained by polymerization of a first mixture. The first mixture includes a diol compound represented by formula (A-I) (a-1-1), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its acid anhydride (a-1-3).

[0061] The diol compound represented by formula (A-I) (a-1-1)

[0062] The diol compound (a-1-1) is represented by the following formula (A-I):

[0063]

[0064] In formula (A-I), each of A1and A1' is R a SR b , the R a is a single bond, an alkylene group having 1 to 10 carbons, or an arylene group having 6 to 15 carbons, and the R b is an alkyl group having 1 to 10 carbons or an aryl group having 6 to 15 carbons; n is an integer of 1 to 6; and each of A2and A2' is hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group, or a halogen substituent.

[0065] The alkyl group having 1 to 10 carbons is linear or branched, and examples thereof can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, and a decyl group. The aryl group having 6 to 15 carbons can be, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or the like. The alkylene group having 1 to 10 carbons and the arylene group having 6 to 15 carbons can be, respectively, the alkylene group and the arylene group corresponding to the above-mentioned alkyl group having 1 to 10 carbons and the aryl group having 6 to 15 carbons.

[0066] The tetracarboxylic acid or its acid dianhydride (a-1-2)

[0067] The tetracarboxylic acid or its acid dianhydride (a-1-2) includes a tetracarboxylic acid containing a fluorine atom, a linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or a dianhydride compound of the above-mentioned tetracarboxylic acid, or a combination thereof.

[0068] Specific examples of the tetracarboxylic acid containing fluorine atom or its acid dianhydride include 4,4'-hexafluoroisopropylidene dibenzenepropanedicarboxylic acid, 1,4-difluorophthalic acid, 1-monofluorophthalic acid, 1,4-bis(trifluoromethyl)phthalic acid, 3,3'-hexafluoroisopropylidene dibenzenepropanedicarboxylic acid, 5,5'-[2,2,2-trifluoro-l-[3-(trifluoromethyl)phenyl]ethylidene]dibenzenepropanedicarboxylic acid, 5,5'-[2,2,3,3,3-pentafluoro-l-(trifluoromethyl)propylidene]dibenzenepropanedicarboxylic acid, 5,5'-oxybis[4,6,7-trifluoro-phthalic acid], 3,6-bis(trifluoromethyl)phthalic acid, 4-(trifluoromethyl)phthalic acid, 1,4-bis(3,4-dicarboxytrifluorophenoxy)benzene, and the like fluorine-containing tetracarboxylic acid, or a dianhydride compound of the above-mentioned tetracarboxylic acid, or a combination of the above-mentioned compounds.

[0069] Specific examples of the saturated straight-chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, or a combination of the above-mentioned compounds. The saturated straight-chain hydrocarbon tetracarboxylic acid can also have a substituent.

[0070] Specific examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, norbornane tetracarboxylic acid, or a combination of the above-mentioned compounds. The alicyclic tetracarboxylic acid can also have a substituent.

[0071] Specific examples of the dianhydride compound of the alicyclic tetracarboxylic acid include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride, or 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, or a combination of the above-mentioned compounds.

[0072] Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, or a combination of the above-mentioned compounds. The aromatic tetracarboxylic acid can also have a substituent.

[0073] Specific examples of the dianhydride compound of the aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorinated dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or a combination of the above compounds.

[0074] The dicarboxylic acid or anhydride thereof (a-1-3) includes a fluorine atom-containing dicarboxylic acid, a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid, another dicarboxylic acid, or an anhydride of the above-mentioned dicarboxylic acid compound, or a combination of the above-mentioned compounds.

[0075] The dicarboxylic acid or anhydride thereof (a-1-3) includes a fluorine atom-containing dicarboxylic acid, a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid, another dicarboxylic acid, or an anhydride of the above-mentioned dicarboxylic acid compound, or a combination of the above-mentioned compounds.

[0076] Specific examples of the fluorine atom-containing dicarboxylic acid or anhydride thereof include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, tetrafluorosuccinic acid, or an anhydride compound of the above-mentioned dicarboxylic acid, or a combination of the above-mentioned compounds.

[0077] Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citraconic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a combination of the above-mentioned compounds. The hydrocarbon group in the saturated linear hydrocarbon dicarboxylic acid can also be substituted.

[0078] Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid, or a combination of the above-mentioned compounds. The saturated cyclic hydrocarbon dicarboxylic acid can also be an alicyclic dicarboxylic acid in which a saturated hydrocarbon is substituted.

[0079] Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, chloromethylbenzene acid, trimellitic acid, or a combination thereof.

[0080] Specific examples of the other dicarboxylic acid or its anhydride include trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, triethoxysilylbutyl succinic anhydride, methyldiethoxysilylbutyl succinic anhydride, p-(trimethoxysilyl)phenyl succinic anhydride, p-(triethoxysilyl)phenyl succinic anhydride, p-(methyldimethoxysilyl)phenyl succinic anhydride, p-(methyldiethoxysilyl)phenyl succinic anhydride, m-(trimethoxysilyl)phenyl succinic anhydride, m-(triethoxysilyl)phenyl succinic anhydride, m-(methyldiethoxysilyl)phenyl succinic anhydride, or the like, or a dicarboxylic acid compound thereof, or a combination thereof.

[0081] The method for synthesizing the alkali-soluble resin (A-1) is not particularly limited, and can be obtained by reacting a diol compound (a-1-1) represented by Formula (A-I), a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or its anhydride (a-1-3).

[0082] However, it is preferable to first perform a polymerization reaction of the diol compound (a-1-1) represented by Formula (A-I) and the tetracarboxylic acid or its acid dianhydride (a-1-2), for example, at 100°C to 130°C, preferably at 110°C to 120°C, for 2 hours to 24 hours, preferably for 4 hours to 12 hours.

[0083] The amount of the diol compound (a-1-1) represented by Formula (A-I) used is 100 parts by weight, and the amount of the tetracarboxylic acid or its acid dianhydride (a-1-2) used is 5 to 40 parts by weight, preferably 10 parts by weight to 30 parts by weight, and more preferably 10 parts by weight to 20 parts by weight.

[0084] After the aforementioned polymerization reaction is initiated, the dicarboxylic acid or its anhydride (a-1-3) is added, for example, at 100°C to 130°C, preferably at 110°C to 120°C, for 30 minutes to 4 hours, preferably for 1 hour to 3 hours.

[0085] The amount of the diol compound (a-1-1) represented by Formula (A-I) used is 100 parts by weight, and the amount of the dicarboxylic acid or its anhydride (a-1-3) used is 2 to 10 parts by weight, preferably 2 parts by weight to 5 parts by weight, and more preferably 3 parts by weight to 5 parts by weight.

[0086] The weight average molecular weight of the alkali-soluble resin (A-1) as measured by gel permeation chromatography (GPC) can be 1,000 g / mol to 100,000 g / mol, preferably 2,000 g / mol to 50,000 g / mol, and more preferably 3,000 g / mol to 10,000 g / mol. In addition, the dispersity of the alkali-soluble resin (A-1) as measured by GPC can be in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0.

[0087] The alkali-soluble resin (A-1) is used in an amount of 10 to 100 parts by weight, preferably 10 parts by weight to 90 parts by weight, and more preferably 15 parts by weight to 80 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0088] If the alkali-soluble resin (A-1) is not used in the black photosensitive resin composition, a good taper angle cannot be obtained.

[0089] Alkali-soluble resin (A-2)

[0090] The alkali-soluble resin (A-2) is obtained by polymerizing a second mixture. The second mixture includes a diol compound containing a polymerizable unsaturated group (a-2-1), a tetracarboxylic acid or an acid dianhydride thereof (a-2-2), and a dicarboxylic acid or an acid anhydride thereof (a-2-3).

[0091] Diol compound containing a polymerizable unsaturated group (a-2-1)

[0092] The diol compound containing a polymerizable unsaturated group (a-2-1) is obtained by reacting an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenic unsaturated group.

[0093] The epoxy compound having at least two epoxy groups has a structure represented by formula (A-2-1-I), a structure represented by formula (A-2-1-II), or a structure represented by formula (A-2-1-III), or a combination of the above three structures. The structure represented by formula (A-2-1-I), the structure represented by formula (A-2-1-II), and the structure represented by formula (A-2-1-III) will be described below.

[0094] Specifically, the structure represented by formula (A-2-1-I) is as follows:

[0095]

[0096] In formula (A-2-1-I), W 1 , W 2 , W 3 , and W4 each independently represents a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 5, an alkoxy group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 12, or an aralkyl group having a carbon number of 6 to 12.

[0097] The epoxy compound having at least two epoxy groups containing a structure represented by Formula (A-2-1-I) can include a bisphenol fluorene type compound having an epoxy group obtained by reacting a bisphenol fluorene type compound with a halogenated epoxy propane.

[0098] Specific examples of the bisphenol fluorene type compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, or the like, or a combination thereof.

[0099] Specific examples of the halogenated epoxy propane include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or the like, or a combination thereof.

[0100] Specific examples of the bisphenol fluorene type compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical: for example, ESF-300, or the like; (2) a product manufactured by Osaka Gas: for example, PG-100, EG-210, or the like; (3) a product manufactured by S.M.S. Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, or the like.

[0101] In addition, specifically, the structure represented by Formula (A-2-1-II) is as follows:

[0102]

[0103] In Formula (A-2-1-II), W 5 to W 18 each independently represents a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 8, or an aromatic group having a carbon number of 6 to 15, and s represents an integer of 0 to 10.

[0104] The epoxy compound having at least two epoxy groups containing a structure represented by Formula (A-2-1-II) can be obtained by reacting a compound having a structure of the following Formula (A-2-1-II-I) with a halogenated epoxy propane in the presence of an alkali metal hydroxide.

[0105]

[0106] In formula (A-2-1-II-I), W 5 to W 18 and the definition of s is the same as that of W 5 to W 18 and the definition of s is the same as that of W

[0107] The synthesis method of the epoxy compound having at least two epoxy groups containing the structure represented by formula (A-2-1-II) can refer to the patent of Taiwan publication number TW201508418.

[0108] Specific examples of the epoxy compound having at least two epoxy groups containing the structure represented by formula (A-2-1-II) include the products with trade names of NC-3000, NC-3000H, NC-3000S, and NC-3000P, etc. manufactured by Japan Chemicals.

[0109] In addition, specifically, the structure represented by formula (A-2-1-III) is as follows:

[0110]

[0111] In formula (A-2-1-III), Ar3represents a naphthalene ring, W 19 represents a cyano group, a halogen, or a hydrocarbon group, W 20 represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a halogen, a nitro group, a cyano group, or a substituted amino group, W 21 represents an alkylene group, a represents an integer of 0 to 4, and b and c represent an integer of 0 or above.

[0112] Specific examples of the epoxy compound having at least two epoxy groups containing the structure represented by formula (A-2-1-III) include 9,9-bis(glycidyloxynaphthyl)fluorene, and for example, 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene or 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene, and the like.

[0113] The compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the following groups (1) to (3):

[0114] (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 hydrogenphthalic acid, or the like;

[0115] (2) a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein specific examples of the dicarboxylic acid compound include adipic acid, succinic acid, maleic acid, phthalic acid, or the like; and

[0116] (3) a half-ester compound obtained by reacting a (meth)acrylate having a hydroxyl group with a carboxylic anhydride compound, wherein specific examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate, or the like.

[0117] In addition, the carboxylic anhydride compound described herein is the same as the tetracarboxylic dianhydride or the dicarboxylic anhydride described above, and thus is not described again here.

[0118] The types of the tetracarboxylic acid or the acid dianhydride thereof (a-2-2) and the dicarboxylic acid or the acid anhydride thereof (a-2-3) used in the alkali-soluble resin (A-2) can be the same as those of the tetracarboxylic acid or the acid dianhydride thereof (a-1-2) and the dicarboxylic acid or the acid anhydride thereof (a-1-3) used in the alkali-soluble resin (A-1) described above, respectively, and thus are not described again here.

[0119] The synthesis method of the alkali-soluble resin (A-2) is not particularly limited, as long as the glycol compound containing a polymerizable unsaturated group (a-2-1), the tetracarboxylic acid or the acid dianhydride thereof (a-2-2), and the dicarboxylic acid or the acid anhydride thereof (a-2-3) are reacted to obtain, and can be synthesized by referring to the patent with publication number TW201508418.

[0120] The weight average molecular weight of the alkali-soluble resin (A-2) in terms of polystyrene as determined by GPC is preferably 800 g / mol to 8000 g / mol, more preferably 1,000 g / mol to 6,000 g / mol.

[0121] The alkali-soluble resin (A-2) is preferably used in an amount of 0 to 90 parts by weight, more preferably 10 parts by weight to 90 parts by weight, and even more preferably 20 parts by weight to 85 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0122] When the alkali-soluble resin (A-2) is used, the taper angle of the black pattern produced from the black photosensitive resin composition of the present application can be further improved.

[0123] Compound (B) having ethylenically unsaturated group

[0124] The compound (B) having ethylenically unsaturated group includes a compound (B-1) having an acid group and at least three ethylenically unsaturated groups, and other compounds (B-2) having ethylenically unsaturated group.

[0125] Compound (B-1) having acid group and at least three ethylenically unsaturated groups

[0126] The acid group in the compound (B-1) having acid group and at least three ethylenically unsaturated groups can react with an alkali developer. Specific examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like. Among them, the acid group is preferably a carboxyl group which can react well with an alkali developer.

[0127] The compound (B-1) having acid group and at least three ethylenically unsaturated groups can be (1) a multifunctional (meth)acrylate containing a carboxyl group synthesized by subjecting a multifunctional (meth)acrylate containing a hydroxyl group to a modification reaction with a dibasic anhydride or a dibasic acid, or (2) a multifunctional (meth)acrylate containing a sulfonic acid group synthesized by subjecting an aromatic multifunctional (meth)acrylate to a modification reaction with concentrated sulfuric acid or fuming sulfuric acid.

[0128] Preferably, the compound (B-1) having acid group and at least three ethylenically unsaturated groups has a structure represented by the following formula (B-1-I) or formula (B-1-II):

[0129]

[0130] In the formula (B-1-I), T 1 represents -CH2-, -OCH2-, -OCH2CH2-, -OCH2CH2CH2-, or -OCH2CH2CH2CH2-; T 2 represents a structure represented by the following formula (B-1-I-1) or formula (B-1-I-2); T 3represents the structure shown in the following formula (B-1-I-3), formula (B-1-I-4) or formula (B-1-I-5), wherein the benzene ring in the structure shown in formula (B-1-I-5) can also be tetrahydrogenated or hexahydrogenated, and e represents an integer of 1 to 8; d represents an integer of 0 to 14:

[0131]

[0132]

[0133] In formula (B-1-II), T 1 , T 2 and T 3 are the same as described above; T 4 represents -O- or the structure shown in the following formula (B-1-II-1); e and d are the same as described above, and f represents an integer of 1 to 8:

[0134]

[0135] In formula (B-1-I) or formula (B-1-II), when T 1 and T 2 exist in plural, T 1 and T 2 may be the same or different, respectively.

[0136] In the specific examples of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups shown in the aforementioned formula (B-1-I) or formula (B-1-II), there can be mentioned a monoester compound containing a carboxyl group formed from a mono-hydroxy oligomeric acrylate or mono-hydroxy oligomeric methacrylate such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate, and a diacid such as malonic acid, succinic acid, glutaric acid, isophthalic acid, terephthalic acid and phthalic acid.

[0137] The compound (B-1) having an acidic group and at least three ethylenically unsaturated groups is preferably a monoester compound containing a carboxyl group formed from pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and succinic acid, phthalic acid and glutaric acid.

[0138] The total amount of use of the alkali-soluble resin (A) is 100 parts by weight, and the amount of use of the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups is 20 parts by weight to 180 parts by weight, preferably 25 parts by weight to 170 parts by weight, and more preferably 30 parts by weight to 160 parts by weight.

[0139] If the compound (B-1) having an acid group and at least three ethylenically unsaturated groups is used in the black photosensitive resin composition, the taper angle of the black pattern can be further improved.

[0140] Other compounds (B-2) having ethylenically unsaturated groups

[0141] The other compounds (B-2) having ethylenically unsaturated groups can be selected from a compound having one ethylenically unsaturated group or a compound having two or more ethylenically unsaturated groups.

[0142] The compound having one ethylenically unsaturated group can include, but is not limited to, a (meth)acrylamide, a (meth)acrylmorpholine, a (meth)acrylic acid-7-amino-3,7-dimethyloctyl ester, an isobutyloxy methyl (meth)acrylamide, a (meth)acrylic acid isobornyl oxyethyl ester, a (meth)acrylic acid isobornyl ester, a (meth)acrylic acid-2-ethylhexyl ester, an ethyl diglycol (meth)acrylate, a tertiary octyl (meth)acrylamide, a diacetone (meth)acrylamide, a (meth)acrylic acid dimethylaminoethyl ester, a (meth)acrylic acid dodecyl ester, a (meth)acrylic acid dicyclopentenoxyethyl ester, a (meth)acrylic acid dicyclopentenyl ester, an N,N-dimethyl (meth)acrylamide, a (meth)acrylic acid tetrachlorophenyl ester, a (meth)acrylic acid-2-tetrachlorophenoxyethyl ester, a (meth)acrylic acid tetrahydrofurfuryl ester, a (meth)acrylic acid tetrabromophenyl ester, a (meth)acrylic acid-2-tetrabromophenoxyethyl ester, a (meth)acrylic acid-2-trichlorophenoxyethyl ester, a (meth)acrylic acid tribromophenyl ester, a (meth)acrylic acid-2-tribromophenoxyethyl ester, a 2-hydroxy-(meth)acrylic acid ethyl ester, a 2-hydroxy-(meth)acrylic acid propyl ester, a vinyl caprolactam, an N-vinyl pyrrolidone, a (meth)acrylic acid phenoxyethyl ester, a (meth)acrylic acid pentachlorophenyl ester, a (meth)acrylic acid pentabromophenyl ester, a poly mono (meth)acrylic acid ethylene ester, a poly mono (meth)acrylic acid propylene ester, or a (meth)acrylic acid bornyl ester, and the like. The compound having one ethylenically unsaturated group can be used alone or in a mixture of a plurality of kinds.

[0143] The compound having two or more ethylenically unsaturated groups can include, but is 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) isocyanurate di(meth)acrylate, tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone-modified tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, oxirane (EO)-modified trimethylolpropane tri(meth)acrylate, oxirane (PO)-modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, oxirane-modified bisphenol A di(meth)acrylate, oxirane-modified bisphenol A di(meth)acrylate, oxirane-modified hydrogenated bisphenol A di(meth)acrylate, oxirane-modified hydrogenated bisphenol A di(meth)acrylate, oxirane-modified bisphenol F di(meth)acrylate, or novolak polyglycidyl ether (meth)acrylate. The compound having two or more (including two) ethylenically unsaturated groups can be used alone or in a mixture of two or more.

[0144] Specific examples of other compounds having ethylenically unsaturated groups (B-2) include, for example, trimethylolpropane triacrylate, oxirane-modified trimethylolpropane triacrylate, oxirane-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, oxirane-modified glycerol triacrylate, or any combination of the above compounds.

[0145] The amount of the compound having ethylenically unsaturated groups (B) is 20 parts by weight to 200 parts by weight, preferably 25 parts by weight to 190 parts by weight, and more preferably 30 parts by weight to 180 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0146] Photoinitiator (C)

[0147] The photoinitiator (C) includes a first photoinitiator (C-1) represented by formula (C-I), and a second photoinitiator (C-2).

[0148] The first photoinitiator (C-1)

[0149] The first photoinitiator (C-1) is represented by the following formula (C-I):

[0150]

[0151] In formula (C-I), X1and X2independently represent a group represented by formula (C-II); k represents 0 or 1; when k = 0, G represents a monovalent aromatic phosphine oxide group having a carbon number of 12 to 19; when k = 1, G represents a single bond or an alkylene group having a carbon number of 1 to 6;

[0152]

[0153] In formula (C-II), R1and R2independently represent a hydrogen atom, a halogen atom, or an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aromatic group having a carbon number of 1 to 12; m represents 1 or 2; R3independently represents a single bond or an organic group having a carbon number of 1 to 24; and R4represents NO2, an aroyl group having a carbon number of 7 to 11, or an aromatic group having a carbon number of 7 to 12 formed with R1.

[0154] M1represents a single bond or is absent; when M1represents a single bond, M2represents NR5, and R5represents a single bond or an alkyl group having a carbon number of 1 to 6; and when M1is absent, M2represents a sulfur atom;

[0155] C-M3represents C=O, C=N-OH, C-OH, or C=N-OCOR6, R6represents an organic group having a carbon number of 1 to 11, and at least one group represented by C=N-OCOR6is present in the compound represented by formula (C-I);

[0156] In formula (C-II), the bonding site with the group G is R3or R5.

[0157] More specifically, the first photoinitiator (C-1) can include the compounds represented by the following formulae (C-I-1) to (C-I-17):

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] The first photoinitiator (C-1) is used in an amount of 10 to 60 parts by weight, preferably 12 parts by weight to 55 parts by weight, and more preferably 15 parts by weight to 50 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0166] If the first photoinitiator (C-1) is not used in the black photosensitive resin composition, good development adhesion cannot be obtained.

[0167] Second photoinitiator (C-2)

[0168] Specific examples of the second photoinitiator (C-2) include other oxygen-acyloxime compounds or non-oxygen-acyloxime photoinitiators.

[0169] Other oxygen-acyloxime compounds

[0170] Specific examples of the other oxygen-acyloxime compounds include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyloxime), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime), or a combination of the above compounds. The 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime) can be a product manufactured by Ciba Specialty Chemicals Co., Ltd., model number IRGACURE OXE-01.

[0171] Further, specific examples of other oxime-acyl compounds include 1-[4-(benzoyl)phenyl]-heptane-1,2-dione-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl-methoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl-methoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyl oxime), or a combination thereof. 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime) can be a product manufactured by Ciba Specialty Chemicals, Inc. under the trade designation IRGACURE OXE-02.

[0172] Other oxime-acyl compounds can be used alone or in combination.

[0173] Non-oxime-acyl photoinitiators

[0174] Specific examples of the non-oxygen-acyl oxime photoinitiator include a triazene compound, a phenylalkanone compound, a diimidazole compound, a benzophenone compound, an a-diketone compound, an alcoholone compound, an alcoholone ether compound, an acylphosphine oxide compound, a quinone compound, a halogen-containing compound, a peroxide, or a combination thereof.

[0175] Specific examples of the triazene compound include a vinyl-halomethyl-s-triazene compound, a 2-(naphtho-l-substituent)-4,6-di(halomethyl)-s-triazene compound, a 4-(p-aminophenyl)-2,6-di(halomethyl)-s-triazene compound, or a combination thereof.

[0176] Specific examples of the vinyl-halomethyl-s-triazene compound include 2,4-di(trichloromethyl)-6-p-methoxyphenylstyryl-s-triazene, 2,4-di(trichloromethyl)-3-(l-p-dimethylaminophenyl-l,3-butadienyl)-s-triazene, 2-trichloromethyl-3-amino-6-p-methoxyphenylstyryl-s-triazene, or a combination thereof.

[0177] Specific examples of the 2-(naphtho-1 -substituent)-4,6-di(halomethyl)-s-triazine compounds include 2-(naphtho-1 -substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(4-methoxy- naphtho-1 -substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(4-ethoxy-naphtho-1 -substituent)- 4,6-di(trichloromethyl)-s-triazine, 2-(4-butoxy-naphtho-1 -substituent)-4,6-di(trichloromethyl)- s-triazine, 2-[4-(2-methoxyethyl)-naphtho-1 -substituent]-4,6-di(trichloromethyl)-s-triazine, 2-[4-(2-ethoxyethyl)-naphtho-1 -substituent]-4,6-di(trichloromethyl)-s-triazine, 2-[4-(2- butoxyethyl)-naphtho-1 -substituent]-4,6-di(trichloromethyl)-s-triazine, 2-(2-methoxy-naphtho-1 - substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(6-methoxy-5-methyl-naphtho-2-substituent)- 4,6-di(trichloromethyl)-s-triazine, 2-(6-methoxy-naphtho-2-substituent)-4,6-di(trichloromethyl)- s-triazine, 2-(5-methoxy-naphtho-1 -substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(4,7- dimethoxy-naphtho-1 -substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(6-ethoxy-naphtho-2- substituent)-4,6-di(trichloromethyl)-s-triazine, 2-(4,5-dimethoxy-naphtho-1 -substituent)-4,6- di(trichloromethyl)-s-triazine, or a combination thereof.

[0178] Specific examples of 4-(p-aminophenyl)-2,6-di(halomethyl)-s-triazabenzene compounds 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-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, and 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s- Triazabenzene, 4-(p-N-ethoxycarbonylmethylaminophenyl)-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, 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(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-triazine, 4-(m-bromo-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxycarbonylmethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethylamino phenyl)-2,6-di(trichloromethyl)-s-triazine, 2,4-di(trichloromethyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino] phenyl]-l,3,5-triazine, or a combination of the above compounds. The triazine compound can be used alone or in combination.

[0179] The triazine compound is preferably 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl)amino phenyl]-2,6-di(trichloromethyl)-s-triazine, 2,4-di(trichloromethyl)-6-p-methoxyphenethyl-s-triazine, or a combination of the above compounds.

[0180] Specific examples of the phenylalkanone compound include p-dimethylaminophenyl alkano ne, α,α'-dimethoxyphenyl alkano ne, 2,2'-dimethyl-2-phenyl phenyl alkano ne, p-methoxyphenyl alkano ne, 2-methyl-l-(4-methylthiophenyl)-2-morpholino-l-propanone, 2-benzyl-2-N,N-dimethylamino-l-(4-morpholinophenyl)-l-butanone, or a combination of the above compounds.

[0181] The phenylalkanone compound can be used alone or in combination.

[0182] 2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone is available as product IRGACURE 907, manufactured by Ciba Specialty Chemicals Ltd. 2-Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone is available as product IRGACURE 369, manufactured by Ciba Specialty Chemicals Ltd.

[0183] Phenylacetone compounds are preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, or combinations thereof.

[0184] 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.

[0185] Diimidazole compounds can be used alone or in combination.

[0186] The preferred diimidazole compound is 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

[0187] Specific examples of benzophenone compounds include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4,4'-bis(diethylamine)benzophenone, or combinations thereof. Benzophenone compounds can be used alone or in combination. 4,4'-bis(diethylamine)benzophenone is preferred.

[0188] Specific examples of α-diketone compounds include benzoyl, diacetyl, or combinations thereof. α-diketone compounds can be used alone or in combination.

[0189] Specific examples of ketols include diphenylethanol ketone. Ketones can be used alone or in combination.

[0190] Specific examples of the ketone alcohol ether compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or a combination of the above compounds. The ketone alcohol ether compound can be used alone or in combination.

[0191] Specific examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide, or a combination of the above compounds. The acyl phosphine oxide compound can be used alone or in combination.

[0192] Specific examples of the quinone compound include anthraquinone, 1,4-naphthoquinone, or a combination of the above compounds. The quinone compound can be used alone or in combination.

[0193] Specific examples of the halogen-containing compound include benzoyl methyl chloride, tribromomethyl phenyl sulfone, tris(trichloromethyl)-s-triazine, or a combination of the above compounds. The halogen-containing compound can be used alone or in combination.

[0194] Specific examples of the peroxide include di-tert-butyl peroxide, and the like. The peroxide can be used alone or in combination.

[0195] The amount of the photoinitiator (C) is 10 parts by weight to 70 parts by weight, preferably 12 parts by weight to 65 parts by weight, and more preferably 15 parts by weight to 60 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

[0196] Solvent (D)

[0197] The solvent (D) refers to a solvent that can dissolve the alkali-soluble resin (A), the compound (B) having ethylenic unsaturation, the photoinitiator (C), and the black pigment (E), and the compound (F) having an epoxy group structure described below, and the additive (G), but does not react with the above components, and is preferably one having appropriate volatility.

[0198] Specific examples of the solvent (D) include: an alkyl glycol monoalkyl ether compound, an alkyl glycol monoalkyl ether acetate compound, a diethylene glycol alkyl ether, other ether compounds, a ketone compound, an alkyl lactate compound, other ester compounds, an aromatic hydrocarbon compound, a carboxylic acid amine compound, or a combination of the above compounds.

[0199] Specific examples of the alkyl glycol monoalkyl ether compound include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mononormal propyl ether, diethylene glycol mononormal 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 mononormal propyl ether, dipropylene glycol mononormal butyl ether, tripropylene glycol monomethyl ether, or tripropylene glycol monoethyl ether, or the like, or a combination thereof.

[0200] Specific examples of the alkyl glycol monoalkyl ether acetate compound include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, or propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate, or the like, or a combination thereof.

[0201] Specific examples of the diethylene glycol alkyl ether include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, or the like, or a combination thereof.

[0202] Specific examples of the other ether compound include tetrahydrofuran, or the like.

[0203] Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diaceton alcohol, or the like, or a combination thereof.

[0204] Specific examples of the alkyl lactate compound include methyl lactate, ethyl lactate, or the like, or a combination thereof.

[0205] Specific examples of the other ester compound include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, normal propyl acetate, isopropyl acetate, normal butyl acetate, isobutyl acetate, normal amyl acetate, isoamyl acetate, normal butyl propionate, ethyl butyrate, normal propyl butyrate, isopropyl butyrate, normal butyl butyrate, methyl pyruvate, ethyl pyruvate, normal propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, or the like, or a combination thereof.

[0206] Specific examples of the aromatic hydrocarbon compound include toluene, xylene, or the like, or a combination thereof.

[0207] Specific examples of the carboxylic acid amine compound include N-methyl pyrrolidone, N,N-dimethyl formamide, N,N-dimethyl acetamide, or the like, or a combination thereof. The above solvent (D) can be used alone or in combination of a plurality of kinds.

[0208] The solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone, or ethyl 3-ethoxypropionate.

[0209] The solvent (D) is used in an amount of 600 to 5,000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight, and more preferably 1,000 parts by weight to 4,000 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0210] Black pigment (E)

[0211] The black pigment (E) is preferably a black pigment having heat resistance, light resistance, and solvent resistance.

[0212] Specific examples of the black pigment (E) include a black organic pigment such as perylene black, cyanine black, or aniline black; a mixed color organic pigment in which two or more kinds of pigments selected from among red, blue, green, purple, yellow, cyanine, and magenta are mixed to form a color close to black; and a light shielding material such as carbon black, chromium oxide, iron oxide, titanium black, or graphite, wherein specific examples of the carbon black include C.I. pigment black 7 or a commercially available product manufactured by Mitsubishi Chemical (trade name: MA100, MA230, MA8, #970, #1000, #2350, or #2650). The black pigment (E) can be used alone or in combination with a plurality of kinds.

[0213] The black pigment (E) is preferably carbon black, and the carbon black is, for example, a commercially available product MA100 or MA230 manufactured by Mitsubishi Chemical.

[0214] The black pigment (E) is used in an amount of 50 to 450 parts by weight, preferably 60 parts by weight to 400 parts by weight, and more preferably 70 parts by weight to 350 parts by weight, based on 100 parts by weight of the total amount of use of the alkali-soluble resin (A).

[0215] Compound (F) having an epoxy group structure

[0216] The compound (F) having an epoxy group structure has a structure represented by the following formula (F-I):

[0217]

[0218] In formula (F-I), each of the plurality of Z independently represents a halogen atom or an alkyl group having a carbon number of 1 to 5; each of the plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 to 10; each of the plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 to 10; each of the plurality of Y3 independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), wherein at least one of Y3 is a group represented by formula (F-II) or formula (F-III); each of the plurality of L1 independently represents a hydrogen atom or a methyl group; each of i independently represents an integer of 0 to 4; and j represents an integer of 0 to 2.

[0219]

[0220] In formula (F-II) and formula (F-III), each of the plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 5; L3 represents a single bond or an alkylene group having a carbon number of 1 to 10; * represents a bonding site, and in the alkylene group having a carbon number of 1 to 10 among Y1, Y2, and L3, any -CH2- can be replaced with -O-, -CH=CH-, or -C≡C-, and any hydrogen atom can be replaced with a halogen atom.

[0221] In formula (F-I), each of the plurality of Z independently represents a fluorine atom, a chlorine atom, or an alkyl group having a carbon number of 1 to 3; each of the plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 to 5; each of the plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 to 5; each of the plurality of Y3 independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), wherein at least one of Y3 is a group represented by formula (F-II) or formula (F-III); each of the plurality of L1 independently represents a hydrogen atom or a methyl group; each of i independently represents an integer of 0 to 2; and j represents an integer of 0 to 2.

[0222] In formula (F-II) and formula (F-III), each of the plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 3; L3 represents a single bond or an alkylene group having a carbon number of 1 to 5; * represents a bonding site, and in the alkylene group having a carbon number of 1 to 5 among Y1, Y2, and L3, any -CH2- can be replaced with -O-, and any hydrogen atom can be replaced with a fluorine atom or a chlorine atom.

[0223] More preferably, in formula (F-I), each of the plurality of Z independently represents a fluorine atom, a chlorine atom, or an alkyl group having a carbon number of 1 to 2; each of the plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 or 2; each of the plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 or 2; each of the plurality of Y3 independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), wherein at least one of Y3 is a group represented by formula (F-II) or formula (F-III); each of the plurality of L1 independently represents a hydrogen atom or a methyl group; and each of i independently represents an integer of 0 to 2. i represents an integer of 0 to 2.

[0224] In formula (F-II) and formula (F-III), each of the plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 or 2; L3 represents a single bond or an alkylene group having a carbon number of 1 or 2; * represents a bonding site, and in the alkylene group having a carbon number of 1 or 2 among Y1, Y2, and L3, any -CH2- can be replaced with -O-, and any hydrogen atom can be replaced with a fluorine atom or a chlorine atom.

[0225] More preferably, in formula (F-I), each of the plurality of Z independently represents a fluorine atom or an alkyl group having a carbon number of 1 to 2; each of the plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 or 2; each of the plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 or 2; each of the plurality of Y3 independently represents a hydrogen atom, a group represented by formula (F-II) or formula (F-III), wherein at least one of Y3 is a group represented by formula (F-II) or formula (F-III); each of the plurality of L1 independently represents a hydrogen atom or a methyl group; and each of i independently represents an integer of 0 or 1. i represents an integer of 0 to 2.

[0226] In formula (F-II) and formula (F-III), each of the plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 or 2; L3 represents a single bond or an alkylene group having a carbon number of 1 or 2; * represents a bonding site, and in the alkylene group having a carbon number of 1 or 2 among Y1, Y2, and L3, any -CH2- can be replaced with -O-, and any hydrogen atom can be replaced with a fluorine atom or a chlorine atom.

[0227] Here, the "compound (F) having an epoxy group structure represented by formula (F-I)" means that the compound falls within the scope of the compound (F) having an epoxy group structure described in the present application as long as the compound contains a structure represented by formula (F-I) in a partial structure of the compound.

[0228] Specific examples of the compound (F) having an epoxy group structure include a compound having a structure represented by the following formula (F-IV), a compound having a structure represented by the following formula (F-V), or commercially available products such as TECHMORE VG3101, TECHMORE VG3101L, TECHMORE VG3101H (manufactured by Mitsui Chemicals, Inc.), NC-6000, NC-6300, NC-6300C, NC-6300H, NC-6500 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0229]

[0230] Further, the compound (F) having an epoxy group structure of the present application can also be used in combination with a compound not having an epoxy group structure represented by the formula (F-I). The use amount of the compound not having an epoxy group structure represented by the formula (F-I) in the compound (F) having an epoxy group structure is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less. By using the compound not having an epoxy group structure represented by the formula (F-I) in combination, the compatibility of the compound (F) having an epoxy group structure with other components in the black photosensitive resin composition can be improved.

[0231] Specific examples of the compound not having an epoxy group structure represented by the formula (F-I) include a homopolymer of a monomer having an epoxy group, a copolymer of two or more kinds of monomers having an epoxy group, a copolymer of a monomer having an epoxy group and a monomer not having an epoxy group, a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a glycidyl ether type epoxy resin, a bisphenol A novolac type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolac type epoxy resin, and the like.

[0232] The compound (F) having an epoxy group structure can be used alone or in combination with a plurality of kinds.

[0233] The use amount of the compound (F) having an epoxy group structure is 30 to 250 parts by weight, preferably 40 parts by weight to 230 parts by weight, and more preferably 50 parts by weight to 200 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

[0234] When the compound (F) having an epoxy group structure is used in the black photosensitive resin composition, the taper angle of the black pattern can be further improved.

[0235] Additive (G)

[0236] The black photosensitive resin composition of the present application can further optionally add an additive (G) without affecting the efficacy of the present application. Specific examples of the additive (G) include an interface active agent, a filler, a polymer (referring to the polymer other than the alkali-soluble resin (A) described above), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulation agent, or other coloring agents.

[0237] The interface active agent helps to improve the coatability of the black photosensitive resin composition. Specific examples of the interface active agent include a cationic interface active agent, an anionic interface active agent, a nonionic interface active agent, an amphoteric interface active agent, a polysiloxane interface active agent, a fluorine interface active agent, or a combination of the above interface active agents.

[0238] Specifically, the interface active agent is, for example, a polyoxyethylene alkyl ether such as polyoxyethylene dodecyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like; a polyoxyethylene alkyl phenyl ether such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like; a polyethylene glycol diester such as polyethylene glycol dilaurate, polyethylene glycol distearate, and the like; a sorbitan fatty acid ester; a fatty acid-modified polyester; or a tertiary amine-modified polyurethane. The above interface active agents can be used alone or in combination of a plurality of them.

[0239] Specific examples of the interface active agent include a KP product manufactured by Shin-Etsu Chemical Co., Ltd., an SF-8427 product manufactured by DoW Coming Toray Co., Ltd., a Polyflow product manufactured by Kyoeisha Chemical Co., Ltd., an F-Top product manufactured by Tochem Products Co., Ltd., a Megafac product manufactured by Dainippon Ink and Chemicals, Inc., a Fluorade product manufactured by Sumitomo 3M, an Asahi Guard product manufactured by Asahi Glass Co., Ltd., or a Surflon product manufactured by Asahi Glass Co., Ltd.

[0240] Specific examples of the filler include glass, aluminum, and the like.

[0241] Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroacryl alkyl ester, or a combination of the above polymers.

[0242] Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a combination thereof.

[0243] Specific examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or a combination thereof.

[0244] Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azine, alkoxy phenone, or a combination thereof.

[0245] Specific examples of the anti-coagulation agent include sodium polyacrylate and the like.

[0246] Other colorants include inorganic pigments, organic pigments, or a combination thereof.

[0247] Specific examples of the inorganic pigments include metal compounds of metal oxides, metal complex salts, and the like (e.g., metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, plumbous, antimony, and the like) or composite oxides of the above-listed metals.

[0248] Specific examples of the organic pigment include C.I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 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; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; C.I. Pigment Blue 1, 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 66; C.I. Pigment Green 7, 36, 37; C.I. Pigment Brown 23, 25, 28, or a combination of the above pigments.

[0249] <Method for producing black photosensitive resin composition>

[0250] A method for preparing the black photosensitive resin composition can be, for example, placing the alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the solvent (D), and the black pigment (E) in a stirrer and stirring to uniformly mix them into a solution state, and, if necessary, adding the compound having an epoxy group structure (F) and the additive (G) and uniformly mixing them to obtain the photosensitive resin composition in a solution state.

[0251] Further, the method for preparing the black photosensitive resin composition is not particularly limited. The method for preparing the black photosensitive resin composition can be, for example, first dispersing a part of the alkali-soluble resin (A) and the compound having an ethylenically unsaturated group (B) in a part of the solvent (D) to form a dispersion solution, and then mixing the remaining alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the solvent (D), and the black pigment (E).

[0252] Alternatively, the black photosensitive resin composition can be prepared by first dispersing a part of the black pigment (E) in a mixture of a part of the alkali-soluble resin (A) and a part of the solvent (D) to form a black pigment dispersion solution, and then adding the alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the solvent (D), and the black pigment (E). Further, the dispersion process of the black pigment (E) described above can be performed by mixing using a mixer such as a beads mill or a roll mill.

[0253] <Method for manufacturing black pattern>

[0254] The black pattern is manufactured by sequentially applying pre-baking, exposure, development, and post-exposure baking to the black photosensitive resin composition described above on a substrate. Further, when the film thickness of the obtained black pattern is 1 μm, the optical density can be 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The method for manufacturing the black pattern is described in detail below.

[0255] First, the black photosensitive resin composition in a solution state is uniformly coated on a substrate by a coating method such as spin coating or cast coating to form a coating film. Specific examples of the substrate include an alkali-free glass, a soda-lime glass, a hard glass (Pyrex glass), a quartz glass, and a glass on which a transparent conductive film is attached, which are used in liquid crystal display devices and the like, or a photoelectric conversion device substrate (e.g., a silicon substrate), which is used in solid-state imaging devices and the like.

[0256] After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the remaining solvent is completely removed by pre-baking to form a pre-baked coating film. It is noted that the conditions of the drying under reduced pressure and the pre-baking are changed depending on the kind and ratio of each component. Generally, the drying under reduced pressure is performed at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the pre-baking is a heating treatment of the coating film at a temperature of 70°C to 110°C for 1 minute to 15 minutes.

[0257] Next, the pre-baked coating film is exposed to light with a mask having a specific pattern. The light used in the exposure is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet light irradiation device can be a (ultra) high-pressure mercury lamp or a metal halide lamp.

[0258] Then, the exposed pre-baked coating film is immersed in a developing solution at a temperature of 23 ± 2°C to remove the pre-baked coating film of the unexposed portion, whereby a specific pattern can be formed on the substrate.

[0259] The developing solution is, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsiliconate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene, or the like. The concentration of the developing solution is generally 0.001 wt% to 10 wt%, preferably 0.005 wt% to 5 wt%, and more preferably 0.01 wt% to 1 wt%.

[0260] After the pre-baked coating film is developed, the substrate having the specific pattern is washed with water, and then the specific pattern is air-dried with compressed air or compressed nitrogen. Then, a post-baking treatment is performed with a heating device such as a hot plate or an oven. The post-baking temperature is generally 150 to 250°C, the heating time with a hot plate is 5 minutes to 60 minutes, and the heating time with an oven is 15 minutes to 150 minutes. After the above-mentioned treatment process, a black pattern can be formed on the substrate.

[0261] <Method for manufacturing color filter>

[0262] The manufacturing method of the color filter is similar to the manufacturing method of the black pattern. Specifically, the photosensitive composition for color filter is coated on the substrate on which the black pattern has been formed, and then the pre-baking, exposure, development, and post-baking processes are sequentially performed to obtain. However, the reduced pressure drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds in the condition of reduced pressure drying. After the above-mentioned processing procedure, a specific pattern is fixed, thereby forming a pixel layer. Furthermore, the above-mentioned procedure is repeated to sequentially form red, green, blue, and other pixel layers on the substrate, thereby obtaining the substrate on which the black pattern and the pixel layer are formed (i.e., the color filter having the pixel layer).

[0263] <liquid crystal display device>

[0264] First, the color filter formed by the above-mentioned manufacturing method of the color filter and the substrate provided with a thin film transistor (TFT) are arranged in opposition to each other, and a gap (cell gap) is provided between the two. Then, the peripheral portion of the color filter and the substrate is bonded with an adhesive, and a hole for injection is left. Then, liquid crystal is injected into the gap between the substrate surface and the gap separated by the adhesive through the injection hole, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided on the other side of the color filter in contact with the liquid crystal layer and on the other side of the substrate in contact with the liquid crystal layer to manufacture a liquid crystal display device. The liquid crystal used here, i.e., the liquid crystal compound or the liquid crystal composition, is not particularly limited. However, any liquid crystal compound and liquid crystal composition can be used.

[0265] Furthermore, the liquid crystal alignment film used in the manufacture of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic or organic substances can be used, and the present application is not limited thereto.

[0266] The following examples will be described in detail to illustrate the present application, but the present application is not limited to the contents disclosed in these examples.

[0267] <Example>

[0268] Preparation Example of the diol compound (a-I-1) represented by Formula (A-I)

[0269] Step A: A reflux condenser and a thermometer were provided in a three-necked flask, 42.5 g of 9,9-bisphenylfluorene was added, and 220 mL of 2-(chloromethyl)oxirane was injected quantitatively. After 100 mg of tetrabutylammonium bromide was added, it was stirred and warmed to 90°C. After confirming that the unreacted content was less than 0.3%, reduced pressure distillation was performed.

[0270] Process B: After cooling to 30°C, dichloromethane was injected and NaOH was slowly added. The yield was confirmed to be 96% or more by high performance liquid chromatography (HPLC), and then the reaction was terminated by dropwise addition of 5% HC1. The reaction was separated and extracted, and the organic phase was washed with water until neutral. Then, the organic layer was dried with MgS04, and concentrated under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and while being stirred, methanol was added while being warmed to 40°C. Then, the solution was cooled and stirred. The resulting solid was filtered and dried under vacuum at room temperature to obtain 52.7 g of white solid powder (recovery rate 94%), the structure of which was confirmed by1H NMR, as shown in the following formula (la):

[0271]

[0272] Process C: A three-necked flask was equipped with a reflux condenser and a thermometer, and 1000 g of the compound of formula (la) obtained by the above synthesis, 524 g of thiophenol, and 617 g of ethanol were added and stirred. Then, 328 g of triethylamine was added dropwise to the reaction solution. After confirming the disappearance of the reactants by HPLC, the reaction was terminated. After the reaction was completed, ethanol was removed by distillation under reduced pressure. The organic matter was dissolved in dichloromethane, and then washed with water. The dichloromethane was removed by distillation under reduced pressure. The concentrated organic matter was dissolved in ethyl acetate, and then ether solvent was added dropwise and stirred for 30 minutes. Then, the compound was distilled under reduced pressure to obtain 945 g (yield 64%) of a light yellow oily substance, the structure of which was confirmed by1H NMR, as shown in the following formula (A-I-l): 1 HNMR, as shown in the following formula (A-I-l):

[0273]

[0274] Synthesis Example of Alkali-soluble Resin (A-1)

[0275] The following describes synthesis examples A-l-1 to synthesis example A-l-5 of the alkali-soluble resin (A-1):

[0276] Synthesis Example A-l-1

[0277] A three-necked flask equipped with a reflux condenser and a thermometer was charged with 200 g of the compound of Formula (A-I-1) above dissolved in 50% propylene glycol methyl ether acetate (PGMEA) and heated to 115°C. After the addition of 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride at 115°C, the reaction was maintained at 115°C for 6 hours with continuous stirring. After the addition of 7.35 g of phthalic anhydride and 2 hours of continuous stirring, the reaction was terminated. After cooling, a first base soluble resin A-I-1 having a weight average molecular weight of 3,500 g / mol was obtained, the structure of which is shown in Formula (A-I-a) below:

[0278]

[0279]

[0280] Synthesis Example A-I-2

[0281] Synthesis Example A-I-1 was repeated, except that 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was replaced with 28.4 g of benzophenone tetracarboxylic dianhydride, and the other components and conditions were the same as described above, to obtain a first base soluble resin A-I-2 having a weight average molecular weight of 5,000 g / mol, the structure of which is shown in Formula (A-I-b) below:

[0282]

[0283] Synthesis Example A-I-3

[0284] Synthesis Example A-I-1 was repeated, except that 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was replaced with 21.1 g of pyromellitic dianhydride, and the other components and conditions were the same as described above, to obtain a first base soluble resin A-I-3 having a weight average molecular weight of 4,500 g / mol, the structure of which is shown in Formula (A-I-c) below:

[0285]

[0286] Synthesis Example A-I-4

[0287] In Synthesis Example A-1-1, 31.1 g of 3,3′,4,4′-biphenyltetracarboxylic anhydride was replaced with 21.7 g of cyclohexyl dianhydride. All other components and conditions remained the same as described above, resulting in a first-base soluble resin A-1-4 with a weight-average molecular weight of 4,200 g / mol, the structure of which is shown in the following formula (A-1-d):

[0288]

[0289] Synthesis Example A-1-5

[0290] In Synthesis Example A-1-1, 31.1 g of 3,3′,4,4′-biphenyltetracarboxylic anhydride was replaced with 18.7 g of cyclobutyl dianhydride. All other components and conditions remained the same as described above, resulting in a first-base soluble resin A-1-5 with a weight-average molecular weight of 4,200 g / mol, the structure of which is shown in the following formula (A-1-e):

[0291]

[0292] Synthesis example of alkali-soluble resin (A-2)

[0293] The following describes the synthesis examples A-2-1 to A-2-2 of the alkali-soluble resin (A-2):

[0294] Synthesis Example A-2-1

[0295] 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 methyl ether acetate were continuously added 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 a diol compound (a-2-1-a) containing polymerizable unsaturated groups with a solid content of 99.9% by weight.

[0296] Next, 1.0 mole of the diol compound having a polymerizable unsaturated group (a-2-1-a), 0.3 mole of diphenyltetracarboxylic acid, 1.4 moles of succinic acid, 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-t-butyl-p-cresol, 700 g of propylene glycol methyl ether acetate, and 100 g of ethyl 3-ethoxypropionate were added to a 500-ml four-necked flask in a simultaneous addition manner to form a reaction solution. Next, the above reaction solution was heated to 110°C, and reacted for 2 hours to obtain a second alkali-soluble resin A-2-1.

[0297] Synthesis Example A-2-2

[0298] First, 100 parts by weight of a fluorene epoxy compound (type PG-100, Osaka Gas Manufacturing; 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-t-butyl-p-cresol, and 135 parts by weight of propylene glycol methyl ether acetate were added to a 500-ml four-necked flask in a continuous addition manner. The feeding rate was controlled at 25 parts by weight per minute, and the temperature during the reaction process was maintained at 100°C to 110°C, and after 15 hours of reaction, a light yellow transparent mixture liquid having a solid content of 50% by weight was obtained. The above light yellow transparent mixture liquid was subjected to the processes of extraction, filtration, and heat drying to obtain a diol compound having a polymerizable unsaturated group (a-2-1-b) having a solid content of 99.9% by weight.

[0299] Next, 1.0 mole of the diol compound having a polymerizable unsaturated group (a-2-1-a), 0.3 mole of diphenyltetracarboxylic acid, 1.4 moles of succinic acid, 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2,6-di-t-butyl-p-cresol, 700 g of propylene glycol methyl ether acetate, and 100 g of ethyl 3-ethoxypropionate were added to a 500-ml four-necked flask in a simultaneous addition manner to form a reaction solution. Next, the above reaction solution was heated to 110°C, and reacted for 2 hours to obtain a second alkali-soluble resin A-2-1.

[0300] Synthesis Example of the First Photoinitiator (C-1)

[0301] Synthesis Example C-1-1: Synthesis of a compound represented by formula (C-I-1)

[0302]

[0303] Procedure 1: Under ice-water bath, 2.4 g of NaOH was dissolved in 50 mL of dry dimethylformamide (hereinafter referred to as DMF) and stirred for 10 minutes. Then 5 g of carbazole was added in portions and stirred for another half an hour. 2.7 mL of bromoethane was added dropwise. After the addition was completed, the ice-water bath was removed and the stirring was continued at room temperature for 5-8 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into an ice-water bath and extracted with 100 mL of ethyl acetate for 4 times. The collected extract was dried over sodium sulfate and concentrated by rotary evaporation to obtain the crude product. Then the product was dissolved in a proper amount of dichloromethane (until dissolved) and filtered through a Buchner funnel with a 5 cm thick silica gel layer. The silica gel layer was washed with dichloromethane (20 mL each time) for 3 times (TLC detection). The collected mother liquor was concentrated by rotary evaporation and dried to obtain 5.6 g of white product, N-ethylcarbazole, with a yield of about 95%.

[0304] Procedure 2: Under ice-water bath, 1.95 g of N-ethylcarbazole was dissolved in 20 mL of dry dichloromethane, and then 1.46 g of anhydrous AlCl3 was slowly added and stirred for 10 minutes. Then 1.85 g of benzoylformyl chloride, PhC(O)C(O)Cl, was slowly added dropwise. After the addition was completed, the ice-water bath was removed and the stirring was continued at room temperature for 1-2 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into a hydrochloric acid-ice water bath and extracted with 20 mL of dichloromethane for 3 times (TLC detection). The collected mother liquor was concentrated by rotary evaporation and dried to obtain 3.1 g of yellow product, with a yield of about 95%.

[0305] Procedure 3: At room temperature, 1.64 g of the above compound was dissolved in 20 mL of a mixture of 1,4-dioxane and water (volume ratio 1 / 4) and stirred until completely dissolved. Then 1.1 mL of diphenylphosphine chloride was slowly added dropwise. After the addition was completed, the temperature was raised to 80°C and the stirring was continued for 2-3 hours (TLC tracking). After the reaction was completed, the reaction solution was extracted with 15 mL of ethyl acetate for 3 times (TLC detection). The collected extract was concentrated by rotary evaporation and then separated by flash silica gel column chromatography to obtain about 2.5 g of white product, with a yield of about 95%.

[0306] Procedure 4: At room temperature, 2.65 g of the above compound was dissolved in 20 mL of dichloroethane, and then 0.5 mL of nitric acid (68%) solution was slowly added dropwise. After the addition was completed, the stirring was continued for 2-3 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 100 mL of water and extracted with 20 mL of ethyl acetate for 3-5 times (TLC detection). The collected mother liquor was concentrated by rotary evaporation and then separated by flash silica gel column chromatography to obtain 2.58 g of yellow product, with a yield of about 90%.

[0307] Procedure 5: 2.87 g of the above compound and 0.42 g of hydroxylamine hydrochloride were taken in 20 mL of dry pyridine and stirred at 60 °C for 2-3 hours (TLC tracking). After completion of the reaction, the obtained oxime intermediate was cooled to about 0 °C, and 0.43 mL of acetyl chloride was slowly added dropwise under an ice-water bath. After the addition was completed, stirring was continued at room temperature for 2-3 hours (TLC tracking). After completion of the reaction, 100 mL of water was added and extracted with ethyl acetate (15 mL each) three times (TLC detection), and the mother liquor was collected and concentrated by rotary evaporation, and then separated by flash silica gel column chromatography to obtain 3.0 g of the light yellow target compound with a yield of about 95%.

[0308] Synthesis Example C-1-2: Synthesis of a compound represented by formula (C-I-4)

[0309]

[0310] Procedure 1: The same as procedure 1 in Synthesis Example C-1-1

[0311] Procedure 2: 3 g of 2-mercaptobenzoic acid was slowly added to 30 mL of concentrated sulfuric acid at room temperature, and 20 g of N-ethylcarbazole powder was slowly added with sufficient stirring. The mixture was reacted at room temperature for 2 hours and then heated to 80 °C for 2 hours. After cooling to room temperature, it was left overnight. The mixture was poured into a large amount of water with stirring, and a precipitate was separated. After filtration, it was washed with a small amount of water and dichloromethane in sequence to obtain 4.8 g of a thioxanthone complex carbazole intermediate structure with a yield of 78%.

[0312] Procedure 3: The same as procedure 2 in Synthesis Example C-1-1

[0313] Procedure 4: The same as procedure 3 in Synthesis Example C-1-1

[0314] Procedure 5: The same as procedure 5 in Synthesis Example C-1-1, and 1.8 g of the light yellow target compound was obtained with a yield of 17%.

[0315] Synthesis Example C-1-3: Synthesis of a compound represented by formula (C-I-6)

[0316]

[0317] Procedure 1 : 4.8 g of NaH (60% dispersion in paraffin oil) was taken in 100 mL of dry DMF and carbazole 10 g was added portion wise under stirring and stirring was continued for half an hour after which 1,6-dibromohexane 4.61 mL was added drop wise. After completion of addition, ice water bath was removed and stirring was continued at room temperature for 10-12 hours (TLC tracking). After completion of reaction, reaction mass was slowly poured into ice water bath and solid was separated which was collected by filtration. The solid was dissolved in dichloromethane (just enough to dissolve) and was filtered through a Buchner funnel packed with 5 cm thick silica gel and the silica gel layer was washed with dichloromethane (20 mL each) for 3 times (TLC tracking) and the mother liquor was collected and concentrated under vacuum and dried to get 11.3 g of white colored product 1,6-biscarbazolylhexane in 90% yield.

[0318] Procedure 2: 5.6 g of the above compound was taken and reaction was carried out as per the procedure 2 of synthetic example C-1-1

[0319] Procedure 3: Same as procedure 3 of synthetic example C-1-1

[0320] Procedure 4: Same as procedure 4 of synthetic example C-1-1

[0321] Procedure 5: Same as procedure 5 of synthetic example C-1-1. 3.1 g of the pale yellow target compound was obtained in 17% yield.

[0322] Synthetic example C-1-4: Synthesis of compound of formula (C-I-8)

[0323]

[0324] Procedure 1 : 1.95 g of N-ethylcarbazole was dissolved in 10 mL of dry dichloromethane and then 1.33 g of anhydrous aluminum trichloride was added slowly under ice water bath and stirring was continued for 5 minutes (two such preparations were done in parallel). After this, 0.95 mL of oxalyl chloride was added slowly to one of the preparations and after completion of addition, ice water bath was removed and the above solution was added slowly drop wise to the other parallel preparation under stirring at room temperature and after completion of addition, ice water bath was removed and stirring was continued at room temperature for 1-2 hours (TLC tracking). The reaction mass was poured slowly into hydrochloric acid-ice water bath and was extracted with ethyl acetate (20 mL each) for 3 times (TLC tracking) and concentrated under vacuum and purified by silica gel column chromatography to get 1.33 g of pale yellow diketone bis N-ethylcarbazole compound in about 30% yield.

[0325] Procedure 2: 2.22 g of the above compound was dissolved in 20 mL of 1,2-dichloroethane at room temperature, and then 1.0 mL of a nitric acid (68%) solution was slowly added dropwise. After the dropwise addition was completed, stirring was continued for 2-3 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 100 mL of water, and extraction was performed three times with 20 mL of ethyl acetate each time (TLC detection). The extracted solution was collected and concentrated under reduced pressure to obtain 4.8 g of a yellow product, a nitration product, at a yield of about 90%.

[0326] Procedure 3: 2.67 g of the compound obtained in the above procedure and 0.84 g of hydroxylamine hydrochloride were placed in 20 mL of dry pyridine under nitrogen protection, and stirring was performed at 60°C for 3 hours (TLC tracking). After the reaction was completed, it was cooled to about 0°C, and 2.84 g of a pre-prepared acyl chloride compound MeOCH2CHMeOC(O)-(CH2)4-C(O)Cl [prepared by directly mono-esterifying and condensing adipoyl chloride and an alcohol MeOCH2CHMeOH] was slowly added dropwise under an ice water bath. After the dropwise addition was completed, the mixture was further stirred at room temperature for 2 hours (TLC tracking). The reaction solution was slowly poured into 100 mL of water, and extraction was performed three times with 20 mL of ethyl acetate each time (TLC detection). The extracted solution was collected and concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 4.3 g of a yellow target compound at a yield of about 90%.

[0327] Synthesis Example C-1-5: Synthesis of a compound represented by formula (C-I-10)

[0328]

[0329] Procedure 1: A carboxylic acid precursor 10a was prepared by ring-opening reaction of phthalic anhydride and MeOCH2CH(OH)Me in the presence of DMAP, at a yield of 96%.

[0330] Procedure 2: An acyl chloride precursor 10b was prepared by reaction of SOCl2 and the carboxylic acid 10a, and was directly used in the next reaction without isolation and purification.

[0331] Procedure 3: 3.4 g of the acyl chloride precursor 10b and 3.7 g of the bisoxime compound 10c were synthesized under the reaction conditions of procedure 3 in Synthesis Example C-1-8, to obtain 6.1 g of a yellow target compound at a yield of 91%.

[0332] Synthesis Example C-1-6: Synthesis of a compound represented by formula (C-I-12)

[0333]

[0334] Procedure 1 : Under nitrogen, 4.1 g of the diketone bis-N-ethylcarbazole compound prepared in the procedure 1 of Reference Synthesis Example C-1-4 was dissolved in 120 mL of freshly distilled THF, and the solution was cooled to -40°C with stirring. Freshly prepared THF solution containing 1.92 g of Ph2PLi (prepared according to the procedure of Organometallies, 2009, 28, 6546-6558) was added dropwise to the solution, and the mixture was stirred for 4 hours after being warmed to room temperature. The reaction solution was quenched with 5 mL of saturated ammonium chloride solution, and most of the solvent was removed by concentration. The residue was diluted with 200 mL of toluene and 100 mL of water, and the pH of the aqueous phase was adjusted to about 4. Then, 1.6 equivalents of 30% hydrogen peroxide solution were added, and the mixture was stirred at 60°C for 4 hours. The progress of the oxidation reaction was followed by TLC. The organic phase was washed with saturated NaHCO3 and brine, and then dried over magnesium sulfate. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography to obtain 3.6 g of the phosphine oxide compound at a yield of 61%.

[0335] Procedure 2: Same as Procedure 2 of Synthesis Example C-1-4

[0336] Procedure 3: Same as Procedure 5 of Synthesis Example C-1-1. 2.7 g of the pale yellow target compound was obtained at a yield of 62%.

[0337] Synthesis Example C-1-7: Synthesis of a compound represented by formula (C-I-13)

[0338]

[0339] Procedure 1 : Friedel Crafts bis-acylation reaction, 10 g of the intermediate 1,6- bis-carbazolylhexane synthesized in Synthesis Example C-1-3 was dissolved in 140 mL of dry dichloromethane, and then 6.7 g of anhydrous AlCl3 was slowly added with stirring for 10 minutes. Then, 14.5 g of freshly prepared acyl chloride EtOCH2CH(Me)OC(O)-(CH2)4-C(O)Cl was slowly added dropwise. After the completion of the dropwise addition, the ice water bath was removed, and the mixture was stirred at room temperature for 4 hours (TLC was used to follow the progress of the reaction). After the completion of the reaction, the reaction solution was slowly poured into 800 mL of 1 N hydrochloric acid-ice water bath, and extracted with dichloromethane (3 x 250 mL). The combined extract was concentrated by rotary evaporation to obtain a crude product, which was purified by silica gel column chromatography to obtain 16.8 g of the bis-acylated 1,6-bis-carbazolylhexane at a yield of 83%.

[0340] Procedure 2: Friedel Crafts mono-acylation reaction, the above bis-acylated 1,6-biscarbazoyl hexane was dissolved in 150 mL of dry dichloromethane under ice-water bath, then 2.80 g of anhydrous AlCl3 was added slowly and stirred for 10 minutes, after which 6.58 mL of o-tolyl benzoyl chloride was added dropwise. After the addition was completed, the ice-water bath was removed and stirring was continued at 40 °C for 1-2 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 1 N hydrochloric acid-ice water bath, extracted with dichloromethane (80 mL each time) for 3 times (TLC detection), the organic layers were combined, dried over anhydrous MgSO4, concentrated, and separated by silica gel column chromatography to obtain 8.2 g of white product, compound, with a yield of 43%.

[0341] Procedure 3: nitration reaction of carbazole ring, 4.8 g of the intermediate compound in the above step was dissolved in 80 mL of glacial acetic acid at room temperature, then a mixture of 0.55 mL of nitric acid (68%) and 1 mL of glacial acetic acid was added dropwise slowly, after the addition was completed, stirring was continued for 6 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 400 mL of water, and the light yellow solid precipitate was collected by filtration, washed with water (50 mL each time) for 3 times, and the product was collected and dried to obtain 2.8 g of light yellow nitration product.

[0342] Procedure 4: bis-oxime esterification reaction, 2.0 g of the above nitration product and 0.4 g of hydroxylamine hydrochloride were placed in 100 mL of dry pyridine, and stirred at 60 °C for 3-5 hours (TLC tracking). After the reaction was completed, it was cooled to about 0 °C, and 0.34 mL of acetyl chloride was added dropwise slowly under ice-water bath, after the addition was completed, stirring was continued at room temperature for 2-3 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into an ice-water bath and solid was precipitated, which was filtered, washed with an appropriate amount of petroleum ether, and the product was collected and dried to obtain 1.9 g of light yellow target compound product, with a yield of 86%.

[0343] Synthesis Example C-1-8: Synthesis of a compound represented by formula (C-I-14)

[0344]

[0345] Procedure 1: 5.1 g of bis-acylated 1,6-biscarbazoyl hexane was synthesized under the reaction conditions of procedure 3 in Synthesis Example C-1-7.

[0346] Procedure 2: same as procedure 4 in Synthesis Example C-1-7, 2.0 g of light yellow target compound was obtained with a yield of 31%.

[0347] Synthesis Example C-1-9: Synthesis of a compound represented by formula (C-I-15)

[0348]

[0349] Step 1: 8.0 g of the intermediate product 1,6-biscarbazylhexane synthesized in Synthesis Example C-1-3 was dissolved in 120 mL of dry dichloromethane under an ice water bath, and then 5.4 g of anhydrous AlCl3 was slowly added. After that, 4.9 g of isobutyryl chloride was slowly added dropwise for 2 hours while stirring. After the addition was completed, the ice water bath was removed and stirring was continued for 4 hours at room temperature (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 800 mL of 1 N hydrochloric acid-ice water bath, and extracted with dichloromethane (100 mL each time) for 3 times (TLC detection). The combined extract was concentrated by rotary evaporation to obtain a crude product. Then, it was dissolved in an appropriate amount of dichloromethane (until dissolved), and filtered through a 5 cm thick silica gel layer in a Buchner funnel. The silica gel layer was washed with dichloromethane (20 mL each time) for 5 times (TLC detection), and the mother liquor was collected, concentrated by rotary evaporation and dried to obtain 9.5 g of white diisobutyrylated 1,6-biscarbazylhexane with a yield of 89%.

[0350] Step 2: 8.5 g of the above diisobutyrylated 1,6-biscarbazylhexane was dissolved in 200 mL of dry dichloromethane at room temperature, and 5.4 g of bromine was added. After stirring for 4 hours, the residual hydrogen bromide was removed by air blowing, and the dichloromethane solvent was removed. Then, the residue was mixed with 120 mL of anhydrous methanol, and 2.1 g of sodium methoxide powder was added. After stirring for 8 hours, most of the methanol solvent was removed, and the residual solid was poured into a mixture of 150 mL of dichloromethane and 250 mL of water. After shaking, the organic phase was separated, and the aqueous phase was extracted with 100 mL of dichloromethane twice. The combined organic phase was concentrated to remove the solvent. The residue was mixed with 200 mL of 2 N NaOH solution, and stirred at room temperature overnight. The mixture was extracted with dichloromethane (100 mL each time) for 3 times, and the combined organic phase was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography on silica gel to obtain 8.2 g of diisobutyrylhydroxyketone compound with a yield of 91%.

[0351] Step 3: 3.0 g of the above diisobutyrylhydroxyketone compound was dissolved in 50 mL of glacial acetic acid at room temperature, and then a mixture of 1.5 mL of nitric acid (68%) and 1 mL of glacial acetic acid was slowly added dropwise. After the addition was completed, stirring was continued for 4-5 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into 500 mL of water, and the precipitated solid was collected by centrifugation and washed with water (50 mL each time) for 3 times. The product was collected and dried to obtain 2.6 g of yellow nitration product with a yield of 74%.

[0352] Procedure 4: 1.8 g of the above nitration product and 0.4 g of hydroxylamine hydrochloride were taken in 20 mL of dry pyridine and stirred at 60°C for 3-5 hours (TLC tracking). After the reaction was completed, it was cooled to about 0°C, and 1.3 g of freshly prepared acyl chloride compound MeOCH2CHMeOC(O)-(CH2)4-C(O)Cl [prepared by directly mono-esterifying and condensing adipoyl chloride and alcohol MeOCH2CHMeOH, and dissolved in 5 mL of dry dichloromethane] was slowly added dropwise in an ice-water bath. After the dropwise addition was completed, stirring was continued at room temperature for 2-3 hours (TLC tracking). After the reaction was completed, the reaction solution was slowly poured into an ice-water bath, and a solid was precipitated, which was filtered, washed with water and petroleum ether, and the product was collected and dried to obtain 2.6 g of the target compound product as a light yellow solid in a yield of 88%.

[0353] Synthesis Example C-1-10: Synthesis of a compound represented by formula (C-I-16)

[0354]

[0355] Procedure 1: 6.8 g of the bis-isobutyrylated 1,6-biscarbazylhexane synthesized in Synthesis Example C-1-9 was dissolved in 200 mL of dry dichloromethane, and 4.3 g of bromine was added at room temperature. After stirring for 4 hours, residual hydrogen bromide was removed by air blowing, and the dichloromethane solvent was removed. The residue was mixed with 120 mL of anhydrous methanol, and 1.7 g of sodium methoxide powder was added. After stirring for 8 hours, most of the methanol solvent was removed, and the residual solid was poured into a mixture of 150 mL of dichloromethane and 250 mL of water. After shaking, the organic phase was separated, the aqueous phase was extracted twice with 100 mL of dichloromethane, and the combined organic phases were concentrated to remove the solvent. The residue was mixed with 60 mL of toluene, 15 mL of morpholine was added, and refluxing was performed for 8 hours. Thereafter, the reaction system was concentrated under reduced pressure in vacuum, and the residue was poured into 200 mL of water and extracted three times with dichloromethane (100 mL each time). The combined organic phases were dried over magnesium sulfate, filtered, concentrated, and the residue was purified by column chromatography on silica gel to obtain 5.4 g of a bis-isobutyryl morpholinone compound in a yield of 61%.

[0356] Procedure 2: Synthesis was performed under the reaction conditions of Procedure 3 in Synthesis Example C-1-9 to obtain 2.3 g of a light yellow nitration product in a yield of 57%.

[0357] Procedure 3: 2.3 g of the above nitration product was synthesized under the reaction conditions of Procedure 4 in Synthesis Example C-1-9 to obtain 2.5 g of the target compound.

[0358] Examples of black photosensitive resin compositions

[0359] Examples 1 to 10 and Comparative Examples 1 to 4 of the black photosensitive resin composition are described below.

[0360] Example 1

[0361] Example 1 was prepared by adding 10 parts by weight of alkali-soluble resin A-1-1, 90 parts by weight of alkali-soluble resin A-2-1, 20 parts by weight of esterified product of pentaerythritol triacrylate and phthalic acid (abbreviated as B-1-1), 10 parts by weight of photoinitiator represented by formula (C-I-1) (abbreviated as C-1-1), and 100 parts by weight of black pigment MA100 (abbreviated as E-1) into 600 parts by weight of ethyl 3-ethoxypropionate (abbreviated as D-1), and stirring them uniformly with a shaking stirrer.

[0362] Examples 2 to 10

[0363] The black photosensitive resin compositions of Examples 2 to 10 were prepared in the same procedure as Example 1, except that the kind and amount of the components of the black photosensitive resin composition were changed (as shown in Table 1).

[0364] Comparative Examples 1 to 4

[0365] The black photosensitive resin compositions of Comparative Examples 1 to 4 were prepared in the same procedure as Example 1, except that the kind and amount of the components of the black photosensitive resin composition were changed (as shown in Table 2).

[0366] The compounds corresponding to the reference numbers in Table 1 and Table 2 are shown below.

[0367]

[0368]

[0369]

[0370]

[0371]

[0372] Evaluation method

[0373] Taper angle

[0374] The black photosensitive resin compositions prepared in each of the above examples and comparative examples were applied to glass substrates each having a length and width of 100 mm by spin coating using a coater (model MS-A150, available from Shinko Trading). Then, the glass substrates were prebaked at 100°C for 2 minutes to form a prebaked coating film having a thickness of 2.4 μm. Then, the prebaked coating film was exposed to light under a specific mask using an ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology) at 80 mJ / cm 2 After that, the unexposed portion of the coating film on the substrate was removed by development with a 0.045% aqueous potassium hydroxide solution at 23°C for 1 minute, and then washed with water and postbaked at 235°C for 30 minutes to form a black pattern having a specific pattern on the glass substrate with a thickness of about 2.0 μm.

[0375] The taper angle was evaluated by observing the black pattern having a specific pattern described above using a scanning electron microscope (manufactured by Hitachi High-Technologies, model S-4800) and measuring the taper angle. FIG. 7 shows a cross-sectional view of the taper angle θ of the black pattern observed according to the evaluation method of the taper angle according to an embodiment of the present application. In FIG. 7, 701 is a glass substrate and 703 is a black pattern. The taper angle θ was evaluated according to the following criteria: Figure 1

[0376] ◎: 30 degrees ≤ taper angle ≤ 40 degrees

[0377] O: 40 degrees < taper angle ≤ 60 degrees

[0378] Δ: 60 degrees < taper angle ≤ 80 degrees

[0379] X: taper angle > 80 degrees or taper angle < 30 degrees

[0380] Development adhesion

[0381] The black photosensitive resin compositions prepared in each of the above examples and comparative examples were applied to glass substrates each having a length and width of 100 mm by spin coating using a coater (model MS-A150, available from Shinko Trading). Then, the glass substrates were prebaked at 100°C for 2 minutes to form a prebaked coating film having a thickness of 2.4 μm. Then, the prebaked coating film was exposed to light under a specific mask using an ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology) at 80 mJ / cm 2 ​The substrate was exposed to ultraviolet light (exposure machine model AG500-4N; manufactured by M&R NanoTechnology). Next, the unexposed portions of the coating film on the substrate were removed by development with a 0.045% aqueous potassium hydroxide solution at 23°C for 1 minute, and then washed with water to obtain a glass substrate having a specific pattern.

[0382] Finally, the line width of the pattern was evaluated in the following manner. Note that the smaller the minimum pattern line width, the better the development adhesion of the pattern formed from the black matrix using the negative photosensitive resin composition.

[0383] : Minimum pattern line width < 4 μm

[0384] : 4 μm < Minimum pattern line width < 6 μm

[0385] : 6 μm < Minimum pattern line width < 8 μm

[0386] : Minimum pattern line width > 8 μm

[0387] [Table 1]

[0388]

[0389] [Table 2]

[0390]

[0391] <Results of Evaluation>

[0392] As is clear from Tables 1 and 2, the taper angle and development adhesion of the black pattern of Comparative Examples 1 to 4 were not good compared with the black pattern (Examples 1 to 10) formed from the black photosensitive resin composition containing the base-soluble resin (A-1) having a specific structure and the first photoinitiator (C-1).

[0393] Further, the taper angle of the black pattern (Examples 1 to 7) formed from the black photosensitive resin composition containing the compound (B-1) having an acid group and at least three ethylenic unsaturated groups was good.

[0394] Furthermore, when the black photosensitive resin composition further contained the compound (F) having an epoxy group structure (Examples 2 to 8), the taper angle of the black pattern was also good.

[0395] In summary, the black photosensitive resin composition of the present application, which uses the base-soluble resin (A-1) having a specific structure and the first photoinitiator (C-1), can improve the technical problems of poor taper angle and development adhesion of the prior art.

[0396] Further, when the black photosensitive resin composition further contains the compound (B-1) having an acid group and at least three ethylenically unsaturated groups, the taper angle of the black pattern can be further improved.

[0397] Further, when the black photosensitive resin composition further contains the compound (F) having an epoxy group structure, the taper angle of the black pattern can be further improved.

[0398] Although the present application has been disclosed with reference to the examples as above, it is not intended to limit the present application, and any person skilled in the art can make some changes and modifications without departing from the spirit and scope of the present application, and the scope of protection of the present application is defined by the appended claims.

Claims

1. A black photosensitive resin composition, characterized by comprising: comprises: an alkali-soluble resin (A); a compound having an ethylenically unsaturated group (B); a photoinitiator (C); a solvent (D); and a black pigment (E), the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerization of a first mixture, the first mixture comprises a diol compound (a-1-1) represented by Formula (A-I), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3), the photoinitiator (C) comprises a first photoinitiator (C-1) represented by Formula (C-I), in Formula (C-I), X1, X2 each independently represent a group represented by Formula (C-II); k represents 0 or 1; when k = 0, G represents a monovalent aromatic phosphine oxide group having a carbon number of 12 to 19; when k = 1, G represents a single bond or an alkylene group having a carbon number of 1 to 6; In formula (A-I), each of A1, A1' is R a SR b , the R a is a single bond, an alkylene group having 1 to 10 carbons, or an arylene group having 6 to 15 carbons, the R b is an alkyl group having 1 to 10 carbons or an aryl group having 6 to 15 carbons; n is an integer of 1 to 6; each of A2, A2' is hydrogen, a hydroxyl group, a thiol group, an amine group, a nitro group, or a halogen substituent, in Formula (C-II), R1, R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aromatic group each having a carbon number of 1 to 12; m represents 1 or 2; R3 each independently represents a single bond or an organic group having a carbon number of 1 to 24; R4 represents NO2, an aromatic acyl group having a carbon number of 7 to 11, or an aromatic group having a carbon number of 7 to 12 formed with R1; M1 represents a single bond or is absent; when M1 represents a single bond, M2 represents NR5, and R5 represents a single bond or an alkyl group having a carbon number of 1 to 6; when M1 is absent, M2 represents a sulfur atom; C-M3 represents C=O, C=N-OH, C-OH, or C=N-OCOR6, R6 represents an organic group having a carbon number of 1 to 11, and at least one group represented by C=N-OCOR6 is present in the compound represented by Formula (C-I); in Formula (C-II), the bonding site with the group G is R3 or R5.

2. The black photosensitive resin composition according to claim 1, wherein the compound having an ethylenically unsaturated group (B) comprises a compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.

3. The black photosensitive resin composition according to claim 1, further comprising a compound (F) having an epoxy group structure represented by Formula (F-I), in Formula (F-I), each of a plurality of Z independently represents a halogen atom or an alkyl group having a carbon number of 1 to 5; each of a plurality of Y1 independently represents a single bond or an alkylene group having a carbon number of 1 to 10; each of a plurality of Y2 independently represents a single bond, O, or an alkylene group having a carbon number of 1 to 10; each of a plurality of Y3 independently represents a hydrogen atom, a group represented by Formula (F-II) or Formula (F-III), wherein at least one of Y3 is a group represented by Formula (F-II) or Formula (F-III); each of a plurality of L1 independently represents a hydrogen atom or a methyl group; each of i independently represents an integer of 0 to 4; j represents an integer of 0 to 2, in Formula (F-II) and Formula (F-III), each of a plurality of L2 independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 5; L3 represents a single bond or an alkylene group having a carbon number of 1 to 10; * represents a bonding site, ​ In the alkylene group having 1 to 10 carbon atoms in said Y1, said Y2, and said L3, any -CH2- can be replaced with -O-, -CH=CH- or -C≡C-, and any hydrogen atom can be replaced with a halogen atom.

4. The black photosensitive resin composition according to claim 1, wherein the total amount of use of the alkali-soluble resin (A) is 100 parts by weight, the amount of use of the first alkali-soluble resin (A-1) is 10 parts by weight to 100 parts by weight, the amount of use of the compound (B) having ethylenic unsaturation is 20 parts by weight to 200 parts by weight, the amount of use of the photoinitiator (C) is 10 parts by weight to 70 parts by weight, and the amount of use of the first photoinitiator (C-1) is 10 parts by weight to 60 parts by weight, the total amount of use of the solvent (D) is 600 parts by weight to 5000 parts by weight, and the amount of use of the black pigment (E) is 50 parts by weight to 450 parts by weight.

5. The black photosensitive resin composition according to claim 2, wherein the total amount of use of the alkali-soluble resin (A) is 100 parts by weight, the amount of use of the compound (B-1) having an acidic group and at least three ethylenic unsaturation is 20 parts by weight to 180 parts by weight.

6. The black photosensitive resin composition according to claim 3, wherein the total amount of use of the alkali-soluble resin (A) is 100 parts by weight, the amount of use of the compound (F) having an epoxy group structure is 30 parts by weight to 250 parts by weight.

7. The black photosensitive resin composition according to claim 1, wherein the first photoinitiator (C-1) includes at least one selected from the group consisting of compounds represented by the following formulae (C-I-1) to (C-I-17), 8. A color filter comprising a black pattern, the black pattern is formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 7 to a pre-baking treatment, an exposure treatment, a development treatment, and a post-baking treatment.

9. A liquid crystal display device comprising the color filter according to claim 8.

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