CN112147842A - Black photosensitive resin composition, black pattern and liquid crystal display device - Google Patents

Black photosensitive resin composition, black pattern and liquid crystal display device Download PDF

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CN112147842A
CN112147842A CN202010558077.6A CN202010558077A CN112147842A CN 112147842 A CN112147842 A CN 112147842A CN 202010558077 A CN202010558077 A CN 202010558077A CN 112147842 A CN112147842 A CN 112147842A
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alkyl
group
weight
alkali
black
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朱振忠
廖豪伟
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Chi Mei Corp
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Chi Mei Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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Abstract

The invention provides a black photosensitive resin composition, a black pattern and a liquid crystal display device. The black photosensitive resin composition comprises an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D) and a black pigment (E). The invention also provides a black pattern formed by using the black photosensitive resin composition. The present invention further provides a liquid crystal display device including the black pattern. The black pattern i formed by the black photosensitive resin composition of the present invention has the advantages of excellent taper angle and drying property.

Description

Black photosensitive resin composition, black pattern and liquid crystal display device
Technical Field
The invention relates to a black photosensitive resin composition, a black pattern formed by using the black photosensitive resin composition and a liquid crystal display device comprising the black pattern; in particular, it provides a black photosensitive resin composition, which can form black patterns with excellent taper angle and drying property.
Background
In recent years, with the rapid development of various technologies of liquid crystal display devices, in order to improve the contrast and display quality of the liquid crystal display devices, a black pattern, such as a black matrix (black matrix), is generally provided between the stripes (stripes) and dots (dots) of a color filter in the liquid crystal display devices. The black matrix can prevent the defects of contrast (contrast ratio) reduction and color purity (color purity) reduction caused by light leakage (light leakage) among pixels.
Japanese Kokai publication 2008-268854 discloses a photosensitive resin composition for black matrix. The photosensitive resin composition comprises an alkali-soluble resin having a carboxylic 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 a black matrix formed of a photosensitive resin composition having a high content of black pigment by using a specific alkali-soluble resin. Further, jp 2009-. The photosensitive resin composition comprises a monomer containing an ethylene unsaturated group, a photopolymerization initiator, a black pigment and a resin. The resin is selected from the group consisting of thermosetting resins, photosensitive resins, thermoplastic resins, and combinations thereof. The patent improves the problems of low photosensitivity and poor developing property of the photosensitive resin composition with high content of black pigment in the photoetching process by regulating and controlling the content of the black pigment in the solid part of the photosensitive resin composition.
However, since the requirement for the light-shielding property of the black matrix is becoming higher in the present circumstances, the solution is to increase the content of the black pigment to improve the light-shielding property of the black matrix, however, the taper angle and the drying property of the black pattern obtained from the black photosensitive resin composition are inferior. When the taper angle is not good, the shape control of the color photoresist in the subsequent process is difficult; if the drying property is not good, foreign matter is easily generated, resulting in defects.
In view of the above, it is an object of the present invention to provide a black pattern, such as a black matrix, made from a black photosensitive resin composition, which has good taper angle and drying property, so as to meet the current requirements of the industry.
Disclosure of Invention
The invention provides a black photosensitive resin composition containing a special component combination, a black pattern formed by the black photosensitive resin composition and having good taper angle and drying property, and a liquid crystal display device comprising the black pattern.
Accordingly, the present invention provides a black photosensitive resin composition comprising:
an alkali-soluble resin (A);
a compound (B) having an ethylenically unsaturated group;
a photoinitiator (C);
a solvent (D); and
a black pigment (E);
wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture comprising a diol compound (a-1-1) represented by formula (1), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3);
Figure BDA0002545218730000021
in the formula (1), A1、A1' each is RaSRbSaid R isaIs a single bond, C1-C10Alkylene (Alkylene) or C6-C15Arylene (Arylene), said RbIs C1-C10Alkyl or C6-C15An aryl group; n is an integer of 1 to 6; a. the2、A2' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents;
the solvent (D) comprises a first solvent (D-1) represented by formula (2);
Figure BDA0002545218730000022
in the formula (2), D1Is C having a straight or branched chain1-C8Alkylene group, D2Is C having a straight or branched chain1-C8An alkyl group; a is an integer of 2 to 4, and a plurality of D1The same or different.
The invention also provides a black pattern which is formed by the black photosensitive resin composition through a pre-baking treatment, an exposure treatment, a developing treatment and a post-baking treatment.
The invention also provides a liquid crystal display device, which comprises the black pattern.
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Fig. 1 is a schematic cross-sectional view of a taper angle θ of a black matrix observed in an evaluation manner of the taper angle according to an embodiment of the invention.
Description of the symbols
701 a glass substrate; 703 a black matrix; theta angle of taper.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Accordingly, the present invention provides a black photosensitive resin composition comprising:
an alkali-soluble resin (A);
a compound (B) having an ethylenically unsaturated group;
a photoinitiator (C);
a solvent (D); and
a black pigment (E);
wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture comprising a diol compound (a-1-1) represented by formula (1), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3);
Figure BDA0002545218730000031
in the formula (1), A1、A1' each is RaSRbSaid R isaIs a single bond, C1-C10Alkylene or C6-C15Arylene radical, said RbIs C1-C10Alkyl or C6-C15An aryl group; n is an integer of 1 to 6; a. the2、A2' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents;
the solvent (D) comprises a first solvent (D-1) represented by formula (2);
Figure BDA0002545218730000041
in the formula (2), D1Is C having a straight or branched chain1-C8Alkylene group, D2Is C having a straight or branched chain1-C8An alkyl group; a is an integer of 2 to 4, and a plurality of D1May be the same or different.
The alkali-soluble resin (a) according to the present invention comprises a first alkali-soluble resin (a-1), the first alkali-soluble resin (a-1) being polymerized from a first mixture. The first mixture may include a diol compound (a-1-1) represented by formula (1), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an anhydride thereof (a-1-3);
Figure BDA0002545218730000042
in the formula (1), A1、A1' each is RaSRbSaid R isaIs a single bond, C1-C10Alkylene or C6-C15Arylene radical, said RbIs C1-C10Alkyl or C6-C15An aryl group; n is an integer of 1 to 6; a. the2、A2' each is hydrogen, hydroxyThiol, amino, nitro or halogen substituents.
C1-C10The alkyl group is a straight chain or a branched chain, and examples thereof may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a second butyl group, an isobutyl group, a third butyl group, a pentyl group, a hexyl group, a heptyl group, a2, 4, 4-trimethylpentyl group, a 2-ethylhexyl group, an octyl group, a nonyl group and a decyl group; c6-C15Aryl groups can be, for example, phenyl, naphthyl, anthryl, phenanthryl, and the like. C1-C10Alkylene group and C6-C15The arylene group can be independently of the above C1-C10Alkyl and C6-C15Aryl groups are alkylene and arylene groups corresponding to the aryl groups.
The tetracarboxylic acid or its acid dianhydride (a-1-2) of the present invention includes a tetracarboxylic acid containing a fluorine atom, a straight-chain hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or a combination thereof.
Specific examples of the fluorine atom-containing tetracarboxylic acid or acid dianhydride thereof include 4,4' -hexafluoroisopropylidene diphthalic acid, 1, 4-difluoropyromellitic acid, 1-monofluoropyromellitic acid, 1, 4-bis (trifluoromethyl) pyromellitic acid, 3,3' -hexafluoroisopropylidene diphthalic acid, 5' - [2,2, 2-trifluoro-1- [3- (trifluoromethyl) phenyl ] ethylene ] diphthalic acid, 5' - [2,2,3,3, 3-pentafluoro-1- (trifluoromethyl) propylene ] diphthalic acid, 5' -oxybis [4,6, 7-trifluoro-pyromellitic acid ], 3, 6-bis (trifluoromethyl) pyromellitic acid, 4-hexafluoroisopropylidene diphthalic acid, Fluorine-containing tetracarboxylic acid such as 1, 4-bis (3, 4-dicarboxylic acid trifluorophenoxy) tetrafluorobenzene, dianhydride compound of the above tetracarboxylic acid, or a combination of the above compounds.
The linear hydrocarbon tetracarboxylic acid may be a saturated linear hydrocarbon tetracarboxylic acid. Specific examples of the saturated linear hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, or a combination of the above compounds. The saturated linear hydrocarbon tetracarboxylic acid may have a substituent.
Specific examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid, or a combination of the above compounds. The alicyclic tetracarboxylic acid may have a substituent.
Specific examples of the dianhydride compound of the alicyclic tetracarboxylic acid include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,3, 4-cyclohexanetetracarboxylic dianhydride or 3,3',4,4' -diphenylsulfonetetracarboxylic dianhydride, or a combination of the above compounds.
Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, 1,2,3, 6-tetrahydrophthalic acid, or a combination of the above compounds. The aromatic tetracarboxylic acid may have a substituent.
Specific examples of the dianhydride compound of an 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-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 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-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorinated dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, or a combination of the above compounds.
The dicarboxylic acid or its anhydride (a-1-3) of the present invention includes dicarboxylic acids containing a fluorine atom, saturated straight-chain hydrocarbon dicarboxylic acids, saturated cyclic hydrocarbon dicarboxylic acids, unsaturated dicarboxylic acids, other dicarboxylic acids, anhydrides of the above dicarboxylic acid compounds, or combinations of the above compounds.
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 dicarboxylic acid, or a combination of the above compounds.
Specific examples of the saturated straight chain hydrocarbon dicarboxylic acid include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic 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 compounds. The hydrocarbon group in the saturated straight-chain hydrocarbon dicarboxylic acid may also be substituted.
Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, or a combination of the above compounds. The saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon-substituted alicyclic dicarboxylic acid.
Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, trimellitic acid, or a combination of the above compounds.
Specific examples of the other dicarboxylic acid or anhydride thereof include dicarboxylic anhydrides such as trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, triethoxysilylbutyl succinic anhydride, methyldiethoxysilylbutyl succinic anhydride, p- (trimethoxysilyl) phenylbutanedioic anhydride, p- (triethoxysilyl) phenylbutanedioic anhydride, p- (methyldimethoxysilyl) phenylbutanedioic anhydride, p- (methyldiethoxysilyl) phenylbutanedioic anhydride, m- (trimethoxysilyl) phenylbutanedioic anhydride, m- (triethoxysilyl) phenylbutanedioic anhydride, m- (methyldiethoxysilyl) phenylbutanedioic anhydride and the like, or dicarboxylic acid compounds of the above dicarboxylic anhydrides, or combinations of the foregoing.
The method for synthesizing the first alkali-soluble resin (a-1) is not particularly limited as long as the diol compound (a-1-1) represented by the formula (1), the tetracarboxylic acid or acid dianhydride thereof (a-1-2), and the dicarboxylic acid or acid anhydride thereof (a-1-3) are reacted.
However, it is preferable to first carry out the polymerization reaction of the diol compound (a-1-1) represented by the formula (1) and the tetracarboxylic acid or its acid dianhydride (a-1-2), for example, at 100 ℃ to 130 ℃, preferably at 110 ℃ to 120 ℃ for 2 hours to 24 hours, preferably 4 hours to 12 hours.
The tetracarboxylic acid or its acid dianhydride (a-1-2) is used in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, and more preferably 10 to 20 parts by weight, based on 100 parts by weight of the diol compound (a-1-1) represented by the formula (1).
After the polymerization is started, the dicarboxylic acid or its anhydride (a-1-3) is added, for example, at 100 ℃ to 130 ℃, preferably at 110 ℃ to 120 ℃ for 30 minutes to 4 hours, preferably 1 hour to 3 hours.
The dicarboxylic acid or anhydride thereof (a-1-3) is used in an amount of 2 to 10 parts by weight, preferably 2 to 5 parts by weight, and more preferably 3 to 5 parts by weight, based on 100 parts by weight of the diol compound (a-1-1) represented by the formula (1).
The weight average molecular weight of the above-mentioned first alkali-soluble resin (A-1) as determined by Gel Permeation Chromatography (GPC) may be 1,000g/mol to 100,000g/mol, preferably 2,000g/mol to 50,000g/mol, more preferably 3,000g/mol to 10,000 g/mol. Further, the dispersibility of the above-mentioned first alkali-soluble resin (a-1) measured by GPC may be in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0.
The first alkali-soluble resin (a-1) is used in an amount of 30 to 100 parts by weight, preferably 40 to 90 parts by weight, and more preferably 50 to 90 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a). When the first alkali-soluble resin (A-1) is not used, the black pattern produced by the black photosensitive resin composition of the present invention has a problem of poor taper angle.
The alkali-soluble resin (a) of the present invention may further comprise a second alkali-soluble resin (a-2), the second alkali-soluble resin (a-2) being obtained by polymerizing a second mixture, and the second mixture comprising a diol compound (a-2-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride thereof (a-2-2), and a dicarboxylic acid or an anhydride thereof (a-2-3).
The polymerizable unsaturated group-containing diol compound (a-2-1) of the present invention is obtained by reacting an epoxy compound having at least two epoxy groups with a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group.
The epoxy compound having at least two epoxy groups includes a structure represented by the formula (a-2-1-1), a structure represented by the formula (a-2-1-2), a structure represented by the formula (a-2-1-3), or the three structures. The structure represented by the formula (a-2-1-1), the structure represented by the formula (a-2-1-2), and the structure represented by the formula (a-2-1-3) will be specifically described below.
Specifically, the structure represented by the formula (a-2-1-1) is as follows:
Figure BDA0002545218730000071
in the formula (a-2-1-1), W1、W2、W3And W4Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms.
Said epoxy compound having at least two epoxy groups containing a structure represented by the formula (a-2-1-1) may include a bisphenol fluorene type compound having an epoxy group obtained by reacting a bisphenol fluorene type compound with a halogenated propylene oxide.
In detail, specific examples of said bisphenol fluorene type compounds include: 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene or an analogue thereof, or a combination of the above compounds.
Specific examples of the halogenated propylene oxide include 3-chloro-1, 2-propylene oxide or 3-bromo-1, 2-propylene oxide or the like, or a combination of the above compounds.
Specific examples of said bisphenol fluorene type compounds having an epoxy group include (1) commercial products manufactured by Nissie iron chemistry: such as ESF-300 or the like; (2) a commercial product manufactured by osaka gas: such as PG-100, EG-210, or the like; (3) commercial product manufactured by s.m.s Technology co: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, or the like.
Specifically, the structure represented by the formula (a-2-1-2) is as follows:
Figure BDA0002545218730000081
in the formula (a-2-1-2), W5To W18Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, and s represents an integer of 0 to 10.
The epoxy compound having at least two epoxy groups, which contains the structure represented by the formula (a-2-1-2), may be obtained by reacting a compound having the structure represented by the following formula (a-2-1-2-I) with a halogenated propylene oxide in the presence of an alkali metal hydroxide.
Figure BDA0002545218730000082
In the above formula (a-2-1-2-I), W5To W18And s is defined as being respectively W in the formula (a-2-1-2)5To W18And s are defined the same and are not repeated herein.
As a method for synthesizing the epoxy compound having at least two epoxy groups, which contains the structure represented by the formula (a-2-1-2), reference is made to taiwan patent No. TW 201508418.
Specific examples of the epoxy compound having at least two epoxy groups and containing the structure represented by the formula (a-2-1-2) include those manufactured by Nippon chemicals under the trade names NC-3000, NC-3000H, NC-3000S and NC-3000P.
Specifically, the structure represented by the formula (a-2-1-3) is as follows:
Figure BDA0002545218730000091
in the formula (a-2-1-3), Ar3Represents a naphthalene ring, W19Represents cyano, halogen or hydrocarbyl, W20Represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkoxy 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, W21Represents an alkylene group, a represents an integer of 0 to 4, and b and c represent an integer of 0 or more.
Specific examples of the above epoxy compound having at least two epoxy groups, which contains a structure represented by the formula (a-2-1-3), include: 9, 9-bis (glycidyloxynaphthyl) fluorene, and is, for example, 9-bis (6-glycidyloxy-2-naphthyl) fluorene or 9, 9-bis (5-glycidyloxy-1-naphthyl) fluorene and the like.
The compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the group consisting of the following (1) to (3):
(1) acrylic acid, methacrylic acid, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyladipic acid, 2-methacryloyloxybutyladipic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloxypropylmaleic acid, 2-methacryloxybutylmaleic acid, 2-methacryloxypropylsuccinic acid, 2-methacryloxypropyladipic acid, 2-methacryloxypropyltetrahydrophthalic acid, 2-methacryloxypropylphthalic acid, 2-methacryloxybutylphthalic acid, 2-methacryloxybutylhydrogenphthalic acid, or the like;
(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
(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.
The carboxylic anhydride compound is the same as the tetracarboxylic dianhydride or dicarboxylic anhydride described above, and therefore, the description thereof is omitted.
The kinds of tetracarboxylic acid or acid dianhydride thereof (a-2-2) and dicarboxylic acid or acid anhydride thereof (a-2-3) used for the second alkali-soluble resin (A-2) may be the same as those of the tetracarboxylic acid or acid dianhydride thereof (a-1-2) and dicarboxylic acid or acid anhydride thereof (a-1-3) used for the first alkali-soluble resin (A-1), respectively, and thus, they will not be described again.
The method for synthesizing the second alkali-soluble resin (a-2) is not particularly limited as long as the diol compound (a-2-1) containing a polymerizable unsaturated group, the tetracarboxylic acid or acid dianhydride thereof (a-2-2), and the dicarboxylic acid or acid anhydride thereof (a-2-3) are reacted to obtain the resin, and the resin can be synthesized with reference to taiwan patent publication No. TW 201508418.
The number average molecular weight of the above second alkali-soluble resin (A-2) in terms of polystyrene as determined by GPC is preferably 800 to 8000, more preferably 1,000 to 6,000.
The second alkali-soluble resin (a-2) is used in an amount of 0 to 70 parts by weight, for example, 10 to 70 parts by weight, preferably 10 to 60 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a). When the second alkali-soluble resin (A-2) is used, the taper angle of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.
The compound (B) having an ethylenically unsaturated group may be selected from a compound having one ethylenically unsaturated group and a compound having two or more (including two) ethylenically unsaturated groups.
The compound having one ethylenically unsaturated group may include, but is not limited to, (meth) acrylamide, (meth) acryloylmorpholine, 7-amino-3, 7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, and the like, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, ethyl 2-hydroxy- (meth) acrylate, 2-hydroxy-propyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene mono (meth) acrylate, polypropylene mono (meth) acrylate, or bornyl (meth) acrylate. The compounds having one ethylenically unsaturated group may be used singly or in combination.
The compound having two or more (two-membered) ethylenically unsaturated groups may 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, tris (2-hydroxyethyl) isocyanato tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanato tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Ethylene Oxide (EO) -modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified PO tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di, 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, ditrimethylolpropyl tetra (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, or novolac polyglycidyl ether (meth) acrylate ) Acrylate, and the like. The compounds having two or more (containing two) ethylenically unsaturated groups may be used singly or in admixture of a plurality of kinds.
Specific examples of the compound (B) having an ethylenically unsaturated group may include, but are not limited to: trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate, propylene oxide-modified glycerol triacrylate, or any combination of the foregoing.
The compound (B) having an ethylenically unsaturated group may preferably be trimethylolpropane triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or any combination of the above compounds.
The compound (B) having an ethylenically unsaturated group is used in an amount of 10 to 100 parts by weight, preferably 15 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
The photoinitiator (C) of the present invention comprises a photoinitiator (C-1) represented by formula (3):
Figure BDA0002545218730000121
wherein R is1、R2、R3、R4、R5、R6、R7And R8Independently of one another are hydrogen, C1-C20Alkyl radical, COR16Or is
Figure BDA0002545218730000122
Or R1And R2、R2And R3、R3And R4、R5And R6、R6And R7Or R7And R8Independently of one another together are
Figure BDA0002545218730000123
With the proviso that R1And R2、R2And R3、R3And R4、R5And R6、R6And R7Or R7And R8At least one pair of (A) is
Figure BDA0002545218730000124
R9、R10、R11And R12Independently of one another are hydrogen, C1-C20Alkyl radical, said C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl;
or R9、R10、R11And R12Independently of one another, unsubstituted phenyl or phenyl substituted by one or more of the following groups: c1-C6Alkyl, halogen;
x represents CO or a direct bond;
R13is represented by C1-C20Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R17、COOR17、OR17；
Or R13Is represented by C2-C20Alkyl interrupted by one or more O or CO, wherein said interrupted C2-C20Alkyl is unsubstituted or substituted with one or more halogen;
or R13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by one or more of the following groups: c1-C20Alkyl radical, C1-C4A haloalkyl group;
R14represents hydrogen, C1-C20Alkoxy or C1-C20An alkyl group;
R15is C6-C20Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4Haloalkyl, OR17C interrupted by one or more O2-C20An alkyl group; or each channel thereof C1-C20Alkyl substitution, said C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR17Phenyl, OR17；
Or R15Represents hydrogen, C3-C8A cycloalkyl group; or R15Is C1-C20Alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, C3-C8A cycloalkyl group;
R16is represented by C6-C20Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4Haloalkyl, OR17(ii) a Or each of which is passed through one or more C1-C20Alkyl substitution, said C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR17；
R17Represents hydrogen, C1-C20Alkyl, which is unsubstituted or substituted by one or more of the following groupsAnd (3) substitution: halogen or C interrupted by one or more O3-C20A cycloalkyl group;
or R17Is represented by C2-C20Alkyl interrupted by one or more O;
or R17Represents phenyl, each of which is unsubstituted or substituted by one or more of the following groups: halogen, C1-C12Alkyl radical, C1-C12An alkoxy group;
with the proviso that at least one member is present in the formula (3)
Figure BDA0002545218730000131
The photoinitiator (C-1) represented by formula (3) is characterized in that its phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring, i.e., it contains one or more annulated unsaturated rings on the carbazole moiety. In other words, R1And R2、R2And R3、R3And R4、R5And R6、R6And R7Or R7And R8At least one pair of them is
Figure BDA0002545218730000132
C1-C20The alkyl group is a straight chain or a branched chain, and examples thereof may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a third butyl group, a pentyl group, a hexyl group, a heptyl group, a2, 4, 4-trimethylpentyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an octadecyl group and an eicosyl group.
C1-C4Haloalkyl may be C as defined above1-C4Alkyl, and which is substituted with halogen as defined below. The alkyl group may be mono-or polyhalogenated, or all hydrogen atoms may be replaced with halogens. It may be, for example, CzHxHalyWherein x + y is 2z +1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.
C interrupted by one or more O2-C20Alkyl groups may be interrupted, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 or 2 times by O. The two O atoms are separated by at least one ethylene group, preferably at least two ethylene groups (i.e., ethylene groups). These alkyl groups may be straight-chain or branched. For example, the following structural units may be mentioned: -CH2-CH2-O-CH2CH3、-[CH2CH2O]y-CH3(wherein y ═ l to 9), - (CH)2-CH2O)7-CH2CH3、-CH2-CH(CH3)、-O-CH2-CH2CH3、-CH2-CH(CH3)-O-CH2-CH3。
C1-C12Alkoxy being C substituted by one O atom1-C12An alkyl group.
C6-C20The aryl group may be, for example, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl,
Figure BDA0002545218730000143
Mesityl, tetracenyl, terphenylene, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.
Substituted aryl radicals (phenyl, naphthyl, C)6-C20Aryl) may be substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, in particular 1,2 or 3 times, respectively. It is obvious that the aryl group here has no more substituents than the number of free positions on its aryl ring.
The substituents on the phenyl ring are preferably in position 4 on the phenyl ring, or in the 3,4-, 3,4,5-, 2,6-, 2, 4-or 2,4, 6-configuration.
The interrupted group can be interrupted, for example, 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times. Obviously, the number of atoms of the interstice depends on the number of C atoms of the intended interstice group. The substituted radicals may have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.
The substituted group may have one substituent, or a plurality of the same or different substituents. The halogen may be fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R is1And R2、R2And R3、R3And R4Or R5And R6、R6And R7、R7And R8Independently of one another together are
Figure BDA0002545218730000141
Then, for example, structures represented by the following formulae (Ia) to (Ii) are formed:
Figure BDA0002545218730000142
Figure BDA0002545218730000151
among them, preferred are formula (Ia), formula (Ib), formula (Ic), more preferred are formula (Ia) or formula (Ic), or formula (Ia), formula (Ic) or formula (Id), particularly preferred is formula (Ia).
In one example, R15Represents hydrogen, phenyl, naphthyl, each of which is unsubstituted or C1-C8Alkyl, OR17Substitution; or R15Is represented by C1-C20An alkyl group; or R15Is represented by C2-C20Alkyl interrupted by one or more O.
In one example, R16Is represented by C6-C20Aryl (preferably phenyl or naphthyl, more preferably phenyl), each of which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4Haloalkyl, OR17(ii) a Or each of which is passed through one or more C1-C20Alkyl substitution of the C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR17. Or, R16Preferably phenyl or naphthyl, more preferably phenyl or carbazole, each of which is unsubstituted or substituted by one or moreThe following groups are substituted: halogen, C1-C4Haloalkyl, OR17Or C1-C20An alkyl group. Or, R16Preferably phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OR17Or C1-C20An alkyl group. Or, R16More preferably phenyl, which is unsubstituted or substituted with one or more of the following groups: OR (OR)17Or C1-C20An alkyl group. R16Particularly preferably phenyl, which is substituted by one or more C1-C20Alkyl substitution.
In one example, R17Represents hydrogen, C1-C20Alkyl, unsubstituted or substituted with one or more of the following groups: halogen or C interrupted by one or more O3-C20A cycloalkyl group; or R17Represents phenyl, each of which is unsubstituted or substituted by one or more of the following groups: halogen, C1-C12Alkyl radical, C1-C12An alkoxy group.
Examples of the photoinitiator (C-1) represented by formula (3) include the following compounds represented by formulae (3-1) to (3-22):
Figure BDA0002545218730000152
Figure BDA0002545218730000161
Figure BDA0002545218730000171
Figure BDA0002545218730000181
the photoinitiator (C-1) represented by formula (3) is used in an amount of 5 to 50 parts by weight, preferably 7 to 45 parts by weight, and more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the photoinitiator (C). When the photo initiator (C-1) represented by the formula (3) is used, the taper angle of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.
The black photosensitive resin composition of the present invention may optionally contain other photoinitiator (C-2).
Specific examples of the other photoinitiator (C-2) include other O-acyloxime compounds (O-acyloxime) or non-O-acyloxime photoinitiators.
Specific examples of such other oxy-acyloximes include 1- [4- (phenylthio) phenyl ] -propane-3-cyclopentane-1, 2-dione 2- (O-benzoyl oxime), 1- [4- (phenylthio) phenyl ] -heptane-1, 2-dione 2- (O-benzoyl oxime), 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione-2- (O-benzoyl oxime), or a combination thereof. 1- [4- (Phenylthio) phenyl ] -octane-1, 2-dione-2- (O-benzoyl oxime) is available from Ciba Specialty Chemicals, Inc. under the type IRGACURE OXE-01.
In addition, specific examples of the other oxy-acyloximes include 1- [4- (benzoyl) phenyl ] -heptane-1, 2-dione-2- (O-benzoyl oxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-substituent ] -ethaneketone-1- (O-acetyl oxime), 1- [ 9-ethyl-6- (3-methylbenzoyl) -9H-carbazol-3-substituent ] -ethaneketone-1- (O-acetyl oxime), 1- [ 9-ethyl-6-benzoyl-9H-carbazol-3-substituent ] -ethaneketone-1- (O-acetyl oxime), 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylphenoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranylphenoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime), 1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofuranylphenoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime, and mixtures thereof, 1- [ 9-ethyl-6- (2-methyl-5-tetrahydropyranyl-benzoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranyl-methoxybenzoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranyl-methoxybenzoyl) -9H-carbazole-3-substituent ] -1- (O-acetyloxime), 1- [ 9-Ethyl-6- (2-methyl-5-tetrahydrofurylmethoxybenzoyl) -9H-carbazol-3-substituent ] -1- (O-acetyloxime), ethanone-1- [ 9-Ethyl-6- (2-methyl-5-tetrahydropyrylmethoxybenzoyl) -9H-carbazol-3-substituent ] -1- (O-acetyloxime), ethanone-1- [ 9-Ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxanone-pentanoyl) benzoyl } -9H-carbazol-3-substituent ] -1- (O-acetyloxime, 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-substituent ] -1- (O-acetyl oxime), or a combination of the above. 1- [ 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-substituent ] -methanone-1- (O-acetyloxime) is available from Ciba specialty Chemicals, Inc. under the IRGACURE OXE-02 model.
The other oxo-acyloximes can be used alone or in combination of a plurality of them.
Specific examples of the non-oxo-acyloxime photoinitiator include triazabenzene compounds, phenylethanone compounds, bisimidazoles, benzophenones, alpha-diketones, alcohol ketones, alcohol ketone ethers, phosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or combinations thereof.
Specific examples of the triazabenzene compounds include vinyl-halomethyl-s-triazabenzene compounds, 2- (naphtho-1-substituent) -4, 6-bis (halomethyl) -s-triazabenzene compounds, 4- (p-aminophenyl) -2, 6-bis (halomethyl) -s-triazabenzene compounds, or combinations thereof.
Specific examples of the vinyl-halomethyl-s-triazabenzene compound include 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, 2, 4-bis (trichloromethyl) -3- (1-p-dimethylaminophenyl-1, 3-butadienyl) -s-triazabenzene, 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene, or a combination thereof.
Specific examples of the 2- (naphtho-1-substituent) -4, 6-bis (halomethyl) -s-triazabenzene compound include 2- (naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (4-methoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (4-ethoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (4-butoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, and the like, 2- [4- (2-methoxyethyl) -naphtho-1-substituent ] -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- [4- (2-ethoxyethyl) -naphtho-1-substituent ] -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- [4- (2-butoxyethyl) -naphtho-1-substituent ] -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (2-methoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (6-methoxy-5-methyl-naphtho-2-substituent) -4 6-bis (trichloromethyl) -s-triazabenzene, 2- (6-methoxy-naphtho-2-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (5-methoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (4, 7-dimethoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (6-ethoxy-naphtho-2-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, 2- (4, 5-dimethoxy-naphtho-1-substituent) -4, 6-bis (trichloromethyl) -s-triazabenzene, or combinations thereof.
Specific examples of the 4- (p-aminophenyl) -2, 6-bis (halomethyl) -s-triazobenzene compound include 4- [ p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ o-methyl-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ o-methyl-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ p-N, N-bis (phenyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-chloroethylcarbonylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ p-N- (p-methoxyphenyl) carbonylaminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 2, 6-bis (ethoxycarbonylmethyl) -s-triazobenzene, 4-bis (ethoxycarbonylmethyl) aminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p, 4- [ o-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl-2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-bromo-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, N-tert-butyl-N, N-di (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, N-di (chloroethyl) aminophenyl-2, 6-bis (, 4- [ o-chloro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ o-fluoro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-bromo-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-chloro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p-N, n-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-chloro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, and mixtures thereof, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 2, 4-bis (trichloromethyl) -6- [ 3-bromo-4- [ N, n-bis (ethoxycarbonylmethyl) amino ] phenyl ] -1,3, 5-triazabenzene, or combinations thereof. The triazine compounds may be used alone or in combination of two or more.
The triazabenzene compound preferably comprises 4- [ m-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, or combinations thereof.
Specific examples of the phenylethanone compounds include p-dimethylamine-phenethyl-ketone, α '-dimethoxyazoxyphenethyl-ketone, 2' -dimethyl-2-phenylethan-ketone, p-methoxy-phenethyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone, or a combination of the above compounds.
The phenylethanone compounds may be used alone or in combination of a plurality.
The 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone can be a commercial product made by Ciba specialty Chemicals, Inc. under model number IRGACURE 907. 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone is a commercial product made by Ciba specialty Chemicals, Inc. under model number IRGACURE 369.
The phenylethanones preferably comprise 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone, or combinations thereof.
Specific examples of the diimidazole compounds include 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (o-fluorophenyl) -4, 4', 5,5' -tetraphenyldiimidazole, 2 '-bis (o-methylphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (o-methoxyphenyl) -4, 4', 5,5' -tetraphenyldiimidazole, 2 '-bis (o-ethylphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (p-methoxyphenyl) -4, 4', 5,5' -tetraphenyldiimidazole, 2,2' -bis (2, 2', 4,4' -tetramethoxyphenyl) -4, 4', 5,5' -tetraphenyldiimidazole, 2' -bis (2-chlorophenyl) -4, 4', 5,5' -tetraphenyldiimidazole, 2' -bis (2, 4-dichlorophenyl) -4, 4', 5,5' -tetraphenyldiimidazole, or a combination of the foregoing.
The bisimidazoles can be used alone or in combination of a plurality of them.
The diimidazole compound is preferably 2,2' -bis (2, 4-dichlorophenyl) -4, 4', 5,5' -tetraphenyldiimidazole.
Specific examples of the benzophenone-based compound include thioxanthone, 2, 4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4 '-bis (dimethylamine) benzophenone, 4' -bis (diethylamine) benzophenone, or a combination of the above compounds. The benzophenone compounds can be used singly or in combination. The benzophenone compound is preferably 4,4' -bis (diethylamine) benzophenone.
Specific examples of the α -diketones include benzil, diacetyl, or a combination of the foregoing. The α -diketones can be used alone or in combination of two or more.
Specific examples of the ketol compound include benzoin. The ketone alcohol compound may be used alone or in combination of two or more.
Specific examples of the ketol ether type compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or a combination of the above compounds. The ketone alcohol ether compounds may be used alone or in combination of two or more.
Specific examples of the acylphosphine oxide-based compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylphenylphosphine oxide, or a combination of the above compounds. The acylphosphine oxide-based compounds may be used alone or in combination of two or more.
Specific examples of the quinone compound include anthraquinone, 1, 4-naphthoquinone, or a combination of the above compounds. The quinone compounds can be used alone or in combination of two or more.
Specific examples of the halogen-containing compound include phenacyl chloride, tribromomethyl phenylsulfone, tris (trichloromethyl) -s-triazobenzene, or a combination of the foregoing compounds. The halogen-containing compound may be used alone or in combination of two or more.
Specific examples of the peroxide include di-tert-butyl peroxide and the like. The peroxides may be used alone or in combination of plural kinds.
The photoinitiator (C) is used in an amount of 5 to 80 parts by weight, preferably 7 to 75 parts by weight, and more preferably 10 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
The solvent (D) of the present invention comprises a first solvent (D-1) represented by the formula (2):
Figure BDA0002545218730000231
in the formula (2), D1Is C having a straight or branched chain1-C8Alkylene group, D2Is C having a straight or branched chain1-C8An alkyl group; a is an integer of 2 to 4, and a plurality of D1May be the same or different.
Examples of the first solvent (D-1) include, but are not limited to, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol n-butyl ether acetate, diethylene glycol t-butyl ether acetate, diethylene glycol n-pentyl ether acetate, diethylene glycol isoamyl ether acetate, diethylene glycol n-hexyl ether acetate, diethylene glycol n-heptyl ether acetate, diethylene glycol n-octyl ether acetate, diethylene glycol-1, 1,3, 3-tetramethylbutyl ether acetate, dipropylene glycol methyl ether acetate, di-1, 2-propanediol t-butyl ether acetate, di-1, 3-butanediol ethyl ether acetate, di-2-methyl-1, 3-propanediol ethyl ether acetate, diethylene glycol neopentyl glycol acetate, di-2, 4-hexanediol ethyl ether acetate, di-1, 3-propanediol ethyl ether acetate, di-2, 4-hexanediol ethyl ether acetate, di-n-butyl ether, Di-1, 7-heptanediol ethyl ether acetate, di-1, 2-octanediol ethyl ether acetate, di-2, 5-dimethyl-2, 5-hexanediol ethyl ether acetate, triethylene glycol ethyl ether acetate, tetraethylene glycol ethyl ether acetate, tetra-1, 7-octanediol n-octyl ether acetate, ethylene glycol propylene glycol n-butyl glycol neopentyl glycol t-butyl ether acetate, diethylene glycol dipropylene glycol n-hexyl ether acetate, di-3-methyl-1, 4-pentanediol isoamyl ether acetate, and the like.
The first solvent (D-1) is used in an amount of 150 to 1500 parts by weight, preferably 200 to 1400 parts by weight, and more preferably 250 to 1300 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a). When the first solvent (D-1) is not used, the black pattern produced by the black photosensitive resin composition of the present invention has a problem of poor drying property.
The solvent (D) of the present invention may further comprise a second solvent (D-2) represented by the formula (4):
Figure BDA0002545218730000232
wherein D is3Is C having a straight or branched chain1-C3Alkyl radical, D4Is C having a straight or branched chain1-C4An alkyl group.
Examples of the second solvent (D-2) include, but are not limited to, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, methyl n-butyrate, ethyl n-butyrate, n-propyl butyrate, isopropyl n-butyrate, n-butyl butyrate, isobutyl n-butyrate, sec-butyl butyrate, tert-butyl butyrate, methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate, isopropyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, sec-butyl isobutyrate, tert-butyl isobutyrate, methyl 2-methylpropionate, ethyl 2-methylpropionate, n-propyl 2-methylpropionate, isopropyl isobutyrate, methyl butyrate, n-butyl isobutyrate, n-butyl 2-methylpropionate, isobutyl 2-methylpropionate, sec-butyl 2-methylpropionate, tert-butyl 2-methylpropionate, and the like.
The second solvent (D-2) is used in an amount of 100 to 1300 parts by weight, preferably 150 to 1200 parts by weight, and more preferably 200 to 1100 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a). When the second solvent (D-2) is used, the drying property of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.
When the ratio of the first solvent (D-1) to the second solvent (D-2) (defined as the amount of the first solvent (D-1) divided by the amount of the second solvent (D-2)) is 0.5 to 3, preferably 0.8 to 2.5, more preferably 1.0 to 2.0, the drying property of the black pattern produced by the black photosensitive resin composition of the present invention can be further improved.
The black photosensitive resin composition of the present invention may optionally contain other solvents (D-3).
Examples of the other solvent (D-3) include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or the like; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate or the like; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxybutyrate or the like; toluene, xylene or the like; n-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, or the like.
The solvent (D) is used in an amount of 250 to 5000 parts by weight, preferably 350 to 4800 parts by weight, and more preferably 450 to 4600 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a).
The black pigment (E) suitable for use in the present invention is preferably a black pigment having heat resistance, light resistance and solvent resistance.
Specific examples of the black pigment (E) include: black organic pigments such as perylene black, cyanine black, aniline black, and the like; a mixed color organic pigment prepared by mixing two or more pigments selected from red, blue, green, violet, yellow, cyanine, and magenta pigments to make the color nearly black; examples of the light-shielding material include carbon black (carbon black), chromium oxide, iron oxide, titanium black (titanium black), and graphite, and the carbon black may include, but are not limited to, c.i. pigment black 7, and specific examples of the carbon black include commercially available products (trade names MA100, MA230, MA8, #970, #1000, #2350, #2650) manufactured by mitsubishi chemical corporation. The black pigment (E) may be used singly or in combination of two or more.
The black pigment (E) is used in an amount of 50 to 600 parts by weight, preferably 60 to 550 parts by weight, more preferably 70 to 500 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
On the premise of not influencing the efficacy of the invention, the black photosensitive resin composition of the invention can be further added with an additive (F) selectively. Specific examples of the additive (F) may include a surfactant, a filler, an adhesion promoter, an antioxidant, an anti-aggregation agent, or other polymers capable of enhancing various properties (e.g., mechanical properties) other than the above-mentioned alkali-soluble resin (A).
Specific examples of the above-mentioned surfactant may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine surfactant, or any combination of the above-mentioned surfactants.
Specific examples of the surfactant may include, but are not limited to, polyethoxyalkyl ethers such as polyethoxyethylecyl ether, polyethoxy stearyl ether or polyethoxy oleyl ether; polyethoxyalkylphenyl ethers such as polyethoxyoctylphenyl ether and polyethoxylatenonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; a sorbitan fatty acid ester compound; a fatty acid-modified polyester compound; a tertiary amine-modified polyurethane compound; or a commercially available product. Wherein the commercial product can be a product manufactured by shin-Etsu chemical industry company, and the type number of the commercial product is KP; a product manufactured by Dow Corning Toray co, Ltd, and having a model number SF-8427; a product manufactured by Corongyo oil chemical industry, and the model number of the product is Polyflow; a product manufactured by Tochem Products Co., Ltd., and having a model number of F-Top; a product manufactured by the great japan ink chemical industry and having a model number of Megafac; a product manufactured by sumitomo 3M and its model number Fluorade; or a product manufactured by Asahi glass company and having a model number of Asahi Guard or Surflon. The surfactant may be used singly or in combination of two or more.
Specific examples of the filler may include glass, aluminum, and the like.
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 (a product of shin-Etsu chemical Co., Ltd., KBM-403), EPPN501H (manufactured by Nippon chemical Co., Ltd.), EPIKE 152 (manufactured by Shell chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropanoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane or any combination thereof.
Specific examples of the above antioxidant may include 2, 2-thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butylphenol, or any combination of the above compounds.
Specific examples of the above-mentioned anti-coagulant include sodium polyacrylate and the like.
The amount of the filler, adhesion promoter, antioxidant, anti-aggregation agent or polymer other than the alkali-soluble resin (a) in the additive (F) is not more than 10 parts by weight, and preferably not more than 6 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
The black photosensitive resin composition of the present invention is generally prepared by mixing the above-mentioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D) and the black pigment (E) in a mixer, and then uniformly mixing them into a solution state, and if necessary, adding additives (F) such as a surfactant, a filler, an adhesion promoter, a crosslinking agent, an antioxidant and an anti-agglomerating agent, and then uniformly mixing them.
Next, the method for producing the black photosensitive resin composition of the present invention is not particularly limited, and for example, the black photosensitive resin composition may be obtained by directly adding the black pigment (E) to the black photosensitive resin composition and dispersing it, or may be obtained by dispersing a part of the black pigment (E) in a medium containing a part of the alkali-soluble resin (a) and the solvent (D) to form a pigment dispersion liquid, and then mixing the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the alkali-soluble resin (a) and the remaining part of the solvent (D). The step of dispersing the black pigment (E) can be carried out by mixing the above components with a mixer such as a bead mill (roll mill) or a roll mill.
The present invention also provides a black pattern (e.g., black matrix) formed from the black photosensitive resin composition.
The black pattern is prepared by sequentially subjecting the black photosensitive resin composition to prebaking, exposing, developing and post-exposing baking treatments, wherein the optical density range of the black pattern is more than 3.0 when the film thickness is 1 μm. Preferably, the optical density of the black pattern ranges from 3.2 to 5.5 when the film thickness is 1 μm; more preferably, the optical density of the black pattern is in the range of 3.5 to 5.5 at a film thickness of 1 μm.
The black pattern of the present invention can be formed by coating the black photosensitive resin composition on a substrate by a coating method such as spin coating or tape casting, and removing the solvent by drying under reduced pressure and pre-baking, thereby forming a pre-baked coating film on the substrate. The conditions of the reduced pressure drying and the prebaking are varied according to the kinds and the mixing ratio of the components, and the reduced pressure drying is usually performed at a pressure of less than 200mmHg for 1 to 20 seconds, and the prebaking is performed at a temperature of 70 to 110 ℃ for 1 to 15 minutes. After prebaking, the coating film is exposed to light under a prescribed mask and then immersed in a developer at a temperature of 23 ± 2 ℃ for 15 seconds to 5 minutes to remove unnecessary portions to form a specific pattern. The light used for the exposure is preferably ultraviolet rays such as g-rays, h-rays or i-rays, and the ultraviolet irradiation apparatus may be an (ultra) high pressure mercury lamp or a metal halide lamp.
Specific examples of the suitable developer include: and basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium silicate, sodium methylsilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo- [5,4,0] -7-undecene. The concentration of the developer is generally 0.001 weight percent (wt%) to 10 wt%, preferably 0.005 wt% to 5 wt%, and more preferably 0.01 wt% to 1 wt%.
When these developers are used, they are generally washed with water after development, air-dried with compressed air or compressed nitrogen, and post-baked with a heating device such as a hot plate or an oven. The post-baking temperature is usually 150 to 250 ℃, wherein the heating time using a hot plate is 5 to 60 minutes, and the heating time using an oven is 15 to 150 minutes. After the above processing steps, a black pattern can be formed on the substrate.
Specific examples of the base material include: alkali-free glass, soda lime glass, hard glass (pyrex glass), quartz glass used for liquid crystal display devices and the like, and transparent conductive films attached to these glasses; or a substrate (e.g., silicon substrate) for a photoelectric conversion device used in a solid-state imaging device or the like.
The invention also provides a color filter, which comprises the black pattern.
The method for forming the color filter of the invention can coat the photosensitive composition for the color filter mixed into a solution state on a substrate by coating methods such as rotary coating, flow casting coating or roll coating, wherein the substrate is formed with a black pattern for separating each pixel coloring layer by the black photosensitive resin composition in advance. After coating, most of the solvent is removed by drying under reduced pressure, and then the solvent is removed by pre-baking to form a pre-baked coating. Wherein the conditions of reduced pressure drying and prebaking vary depending on the kinds of the respective components and the mixing ratio, and generally, the reduced pressure drying is carried out under a pressure of 0mmHg to 200mmHg for 1 second to 60 seconds, and the prebaking is carried out at a temperature of 70 ℃ to 110 ℃ for 1 minute to 15 minutes. After prebaking, the prebaked coating film is exposed between specified masks, and is immersed in the above-mentioned developer at a temperature of 23 ± 2 ℃ for 15 seconds to 5 minutes to develop, and unnecessary portions are removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-rays, h-rays, i-rays, etc., and the ultraviolet ray device may be an (ultra) high pressure mercury lamp or a metal halide lamp.
After the development, the pattern is washed with water, dried with compressed air or compressed nitrogen, and then post-baked with a heating device such as a hot plate or an oven, the conditions of the post-baking are as described above, which are not described herein.
Repeating the above steps for each color (mainly including three colors of red, green and blue) to obtain the pixel layer of the color filter. Then, an Indium Tin Oxide (ITO) vapor deposition film is formed on the pixel layer in a vacuum environment at a temperature of 220 ℃ to 250 ℃, and if necessary, the ITO deposition film is etched and wired, then polyimide for a liquid crystal alignment film is coated, and then the film is fired, thereby obtaining a color filter for a liquid crystal display element.
The invention further provides a liquid crystal display element, which comprises the color filter and the black pattern therein.
The liquid crystal display device of the present invention is a liquid crystal display device in which a color filter substrate formed by the above-described method for manufacturing a color filter and a driving substrate provided with a Thin Film Transistor (TFT) are arranged in an opposed manner with a gap (cell gap) interposed between the two substrates, the peripheral portions of the two substrates are bonded to each other with a sealant, a liquid crystal is filled into the gap defined between the substrate surface and the sealant, and the filling hole is sealed to form a liquid crystal cell (cell). Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other side surface of each substrate constituting the liquid crystal cell, to obtain a liquid crystal display device.
The liquid crystal used above, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited herein, but any liquid crystal compound or liquid crystal composition may be used.
The liquid crystal alignment film used in the above is not particularly limited as long as it is used to restrict the alignment of liquid crystal molecules, and any of inorganic substances and organic substances may be used. The technology for forming the liquid crystal alignment film is well known to those skilled in the art and is not the focus of the present invention, and thus is not described herein.
The invention is now described in more detail by the following examples, but it is not intended that the invention be limited to only those examples provided.
Preparation example of diol Compound (a-1-1) represented by formula (1)
Step A: a reflux condenser and a thermometer were placed in a three-necked flask, 42.5g of 9, 9-bisphenol fluorene was added, and 220mL of 2- (chloromethyl) oxirane was quantitatively injected. After addition of 100mg of tetrabutylammonium bromide, stirring and warming to 90 ℃. The content of unreacted product was confirmed to be less than 0.3%, and then distillation under reduced pressure was carried out.
And B: after cooling to 30 ℃, 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% HCl. The reaction mixture was extracted by liquid separation, and the organic phase was washed with water to neutrality. Then, with MgSO4After the organic layer was dried, it was distilled under reduced pressure with a rotary concentrator and concentrated. Adding dichloromethane into the concentrated product, and heatingWhile stirring and adding methanol to 40 ℃, the solution was then cooled and stirred. The solid formed by filtration was dried in vacuo at ordinary temperature to give 52.7g of a white solid powder (recovery rate 94%), the structure of which was confirmed by 1H NMR as shown in the following formula (1 a):
Figure BDA0002545218730000291
CDCl31H NMR: 7.75(2H), 7.36 to 7.25(6H), 7.09(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H), 2.71 (2H).
And C: a three-necked flask was equipped with a reflux condenser and a thermometer, 1000g of the compound of formula (1a) synthesized as described above, 524g of thiophenol and 617g of ethanol were added thereto under stirring, and 328g of triethylamine was further added dropwise to the reaction solution. After confirming the disappearance of the reaction product by HPLC, the reaction was terminated. After the reaction was completed, ethanol was distilled off under reduced pressure. The organic material was dissolved in methylene chloride, followed by washing with water and distillation under reduced pressure to remove methylene chloride. The concentrated organic matter was dissolved in ethyl acetate, and an ether solvent was added dropwise thereto and stirred for 30 minutes. Then, the compound was distilled under reduced pressure to give 945g (yield 64%) of a pale yellow oil, the structure of which was confirmed by 1H NMR as shown in the following formula (1 b):
Figure BDA0002545218730000292
CDCl31H NMR: 7.82(2H), 7.38 to 6.72(20H), 6.51(4H), 4.00(2H), 3.97(2H), 3.89(2H), 3.20(2H), 3.01(2H), 2.64 (2H).
Preparation example of first alkali-soluble resin (A-1)
Synthesis example A-1
200g of the compound of formula (1b) synthesized as described above was dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) in a three-necked flask equipped with a reflux condenser and a thermometer, and heated to 115 ℃. 31.1g of 3,3',4,4' -Biphenyltetracarboxylic acid anhydride (Biphenyltetracarboxylic acid anhydride) was added dropwise at 115 ℃ and then kept at 115 ℃ for 6 hours with continuous stirring. 7.35g of Phthalic anhydride (Phthalic anhydride) was added, and stirring was continued for 2 hours, after which the reaction was terminated. After cooling, a first alkali-soluble resin A-1-1 having a weight average molecular weight of 3,500g/mol was obtained, the structure of which is shown by the following formula (a-1-a):
Figure BDA0002545218730000301
synthesis example A-1-2
The same procedures as described above were repeated except for replacing 31.1g of 3,3',4,4' -biphenyltetracarboxylic anhydride of preparation example 1 with 28.4g of 3,3',4,4' -Benzophenonetetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride), to obtain a first alkali-soluble resin A-1-2 having a weight-average molecular weight of 5,000g/mol and having the following structure (a-1-b):
Figure BDA0002545218730000302
synthesis examples A-1 to 3
A first alkali-soluble resin A-1-3 having a weight-average molecular weight of 4,500g/mol, whose structure is shown by the following formula (a-1-c), was obtained by replacing 31.1g of 3,3',4,4' -biphenyltetracarboxylic anhydride of preparation example 1 with 21.1g of Pyromellitic dianhydride (Pyromellitic dianhydride) and using the same components and conditions as described above:
Figure BDA0002545218730000311
synthesis examples A-1 to 4
The first alkali-soluble resin A-1-4 having a weight-average molecular weight of 4,200g/mol was obtained by replacing 31.1g of 3,3',4,4' -biphenyltetracarboxylic anhydride of preparation example 1 with 21.7g of Cyclohexyl dianhydride (cyclohexoxy dianhydride) and the other components and conditions were the same as described above, and the structure thereof was as shown in the following formula (a-1-d):
Figure BDA0002545218730000312
synthesis examples A-1 to 5
The same procedures as described above were repeated except for replacing 31.1g of 3,3',4,4' -biphenyltetracarboxylic acid anhydride of preparation example 1 with 18.7g of Cyclobutyl dianhydride (cyclobutyldianhydrides), to give a first alkali-soluble resin A-1-5 having a weight-average molecular weight of 4,200g/mol, which has the following structure (a-1-e):
Figure BDA0002545218730000313
preparation example of diol Compound (a-2-1) containing polymerizable unsaturated group
Preparation example 1
First, 100 parts by weight of a fluorene epoxy compound (type ESF-300, manufactured by Nippon iron chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 part by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2, 6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were charged in a 500-ml four-necked flask by continuous addition. The feeding speed is controlled at 25 weight portions/min, the temperature in the reaction process is maintained at 100-110 ℃, and after 15 hours of reaction, a light yellow transparent mixed solution with the solid content concentration of 50 weight percent can be obtained. Then, the above pale yellow transparent mixed solution was subjected to extraction, filtration and heat-drying to obtain the diol compound (a-2-1-a) having a solid content of 99.9% by weight and containing a polymerizable unsaturated group of production example 1.
Preparation example 2
First, 100 parts by weight of a fluorene epoxy compound (model PG-100, manufactured by Osaka gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 part by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2, 6-di-tert-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were charged in a 500-ml four-necked flask by continuous addition. The feeding speed is controlled at 25 weight portions/min, the temperature in the reaction process is maintained at 100-110 ℃, and after 15 hours of reaction, a light yellow transparent mixed solution with the solid content of 50 weight percent can be obtained. The above pale yellow transparent mixed solution was subjected to extraction, filtration and heat-drying to obtain the diol compound (a-2-1-b) containing a polymerizable unsaturated group of production example 2 having a solid content of 99.9% by weight.
Preparation example 3
100 parts by weight of a fluorene epoxy compound (type ESF-300, manufactured by Nippon iron chemical Co., Ltd.; epoxy equivalent 231), 100 parts by weight of 2-methacryloyloxyethylsuccinate, 0.3 part by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2, 6-di-t-butyl-p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate were charged in a 500-ml four-necked flask by continuous addition. The feeding speed is controlled at 25 weight portions/min, the temperature in the reaction process is maintained at 100-110 ℃, and after 15 hours of reaction, light yellow transparent mixed liquor with the solid content of 50 weight percent can be obtained. The above pale yellow transparent mixed solution was subjected to the steps of extraction, filtration and heat-drying, to obtain the diol compound (a-2-1-c) containing a polymerizable unsaturated group of production example 3 having a solid content of 99.9% by weight.
Preparation example of second alkali-soluble resin (A-2)
Synthesis example A-2-1
First, 1.0 mol of the diol compound having a polymerizable unsaturated group (a-2-1-a) of production example 1, 0.3 mol of biphenyltetracarboxylic acid (a-2-2-b), 1.4 mol of succinic acid (a-2-3-d), 1.9 g of benzyltriethylammonium chloride, 0.6 g of 2, 6-ditertiarybutyl-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. Here, "simultaneous addition" means that the tetracarboxylic acid or its acid dianhydride (a-2-2) and the dicarboxylic acid or its anhydride (a-2-3) are added in the same reaction time. Then, the reaction solution is heated to 110 ℃ and reacted for 2 hours, and the second alkali-soluble resin A-2-1 can be obtained.
Synthesis example A-2
1.0 mol of the diol compound having a polymerizable unsaturated group (a-2-1-b) of production example 2, 2.9 g of benzyltriethylammonium chloride and 950 g of propylene glycol methyl ether acetate were added to a 500-ml four-necked flask to form a reaction solution. Next, 0.6 mol of benzophenone tetracarboxylic dianhydride (a-2-2-c) was added and reacted at 90 ℃ for 2 hours. Then, 0.8 mol of maleic acid (a-2-3-b) was added and reacted at 90 ℃ for 4 hours. Here, "stepwise addition" means that the tetracarboxylic acid or its acid dianhydride (a-2-2) and the dicarboxylic acid or its anhydride (a-2-3) are added separately at different reaction times, that is, the tetracarboxylic acid or its acid dianhydride (a-2-2) is added first, and then the dicarboxylic acid or its anhydride (a-2-3) is added. Through the synthesis steps, the resin A-2-2 with unsaturated groups can be obtained.
Synthesis examples A-2-3, A-2-5 and A-2-6
The resins having unsaturated groups of Synthesis examples A-2-3, A-2-5 and A-2-6 were prepared in the same procedure as in Synthesis example A-2-2, and they were different in that: the kind and amount of the unsaturated group-containing resin component, the reaction time, the reaction temperature, and the reactant addition time were varied (see tables 1-1 and 1-2).
Synthesis example A-2-4
The resin having an unsaturated group of Synthesis example A-2-4 was prepared in the same procedure as in Synthesis example A-2-1, and it was different in that: the kind and amount of the unsaturated group-containing resin component, the reaction time, the reaction temperature, and the reactant addition time were varied (as shown in tables 1-1 and 1-2).
TABLE 1-1
Figure BDA0002545218730000331
Figure BDA0002545218730000341
Tables 1 to 2
Figure BDA0002545218730000342
In tables 1-1 and 1-2:
a-2-1-a is the polymerizable unsaturated group-containing diol compound (a-2-1-a) of preparation example 1;
a-2-1-b is the polymerizable unsaturated group-containing diol compound (a-2-1-b) of preparation example 2;
a-2-1-c is the polymerizable unsaturated group-containing diol compound (a-2-1-c) of production example 3;
a-2-2-a is 4,4 '-hexafluoroisopropylidene diphthalic dianhydride (4,4' -hexafluoroisopropylidene dianhydhdide; 6 FDA);
a-2-2-b is Biphenyl tetracarboxylic acid (Biphenyl tetracarboxylic acid);
a-2-2-c is Benzophenone tetracarboxylic dianhydride;
a-2-2-d is Pyromellitic dianhydride;
a-2-3-a is 3-fluorophthalic anhydride (3-fluorophthalic anhydride);
a-2-3-b is Maleic acid (Maleic acid);
a-2-3-c is Tetrahydrophthalic anhydride (Tetrahydrophthalic anhydride);
a-2-3-d is Succinic acid (Succinic acid);
PGMEA is Propylene Glycol Monomethyl Ether Acetate (PGMEA);
EEP is Ethyl 3-ethoxypropionate (EEP).
Examples and comparative examples of black photosensitive resin compositions
Example 1
The black photosensitive resin composition of example 1 was prepared by adding 100 parts by weight of the first alkali-soluble resin (A-1-1), 10 parts by weight of ethylene glycol dimethacrylate (abbreviated as B-1), 10 parts by weight of the compound represented by the formula (3-1) (abbreviated as C-1-1), 5 parts by weight of IRGACURE OXE-02 (abbreviated as C-2-1) and 100 parts by weight of the black pigment MA100 (abbreviated as E-1) to 150 parts by weight of diethylene glycol ethyl ether acetate (abbreviated as D-1-1) and 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as D-3) and stirring them uniformly by means of a shaking stirrer.
Examples 2 to 12 and comparative examples 1 to 3
The black photosensitive resin compositions of examples 2 to 12 and comparative examples 1 to 3 were prepared by the same procedure as in example 1 except that: the kinds and the amounts of the components of the black photosensitive resin composition (shown in tables 2-1 and 2-2) are not repeated herein.
Evaluation method
Black matrix
The negative photosensitive resin compositions for black matrix prepared in the above examples and comparative examples were coated on a glass substrate having a length and width of 100 millimeters (mm) by spin coating using a coater (model number MS-a150, available from novice trade). Then, the above glass substrate was pre-baked at 100 ℃ for 2 minutes to form a pre-baked coating film having a film thickness of 1.2 micrometers (μm). Then, the prebaked coating film was placed under a specific photomask and applied at 50mJ/cm2Ultraviolet light (Exposure machine model AG 500-4N; from M)&R Nano Technology) for exposure. Then, the substrate was developed with 0.045% aqueous potassium hydroxide at 23 ℃ for 1 minute to remove the coating film on the unexposed portion of the substrate, and then, the substrate was washed with water and post-baked at 230 ℃ for 30 minutes to form a black matrix having a specific pattern with a thickness of about 1.0 μm on the glass substrate.
Taper angle
The angle of taper was evaluated by observing the black matrix having the specific pattern described above with a scanning electron microscope (manufactured by Hitachi High-Technologies, and having a model number of S-4800) and measuring the angle of taper. Please refer to fig. 1, which is a schematic cross-sectional view illustrating an angle θ of a black matrix observed according to an evaluation method of the angle of taper according to an embodiment of the invention. Here, 701 denotes a glass substrate, and 703 denotes a black matrix. Based on the measured taper angle θ, the evaluation was performed on the following criteria:
very good: angle of taper is less than or equal to 30 degrees and less than or equal to 40 degrees
O: the taper angle is more than 40 degrees and less than or equal to 60 degrees
And (delta): 60 degrees < taper angle ≦ 80 degrees
Gamma rays: the angle of taper is more than 80 degrees, or the angle of taper is less than 30 degrees
Drying Property
After immersing the glass sheet in the negative photosensitive resin composition for black matrix for 5 seconds, the glass sheet was taken out and air-dried for 55 seconds. The glass piece was again dipped and taken out, the operation was repeated 120 times in total, and then, the black resist surface in the dipped area was observed with an optical microscope and evaluated on the following criteria:
very good: completely without foreign matter remaining on the dried surface
O: very little foreign matter remains on the dry surface
And (delta): obviously, foreign matters are agglutinated and remained on the dry surface
X: a large amount of foreign matters remain on the dried surface
TABLE 2-1
Figure BDA0002545218730000371
Tables 2 to 2
Figure BDA0002545218730000381
In tables 2-1 and 2-2:
Figure BDA0002545218730000391
the above embodiments are merely illustrative of the principles and effects of the present invention, and do not limit the present invention. Modifications and variations of the above-described embodiments may be made by those skilled in the art without departing from the spirit of the invention. The scope of the invention is to be determined by the following claims.

Claims (11)

1. A black photosensitive resin composition comprising:
an alkali-soluble resin (A);
a compound (B) having an ethylenically unsaturated group;
a photoinitiator (C);
a solvent (D); and
a black pigment (E);
wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture comprising a diol compound (a-1-1) represented by formula (1), a tetracarboxylic acid or an acid dianhydride thereof (a-1-2), and a dicarboxylic acid or an acid anhydride thereof (a-1-3);
Figure FDA0002545218720000011
in the formula (1), A1、A1' each is RaSRbSaid R isaIs a single bond, C1-C10Alkylene or C6-C15Arylene radical, said RbIs C1-C10Alkyl or C6-C15An aryl group; n is an integer of 1 to 6; a. the2、A2' are each hydrogen, hydroxyl, thiol, amino, nitro or halogen substituents;
the solvent (D) comprises a first solvent (D-1) represented by formula (2);
Figure FDA0002545218720000012
in the formula (2), D1Is C having a straight or branched chain1-C8Alkylene group, D2Is C having a straight or branched chain1-C8An alkyl group; a is an integer of 2 to 4, and a plurality of D1The same or different.
2. The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises a second alkali-soluble resin (A-2), the second alkali-soluble resin (A-2) is obtained by polymerizing a second mixture, and the second mixture comprises a diol compound (a-2-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride thereof (a-2-2), and a dicarboxylic acid or an acid anhydride thereof (a-2-3).
3. The black photosensitive resin composition according to claim 1, wherein the photoinitiator (C) comprises a photoinitiator (C-1) represented by formula (3):
Figure FDA0002545218720000021
wherein R is1、R2、R3、R4、R5、R6、R7And R8Independently of one another are hydrogen, C1-C20Alkyl radical, COR16Or is
Figure FDA0002545218720000022
Or R1And R2、R2And R3、R3And R4、R5And R6、R6And R7Or R7And R8Independently of one another together are
Figure FDA0002545218720000023
With the proviso that R1And R2、R2And R3、R3And R4、R5And R6、R6And R7Or R7And R8At least one pair of (A) is
Figure FDA0002545218720000024
R9、R10、R11And R12Independently of one another are hydrogen, C1-C20Alkyl radical, said C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl;
or R9、R10、R11And R12Independently of one another, unsubstitutedOr phenyl substituted with one or more of the following groups: c1-C6Alkyl, halogen;
x represents CO or a direct bond;
R13is represented by C1-C20Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R17、COOR17、OR17；
Or R13Is represented by C2-C20Alkyl interrupted by one or more O or CO, wherein said interrupted C2-C20Alkyl is unsubstituted or substituted with one or more halogen;
or R13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by one or more of the following groups: c1-C20Alkyl radical, C1-C4A haloalkyl group;
R14represents hydrogen, C1-C20Alkoxy or C1-C20An alkyl group;
R15is C6-C20Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4Haloalkyl, OR17C interrupted by one or more O2-C20An alkyl group; or each channel thereof C1-C20Alkyl substitution, said C1-C20Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR17Phenyl, OR17；
Or R15Represents hydrogen, C3-C8A cycloalkyl group; or R15Is C1-C20Alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, C3-C8A cycloalkyl group;
R16is represented by C6-C20Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C1-C4Haloalkyl, OR17(ii) a Or each of which is passed through one or more C1-C20Alkyl substitution, said C1-C20Alkyl being unsubstituted or substitutedSubstituted with one or more of the following groups: halogen, OR17；
R17Represents hydrogen, C1-C20Alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen or C interrupted by one or more O3-C20A cycloalkyl group;
or R17Is represented by C2-C20Alkyl interrupted by one or more O;
or R17Represents phenyl, each of which is unsubstituted or substituted by one or more of the following groups: halogen, C1-C12Alkyl radical, C1-C12An alkoxy group;
with the proviso that at least one member is present in the formula (3)
Figure FDA0002545218720000031
4. The black photosensitive resin composition according to claim 1, wherein the solvent (D) further comprises a second solvent (D-2) represented by formula (4):
Figure FDA0002545218720000032
wherein D is3Is C having a straight or branched chain1-C3Alkyl radical, D4Is C having a straight or branched chain1-C4An alkyl group.
5. The black photosensitive resin composition according to claim 1, wherein the first alkali-soluble resin (a-1) is used in an amount of 30 to 100 parts by weight, the compound (B) having an ethylenically unsaturated group is used in an amount of 10 to 100 parts by weight, the photoinitiator (C) is used in an amount of 5 to 80 parts by weight, the solvent (D) is used in an amount of 250 to 5000 parts by weight, the first solvent (D-1) is used in an amount of 150 to 1500 parts by weight, and the black pigment (E) is used in an amount of 50 to 600 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resins (a).
6. The black photosensitive resin composition according to claim 2, wherein the second alkali-soluble resin (A-2) is used in an amount of 10 to 70 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).
7. The black photosensitive resin composition according to claim 3, wherein the photoinitiator (C-1) represented by the formula (3) is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).
8. The black photosensitive resin composition according to claim 4, wherein the second solvent (D-2) is used in an amount of 100 to 1300 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).
9. The black photosensitive resin composition according to claim 4, wherein the first solvent (D-1) and the second solvent (D-2) are used in a ratio of 0.5 to 3.
10. A black pattern formed by subjecting the black photosensitive resin composition of any one of claims 1 to 9 to a pre-baking treatment, an exposure treatment, a developing treatment and a post-baking treatment.
11. A liquid crystal display device comprising the black pattern of claim 10.
CN202010558077.6A 2019-06-28 2020-06-18 Black photosensitive resin composition, black pattern and liquid crystal display device Pending CN112147842A (en)

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