CN108241260B - Negative photosensitive resin composition for black matrix, color filter and liquid crystal display element - Google Patents

Negative photosensitive resin composition for black matrix, color filter and liquid crystal display element Download PDF

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CN108241260B
CN108241260B CN201711335017.2A CN201711335017A CN108241260B CN 108241260 B CN108241260 B CN 108241260B CN 201711335017 A CN201711335017 A CN 201711335017A CN 108241260 B CN108241260 B CN 108241260B
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alkali
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acrylate
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black matrix
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CN108241260A (en
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朱振忠
廖豪伟
蔡宇杰
萧君佑
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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • G02F1/133514—Colour filters
    • 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
    • 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

Abstract

The invention provides a negative photosensitive resin composition for a black matrix, a color filter and a liquid crystal display element. The obtained black matrix has no development residue and excellent adhesion. The negative photosensitive resin composition for black matrix comprises an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D) and a black pigment (E). The alkali-soluble resin (A) includes an alkali-soluble resin (A-1) having a specific group and an alkali-soluble resin (A-2) having a specific group.

Description

Negative photosensitive resin composition for black matrix, color filter, and liquid crystal display element
Technical Field
The present invention relates to a negative photosensitive resin composition for a black matrix, a color filter and a liquid crystal display device, and more particularly, to a negative photosensitive resin composition for a black matrix, which can reduce residues and improve adhesion, a black matrix prepared from the negative photosensitive resin composition for a black matrix, a color filter including the black matrix and a liquid crystal display device including the color filter.
Background
In recent years, with the vigorous development of various liquid crystal display device technologies, in order to improve the contrast and display quality of the liquid crystal display device at present, a Black Matrix (Black Matrix) is generally placed in a Stripe (Stripe) and Dot (Dot) gap of a color filter in the liquid crystal display device. The black matrix can prevent the problems of Contrast Ratio (Contrast Ratio) reduction and Color Purity (Color Purity) reduction caused by Light Leakage (Light Leakage) between pixels.
In general, the materials used for the black matrix are mainly vapor deposited films containing chromium, chromium oxide, or the like. However, when the above-mentioned vapor deposited film is used as a material for a black matrix, there are disadvantages that the handling is complicated and the material is expensive. In order to solve this problem, a technique of forming a black matrix by photolithography (Photo lithography) using a photosensitive resin composition has been proposed.
As the requirement for light-shielding properties of black matrices is increasing, one of the solutions is to increase the amount of black pigment used, thereby increasing the light-shielding properties of the black matrices. For example, japanese patent laid-open No. 2006-259716 discloses a photosensitive resin composition for a black matrix, which comprises a black pigment, an alkali-soluble resin, a photopolymerization initiator, a reactive compound having a bifunctional group, and an organic solvent in a high use amount. It is noted that the reactive compound having a bifunctional group can improve the reaction between the compounds to form a Fine Pattern (Fine Pattern). Therefore, in the photosensitive resin composition, the light shielding performance is improved by increasing the using amount of the black pigment, and the sensitivity of the photosensitive resin composition can be kept.
In addition, japanese patent application laid-open No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition comprises an alkali-soluble resin having a carboxylic group and an unsaturated group, a photopolymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and a black pigment in a high amount. In the photosensitive resin composition for black matrix, the resolution of the photosensitive resin composition with high black pigment consumption is improved by using specific alkali soluble resin.
Although the photosensitive resin composition of the prior art, in which the amount of the black pigment used is increased, can increase the light-shielding property. However, the black matrix formed from the above-mentioned conventional photosensitive resin composition has a development residue and is poor in adhesion.
Therefore, it is an urgent need to solve the problem of the prior art to provide a photosensitive resin composition for black matrix, which can reduce the residue and improve the adhesion of the black matrix.
Patent document
Patent document 1 Japanese patent laid-open No. 2006-259716
Patent document 2 Japanese patent laid-open No. 2008-268854
Disclosure of Invention
Accordingly, the present invention provides a negative photosensitive resin composition for a black matrix of a color filter, and the black matrix prepared by using the negative photosensitive resin composition can improve the problems of development residue and poor adhesion of the black matrix.
The invention provides a negative photosensitive resin composition for a black matrix, which comprises the following components: an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), and a black pigment (E). Wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2), the alkali-soluble resin (A-1) has a branched alkyl group, an acid group and a polymerizable unsaturated bond, and the alkali-soluble resin (A-2) has an aromatic group, an acid group and a polymerizable unsaturated bond.
In an embodiment of the present invention, the alkali-soluble resin (a-1) is obtained by reacting an addition copolymer formed from the first mixture with a polymerizable unsaturated monobasic acid (a 5), and then with a polybasic acid or an anhydride thereof (a 6). The first mixture includes an acrylate compound (a 1) having a branched alkyl group, an acrylic compound (a 2) having an epoxy group, and other unsaturated compounds (a 3).
In an embodiment of the present invention, the alkali-soluble resin (a-2) is obtained by reacting an addition copolymer formed from the second mixture with a polymerizable unsaturated monobasic acid (a 5), and then with a polybasic acid or an anhydride thereof (a 6). The second mixture includes an unsaturated compound (a 4) having an aromatic group, an acrylic compound (a 2) having an epoxy group, and other unsaturated compounds (a 3).
In an embodiment of the invention, the other unsaturated compound (a 3) includes an unsaturated compound (a 3-1). The unsaturated compound (a 3-1) is at least one selected from the group consisting of acrylate compounds having a structure represented by the following formula (a 3-1-1) and formula (a 3-1-2), and compounds represented by the following formula (a 3-1-3):
Figure BDA0001507230270000021
in the formula (a 3-1-3), X and Y independently represent a hydrogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, or a branched hydrocarbon group having 1 to 4 carbon atoms; r 1 、R 2 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carboxylic acid group having 1 to 20 carbon atoms, the hydrocarbon group and the carboxylic acid group being unsubstituted or substituted with a substituent; or R 1 、R 2 Are bonded to each other to form a ring structure.
In one embodiment of the present invention, the total number of moles of the compounds of the first mixture is 1.0 mole, the amount of the acrylate compound (a 1) having a branched alkyl group is 0.05 to 0.4 mole, the amount of the acrylate compound (a 2) having an epoxy group is 0.3 to 0.85 mole, and the amount of the other unsaturated compound (a 3) is 0 to 0.6 mole.
In one embodiment of the present invention, the polymerizable unsaturated monobasic acid (a 5) is used in an amount of 0.25 to 0.85 mole and the polybasic acid or anhydride thereof (a 6) is used in an amount of 0.01 to 0.75 mole, based on 1.0 mole of the total moles of the compounds of the first mixture.
In an embodiment of the invention, based on the total mole number of the compounds of the second mixture being 1.0 mole, the unsaturated compound (a 4) having an aromatic group is used in an amount of 0.03 to 0.45 mole, the acrylic compound (a 2) having an epoxy group is used in an amount of 0.3 to 0.85 mole, and the other unsaturated compound (a 3) is used in an amount of 0 to 0.6 mole.
In one embodiment of the present invention, the polymerizable unsaturated monobasic acid (a 5) is used in an amount of 0.25 to 0.85 mole and the polybasic acid or anhydride thereof (a 6) is used in an amount of 0.01 to 0.75 mole, based on 1.0 mole of the total moles of the compounds of the second mixture.
In one embodiment of the present invention, the unsaturated compound (a 3-1) is used in an amount of 0.01 to 0.09 moles based on 1.0 mole of the total moles of the compounds of the first mixture.
In one embodiment of the present invention, the unsaturated compound (a 3-1) is used in an amount of 0.01 to 0.09 moles based on 1.0 mole of the total moles of the compounds of the second mixture.
In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (a), 10 to 60 parts by weight of the alkali-soluble resin (a-1), 40 to 90 parts by weight of the alkali-soluble resin (a-2), 30 to 300 parts by weight of the ethylenically unsaturated group-containing compound (B), 10 to 100 parts by weight of the photoinitiator (C), 1000 to 9000 parts by weight of the solvent (D), and 100 to 800 parts by weight of the black pigment (E), are used.
The invention also provides a black matrix, which is formed by sequentially carrying out pre-baking treatment, exposure treatment, development treatment and post-baking treatment on the negative photosensitive resin composition for the black matrix.
The invention further provides a color filter comprising the black matrix.
The invention also provides a liquid crystal display element comprising the color filter.
In view of the above, the negative photosensitive resin composition for a black matrix of the present invention contains the specific alkali-soluble resin (a-1) and the alkali-soluble resin (a-2), and therefore, can improve the problems of development residue and poor adhesion of the black matrix, and is further suitable for a color filter and a liquid crystal display device.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Detailed Description
Hereinafter, acrylic acid and/or methacrylic acid is represented by (meth) acrylic acid, and acrylate and/or methacrylate is represented by (meth) acrylate; similarly, (meth) acryloyl represents acryloyl and/or methacryloyl.
Negative photosensitive resin composition for black matrix
The invention provides a negative photosensitive resin composition for a black matrix (hereinafter, also referred to as "photosensitive resin composition"), which comprises an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D) and a black pigment (E). In addition, the photosensitive resin composition may further include an additive (F), if necessary. The respective components of the photosensitive resin composition used in the present invention will be described in detail below.
Alkali soluble resin (A)
The alkali-soluble resin (A) includes an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2). Further, the alkali-soluble resin (A) may further include other alkali-soluble resins (A-3).
Alkali soluble resin (A-1)
The alkali-soluble resin (A-1) has a branched alkyl group, an acid group and a polymerizable unsaturated bond. The alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed from the first mixture with a polymerizable unsaturated monobasic acid (a 5) and then with a polybasic acid or its anhydride (a 6). The first mixture includes an acrylate compound (a 1) having a branched alkyl group, an acrylic compound (a 2) having an epoxy group, and other unsaturated compounds (a 3).
If the alkali-soluble resin (a-1) is not included in the negative photosensitive resin composition for a black matrix, or if the alkali-soluble resin (a-1) does not have a branched alkyl group, an acid group, and a polymerizable unsaturated bond at the same time, a residue remains after development of the negative photosensitive resin composition for a black matrix.
Acrylate Compound (a 1) having branched alkyl group
Specific examples of the acrylate compound (a 1) having a branched alkyl group include (meth) acrylate compounds such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, isotetradecyl (meth) acrylate, and isostearyl (meth) acrylate.
The acrylate compound (a 1) having a branched alkyl group is used in an amount of 0.05 to 0.4 mol, preferably 0.07 to 0.38 mol, more preferably 0.1 to 0.35 mol, based on the total number of moles of the compounds of the first mixture being 1.0 mol.
Acrylic Compound having epoxy group (a 2)
Specific examples of the acrylic compound (a 2) having an epoxy group include glycidyl (meth) acrylate, 2-epoxypropyloxyethyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and lactone adducts thereof (for example, cyclomeria 200 and M100 manufactured by DAICEL chemical industries, inc.), mono (meth) acrylate of 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexane carboxylate, epoxy compound of dicyclopentenyl (meth) acrylate, epoxy compound of dicyclopentenyloxyethyl (meth) acrylate, and the like.
The acrylic compound (a 2) having an epoxy group is used in an amount of 0.3 to 0.85 mol, preferably 0.35 to 0.83 mol, more preferably 0.4 to 0.8 mol, based on the total number of moles of the compounds of the first mixture being 1.0 mol.
Other unsaturated Compounds (a 3)
The other unsaturated compound (a 3) is an unsaturated compound which does not belong to the acrylate compound (a 1) having a branched alkyl group, the acrylic compound (a 2) having an epoxy group, and the unsaturated compound (a 4) having an aromatic group described below. The other unsaturated compound (a 3) includes the unsaturated compound (a 3-1) and the unsaturated compound (a 3-2).
Unsaturated Compound (a 3-1)
The unsaturated compound (a 3-1) is at least one selected from the group consisting of acrylate compounds having a structure represented by the following formula (a 3-1-1) and formula (a 3-1-2), and compounds represented by the following formula (a 3-1-3):
Figure BDA0001507230270000041
in the formula (a 3-1-3), X and Y independently represent a hydrogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, or a branched hydrocarbon group having 1 to 4 carbon atoms; r is 1 、R 2 Each independently representA hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carboxylic acid group having 1 to 20 carbon atoms, the hydrocarbon group and the carboxylic acid group being unsubstituted or substituted with a substituent; or said R is 1 、R 2 Are bonded to each other to form a ring structure.
Specific examples of the acrylate compound having a structure represented by the formula (a 3-1-1) include acrylate compounds having a tricyclodecane skeleton such as dicyclopentanyl (meth) acrylate (trade names FA-513A and FA-513M, manufactured by Hitachi chemical industries, ltd.). Specific examples of the acrylate compound having a structure represented by the formula (a 3-1-2) include tricyclo [5.2.1.0 ] acrylate 2,6 ]Decyl-8-yl ester (trade name: FA-511A, manufactured by Hitachi chemical Co., ltd.), (meth) acrylic acid 2- (tricyclo [ 5.2.1.0) 2,6 ]Decyl-3-ene-8 (9) -oxy) ethyl ester (dicyclopentenyloxyethyl (meth) acrylate, trade name FA-512A, FA-512M, manufactured by Hitachi chemical industries, ltd.) and other acrylate compounds having a dicyclopentadiene skeleton. Specific examples of the compound represented by the formula (a 3-1-3) include norbornene (bicyclo [2.2.1 ]]Hept-2-ene), 5-methylbicyclo [2.2.1]Hept-2-ene, 5-ethylbicyclo [2.2.1 ]]Hept-2-ene, tetracyclo [4.4.0.1 2,5 .1 7,10 ]Dodecyl-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 .1 7,10 ]Dodecyl-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 .1 7,10 ]Dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6 ]Dec-8-ene, tricyclo [5.2.1.0 2,6 ]Dec-3-ene, tricyclo [4.4.0.1 2,5 ]Undec-3-ene, tricyclo [6.2.1.0 1,8 ]Undec-9-ene, tricyclo [6.2.1.0 1,8 ]Undec-4-ene, tetracyclo [4.4.0.1 2,5 .1 7,10 .0 1,6 ]Dodecyl-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 .1 7,10 .0 1,6 ]Dodeca-3-ene, 8-ethylene tetracyclo [4.4.0.1 2,5 .1 7,12 ]Dodecyl-3-ene, 8-ethylene tetracyclo [4.4.0.1 2,5 .1 7,10 .0 1,6 ]Dodecyl-3-ene, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13 ]Pentadec-4-ene, pentacyclic [7.4.0.1 ] 2,5 .1 9,12 .0 8,13 ]Pentadec-3-ene, 5-norbornene-2-carboxylic acid,5-norbornene-2, 3-dicarboxylic acid, and 5-norbornene-2, 3-dicarboxylic anhydride. One or more of the above-listed compounds may be used alone or in combination.
The unsaturated compound (a 3-1) is used in an amount of 0.01 to 0.09 moles, preferably 0.012 to 0.08 moles, more preferably 0.015 to 0.07 moles, based on the total moles of the compounds of the first mixture being 1.0 mole.
When the unsaturated compound (a 3-1) is included in the first mixture or the second mixture described below, the adhesion of the negative photosensitive resin composition for a black matrix can be further improved.
Unsaturated Compound (a 3-2)
Specific examples of the unsaturated compound (a 3-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, n-octadecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate (trade name: AM-90G, manufactured by Ningzhongmura chemical industries, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, allyl (meth) acrylate, propynyl (meth) acrylate, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, and mixtures thereof, (meth) acrylates having no aromatic ring such as furyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, and 3- (N, N-dimethylamino) propyl (meth) acrylate; (meth) acrylates having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms such as dicyclopentenyl (meth) acrylate, dicyclohexyl (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and rosin (meth) acrylate; (meth) acrylic acid amides such as (meth) acrylic acid amide, N-dimethylamide (meth) acrylic acid, N-diethylamide (meth) acrylic acid, N-dipropylamide (meth) acrylic acid, N-diisopropylamide (meth) acrylic acid, and anthracylamide (meth) acrylic acid; vinyl compounds such as anilide (meth) acrylate, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidinone, vinylpyridine, and vinyl acetate; diene compounds such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; n- (meth) acryloylphthalimide, and the like. These monomers may be used alone or in combination of two or more.
The other unsaturated compound (a 3) is used in an amount of 0 to 0.6 mol, preferably 0 to 0.5 mol, more preferably 0 to 0.4 mol, based on the total number of moles of the compounds of the first mixture being 1.0 mol.
Polymerizable unsaturated monobasic acid (a 5)
The polymerizable unsaturated monobasic acid (a 5) used for the reaction with the addition copolymer formed from the first mixture or the second mixture described below may be any acid having a polymerizable unsaturated bond and an acid group, and examples thereof include an unsaturated carboxylic acid, an unsaturated sulfonic acid, and an unsaturated phosphonic acid. Specific examples of the polymerizable unsaturated monobasic acid (a 5) include unsaturated carboxylic acids such as (meth) acrylic acid, α -bromo (meth) acrylic acid, β -furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, and 2-methacryloyloxyethylsuccinate; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, and p-styrenesulfonic acid; unsaturated phosphonic acids such as vinylphosphonic acid, and the like. These unsaturated monocarboxylic acids may be used alone or in combination of 2 or more.
The polymerizable unsaturated monobasic acid (a 5) is used in an amount of 0.25 to 0.85 mole, preferably 0.3 to 0.83 mole, more preferably 0.35 to 0.8 mole, based on the total moles of the compounds of the first mixture of 1.0 mole.
Polybasic acid or anhydride thereof (a 6)
The polybasic acid or anhydride thereof (a 6) used for the reaction with the addition copolymer formed from the first mixture or the second mixture described below may be any of saturated or unsaturated polybasic acids or anhydrides thereof, and specific examples thereof include malonic acid, succinic anhydride, glutaric acid, adipic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, 5-norbornene-2, 3-dicarboxylic acid, 5-norbornene-2, 3-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, dibasic acids such as phthalic anhydride and the like or anhydrides thereof, tribasic acids such as trimellitic acid, trimellitic anhydride and the like or anhydrides thereof, tetrabasic acids such as pyromellitic acid, pyromellitic anhydride and the like or anhydrides thereof and the like. Among these, dibasic acid anhydrides are preferably used.
The polybasic acid or its anhydride (a 6) is used in an amount of 0.01 to 0.75 mole, preferably 0.03 to 0.7 mole, more preferably 0.05 to 0.65 mole, based on the total moles of the compounds of the first mixture being 1.0 mole.
Alkali soluble resin (A-2)
The alkali-soluble resin (A-2) has an aromatic group, an acid group and a polymerizable unsaturated bond. The alkali-soluble resin (A-2) is obtained by reacting the addition copolymer formed from the second mixture with the polymerizable unsaturated monobasic acid (a 5) and then with the polybasic acid or anhydride (a 6). The second mixture includes an unsaturated compound (a 4) having an aromatic group, an acrylic compound (a 2) having an epoxy group, and other unsaturated compounds (a 3).
If the alkali-soluble resin (a-2) is not included in the negative photosensitive resin composition for a black matrix, or if the alkali-soluble resin (a-2) does not have an aromatic group, an acid group, and a polymerizable unsaturated bond at the same time, the negative photosensitive resin composition for a black matrix is poor in adhesion.
Specific examples of the acrylic compound (a 2) having an epoxy group, the other unsaturated compound (a 3), the polymerizable unsaturated monobasic acid (a 5), and the polybasic acid or anhydride thereof (a 6) used in the production process of the alkali-soluble resin (a-2) are the same as those of the acrylic compound (a 2) having an epoxy group, the other unsaturated compound (a 3), the polymerizable unsaturated monobasic acid (a 5), and the polybasic acid or anhydride thereof (a 6) used in the production process of the alkali-soluble resin (a-1), and therefore, description thereof will be omitted.
The acrylic compound (a 2) having an epoxy group is used in an amount of 0.3 to 0.85 mol, preferably 0.35 to 0.83 mol, more preferably 0.4 to 0.8 mol, based on the total number of moles of the compounds of the second mixture being 1.0 mol.
The other unsaturated compound (a 3) is used in an amount of 0 to 0.6 mol, preferably 0 to 0.5 mol, more preferably 0 to 0.4 mol, based on the total number of moles of the compounds of the second mixture being 1.0 mol.
Unsaturated Compound having an aromatic group (a 4)
Specific examples of the unsaturated compound (a 4) having an aromatic group include styrene-based unsaturated compounds such as styrene, α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-aminostyrene, 3-aminostyrene, 4-nitrostyrene, 4-cyanostyrene, 4-acetylaminostyrene and indene; (meth) acrylates having an aromatic ring such as benzyl (meth) acrylate, phenethyl (meth) acrylate, phenylmethyl (meth) acrylate, isopropylphenyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, trityl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, phenoxyethyl acrylate, phenoxy-polyethyleneglycol acrylate (trade name: tetraacrylate P-200A, manufactured by Kyoeisha chemical Co., ltd.), o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, P-phenoxybenzyl acrylate, and the like.
The unsaturated compound (a 4) having an aromatic group is used in an amount of 0.03 to 0.45 mol, preferably 0.05 to 0.43 mol, more preferably 0.08 to 0.4 mol, based on the total number of moles of the compounds of the second mixture being 1.0 mol.
The amount of the polymerizable unsaturated monobasic acid (a 5) used is 0.25 to 0.85 mole, preferably 0.3 to 0.83 mole, more preferably 0.35 to 0.8 mole, based on the total moles of the compounds of the second mixture being 1.0 mole.
The polybasic acid or its anhydride (a 6) is used in an amount of 0.01 to 0.75 mole, preferably 0.03 to 0.7 mole, more preferably 0.05 to 0.65 mole, based on the total moles of the compounds of the second mixture being 1.0 mole.
Alkali-soluble resin (A-1) and method for producing alkali-soluble resin (A-2)
The alkali-soluble resin (a-1) (or the alkali-soluble resin (a-2)) is obtained by reacting an addition copolymer formed from the first mixture (or the second mixture) with a polymerizable unsaturated monobasic acid (a 5), and then reacting the resultant reaction product with a polybasic acid or an anhydride thereof (a 6), and the production method thereof will be described in detail below.
The copolymerization of the addition copolymer formed from the first mixture (or the second mixture) can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method well known in the art. For example, the first mixture (or the second mixture) may be dissolved in a solvent as desired, and then a polymerization initiator may be added to the solution to conduct copolymerization at 50 to 130 ℃ for 1 to 20 hours.
The solvent usable in the copolymerization reaction is not particularly limited, and examples thereof include (poly) alkylene glycol monoalkyl ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.; (poly) alkylene glycol monoalkyl ether acetate compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ester compounds such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; and carboxylic acid amide compounds such as N-methyldipropyrrolidinone, N-dimethylformamide, and N, N-dimethylacetamide. The above solvents may be used alone or in combination of 2 or more.
Among these, preferred are (poly) alkylene glycol monoalkyl ether solvents such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate solvents such as propylene glycol monomethyl ether acetate, that is, glycol ether solvents.
The amount of the polymerization solvent to be used is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the total of the first mixture (or the second mixture). In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in molecular weight of the copolymer due to chain transfer can be suppressed, and the viscosity of the copolymer can be controlled within an appropriate range. Further, by adjusting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, polymerization reaction can be stably performed, and coloring or gelation of the copolymer can be prevented.
The polymerization initiator usable in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These may be used alone or in combination of 2 or more. The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the total amount of the first mixture (or the second mixture).
Then, the following modification reaction is carried out using the epoxy group contained in the addition copolymer thus produced, whereby an alkali-soluble resin having an acid group and a polymerizable unsaturated bond in the side chain, a glass transition temperature of 20 ℃ or lower, and a polystyrene-equivalent weight average molecular weight of 1,000 to 50,000 can be obtained.
The modification reaction comprises the following steps:
the method comprises the following steps: the ring-opening reaction of all the epoxy groups contained in the addition copolymer is carried out by the polymerizable unsaturated monobasic acid (a 5).
Step two: the hydroxyl group generated by the above ring-opening reaction is reacted with the polybasic acid or its anhydride (a 6).
The amount of the polymerizable unsaturated monobasic acid (a 5) used in the first step can be suitably selected according to the amount of unsaturated group equivalent of the curable polymer to be used. The amount of the polymerizable unsaturated monobasic acid (a 5) used is usually 0.90 to 1 mole, preferably 0.95 to 1 mole, based on the total number of moles of epoxy groups contained in the addition copolymer. If the amount of the polymerizable unsaturated monobasic acid (a 5) used is too small, a side reaction may occur in the subsequent reaction.
Step one can be performed according to a conventional method. For example, the addition copolymer and the polymerizable unsaturated monobasic acid may be added to a reaction solvent, and then a catalyst may be further added to the reaction solvent, for example, to carry out the reaction at 50 to 150 ℃, preferably 80 to 130 ℃. Furthermore, in the first step, even if a solvent for copolymerization is included, there is no particular problem, so that the first step can be performed without removing the solvent after the copolymerization is completed.
In step one, a polymerization inhibitor may be added as necessary to prevent gelation. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and the like. The catalyst is not particularly limited, and examples thereof include a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, and a chelate compound of chromium.
In the first step, an unsaturated bond derived from the polymerizable unsaturated monobasic acid (a 5) is introduced into a side chain of the polymer by a ring-opening reaction of an epoxy group in the addition copolymer, and a hydroxyl group derived from the epoxy group is generated. In the present invention, an acid group is introduced into the polymer in the second step of reacting the hydroxyl group with the polybasic acid or its anhydride (a 6).
The amount of the hydroxyl group and the polybasic acid or anhydride thereof (a 6) used in the second step can be suitably selected in accordance with the acid value of the intended curable polymer. The polybasic acid or its anhydride (a 6) is usually used in an amount of 0.01 to 0.9 mole, preferably 0.02 to 0.85 mole, based on the total moles of hydroxyl groups produced in step one. If the amount of the hydroxyl group and the polybasic acid or anhydride thereof (a 6) used is too small, the developability may be insufficient, whereas if it is too large, the sensitivity may be reduced.
Step two can also be carried out according to a common method. For example, the polybasic acid or its anhydride (a 6) may be added to the reaction system after the step one, for example, at 50 to 150 ℃, preferably 80 to 130 ℃. The reaction time may be suitably selected, and is usually 0.05 to 10 hours, preferably 0.1 to 7 hours.
The alkali-soluble resin (A-1) has a polystyrene-reduced weight-average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as measured by Gel Permeation Chromatography (GPC).
The alkali-soluble resin (A-2) has a polystyrene-converted weight-average molecular weight of 1,000 to 50,000, preferably 3,000 to 40,000, as measured by Gel Permeation Chromatography (GPC).
The alkali-soluble resin (A-1) is used in an amount of 10 to 60 parts by weight, preferably 15 to 55 parts by weight, more preferably 20 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).
The alkali-soluble resin (A-2) is used in an amount of 40 to 90 parts by weight, preferably 45 to 85 parts by weight, more preferably 50 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).
Other alkali soluble resins (A-3)
The other alkali-soluble resin (A-3) is a resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). Other alkali-soluble resins (a-3) are, for example, resins having carboxylic acid groups or hydroxyl groups, but are not limited to resins having carboxylic acid groups or hydroxyl groups. Specific examples of the alkali-soluble resin (a-3) include resins such as acrylic resins, fluorene (fluorene) resins, urethane (urethane) resins, and novolak (novolac) resins.
Compound (B) containing ethylenically unsaturated group
The ethylenically unsaturated group-containing compound (B) may be selected from compounds having one ethylenically unsaturated group or compounds having two or more (two-containing) 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, 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, 2-hydroxy-propyl (meth) acrylate, vinyl caprolactam, N-vinyl pyrrolidone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene mono (meth) acrylate, polypropylene mono (meth) acrylate, bornyl (meth) acrylate, and the like. The compound having one ethylenically unsaturated group may be used singly or in combination of plural kinds.
The compound having two or more (containing two) 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, tri (2-hydroxyethyl) isocyanato tri (meth) acrylate, caprolactone-modified tri (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, 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 hexa (meth) acrylate, pentaerythritol di (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 novolak polyglycidyl ether (meth) acrylate. The compound having two or more (containing two) ethylenically unsaturated groups may be used singly or in combination.
Specific examples of the ethylenically unsaturated group-containing compound (B) 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 ethylenically unsaturated group-containing compound (B) may preferably be trimethylolpropane triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or any combination of the above compounds.
The ethylenically unsaturated group-containing compound (B) is used in an amount of 30 to 300 parts by weight, preferably 40 to 270 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).
Photoinitiator (C)
The photoinitiator (C) is, for example, an acetophenone-based compound (acetophenone), a diimidazole-based compound (biimidazole), an acyloxime-based compound (acryl oxime), or a combination of the above compounds.
Specific examples of the acetophenone-based compound include p-dimethylamine acetophenone, α '-dimethoxyazoxyacetophenone, 2' -dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-nitrogen, nitrogen-dimethylamine-1- (4-morpholinophenyl) -1-butanone, or a combination of the above compounds.
Specific examples of the diimidazole-based compound include 2,2 '-bis (o-chlorophenyl) -4,4',5 '-tetraphenyldiimidazole, 2' -bis (o-fluorophenyl) -4, 5 '-tetraphenyldiimidazole, 2' -bis (o-methylphenyl) -4,4',5,5' -tetraphenyldiimidazole, 2 '-bis (o-methoxyphenyl) -4,4',5 '-tetraphenyldiimidazole, 2' -bis (o-ethylphenyl) -4,4',5,5' -tetraphenyldiimidazole, 2 '-bis (p-methoxyphenyl) -4,4',5 '-tetraphenyldiimidazole, 2' -bis (2, 2', 4' -tetramethoxyphenyl) -4,4',5,5' -tetraphenyldiimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyldiimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4', 5' -tetraphenyldiimidazole, or combinations thereof.
Specific examples of the acyloxime-based compound include an alkanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-substituent ] -1- (oxy-acetyloxime) [ Ethanone,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetoxyimine), such as OXE-02 manufactured by Ciba specialty Chemicals, the structure of which is represented by the formula (C-1), 1- (4-phenylthio) phenyl) -octane-1, 2-dione-2-oxime-oxy-benzoate [1- (4-phenylthio-phenyl) -octane-1, 2-dione-2-oxime-1, 2-dione-2-oxoimide-O-ketone, such as OXE-01 manufactured by Ciba specialty Chemicals, the structure of which is represented by the formula (C-2), ethylthio-6-carbazol-3-substituent ] -1- (2-ethylthio) -9H-carbazol-3-yl ] -,1- (O-acetoxy) -1, 2-oxo-benzonate, the structure of which is represented by the formula (C-2-ethylthio-phenyl) -octane-1, 2-oxo-1, 2-carbazol-oxo-3-oxo-2-oxo-2-methyl-1, 2-carbazol-oxo-1- (4-2-oxo-2-oxo-2-phenyl) -oxime, manufactured by Asahi Denka, the structure of which is represented by formula (C-3) or a combination of the above compounds.
Figure BDA0001507230270000111
The photoinitiator (C) is preferably 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-aza, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone, 2' -bis (o-chlorophenyl) -4,4', 5' -tetraphenyldiimidazole, ethanone,1- [9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-substituent ] -,1- (oxy-acetyloxime) or a combination of the above compounds.
The photoinitiator (C) may further contain the following compounds as required: benzophenone-based compounds such as thioxanthone (thioxanthone), 2, 4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4 '-bis (dimethylamine) benzophenone and 4,4' -bis (diethylamine) benzophenone; α -diketones (α -diketones) such as benzil (benzil) and acetyl (acetyl); ketone alcohols (acyloins) such as benzoin; ketone alcohol ethers such as benzoin methyl ether (benzoin ethyl ether), benzoin ethyl ether (benzoin ethyl ether), and benzoin isopropyl ether (benzoin isopropyl ether); acylphosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (2, 4, 6-trimethyl-phenyl-diphenyl-phosphinoxide), bis- (2, 6-dimethoxybenzoyl) -2, 4-trimethylphenylphosphine oxide [ bis- (2, 6-dimethoxy-benzoyl) -2, 4-trimethyl-phenylphosphine oxide ]; quinones such as anthraquinone (anthraquinone) and 1,4-naphthoquinone (1, 4-naphthoquinone); halides such as phenacyl chloride (phenacyl chloride), tribromomethyl-phenylsulfone (tribromomethyl-phenylsulfone), and tris (trichloromethyl) -s-triazine [ tris (trichloromethyl) -s-triazine ]; peroxides such as di-tert-butyl peroxide (di-tert-butyl peroxide); or combinations of the foregoing. The compound added to the photoinitiator (C) is preferably a benzophenone-based compound, and more preferably 4,4' -bis (diethylamine) benzophenone.
The photoinitiator (C) is used in an amount of 10 to 100 parts by weight, preferably 12 to 90 parts by weight, more preferably 15 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).
Solvent (D)
The solvent (D) is a solvent which can dissolve the alkali-soluble resin (a), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), the black pigment (E) and the additive (F) described below, but does not react with the above components, and is preferably a solvent having an appropriate volatility.
Specific examples of the solvent (D) include: alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ethers, other ether compounds, ketone compounds, alkyl lactate compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amine compounds, or a combination thereof.
Specific examples of the alkyl glycol monoalkyl ether compounds include: 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, or combinations thereof.
Specific examples of the alkyl glycol monoalkyl ether acetates include: ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate or the like, or combinations thereof.
Specific examples of the diethylene glycol alkyl ether include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like, or a combination of the above compounds.
Specific examples of the other ether-based compounds include tetrahydrofuran or the like.
Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like, or a combination of the above compounds.
Specific examples of the alkyl lactate-based compound include methyl lactate, ethyl lactate, or the like, or a combination of the above-mentioned compounds.
Specific examples of the other ester compounds include 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, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxybutyrate or the like, or a combination thereof.
Specific examples of the aromatic hydrocarbon compound include toluene, xylene or the like, or a combination of the above compounds.
The carboxylic acid amine compound is N-methyl pyrrolidone, N-dimethyl formamide, N-dimethyl acetamide or the like, or a combination of the compounds.
The solvent (D) may be used alone or in combination of two or more.
The solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.
The amount of the solvent (D) used is 1000 to 9000 parts by weight, preferably 1200 to 8000 parts by weight, more preferably 1500 to 7000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
Black pigment (E)
The black pigment (E) is preferably a black pigment having heat resistance, light resistance and solvent resistance.
Specific examples of the black pigment (E) include: black organic pigments such as perylene black, cyanine black, aniline black, and the like; a mixed color organic pigment which is obtained by mixing two or more selected pigments from red, blue, green, violet, yellow, cyanine (cyanine) and magenta (magenta) pigments to form a near-black color; examples of the light-shielding material include carbon black (carbon black), chromium oxide, iron oxide, titanium black (titanium black), and graphite, and specific examples of the carbon black include c.i. pigment black 7 and commercially available products (trade names MA100, MA230, MA8, #970, #1000, #2350, and # 2650) manufactured by mitsubishi chemical. The black pigment (E) may be used alone or in combination of two or more.
The black pigment (E) is preferably carbon black, and the carbon black is commercially available as MA100 or MA230, manufactured by Mitsubishi chemical.
The black pigment (E) is used in an amount of 100 to 800 parts by weight, preferably 120 to 750 parts by weight, more preferably 150 to 700 parts by weight, based on 100 parts by weight of the above alkali-soluble resin (a).
Additive (F)
On the premise of not influencing the efficacy of the invention, the photosensitive resin composition of the invention can be further selectively added with an additive (F). Specific examples of the additive (F) include a surfactant, a filler, a polymer (which is a polymer other than the alkali-soluble resin (A)), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and other coloring agents.
The surfactant contributes to improving the coating property of the photosensitive resin composition. Specific examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polysiloxane surfactant, a fluorine-based surfactant, or a combination of the above surfactants.
Specifically, examples of the surfactant include polyethoxyalkyl ethers (polyoxyethylene alkyl ethers) such as polyethoxyethyl lauryl ether, polyethoxy stearyl ether and polyethoxy base oil ether; polyethoxyalkylphenyl ethers such as polyethoxyoctylphenyl ether and polyethoxynonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; or tertiary amine modified polyurethanes. The above-mentioned surfactants may be used alone or in combination of two or more.
Specific examples of the surfactant include KP Products manufactured by shin-Etsu chemical industry, SF-8427 Products manufactured by Dow Corning Toray Co., ltd., du Corning, polyflow Products manufactured by Dow oil and fat chemical industry, aifukuron (F-Top) Products manufactured by Dow Products Co., ltd., effolk (Megafac) Products manufactured by Dainippon ink chemical industry, fruoduo (Fluorade) Products manufactured by Sumitomo 3M, asahi Guard (Asahi Guard) Products manufactured by Asahi Niger, or Sufflon (Surflon) Products manufactured by Asahi Nippon.
Specific examples of the filler include glass, aluminum and the like.
Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyalkyl fluoroacrylate, or a combination of the above polymers.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropanoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or a combination of the above compounds.
Specific examples of the antioxidant include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, or a combination of the above compounds.
Specific examples of the ultraviolet absorber include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorophenylazide, alkoxyphenone (alkoxyphenone), or a combination of the above compounds.
Specific examples of the anti-aggregating agent include sodium polyacrylate (sodium polyacrylate) and the like.
Other colorants include inorganic pigments, organic pigments, or a combination of the two.
Specific examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts (for example, metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, etc.) and composite oxides of the above-mentioned metals.
Specific examples of the organic pigment include c.i. pigment yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; c.i. pigment red 1,2, 3,4, 5, 6,7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48; c.i. pigment violet 1, 19, 23, 29, 32, 36, 38, 39; c.i. pigment blue 1,2, 15, 3, 15; c.i. pigment green 7, 36, 37; c.i. pigment brown 23, 25, 28 or a combination of the foregoing pigments.
< method for producing negative photosensitive resin composition for black matrix >
The negative photosensitive resin composition for black matrix can be prepared by the following steps: the negative photosensitive resin composition for black matrix in solution state can be obtained by stirring the alkali-soluble resin (A), the compound (B) containing an ethylenically unsaturated group, the photoinitiator (C), the solvent (D) and the black pigment (E) in a stirrer to uniformly mix them into a solution state, and if necessary, adding the additive (F) to the mixture and uniformly mixing them.
The method for preparing the negative photosensitive resin composition for black matrix is not particularly limited. The negative photosensitive resin composition for black matrix is prepared, for example, by dispersing a part of the alkali-soluble resin (a) and the ethylenically unsaturated group-containing compound (B) in a part of the solvent (D) to form a dispersion solution; and then mixing the rest of the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), the solvent (D), and the black pigment (E).
Alternatively, the negative photosensitive resin composition for a black matrix may be a composition obtained by dispersing a part of the black pigment (E) in a mixture of a part of the alkali-soluble resin (a) and a part of the solvent (D) to form a black pigment dispersion liquid; and adding an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), and a black pigment (E). The step of dispersing the black pigment (E) can be carried out by mixing with a mixer such as a bead mill (roll mill) or a roll mill.
< method for producing Black matrix >
The black matrix is prepared by sequentially carrying out pre-baking, exposure, development and post-baking treatment on the substrate by using the photosensitive resin composition. Further, when the film thickness of the obtained black matrix is 1 μm, the optical density may be in the range of 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The method for preparing the black matrix is described in detail below.
First, a photosensitive resin composition for black matrix in a solution state is uniformly applied on a substrate by an application method such as spin coating (spin coating) or cast coating (cast coating) to form a coating film. Specific examples of the above 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 a transparent conductive film attached to the glass; or a substrate (e.g., silicon substrate) for a photoelectric conversion device used in a solid-state imaging device or the like.
After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-bake (pre-bake) to form a pre-baked coating film. It should be noted that the conditions of the reduced pressure drying and prebaking vary depending on the kind and ratio of each component. Generally, the reduced pressure drying is performed for 1 to 20 seconds under a pressure of less than 200mmHg, and the prebaking is a heat treatment of the coating film for 1 to 15 minutes at a temperature of 70 to 110 ℃.
Then, the prebaked coating is exposed to light using a mask having a specific pattern. The light used in the exposure process 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.
Then, the exposed prebaked coating film is immersed in a developing solution (developing solution) at a temperature of 23 ± 2 ℃ to remove the unexposed portion of the prebaked coating film, whereby a specific pattern can be formed on the substrate.
Examples of the developer include 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 an alkaline compound such as 1, 8-diazabicyclo- [5,4,0] -7-undecene. The concentration of the developer is generally 0.001wt% to 10wt%, preferably 0.005wt% to 5wt%, and more preferably 0.01wt% to 1wt%.
After the prebaked coating film is developed, the substrate having a specific pattern is washed with water, and the specific pattern is air-dried with compressed air or compressed nitrogen. Then, post-bake treatment is performed by a heating device such as a hot plate or an oven. The post-baking temperature is generally 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-mentioned processing steps, a black matrix can be formed on the substrate.
< method for producing color Filter >
The manufacturing method of the color filter is similar to that of the black matrix. Specifically, the photosensitive composition for a color filter is coated on a substrate on which a black matrix is formed, and then pre-baking, exposure, development, and post-baking are sequentially performed to obtain the color filter. However, the reduced pressure drying is carried out under a pressure of 0mmHg to 200mmHg for 1 second to 60 seconds, among the conditions of the reduced pressure drying. After the above-mentioned processing steps, a specific pattern can be fixed, thereby forming a pixel layer. Further, the above steps are repeated to sequentially form pixel layers of red, green, blue, etc. on the substrate, thereby obtaining a substrate (i.e., a color filter having pixel layers) on which the black matrix and the pixel layers are formed.
< method for producing liquid Crystal display device >
First, the color filter formed by the method of manufacturing a color filter and a substrate provided with a Thin Film Transistor (TFT) are arranged to face each other, and a gap (cell gap) is provided between the color filter and the substrate. Then, the color filter is adhered to the periphery of the substrate by an adhesive, and the injection hole is left. Then, liquid crystal is injected into the gap between the surface of the substrate and the adhesive through the injection hole, and finally the injection hole is sealed to form the liquid crystal layer. Subsequently, a liquid crystal display element is manufactured by providing polarizing plates on the other side of the color filter contacting the liquid crystal layer and on the other side of the substrate contacting the liquid crystal layer. The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited, and any liquid crystal compound or liquid crystal composition may be used.
In addition, the liquid crystal alignment film used in the manufacture of the color filter is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the disclosure of these examples.
< example >
Synthesis example of alkali-soluble resin (A-1)
Synthesis examples A-1-1 to A-1-7 of the alkali-soluble resin (A-1) are described below:
synthesis example A-1
262.0g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the temperature was raised to 120 ℃ while stirring under nitrogen gas exchange.
Next, 19.0g of tributylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichikoku Kogyo Co., ltd., perbutyl O) was added to a monomer mixture composed of 5.70g (0.05 mol) of isopropyl acrylate, 121g (0.85 mol) of glycidyl methacrylate, 13.2g (0.06 mol) of dicyclopentanyl methacrylate and 4.00g (0.04 mol) of methyl methacrylate, and the resultant was dropped from the dropping funnel over 2 hours into the flask. After the completion of the dropwise addition, the mixture was stirred at 120 ℃ for 2 hours to effect copolymerization reaction, thereby producing an addition copolymer. Then, the flask was charged with air, 73.2g (0.85 mol) of methacrylic acid, 0.6g of triphenylphosphine (catalyst) and 0.2g of methylhydroquinone were added to the addition copolymer solution, and the reaction was continued by stirring at 110 ℃ for 10 hours, whereby the ring-opening reaction between the epoxy group derived from glycidyl methacrylate and methacrylic acid led to the ring-opening reaction of the epoxy group and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Subsequently, 114g (0.75 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued at 110 ℃ for 3 hours with stirring, and a hydroxyl group produced by the ring-opening reaction of an epoxy group was reacted with an acid anhydride of tetrahydrophthalic anhydride to introduce a carboxyl group into the side chain, whereby an alkali-soluble resin (A-1-1) was obtained.
Synthesis examples A-1-2 to A-1-7
The alkali-soluble resins of Synthesis examples A-1-2 to A-1-7 were prepared in the same procedure as in Synthesis example A-1-1, and they were different in that: the kinds of the monomers and the amounts thereof used were changed (as shown in Table 1).
Synthesis example of alkali-soluble resin (A-2)
Synthesis examples A-2-1 to A-2-7 of the alkali-soluble resin (A-2) are described below:
synthesis example A-2-1
262.0g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the temperature was raised to 120 ℃ while stirring under nitrogen gas exchange.
Next, 19.0g of a tertiary butylperoxy-2-ethylhexanoate (polymerization initiator, perbutyl O, manufactured by Nichikoku Kogyo Co., ltd.) was added to a monomer mixture comprising 45.8g (0.16 mol) of α -methylstyrene, 107g (0.75 mol) of glycidyl methacrylate, 18.5g (0.07 mol) of dicyclopentenyloxyethyl methacrylate and 1.88g (0.02 mol) of norbornene, and the mixture was dropped into the flask from a dropping funnel over a period of 2 hours. After the completion of the dropwise addition, the mixture was stirred at 120 ℃ for 2 hours to effect copolymerization reaction, thereby producing an addition copolymer. Then, the flask was charged with air, 50.4g (0.7 mol) of acrylic acid, 0.6g of triphenylphosphine (catalyst) and 0.2g of methylhydroquinone were added to the addition copolymer solution, and the reaction was continued by stirring at 110 ℃ for 10 hours, whereby the ring-opening reaction of the epoxy group derived from glycidyl methacrylate with acrylic acid was carried out to open the epoxy group and introduce a polymerizable unsaturated bond into the side chain of the polymer. Subsequently, 63.0g (0.63 mol) of succinic anhydride was added to the reaction system, and the reaction was continued by stirring at 110 ℃ for 3 hours, whereby a hydroxyl group produced by the ring-opening reaction of the epoxy group was reacted with an acid anhydride of succinic anhydride to introduce a carboxyl group into the side chain, whereby an alkali-soluble resin (A-2-1) was obtained.
Synthesis examples A-2-2 to A-2-7
The alkali-soluble resins of Synthesis examples A-2-2 to A-1-7 were prepared in the same procedure as in Synthesis example A-2-1, except that: the kinds of the monomers and the amounts thereof used were changed (as shown in Table 2).
The compounds corresponding to the abbreviations in tables 1 and 2 are as follows.
Figure BDA0001507230270000181
[ Table 1]
Figure BDA0001507230270000191
[ Table 2]
Figure BDA0001507230270000201
Synthesis example of other alkali-soluble resin (A-3)
Synthesis examples A-3-1 to A-3-2 of other alkali-soluble resins (A-3) are described below:
synthesis example A-3-1
267.5g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the temperature was raised to 120 ℃ while stirring under nitrogen gas exchange.
Then, 19.2g of a tert-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichikoku Kogyo Co., ltd., perbutyl O) was added to a monomer mixture composed of 55.3g (0.3 mol) of 2-ethylhexyl acrylate, 17.2g (0.2 mol) of methacrylic acid, 11.0g (0.05 mol) of dicyclopentanyl methacrylate, 25.0g (0.25 mol) of methyl methacrylate and 35.2g (0.2 mol) of benzyl methacrylate, and the obtained mixture was dropped into the flask from a dropping funnel over a period of 2 hours. After the completion of the dropwise addition, the mixture was stirred at 120 ℃ for 2 hours to effect copolymerization, thereby obtaining another alkali-soluble resin (A-3-1).
Examples and comparative examples of negative photosensitive resin compositions for black matrix
Examples 1 to 12 and comparative examples 1 to 4 of the negative photosensitive resin composition for black matrix are described below:
example 1
The photosensitive resin composition for black matrix of example 1 was prepared by adding 10 parts by weight of an alkali-soluble resin (a-1-1), 90 parts by weight of an alkali-soluble resin (a-2-1), 30 parts by weight of trimethylolpropane triacrylate (abbreviated as B-1), 10 parts by weight of 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-substituent ] -methanone-1- (O-acetyloxime) (abbreviated as C-1) and 100 parts by weight of black pigment MA100 (abbreviated as E-1) to 1000 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as D-1) and stirring them uniformly by a shaker stirrer.
Examples 2 to 12
The photosensitive resin compositions for black matrix of examples 2 to 12 were prepared by the same procedure as in example 1, except that: the types of components and the amounts of the components used of the photosensitive resin composition for black matrix were changed (as shown in tables 3 and 4).
Comparative examples 1 to 4
Photosensitive resin compositions of comparative examples 1 to 4 were prepared in the same procedure as in example 1, and were different in that: the kinds of components and the amounts of the components used were changed (as shown in Table 4).
The compounds identified by the reference numerals in tables 3 and 4 are shown below.
Figure BDA0001507230270000221
[ Table 3]
Figure BDA0001507230270000231
[ Table 4]
Figure BDA0001507230270000241
< evaluation mode >
Adhesion property
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 MS-a150, available from nova light trade). Then, the above glass substrate was prebaked at 100 ℃ for 2 minutes to form a prebaked coating film having a film thickness of 1.2 micrometers (μm). Then, the above pre-baked coating film was placed under a line and space (line and space) mask (manufactured by NibbonFilcon, japan) and utilized at 50mJ/cm 2 Ultraviolet light (Exposure machine model AG500-4N; from M)&R nano technology) was subjected to 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, and then washed with water to obtain a glass substrate having a specific pattern.
Finally, the line amplitude of the pattern was evaluated in the following manner. It should be noted that the smaller the minimum pattern line width represents the better the adhesion of the pattern formed by the negative photosensitive resin composition for black matrix.
Very good: minimum pattern linewidth ≦ 4 μm
O: 4 μm < minimum pattern linewidth ≦ 6 μm
And (delta): 6 μm < minimum pattern linewidth ≦ 8 μm
Gamma rays: minimum pattern line width of 8 mu m
Development residue
The glass substrate having the specific pattern was observed with a microscope to determine whether or not residue was present in the unexposed portion, and evaluated according to the following criteria:
o: without residue
And (delta): a little residue
Gamma rays: much residue
< evaluation results >
As is clear from tables 3 and 4, the black matrices of comparative examples 1, 3 and 4, which do not contain the alkali-soluble resin (A-1) having a branched alkyl group, an acid group and a polymerizable unsaturated bond, have development residues, as compared with the black matrices (examples 1 to 12) obtained from the photosensitive resin composition for black matrices containing both the specific alkali-soluble resin (A-1) and the alkali-soluble resin (A-2); the black matrices of comparative examples 2 to 4, which did not contain the alkali-soluble resin (a-2) having an aromatic group, an acid group and a polymerizable unsaturated bond, were poor in adhesion.
In addition, when the unsaturated compound (a 3-1) (examples 1 to 9) is included in the first mixture or the second mixture, the adhesiveness of the negative photosensitive resin composition for a black matrix can be further improved.
As described above, the negative photosensitive resin composition for black matrix of the present invention contains the specific alkali-soluble resin (a-1) and the alkali-soluble resin (a-2), and thus can improve the problems of development residue and poor adhesion of the black matrix, and is suitable for color filters and liquid crystal display devices.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims (11)

1. A negative photosensitive resin composition for a black matrix, comprising:
an alkali-soluble resin (A);
a compound (B) containing an ethylenically unsaturated group;
a photoinitiator (C);
a solvent (D); and
a black pigment (E) which is a pigment,
wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2), the alkali-soluble resin (A-1) has a branched alkyl group, an acid group and a polymerizable unsaturated bond, the alkali-soluble resin (A-2) has an aromatic group, an acid group and a polymerizable unsaturated bond,
the alkali-soluble resin (A-1) is obtained by reacting an addition copolymer formed from the first mixture with a polymerizable unsaturated monobasic acid (a 5) and then with a polybasic acid or an anhydride thereof (a 6);
the first mixture includes an acrylate compound (a 1) having a branched alkyl group, an acrylic compound (a 2) having an epoxy group, and other unsaturated compounds (a 3),
the alkali-soluble resin (A-2) is obtained by reacting an addition copolymer formed by the second mixture with a polymerizable unsaturated monobasic acid (a 5) and then reacting with a polybasic acid or anhydride (a 6) thereof;
the second mixture comprises an unsaturated compound (a 4) with an aromatic group, an acrylic compound (a 2) with an epoxy group and other unsaturated compounds (a 3),
the other unsaturated compound (a 3) includes an unsaturated compound (a 3-1), and the unsaturated compound (a 3-1) is at least one selected from the group consisting of acrylate compounds including structures represented by the following formulae (a 3-1-1) and (a 3-1-2), and compounds represented by the following formulae (a 3-1-3):
Figure FDA0003995512480000011
in the formula (a 3-1-3), X and Y independently represent a hydrogen atom, a linear hydrocarbon group having 1 to 4 carbon atoms, or a branched hydrocarbon group having 1 to 4 carbon atoms; r 1 、R 2 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carboxylic acid group having 1 to 20 carbon atoms, the hydrocarbon group and the carboxylic acid group being unsubstituted or substituted with a substituent; or the said R 1 、R 2 Are bonded to each other to form a ring structure.
2. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the acrylate compound (a 1) having a branched alkyl group is used in an amount of 0.05 to 0.4 mol, the acrylate compound (a 2) having an epoxy group is used in an amount of 0.3 to 0.85 mol, and the other unsaturated compound (a 3) is used in an amount of 0 to 0.6 mol, based on the total mole number of the compounds of the first mixture being 1.0 mol.
3. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the polymerizable unsaturated monobasic acid (a 5) is used in an amount of 0.25 to 0.85 mole, and the polybasic acid or its anhydride (a 6) is used in an amount of 0.01 to 0.75 mole, based on 1.0 mole of the total number of moles of the compounds of the first mixture.
4. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the unsaturated compound (a 4) having an aromatic group is used in an amount of 0.03 to 0.45 mol, the acrylic compound (a 2) having an epoxy group is used in an amount of 0.3 to 0.85 mol, and the other unsaturated compound (a 3) is used in an amount of 0 to 0.6 mol, based on 1.0 mol of the total number of moles of the compounds of the second mixture.
5. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the polymerizable unsaturated monobasic acid (a 5) is used in an amount of 0.25 to 0.85 mol, and the polybasic acid or anhydride thereof (a 6) is used in an amount of 0.01 to 0.75 mol, based on 1.0 mol of the total number of moles of the compounds of the second mixture.
6. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the unsaturated compound (a 3-1) is used in an amount of 0.01 to 0.09 mol based on 1.0 mol of the total number of moles of the compounds of the first mixture.
7. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the unsaturated compound (a 3-1) is used in an amount of 0.01 to 0.09 mole based on 1.0 mole of the total number of moles of the compounds of the second mixture.
8. The negative photosensitive resin composition for a black matrix according to claim 1, wherein the alkali-soluble resin (a-1) is used in an amount of 10 to 60 parts by weight, the alkali-soluble resin (a-2) is used in an amount of 40 to 90 parts by weight, the ethylenically unsaturated group-containing compound (B) is used in an amount of 30 to 300 parts by weight, the photoinitiator (C) is used in an amount of 10 to 100 parts by weight, the solvent (D) is used in an amount of 1000 to 9000 parts by weight, and the black pigment (E) is used in an amount of 100 to 800 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
9. A black matrix formed by subjecting the negative type photosensitive resin composition for a black matrix according to any one of claims 1 to 8 to a pre-baking treatment, an exposure treatment, a developing treatment and a post-baking treatment in this order.
10. A color filter comprising the black matrix according to claim 9.
11. A liquid crystal display element comprising the color filter according to claim 10.
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