WO2021078230A1 - Photo-curing resin, photo-curing resin composition and black matrix material - Google Patents
Photo-curing resin, photo-curing resin composition and black matrix material Download PDFInfo
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- WO2021078230A1 WO2021078230A1 PCT/CN2020/123083 CN2020123083W WO2021078230A1 WO 2021078230 A1 WO2021078230 A1 WO 2021078230A1 CN 2020123083 W CN2020123083 W CN 2020123083W WO 2021078230 A1 WO2021078230 A1 WO 2021078230A1
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- BKYGVUDAWIQUCI-UHFFFAOYSA-N c(cc1)cc-2c1Sc1c3c-2cccc3ccc1 Chemical compound c(cc1)cc-2c1Sc1c3c-2cccc3ccc1 BKYGVUDAWIQUCI-UHFFFAOYSA-N 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N O=S(c1ccccc1)(c1ccccc1)=O Chemical compound O=S(c1ccccc1)(c1ccccc1)=O KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N c(cc1)ccc1-c1ccccc1 Chemical compound c(cc1)ccc1-c1ccccc1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- LROIZOQCFGSITO-UHFFFAOYSA-N C[ClH]c1cccc2c1c(Cl)ccc2 Chemical compound C[ClH]c1cccc2c1c(Cl)ccc2 LROIZOQCFGSITO-UHFFFAOYSA-N 0.000 description 1
- QIMMUPPBPVKWKM-UHFFFAOYSA-N Cc1ccc(cccc2)c2c1 Chemical compound Cc1ccc(cccc2)c2c1 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N c(cc1-c2cccc3cccc-4c23)cc2c1c-4ccc2 Chemical compound c(cc1-c2cccc3cccc-4c23)cc2c1c-4ccc2 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- 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
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- 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
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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
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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
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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
- G03F7/075—Silicon-containing compounds
Definitions
- the invention relates to the field of light-curing resins, and in particular to a light-curing resin and a black matrix material of a light-curing resin composition.
- Polymer compounds with a fluorene skeleton have excellent properties such as high heat resistance, high transparency, high refractive index, and low expansion coefficient.
- the Chinese patent with the authorized announcement number CN100564349C and the Chinese patent application with the publication number CN101965375A respectively disclose: Containing a fluorene skeleton polymer compound, it can solve the problem of high refractive index and heat resistance of traditional photo-curable resin composition to a certain extent, but the film layer formed by the obtained photo-curable resin composition has adhesion to the substrate and alkali resistance Solubility, solvent resistance, etc. are difficult to meet the requirements.
- the Chinese patent application with publication number CN109343308A discloses a siloxane-modified acrylate composition whose coating film has a significantly improved resistance to acid, but there is no clear description of alkali resistance and so on.
- the Chinese patent application with publication number CN103718107A discloses a composition containing a silane-modified resin, which has certain deficiencies in alkali solubility, heat resistance, etc., although the adhesion to the developed pattern is improved to a certain extent.
- the main purpose of the present invention is to provide a photocurable resin, a photocurable resin composition and a black matrix material to solve the problem that the photocurable resin in the prior art cannot have both alkali resistance and heat resistance at the same time during application. .
- a light-curing resin having a structure represented by structural formula I:
- R 1 represents any one of a C 6 ⁇ C 20 cycloalkyl group or a C 6 ⁇ C 20 aryl group
- R 2 , R 3 , R 4 , and R 5 are the same or different, and R 2 , R 3 , R 4 and R 5 each independently represent any of H, C 1 ⁇ C 10 alkyl, C 3 ⁇ C 20 cycloalkyl, C 6 ⁇ C 20 aryl
- R 6 has -R The structure represented by 7 -Si-(R 8 )n 1 (OR 9 )n 2 , R 7 represents any one of C 1 ⁇ C 10 alkylene or C 1 ⁇ C 15 alkylene alkoxy ,
- Each R 8 each independently represents any one of a C 1 ⁇ C 10 alkyl group or a C 1 ⁇ C 15 alkoxy group
- each R 9 each independently represents hydrogen, in a C 1 ⁇ C 10 alkyl group
- each R 8 is the same or different, each R 8 is the same or different, each
- R 1 represents any one of a C 6 -C 12 cycloalkyl group and a C 6 -C 12 aromatic group.
- R 2 , R 3 , R 4 , and R 5 are the same, and preferably R 2 , R 3 , R 4 , and R 5 are any one of H, methyl, isopropyl, cyclohexyl, phenyl and benzyl Kind.
- R 7 represents any one of a C 1 to C 5 alkylene group or a C 1 to C 10 alkylene alkoxy group, preferably a C 1 to C 5 alkyl group, C Any one of 3 to C 5 alkylene alkoxy; n 1 is 2, n 2 is 1, and each R 8 represents a C 1 to C 5 alkyl group, in the C 1 to C 10 alkoxy group R 9 represents any one of C 1 ⁇ C 5 alkyl group, C 1 ⁇ C 10 alkoxy group, preferably C 1 ⁇ C 5 alkyl group, C 1 ⁇ C 5 alkoxy group Any of the bases.
- the weight average molecular weight of the above-mentioned photocurable resin is 5000-15000, more preferably 6000-10000.
- a photocurable resin composition comprising a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer and an initiator, and the photocurable acrylate resin is any one of the above Kind of light-curing resin.
- alkali-soluble resin has the following structural formula:
- a and B are substituents, and n 3 is any integer of 1-20.
- the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 20-30 parts by mass, and the photocurable
- the mass ratio of acrylic resin to alkali-soluble resin is 7:10-8:10;
- the photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass;
- the photopolymerization initiator is 1-5 parts by mass, More preferably, it is 1 to 3 parts by mass.
- the above-mentioned photocurable resin composition further includes a coloring agent, and the coloring agent is 30-60 parts by mass, preferably 40-50 parts by mass.
- a black matrix material including a photocurable resin composition, the photocurable resin composition of which is any one of the above-mentioned photocurable resin compositions.
- the photocurable resin with structural formula I suspended the silane group as a side chain group on the polymer main chain.
- the photocurable resin with structural formula I suspended the silane group as a side chain group on the polymer main chain.
- it can form a high substrate adhesion, Film structure with good alkali resistance and good heat resistance.
- the prior art photocurable resin cannot have both alkali resistance and heat resistance at the same time when applied.
- the present application provides a photocurable resin and a photocurable resin. Composition, photoresist and black matrix material.
- a light-curing resin is provided, and the light-curing resin has a structure represented by structural formula I:
- R 1 represents any one of a C 6 ⁇ C 20 cycloalkyl group or a C 6 ⁇ C 20 aryl group
- R 2 , R 3 , R 4 , and R 5 are the same or different, and R 2 , R 3 , R 4 and R 5 each independently represent any of H, C 1 ⁇ C 10 alkyl, C 3 ⁇ C 20 cycloalkyl, C 6 ⁇ C 20 aryl
- R 6 has -R The structure represented by 7 -Si-(R 8 )n 1 (OR 9 )n 2 , R 7 represents any one of C 1 ⁇ C 10 alkylene or C 1 ⁇ C 15 alkylene alkoxy ,
- Each R 8 each independently represents any one of a C 1 ⁇ C 10 alkyl group or a C 1 ⁇ C 15 alkoxy group
- each R 9 each independently represents hydrogen, in a C 1 ⁇ C 10 alkyl group
- each R 8 is the same or different, each R 8 is the same or different, each
- the photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.
- R 1 represents any one of a C 6 -C 12 cycloalkyl group or a C 6 -C 12 aromatic group, and more preferably a cyclohexyl group, a phenyl group, or a benzyl group.
- monomers containing these groups have easier raw materials to obtain, and the hardness and heat resistance can also meet the requirements.
- R 2 , R 3 , R 4 , and R 5 are the same, and it is more preferable that R 2 , R 3 , R 4 , and R 5 are H, methyl, or isopropyl. Any one of phenyl, cyclohexyl, phenyl and benzyl.
- R 6 represents any of a C 1 to C 5 alkylene group or a C 1 to C 10 alkylene alkoxy group.
- R 7 represents a methylene group or a methoxymethylene group
- n 1 Is 2 is 1
- each R 8 represents a C 1 ⁇ C 5 alkyl group, any one of C 1 ⁇ C 10 alkoxy group, preferably each R 8 represents H, methyl, ethyl, Any one of a methoxy group and an ethoxy group
- R 9 represents a C 1 -C 5 alkyl group or a C 1 -C 10 alkoxy group. Either one, preferably a C 1 -C 5 alkane group, any one of C 1 ⁇ C 5 alkoxy group, more preferably R 9 represents H, methyl, ethyl, methoxy, ethoxy any one of.
- the weight average molecular weight of the photocurable resin is preferably 5000-15000, more preferably 6000-10000.
- a photocurable resin composition which includes a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer, an initiator, and a solvent.
- the similar resin is any one of the above-mentioned photocurable resins.
- the photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.
- Alkali-soluble resins in the prior art can be considered to be used in conjunction with the above-mentioned photocurable resins of the present application, preferably alkali-soluble resins containing fluorene groups, and more preferably the above-mentioned alkali-soluble resins have the following structural formula
- a and B are substituents, and n 3 is any integer of 1-20.
- the content of carboxylic acid groups of the above-mentioned alkali-soluble resins is less than that of conventional alkali-soluble resins of the same kind in the prior art, and the content of active groups such as side-chain alcoholic hydroxyl groups is increased, which further reduces the photosensitive resin
- the acid value improves the reactivity and curing rate, so that the photocuring performance, adhesion to the substrate, alkali and solvent resistance, and solvent resistance of the composition are further improved.
- the substituent group represented by A in the above structural formula can theoretically be any chemically acceptable group.
- A is selected from any one of the following groups: * Indicates the possible attachment positions of acid anhydrides.
- the substituent group represented by B in the above structural formula can theoretically be any chemically acceptable group.
- B is selected from any one of the following groups: * Indicates the possible attachment positions of acid anhydrides.
- the total mass parts of the light-curable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photo-curable acrylic resin and the alkali-soluble resin is 20 ⁇ 30 parts by mass, and the mass ratio of the photocurable acrylate resin and the alkali-soluble resin is 7:10-8:10.
- the above-mentioned photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass.
- the photopolymerizable monomer used in the above-mentioned photocurable resin composition is used to improve the photosensitivity, mechanical strength, crosslinkability, chemical resistance and other properties of the photocurable resin composition.
- the polymerizable monomer as long as the compound has one or more unsaturated bonds in the molecule, one or a combination of several of them can be selected as required.
- Illustrative examples of the photopolymerizable monomer selected in the present invention are propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.
- (Meth)acrylic acid adducts of epoxy compounds such as ether, sorbitol triglycidyl ether, glycerol triglycidyl ether; unsaturated organic acids such as maleic acid and their anhydrides; N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N -Methylolmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethyl Acrylamides such as acrylamide; polyethylene glycol di(meth)acrylate (the number of ethylene groups is 2-14); trimethylolpropane di(meth)acrylate, trimethylolpropane tri(methyl) ) Acrylate, trimethylol
- the photopolymerization initiator is preferably 1 to 5 parts by mass, preferably 1 to 3 parts by mass.
- the initiator in the above-mentioned photocurable resin composition is mixed in a state of being dissolved or dispersed in a solvent.
- the initiator used in the present invention is not particularly limited, and can be selected from benzophenone-based initiators, triazine-based initiators, dialkoxyacetophenone-based initiators, ⁇ -hydroxyalkylphenone-based initiators, ⁇ -Amino alkyl phenone initiators, acyl phosphine oxide initiators, benzophenone initiators, benzoin initiators, benzyl initiators, heterocyclic aromatic ketone initiators, oxime esters One or more combinations of photoinitiators. Particularly preferred are oxime ester initiators.
- Exemplary examples are: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, diethoxyacetophenone, 2,4-bis (Trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5 -Triazine, benzoin, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 10-butyl -2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, o-ethoxycarbonyl-a-oxyimino-1-phenylpropanone, 1,2-octanedione, 1 -(4-phenylthio)phenyl-2 (
- (poly)alkylene glycol monoalkyl ethers can be selected, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether Ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether
- organic solvents can be used alone or in a mixture of two or more, among which propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol Solvents such as monomethyl ether and diethylene glycol methyl ethyl ether have good solubility for the photosensitive resin composition of the present invention; further preferred solvents are propylene glycol monomethyl ether acetate and diethylene glycol methyl ethyl ether.
- the amount of the solvent added is such that the solid content of the photocurable resin composition is 10-50% by weight, more preferably 15-40% by weight.
- the above-mentioned photocurable resin composition can optionally be added with colorants commonly used in the art, and color filters can be well formed by adding colorants.
- any organic pigments and inorganic pigments commonly used in the art can be selectively used as the colorant in this application.
- These include water-soluble pigments, water-insoluble azo pigments, phthalocyanine pigments, acridone pigments, isoindoline pigments, indolanthrone pigments, indanthrone pigments, diketopyrrole pigments, etc.
- the above-mentioned pigments can be used alone or mixed, depending on the specific requirements of the product.
- Organic raw materials are more preferable, and specific pigments are exemplified as follows, but are not limited to the following pigments.
- Specific examples of compounds with color index (The Society of Dyers and Colourists) (C.I.) serial number are as follows:
- the colorant When the colorant is used as a light-shielding agent, it is preferable to use a black pigment.
- the black pigment include metal oxides, composite oxides, metal sulfides, and metals such as carbon black, titanium black, copper, iron, and manganese. Sulfate, metal carbonate, etc. Among them, carbon black having high light-shielding properties is preferable.
- the content of the coloring agent may be appropriately determined according to the use of the photosensitive resin composition, and is preferably 30 to 60 parts by mass, and more preferably 40 to 50 parts by mass.
- a dispersant may also be used.
- polyethyleneimine-based, polyurethane resin-based, acrylic resin-based polymer dispersing agents, particularly oleic acrylic resin-based dispersing agents are preferably used.
- the total mass of the photocurable resin composition is calculated as 100 parts by mass :
- the total mass parts of the photocurable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably 20-30 parts by mass;
- the colorant is 20-60 parts by mass, preferably 30-40 parts by mass;
- the photopolymerizable monomer is 1 to 30 parts by mass, preferably 15 to 25 parts by mass;
- photopolymerization initiator is 1 to 5 parts by mass, preferably 1 to 3 parts by mass;
- solvent is 10 to 50 parts by mass, preferably 15 to 40 parts by mass.
- the above-mentioned photocurable resin composition may contain additives, such as fillers, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, etc., but are not limited to this.
- the curing agent is used to improve the deep curing performance and mechanical strength.
- the curing agent can be specifically selected from epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds, but is not limited to these compounds.
- the leveling agent can use commercially available surfactants, which can specifically include silicone surfactants, ester surfactants, ionic surfactants, nonionic surfactants, amphoteric surfactants, etc., which are surface active.
- the agent can be used alone or in combination of two or more.
- the adhesion promoter can use silane compounds, and specific examples include: vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N-(2- Aminoethyl)-30 aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.
- the above-mentioned adhesion promoters may be used alone or in combination of two or more kinds.
- antioxidants include: 4,4'-butylene bis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,3'- Thiobis(4-methyl-6-tert-butylphenol), p-methoxyphenol, etc.
- the ultraviolet absorber can be 2-(3-tert-butyl-2hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.
- a black matrix material including a photocurable resin composition
- the photocurable resin composition is any one of the above-mentioned photocurable resin compositions. Since the photocurable resin composition of the present application has strong adhesion, alkali solubility and high temperature resistance, the adhesion of the formed black matrix has the above advantages.
- the synthetic route of the above-mentioned photocurable resin is to obtain organosilane-modified acrylic by reacting with a carboxyl-containing acrylic copolymer resin through a silane coupling agent containing epoxy, hydroxyl and other active substituent groups in the presence of a catalyst Resin, that is, the light-curable resin of the present application.
- a catalyst Resin that is, the light-curable resin of the present application.
- the acrylic resins 2 to 5 are modified with a silane coupling agent to prepare silane-modified acrylic resins 2 to 15.
- the specific silane coupling agent and modified resin are shown in Tables 2 to 4 below.
- Synthetic comparative example 1 (comparative example resin 1)
- An exemplary photocurable resin composition was prepared, and the application performance of the organosilane modified resin given in the examples of the present invention was evaluated.
- the modified resin prepared in the above-mentioned embodiments is tested and compared.
- the raw materials were uniformly mixed in the following proportions to form a photocurable resin composition.
- the light-curing resin is mixed with part of the solvent first, and then mixed with other components.
- the photocurable resin compositions of Examples 1-20 and Comparative Examples 1 and 2 were coated on a glass substrate (100mm ⁇ 100mm), and pre-baked at 90°C for 90 seconds to form a film thickness 1.0 ⁇ m coating film. Then, a mirror projection was used to align the exposure device, the exposure gap was set to 50 ⁇ m, and a negative image mask having a linear pattern of 20 ⁇ m was used to expose and isolate the exposure. The exposure intensity was set to 4 levels of 20, 40, 60, and 120mJ/cm 2. The exposed sample film was developed in a 0.04% by mass KOH aqueous solution at 26°C for 40s, 60s, and 80s, and then baked at 230°C for 30 minutes to form a linear pattern. The pattern characteristics and the residual rate of film formation were tested. Test its alkali solubility, solvent resistance and other properties.
- the coating film was irradiated with ultraviolet rays with an exposure gap of 50 ⁇ m through a negative image mask formed with linear patterns of 2, 5, 10, and 20 ⁇ m.
- the exposure amount is set to 20mJ/cm 2 .
- post-baking was performed at 230°C for 30 minutes to form a linear pattern.
- the formed pattern was observed with an optical microscope, and the linearity and adhesion of the pattern were evaluated.
- the specific evaluation situation is shown in Table 7 below.
- the application effect of the photoresist resin composition containing the modified resin 1 and the alkali-soluble resin II in different proportions was evaluated, and the specific evaluation conditions are shown in Table 8.
- ⁇ The edge of the pattern line is jagged.
- Example 2 Example 5, Example 9, Example 10, Example 13, Example 14 and the like, at 40mJ / cm 2 exposure, have demonstrated good linearity, 60mJ /
- the examples all showed good linearity at cm 2 exposure, while the linearity of the comparative example was not good, and there were jagged edges.
- the adhesion test showed that the 2 ⁇ m linear pattern, Examples 1-15 have shown certain adhesion; the 5 ⁇ m-10 ⁇ m line width pattern has obviously better adhesion, while the comparative example has peeling off in the 2 ⁇ m linear pattern , 10 ⁇ m linear pattern also has obvious defects.
- Example 18 In comparison of the linearity of Examples 16-20, the 40mJ exposure energy condition is small, and the linearity of Example 18 is better, while the linearity of Example 16, Example 17, Example 19, and Example 20 is slightly insufficient; , With a linear pattern of 5 ⁇ m, Example 17, Example 18, and Example 19 all showed good adhesion, while the adhesion of Example 16 and Example 20 was significantly lower. Therefore, it can be seen from a comprehensive comparison that the ratio of the two resins in Example 18 is a relatively suitable ratio. In other embodiments, this ratio is used for application performance testing.
- the coating film was irradiated with ultraviolet rays with an exposure gap of 50 ⁇ m through a negative image mask formed with linear patterns of 2, 5, 10, and 20 ⁇ m.
- the exposure amount is set to 20mJ/cm 2 .
- post-baking was performed at 230°C for 30 minutes to form a linear pattern.
- the formed pattern was observed with an optical microscope, the heat resistance (the contact angle between the pattern edge and the substrate) and the alkali solubility were evaluated, and the determination was made from the measurement result of the residual film rate.
- the specific evaluation situation is shown in Table 9 below.
- the above-mentioned photocurable resin compositions containing modified resin 1 and alkali-soluble resin II in different proportions were compared, and a better resin ratio was selected. The specific comparison results are shown in Table 10.
- the evaluation criteria are as follows.
- the photocurable resin compositions corresponding to Examples 1-15 all have good alkali resistance; after 230°C post-baking, the contact angles between the edges of the resulting patterns and the substrate are all >45°, The heat resistance is better, and the contact angles of the comparative examples are all ⁇ 40°C, and the heat resistance is relatively poor.
- the organic silane-modified photocurable resin and its composition provided by the present invention have excellent application performance, better heat resistance, better linearity and adhesion, and have broad application prospects.
- the photocurable resin composition prepared by using the photosensitive resin with the above-mentioned specific structural formula I and the alkali-soluble resin in combination has good linearity in development, good adhesion to the substrate, and good post-baking heat resistance. Good alkali resistance and solubility.
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Abstract
Provided are a photo-curing resin, a photo-curing resin composition and a black matrix material. The photo-curing resin has the following structure: (I), wherein R1 is any one of a C6-C20 cycloalkyl and a C6-C20 aryl; R2, R3, R4, and R5 are each independently any one of H, a C1-C10 alkyl, a C3-C20 cycloalkyl, and a C6-C20 aryl; and R6 has a structure as represented by -R7-Si-(R8)n1(OR9)n2, wherein R7 is any one of a C1-C10 alkylene and a C1-C15 alkylenealkoxy, each R8 is independently any one of a C1-C10 alkyl and a C1-C15alkoxy, and each R9 is independently any one of hydrogen and a C1-C10 alkyl. When the above photo-curing resin is used in combination with an alkali-soluble resin, a film layer structure having a high substrate adhesion, a good resistance to alkali dissolution and a good heat resistance can be formed.
Description
本发明涉及光固化树脂领域,具体而言,涉及一种光固化树脂、光固化树脂组合物黑色矩阵材料。The invention relates to the field of light-curing resins, and in particular to a light-curing resin and a black matrix material of a light-curing resin composition.
近年来,平板显示器伴随显示面积的不断扩大,需要采用亮的背光。随着背光变亮,对黑色矩阵的遮光性能,显影的细微度等要求越来越高。为了提高黑色矩阵的遮光性和对比度,往往采用提高颜料含量的方法。随着颜料含量的增多,黑色矩阵对基板的附着力变弱,耐碱溶解性、耐热性等均不同程度受到影响。公开号为JP2006259716A的日本专利通过在感光性树脂组合物中加入二官能团的反应性单体,以提升该感光性树脂组合物于曝光时的交联程度,以形成具有高精细图案的黑色矩阵。In recent years, flat-panel displays need to use bright backlights as the display area continues to expand. As the backlight becomes brighter, the requirements for the black matrix's light-shielding performance and the fineness of development are getting higher and higher. In order to improve the light-shielding and contrast of the black matrix, methods of increasing the pigment content are often used. As the pigment content increases, the adhesion of the black matrix to the substrate becomes weaker, and the alkali solubility and heat resistance are affected to varying degrees. The Japanese Patent Publication No. JP2006259716A adds a difunctional reactive monomer to a photosensitive resin composition to increase the degree of crosslinking of the photosensitive resin composition during exposure to form a black matrix with a high-definition pattern.
具有芴骨架的高分子化合物具有高耐热性、高透明性、高折射率、低膨胀系数等优异特性,如授权公告号为CN100564349C的中国专利、公开号为CN101965375A的中国专利申请分别公开了:含有芴骨架高分子化合物,在一定程度能解决传统光固化树脂组合物不能达到高折射率及耐热的问题,但所得到的光固化树脂组合物形成的膜层对基板的附着性、耐碱溶解性、耐溶剂性等难以达到要求。公开号为CN109343308A的中国专利申请公开了一种硅氧烷改性丙烯酸酯组合物,其涂膜对酸性的耐受能力有明显提高,但对耐碱溶解性等没有明确说明。公开号为CN103718107A的中国专利申请公开了一种含有硅烷改性树脂的组合物,其对虽然对显影图案的密合性有一定提高,但其耐碱溶解性、耐热性等存在一定不足。Polymer compounds with a fluorene skeleton have excellent properties such as high heat resistance, high transparency, high refractive index, and low expansion coefficient. For example, the Chinese patent with the authorized announcement number CN100564349C and the Chinese patent application with the publication number CN101965375A respectively disclose: Containing a fluorene skeleton polymer compound, it can solve the problem of high refractive index and heat resistance of traditional photo-curable resin composition to a certain extent, but the film layer formed by the obtained photo-curable resin composition has adhesion to the substrate and alkali resistance Solubility, solvent resistance, etc. are difficult to meet the requirements. The Chinese patent application with publication number CN109343308A discloses a siloxane-modified acrylate composition whose coating film has a significantly improved resistance to acid, but there is no clear description of alkali resistance and so on. The Chinese patent application with publication number CN103718107A discloses a composition containing a silane-modified resin, which has certain deficiencies in alkali solubility, heat resistance, etc., although the adhesion to the developed pattern is improved to a certain extent.
发明内容Summary of the invention
本发明的主要目的在于提供一种光固化树脂、光固化树脂组合物及黑色矩阵材料,以解决现有技术中的光固化树脂在应用时不能同时兼具耐碱溶解性和耐热性的问题。The main purpose of the present invention is to provide a photocurable resin, a photocurable resin composition and a black matrix material to solve the problem that the photocurable resin in the prior art cannot have both alkali resistance and heat resistance at the same time during application. .
为了实现上述目的,根据本发明的一个方面,提供了一种光固化树脂,该光固化树脂具有结构式I所示结构:In order to achieve the above objective, according to one aspect of the present invention, a light-curing resin is provided, the light-curing resin having a structure represented by structural formula I:
其中,R
1表示C
6~C
20的环烷基、C
6~C
20的芳基中的任意一种;R
2、R
3、R
4、R
5相同或不同,且R
2、R
3、R
4、R
5各自独立的表示H、C
1~C
10的烷基、C
3~C
20的环烷基、C
6~C
20的芳基中的任意一种;R
6具有-R
7-Si-(R
8)n
1(OR
9)n
2所示结构,R
7表示C
1~C
10的亚烷基、C
1~C
15的亚烷基烷氧基中的任意一种,各R
8各自独立地表示C
1~C
10的烷基、C
1~C
15的烷氧基中的任意一种,各R
9各自独立地表示氢、C
1~C
10的烷基中的任意一种,在R
8或R
9为多个的情况下,各R
8相同或不同,各R
9相同或不同,n
1和n
2为正整数且n
1+n
2=3;x,y,z,n各自独立的表示整数,且x和n不为0。
Wherein, R 1 represents any one of a C 6 ~C 20 cycloalkyl group or a C 6 ~C 20 aryl group; R 2 , R 3 , R 4 , and R 5 are the same or different, and R 2 , R 3 , R 4 and R 5 each independently represent any of H, C 1 ~C 10 alkyl, C 3 ~C 20 cycloalkyl, C 6 ~C 20 aryl; R 6 has -R The structure represented by 7 -Si-(R 8 )n 1 (OR 9 )n 2 , R 7 represents any one of C 1 ~C 10 alkylene or C 1 ~C 15 alkylene alkoxy , Each R 8 each independently represents any one of a C 1 ~C 10 alkyl group or a C 1 ~C 15 alkoxy group, and each R 9 each independently represents hydrogen, in a C 1 ~C 10 alkyl group In the case of multiple R 8 or R 9 , each R 8 is the same or different, each R 9 is the same or different, n 1 and n 2 are positive integers and n 1 +n 2 =3; x , Y, z, n each independently represent an integer, and x and n are not 0.
进一步地,上述R
1表示C
6~C
12的环烷基、C
6~C
12芳香基中的任意一种。
Furthermore, the above-mentioned R 1 represents any one of a C 6 -C 12 cycloalkyl group and a C 6 -C 12 aromatic group.
进一步地,上述R
2、R
3、R
4、R
5相同,优选R
2、R
3、R
4、R
5为H、甲基、异丙基、环己基、苯基和苄基的任意一种。
Further, the above-mentioned R 2 , R 3 , R 4 , and R 5 are the same, and preferably R 2 , R 3 , R 4 , and R 5 are any one of H, methyl, isopropyl, cyclohexyl, phenyl and benzyl Kind.
进一步地,上述R
6中,R
7表示C
1~C
5的亚烷基、C
1~C
10的亚烷基烷氧基的任意一种,优选为C
1~C
5的烷基、C
3~C
5的亚烷基烷氧基中的任意一种;n
1为2,n
2为1,各R
8均表示C
1~C
5的烷基,C
1~C
10烷氧基中的任意一种,R
9表示C
1~C
5的烷基、C
1~C
10的烷氧基中的任意一种,优选为C
1~C
5的烷基、C
1~C
5烷氧基中的任意一种。
Further, in the above-mentioned R 6 , R 7 represents any one of a C 1 to C 5 alkylene group or a C 1 to C 10 alkylene alkoxy group, preferably a C 1 to C 5 alkyl group, C Any one of 3 to C 5 alkylene alkoxy; n 1 is 2, n 2 is 1, and each R 8 represents a C 1 to C 5 alkyl group, in the C 1 to C 10 alkoxy group R 9 represents any one of C 1 ~C 5 alkyl group, C 1 ~C 10 alkoxy group, preferably C 1 ~C 5 alkyl group, C 1 ~C 5 alkoxy group Any of the bases.
进一步地,上述光固化树脂的重均分子量为5000~15000,更优选为6000~10000。Furthermore, the weight average molecular weight of the above-mentioned photocurable resin is 5000-15000, more preferably 6000-10000.
根据本发明的另一方面,提供了一种光固化树脂组合物,包括光固化丙烯酸酯类树脂、碱溶性树脂、光聚合性单体和引发剂,该光固化丙烯酸酯类树脂为上述任一种的光固化树脂。According to another aspect of the present invention, there is provided a photocurable resin composition, comprising a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer and an initiator, and the photocurable acrylate resin is any one of the above Kind of light-curing resin.
进一步地,上述碱溶性树脂具有以下结构式:Further, the above-mentioned alkali-soluble resin has the following structural formula:
其中,A和B为取代基,n
3为1~20中的任意一个整数。
Among them, A and B are substituents, and n 3 is any integer of 1-20.
进一步地,上述A选自如下基团中的任意一种:
*表示酸酐可能的连接位置;
Further, the above A is selected from any one of the following groups: * Indicates the possible connection position of acid anhydride;
进一步地,上述B选自如下基团中的任意一种:
*表示酸酐可能的连接位置。
Further, the above-mentioned B is selected from any one of the following groups: * Indicates the possible attachment positions of acid anhydrides.
进一步地,上述光固化丙烯酸酯类树脂和碱溶性树脂的总质量份为10~50质量份,优选光固化丙烯酸酯类树脂和碱溶性树脂的总质量份为20~30质量份,且光固化丙烯酸酯类树脂和碱溶性树脂质量比为7:10~8:10;光聚合性单体为1~30质量份,更优选15~25质量份;光聚合引发剂为1~5质量份,更优选1~3质量份。Further, the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 20-30 parts by mass, and the photocurable The mass ratio of acrylic resin to alkali-soluble resin is 7:10-8:10; the photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass; the photopolymerization initiator is 1-5 parts by mass, More preferably, it is 1 to 3 parts by mass.
进一步地,上述光固化树脂组合物还包括着色剂,着色剂为30~60质量份,优选40~50质量份。Furthermore, the above-mentioned photocurable resin composition further includes a coloring agent, and the coloring agent is 30-60 parts by mass, preferably 40-50 parts by mass.
根据本发明的又一方面,提供了一种黑色矩阵材料,包括光固化树脂组合物,其该光固化树脂组合物为上述任一种的光固化树脂组合物。According to another aspect of the present invention, there is provided a black matrix material, including a photocurable resin composition, the photocurable resin composition of which is any one of the above-mentioned photocurable resin compositions.
应用本发明的技术方案,具有结构式I的光固化树脂将硅烷基团作为侧链基团悬挂于聚合物主链上,在与本领域的碱可溶性树脂配合使用时,可以形成基板附着力高、耐碱溶解性好、耐热性好的膜层结构。Applying the technical solution of the present invention, the photocurable resin with structural formula I suspended the silane group as a side chain group on the polymer main chain. When used in conjunction with alkali-soluble resins in the art, it can form a high substrate adhesion, Film structure with good alkali resistance and good heat resistance.
需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other if there is no conflict. Hereinafter, the present invention will be described in detail with reference to the embodiments.
如本申请背景技术所分析的,现有技术的光固化树脂在应用时不能同时兼具耐碱溶解性和耐热性,为了解决该问题,本申请提供了一种光固化树脂、光固化树脂组合物、光刻胶及黑色矩阵材料。As analyzed in the background art of this application, the prior art photocurable resin cannot have both alkali resistance and heat resistance at the same time when applied. In order to solve this problem, the present application provides a photocurable resin and a photocurable resin. Composition, photoresist and black matrix material.
在本申请一种典型的实施方式中,提供了一种光固化树脂,光固化树脂具有结构式I所示结构:In a typical implementation of the present application, a light-curing resin is provided, and the light-curing resin has a structure represented by structural formula I:
其中,R
1表示C
6~C
20的环烷基、C
6~C
20的芳基中的任意一种;R
2、R
3、R
4、R
5相同或不同,且R
2、R
3、R
4、R
5各自独立的表示H、C
1~C
10的烷基、C
3~C
20的环烷基、C
6~C
20的芳基中的任意一种;R
6具有-R
7-Si-(R
8)n
1(OR
9)n
2所示结构,R
7表示C
1~C
10的亚烷基、C
1~C
15的亚烷基烷氧基中的任意一种,各R
8各自独立地表示C
1~C
10的烷基、C
1~C
15的烷氧基中的任意一种,各R
9各自独立地表示氢、C
1~C
10的烷基中的任意一种,在R
8或R
9为多个的情况下,各R
8相同或不同,各R
9相同或不同,n
1和n
2为正整数且n
1+n
2=3;x,y,z,n各自独立的表示整数,且x和n不为0。
Wherein, R 1 represents any one of a C 6 ~C 20 cycloalkyl group or a C 6 ~C 20 aryl group; R 2 , R 3 , R 4 , and R 5 are the same or different, and R 2 , R 3 , R 4 and R 5 each independently represent any of H, C 1 ~C 10 alkyl, C 3 ~C 20 cycloalkyl, C 6 ~C 20 aryl; R 6 has -R The structure represented by 7 -Si-(R 8 )n 1 (OR 9 )n 2 , R 7 represents any one of C 1 ~C 10 alkylene or C 1 ~C 15 alkylene alkoxy , Each R 8 each independently represents any one of a C 1 ~C 10 alkyl group or a C 1 ~C 15 alkoxy group, and each R 9 each independently represents hydrogen, in a C 1 ~C 10 alkyl group In the case of multiple R 8 or R 9 , each R 8 is the same or different, each R 9 is the same or different, n 1 and n 2 are positive integers and n 1 +n 2 =3; x , Y, z, n each independently represent an integer, and x and n are not 0.
本发明具有结构式I的光固化树脂将硅烷基团作为侧链基团悬挂于聚合物主链上,在与本领域的碱可溶性树脂配合使用时,可以形成基板附着力高、耐碱溶解性好、耐热性好的膜层结构。The photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.
为了提高树脂的硬度和耐热性能,优选上述R
1表示C
6~C
12的环烷基、C
6~C
12芳香基中的任意一种,进一步优选为环己基、苯基或苄基。含有这些基团的单体相对于其他大环状基团的单体来说,原料更易得到,硬度以及耐热性能也能满足要求。
In order to improve the hardness and heat resistance of the resin, it is preferable that the above-mentioned R 1 represents any one of a C 6 -C 12 cycloalkyl group or a C 6 -C 12 aromatic group, and more preferably a cyclohexyl group, a phenyl group, or a benzyl group. Compared with monomers with other macrocyclic groups, monomers containing these groups have easier raw materials to obtain, and the hardness and heat resistance can also meet the requirements.
为了提高结构式I的稳定性以及合成的高效性,优选上述R
2、R
3、R
4、R
5相同,优选更优选R
2、R
3、R
4、R
5为H、甲基、异丙基、环己基、苯基和苄基的任意一种。
In order to improve the stability of structural formula I and the efficiency of synthesis, it is preferable that the above R 2 , R 3 , R 4 , and R 5 are the same, and it is more preferable that R 2 , R 3 , R 4 , and R 5 are H, methyl, or isopropyl. Any one of phenyl, cyclohexyl, phenyl and benzyl.
为了提高树脂的耐热性和基板附着力以及合成的高效性,优选上述R
6中,R
7表示C
1~C
5的亚烷基、C
1~C
10的亚烷基烷氧基的任意一种,优选为C
1~C
5的烷基、C
3~C
5的亚烷基烷氧基中的任意一种,更优选R
7表示亚甲基或甲氧基亚甲基;n
1为2,n
2为1,各R
8均表示C
1~C
5的烷基,C
1~C
10烷氧基中的任意一种,优选各R
8均表示H,甲基、乙基、甲氧基、乙氧基中的任意一种,R
9表示C
1~C
5的烷基、C
1~C
10的烷氧基中的.任意一种,优选为C
1~C
5的烷基、C
1~C
5烷氧基中的任意一种,更优选R
9表示H、甲基、乙基、甲氧基、乙氧基中的任意一种。
In order to improve the heat resistance of the resin, the adhesion of the substrate, and the efficiency of synthesis, it is preferable that in the above-mentioned R 6 , R 7 represents any of a C 1 to C 5 alkylene group or a C 1 to C 10 alkylene alkoxy group. One kind, preferably any one of a C 1 ~C 5 alkyl group and a C 3 ~C 5 alkylene alkoxy group, more preferably R 7 represents a methylene group or a methoxymethylene group; n 1 Is 2, n 2 is 1, each R 8 represents a C 1 ~C 5 alkyl group, any one of C 1 ~C 10 alkoxy group, preferably each R 8 represents H, methyl, ethyl, Any one of a methoxy group and an ethoxy group, R 9 represents a C 1 -C 5 alkyl group or a C 1 -C 10 alkoxy group. Either one, preferably a C 1 -C 5 alkane group, any one of C 1 ~ C 5 alkoxy group, more preferably R 9 represents H, methyl, ethyl, methoxy, ethoxy any one of.
在本申请一种实施例中,为了提高光固化树脂的固化速率,优选上述光固化树脂的重均分子量为5000~15000,更优选为6000~10000。In an embodiment of the present application, in order to increase the curing rate of the photocurable resin, the weight average molecular weight of the photocurable resin is preferably 5000-15000, more preferably 6000-10000.
在本申请另一种典型的实施方式中,提供了一种光固化树脂组合物,包括光固化丙烯酸酯类树脂、碱溶性树脂、光聚合性单体、引发剂和溶剂,该光固化丙烯酸酯类树脂为上述任一种的光固化树脂。In another exemplary embodiment of the present application, a photocurable resin composition is provided, which includes a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer, an initiator, and a solvent. The photocurable acrylate The similar resin is any one of the above-mentioned photocurable resins.
本发明具有结构式I的光固化树脂将硅烷基团作为侧链基团悬挂于聚合物主链上,在与本领域的碱可溶性树脂配合使用时,可以形成基板附着力高、耐碱溶解性好、耐热性好的膜层结构。The photocurable resin with structural formula I of the present invention has silane groups as side chain groups suspended on the polymer main chain. When used in conjunction with alkali-soluble resins in the field, it can form a substrate with high adhesion and good alkali solubility. , Film structure with good heat resistance.
现有技术中碱溶性树脂均可考虑与本申请的上述光固化树脂配合使用,优选含芴基团的碱溶性树脂,进一步优选上述碱溶性树脂具有以下结构式Alkali-soluble resins in the prior art can be considered to be used in conjunction with the above-mentioned photocurable resins of the present application, preferably alkali-soluble resins containing fluorene groups, and more preferably the above-mentioned alkali-soluble resins have the following structural formula
其中,A和B为取代基,n
3为1~20中的任意一个整数。
Among them, A and B are substituents, and n 3 is any integer of 1-20.
上述碱溶性树脂的羧酸基团相对于现有技术中常规的同类碱溶性树脂的羧酸基团含量较少,且侧链醇羟基等活性基团的含量增多,进一步降低了感光性树脂的酸值,提高了反应活性和固化速率,使得组合物的光固化性能、对基板的附着性、耐碱溶剂性、耐溶剂性有了更进一步提高。The content of carboxylic acid groups of the above-mentioned alkali-soluble resins is less than that of conventional alkali-soluble resins of the same kind in the prior art, and the content of active groups such as side-chain alcoholic hydroxyl groups is increased, which further reduces the photosensitive resin The acid value improves the reactivity and curing rate, so that the photocuring performance, adhesion to the substrate, alkali and solvent resistance, and solvent resistance of the composition are further improved.
上述结构式中的A所表示的取代基团理论上可以是任意的化学可接受的基团,为了进一步优化感光性树脂的优势,优选A选自如下基团中的任意一种:
*表示酸酐可能的连接位置。
The substituent group represented by A in the above structural formula can theoretically be any chemically acceptable group. In order to further optimize the advantages of the photosensitive resin, it is preferable that A is selected from any one of the following groups: * Indicates the possible attachment positions of acid anhydrides.
上述结构式中的B所表示的取代基团理论上可以是任意的化学可接受基团,为了使得上述感光性树脂的性能更稳定,优选B选自如下基团中的任意一种:
*表示酸酐可能的连接位置。
The substituent group represented by B in the above structural formula can theoretically be any chemically acceptable group. In order to make the performance of the above photosensitive resin more stable, it is preferable that B is selected from any one of the following groups: * Indicates the possible attachment positions of acid anhydrides.
为了使上述各树脂的优势得到充分发挥,光固化丙烯酸酯类树脂和碱溶性树脂的总质量份为10~50质量份,优选光固化丙烯酸酯类树脂和碱溶性树脂的总质量份为20~30质量份,且光固化丙烯酸酯类树脂和碱溶性树脂质量比为7:10~8:10。In order to make full use of the advantages of the above-mentioned resins, the total mass parts of the light-curable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably the total mass parts of the photo-curable acrylic resin and the alkali-soluble resin is 20~ 30 parts by mass, and the mass ratio of the photocurable acrylate resin and the alkali-soluble resin is 7:10-8:10.
在一种实施例中,上述光聚合性单体为1~30质量份,更优选15~25质量份。上述光固化树脂组合物中用到的光聚合性单体,用以改善光固化树脂组合物的感光性能、机械强度、交联性、耐药品性等性能。作为该聚合性单体,只要分子内具有一个或一个以上不饱和键的化合物,即可根据需要选择其中的一种或者几种的组合。本发明中所选择的光聚合性单体,示例性的举例如:丙二醇二缩水甘油醚、二丙二醇二缩水甘油醚、三丙二醇二缩水甘油醚、四丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、山梨糖醇三缩水甘油醚、丙三醇三缩水甘油醚等环氧化合物的(甲基)丙烯酸加成物;马来酸等不饱和有机酸及其酸酐;N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-羟甲基丙烯酰胺、N-甲基丙烯酰胺、N-乙基甲基丙烯酰胺、N-异丙基甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N,N-二乙基甲基丙烯酰胺等丙烯酰胺类;聚乙二醇二(甲基)丙烯酸酯(亚乙基数为2~14);三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷乙氧基三(甲基)丙烯酸酯、三羟甲基丙烷丙氧基三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯(亚丙基数为2~14);二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、双酚A聚氧乙烯二(甲基)丙烯酸酯、双酚A二氧乙烯二(甲基)丙烯酸酯、双酚A三氧乙烯二(甲基)丙烯酸酯、双酚A氧乙烯基二(甲基)丙烯酸酯、多元羧酸(如邻苯二甲酸酐等)与具有羟基和烯键式不饱和基团的化合物(如(甲基)丙烯酸β-羟乙酯等)的酯化物、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯等(甲基)丙烯酸烷基酯;乙二醇二缩水甘油醚、二甘醇二缩水甘油醚、三乙二醇二缩水甘油醚、四乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、苯乙烯、羟基苯乙烯等苯乙烯类;N-乙烯基吡咯烷酮、N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基咪唑等;上述所列举的各物质可单独使用也可以多种组合使用。In an embodiment, the above-mentioned photopolymerizable monomer is 1-30 parts by mass, more preferably 15-25 parts by mass. The photopolymerizable monomer used in the above-mentioned photocurable resin composition is used to improve the photosensitivity, mechanical strength, crosslinkability, chemical resistance and other properties of the photocurable resin composition. As the polymerizable monomer, as long as the compound has one or more unsaturated bonds in the molecule, one or a combination of several of them can be selected as required. Illustrative examples of the photopolymerizable monomer selected in the present invention are propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. (Meth)acrylic acid adducts of epoxy compounds such as ether, sorbitol triglycidyl ether, glycerol triglycidyl ether; unsaturated organic acids such as maleic acid and their anhydrides; N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N -Methylolmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethyl Acrylamides such as acrylamide; polyethylene glycol di(meth)acrylate (the number of ethylene groups is 2-14); trimethylolpropane di(meth)acrylate, trimethylolpropane tri(methyl) ) Acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, four Hydroxymethylmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (propylene number is 2-14); dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , Bisphenol A polyoxyethylene di(meth)acrylate, bisphenol A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A oxyethylene di(meth)acrylate (Meth) acrylates, polycarboxylic acids (such as phthalic anhydride, etc.) and compounds with hydroxyl and ethylenically unsaturated groups (such as (meth) acrylate β-hydroxyethyl, etc.) Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.; ethylene glycol dishrink Glyceryl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, styrene, hydroxystyrene and other styrenes; N -Vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc.; each of the substances listed above can be used alone or in combination.
在一种实施例中,优选光聚合引发剂为1~5质量份,优选1~3质量份。上述光固化树脂组合物中的引发剂以溶解或分散于溶剂中的状态混合。用于本发明的引发剂没有特别限制,可选自二苯甲酮类引发剂、三嗪类引发剂、二烷氧基苯乙酮类引发剂、α-羟烷基苯酮类引发剂、α-胺烷基苯酮类引发剂、酰基膦氧化物引发剂、二苯甲酮类引发剂、苯偶姻类引发剂、苯偶酰类引发剂、杂环芳酮类引发剂、肟酯类光引发剂中的一种或多种的组合。特别优选肟酯类引发剂。示例性的列举如:二苯甲酮、4-苯基二苯甲酮、4-苯甲酰基-4'-甲基二苯基硫醚、二乙氧基苯乙酮、2,4-双(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-胡椒基-1,3,5-三嗪、苯偶姻、苯偶姻甲醚、苯偶姻异丁醚、2-乙基-9,10-二甲氧基蒽、9,10-二甲氧基蒽、10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、邻乙氧羰基-a-氧亚氨基-1-苯基丙-酮、1,2-辛二酮、1-(4-苯硫基)苯基-2(邻苯甲酰基肟)、1-(9-乙基)-6-(2-甲基苯甲酰基)咔唑-3基-1-(O-乙酰基肟)、OXE-01、NCI-831、2,4,5-三芳基咪唑二聚体、4,4'-双二乙基氨基二苯甲酮、4,4'-二氯苯甲酮、2-甲基噻吨酮、2-异丙基噻吨酮、二苯并环庚酮、三氯苯乙酮、戊 基-4-二甲基氨基苯甲酸酯、9-苯基吖啶、1,7-二(9-吖啶基)庚烷、1,3-二(9-吖啶基)丙烷、2-甲基-4,6-双(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,5-双(三氯甲基)-s-三嗪、2-[2-(4-二乙氨基-2甲基苯基)乙烯基]-4,6-双(三氯甲基)-s-三嗪、2,4-双(三氯甲基)-6-(2-溴-4-甲氧基)苯基-s-三嗪、2,4-双(三氯甲基)-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2,4-双(三氯甲基)-6-(2-溴-4-甲氧基)苯乙烯苯基-s-三嗪、4-苯甲酰基-4'-甲基二甲基硫醚、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸甲酯、苄基-β-甲氧基乙基缩醛、苄基二甲基缩酮、1-苯基-1,2-丙二酮-2(o-乙氧基羰基)肟等化合物中的一种或几种的混合。In an embodiment, the photopolymerization initiator is preferably 1 to 5 parts by mass, preferably 1 to 3 parts by mass. The initiator in the above-mentioned photocurable resin composition is mixed in a state of being dissolved or dispersed in a solvent. The initiator used in the present invention is not particularly limited, and can be selected from benzophenone-based initiators, triazine-based initiators, dialkoxyacetophenone-based initiators, α-hydroxyalkylphenone-based initiators, α-Amino alkyl phenone initiators, acyl phosphine oxide initiators, benzophenone initiators, benzoin initiators, benzyl initiators, heterocyclic aromatic ketone initiators, oxime esters One or more combinations of photoinitiators. Particularly preferred are oxime ester initiators. Exemplary examples are: benzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, diethoxyacetophenone, 2,4-bis (Trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5 -Triazine, benzoin, benzoin methyl ether, benzoin isobutyl ether, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 10-butyl -2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, o-ethoxycarbonyl-a-oxyimino-1-phenylpropanone, 1,2-octanedione, 1 -(4-phenylthio)phenyl-2 (o-benzoyl oxime), 1-(9-ethyl)-6-(2-methylbenzoyl)carbazol-3-yl-1-(O -Acetyl oxime), OXE-01, NCI-831, 2,4,5-triarylimidazole dimer, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzene Methyl ketone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, trichloroacetophenone, pentyl-4-dimethylaminobenzoate, 9-benzene Acridine, 1,7-bis(9-acridinyl)heptane, 1,3-bis(9-acridinyl)propane, 2-methyl-4,6-bis(trichloromethyl)- s-triazine, 2-[2-(furan-2-yl)vinyl]-4,5-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino- 2Methylphenyl)vinyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-(2-bromo-4-methoxy Yl)phenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4- Bis(trichloromethyl)-6-(2-bromo-4-methoxy)styrene phenyl-s-triazine, 4-benzoyl-4'-methyl dimethyl sulfide, 4- Ethyl dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedi One or a mixture of ketone-2 (o-ethoxycarbonyl) oxime and other compounds.
在将本发明的光固化树脂组合物用于滤光片制备等应用的情况下,需要用到分散用的溶剂。作为常用溶剂,可以选择(聚)烷撑二醇单烷基醚类,例如乙二醇单甲醚、乙二醇单乙醚、乙二醇正丙基醚、乙二醇单正丁基醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单正丁基醚、三乙二醇单甲醚、三乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单正丙醚、丙二醇单正丁基醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丁基醚、三丙二醇单甲醚、三丙二醇单乙醚等;芳香烃类,例如:甲苯、二甲苯、三甲苯等;酰胺类化合物,例如:N-甲基吡咯酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等;羧酸酯类化合物,例如:2-氧代丁酸乙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸丁酯、乙酸异丁酯、甲酸正戊酯、乙酸异戊酯、丙酸丁酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮正丙酯、2-羟基丙酸甲酯、2-羟基丙酸乙酯,2-羟基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羟基乙酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯等;同类溶剂,例如:甲乙酮、环己酮、庚酮、3-庚酮等;环醚类化合物,如四氢呋喃和吡喃等;环酯类化合物,如γ-丁内酯等。上述有机溶剂可以单独使用,也可以两种以上混合使用,其中丙二醇单甲醚,乙二醇单甲醚乙酸酯、丙二醇单甲醚乙酸酯,丙二醇单乙醚乙酸酯、二乙二醇单甲醚、二乙二醇甲乙醚等溶剂,对本发明中的感光性树脂组合物具有较好的溶解性;进一步的优选溶剂为丙二醇单甲醚乙酸酯、二乙二醇甲乙醚。优选溶剂的添加量使得光固化树脂组合物的固含量为10-50wt%,更优选为15~40wt%。When the photocurable resin composition of the present invention is used in applications such as filter preparation, a solvent for dispersion is required. As a common solvent, (poly)alkylene glycol monoalkyl ethers can be selected, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether Ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.; Aromatic hydrocarbons, such as: toluene, xylene, trimethylbenzene, etc.; amide compounds, such as: N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; carboxylate Acid ester compounds, such as: ethyl 2-oxobutyrate, methyl acetoacetate, ethyl acetoacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, formic acid N-pentyl ester, isoamyl acetate, butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl acetone , Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl- 3-Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.; similar solvents, such as: methyl ethyl ketone, cyclohexanone, heptanone, 3-heptanone, etc.; cyclic ether Compounds, such as tetrahydrofuran and pyran; cyclic ester compounds, such as γ-butyrolactone. The above organic solvents can be used alone or in a mixture of two or more, among which propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol Solvents such as monomethyl ether and diethylene glycol methyl ethyl ether have good solubility for the photosensitive resin composition of the present invention; further preferred solvents are propylene glycol monomethyl ether acetate and diethylene glycol methyl ethyl ether. Preferably, the amount of the solvent added is such that the solid content of the photocurable resin composition is 10-50% by weight, more preferably 15-40% by weight.
根据产品应用需要,上述光固化树脂组合物还可选择性地添加本领域中常用的着色剂,通过添加着色剂可以很好的形成滤色器。According to product application requirements, the above-mentioned photocurable resin composition can optionally be added with colorants commonly used in the art, and color filters can be well formed by adding colorants.
本领域中通常使用的任何有机颜料、无机颜料均可选择性使用作为本申请的着色剂。其中包括水溶性颜料、水不溶性偶氮颜料、酞菁颜料、吖啶酮颜料、异吲哚啉颜料、吲哚蒽酮颜料、阴丹酮颜料、吡咯二酮颜料等。上述各颜料可以单独使用也可以混合后使用,视产品的具体要求而定。Any organic pigments and inorganic pigments commonly used in the art can be selectively used as the colorant in this application. These include water-soluble pigments, water-insoluble azo pigments, phthalocyanine pigments, acridone pigments, isoindoline pigments, indolanthrone pigments, indanthrone pigments, diketopyrrole pigments, etc. The above-mentioned pigments can be used alone or mixed, depending on the specific requirements of the product.
进一步优选有机原料,具体颜料示例性的列举如下,但不限于以下颜料。具体列举色指数(染色工作者协会(The Society of Dyers and Colourists)(C.I.)序号的化合物如:Organic raw materials are more preferable, and specific pigments are exemplified as follows, but are not limited to the following pigments. Specific examples of compounds with color index (The Society of Dyers and Colourists) (C.I.) serial number are as follows:
C.I.颜料黑1和7等。C.I. Pigment Black 1 and 7 etc.
在将着色剂设为遮光剂的情况下,优选使用黑色颜料,作为黑色颜料,可以举出炭黑、钛黑、铜、铁、锰等的金属氧化物、复合氧化物、金属硫化物、金属硫酸盐、金属碳酸盐等。它们当中优选具有高遮光性的炭黑。着色剂的含量只要根据感光树脂组合物的用途适当的确定即可,优选30~60质量份,更优选40~50质量份。为了使着色剂均匀地分散在光固化树脂组合物中,还可以使用分散剂。作为此种分散剂,优选使用聚乙烯亚胺类、聚氨酯树脂类、丙烯酸树脂类高分子分散剂,特别油酸丙烯酸树脂类分散剂。When the colorant is used as a light-shielding agent, it is preferable to use a black pigment. Examples of the black pigment include metal oxides, composite oxides, metal sulfides, and metals such as carbon black, titanium black, copper, iron, and manganese. Sulfate, metal carbonate, etc. Among them, carbon black having high light-shielding properties is preferable. The content of the coloring agent may be appropriately determined according to the use of the photosensitive resin composition, and is preferably 30 to 60 parts by mass, and more preferably 40 to 50 parts by mass. In order to uniformly disperse the colorant in the photocurable resin composition, a dispersant may also be used. As such a dispersing agent, polyethyleneimine-based, polyurethane resin-based, acrylic resin-based polymer dispersing agents, particularly oleic acrylic resin-based dispersing agents are preferably used.
当光固化树脂组合物含有上述的光固化丙烯酸酯类树脂、碱溶性树脂、光聚合性单体、引发剂、着色剂和溶剂时,以光固化树脂组合物总体质量份数为100质量份计算:光固化丙烯酸酯类树脂和碱溶性树脂总质量份为10~50质量份,优选20~30质量份;着色剂为20~60质量份,优选30~40质量份;光聚合性单体为1~30质量份,优选15~25质量份;光聚合引发剂为1~5质量份,优选1~3质量份;溶剂为10~50质量份,优选15~40质量份。When the photocurable resin composition contains the above-mentioned photocurable acrylate resin, alkali-soluble resin, photopolymerizable monomer, initiator, colorant and solvent, the total mass of the photocurable resin composition is calculated as 100 parts by mass : The total mass parts of the photocurable acrylic resin and the alkali-soluble resin is 10-50 parts by mass, preferably 20-30 parts by mass; the colorant is 20-60 parts by mass, preferably 30-40 parts by mass; the photopolymerizable monomer is 1 to 30 parts by mass, preferably 15 to 25 parts by mass; photopolymerization initiator is 1 to 5 parts by mass, preferably 1 to 3 parts by mass; solvent is 10 to 50 parts by mass, preferably 15 to 40 parts by mass.
在本发明的另一种优选的实施例中,上述光固化树脂组合物可以含有添加剂,例如填料、固化剂、流平剂、粘合促进剂、抗氧剂、紫外线吸收剂等,但不仅限于此。In another preferred embodiment of the present invention, the above-mentioned photocurable resin composition may contain additives, such as fillers, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, etc., but are not limited to this.
其中,固化剂用于提高深度固化性能和机械强度。固化剂具体可选用环氧化合物、多官能异氰酸酯化合物、三聚氰胺类化合物和氧杂环丁烷化合物等,但不仅限于这些化合物。流平剂可使用市售的表面活性剂,具体可包括有机硅类表面活性剂、酯类表面活性剂、离子型表面活性剂、非离子型表面活性剂、两性表面活性剂等,这些表面活性剂可以单独使用,也可以两种以上组合使用。粘合促进剂可以使用硅烷类化合物,具体可以列举如:乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-氨基乙基)-30氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-巯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷等。上述粘合促进剂可以单独使用也可以两种以上组合使用。抗氧剂具体可以列举如:4,4'-亚丁基双(6-叔丁基-3-甲基苯酚)、2,6-二叔丁基-4-甲基苯酚、2,3'-硫代双(4-甲基-6-叔丁基苯酚),对甲.氧基苯酚等。紫外线吸收剂可以选用2-(3-叔丁基-2羟基-5-甲基苯基)-5-氯苯并三唑和烷氧基二苯甲酮等。Among them, the curing agent is used to improve the deep curing performance and mechanical strength. The curing agent can be specifically selected from epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds, but is not limited to these compounds. The leveling agent can use commercially available surfactants, which can specifically include silicone surfactants, ester surfactants, ionic surfactants, nonionic surfactants, amphoteric surfactants, etc., which are surface active. The agent can be used alone or in combination of two or more. The adhesion promoter can use silane compounds, and specific examples include: vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N-(2- Aminoethyl)-30 aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The above-mentioned adhesion promoters may be used alone or in combination of two or more kinds. Specific examples of antioxidants include: 4,4'-butylene bis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,3'- Thiobis(4-methyl-6-tert-butylphenol), p-methoxyphenol, etc. The ultraviolet absorber can be 2-(3-tert-butyl-2hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.
在本申请另一种典型的实施方式中,提供了一种黑色矩阵材料,包括光固化树脂组合物,该光固化树脂组合物为上述任一种的光固化树脂组合物。由于本申请的光固化树脂组合物具有附着力强、耐碱溶性和耐高温的性能,因此所形成的黑色矩阵的附着力具有上述优势。In another exemplary embodiment of the present application, a black matrix material is provided, including a photocurable resin composition, and the photocurable resin composition is any one of the above-mentioned photocurable resin compositions. Since the photocurable resin composition of the present application has strong adhesion, alkali solubility and high temperature resistance, the adhesion of the formed black matrix has the above advantages.
上述光固化树脂的合成路线为,通过含有环氧基、羟基等活性取代基团的硅烷偶联剂,在催化剂存在条件下,与含有羧基的丙烯酸共聚树脂反应,从而得到有机硅烷改性的丙烯酸树脂,即本申请的光固化树脂。以下举例说明光固化树脂的合成方法。The synthetic route of the above-mentioned photocurable resin is to obtain organosilane-modified acrylic by reacting with a carboxyl-containing acrylic copolymer resin through a silane coupling agent containing epoxy, hydroxyl and other active substituent groups in the presence of a catalyst Resin, that is, the light-curable resin of the present application. The synthesis method of the photocurable resin is illustrated below with an example.
合成实施例1Synthesis Example 1
在装有搅拌装置、冷凝管、恒压滴液漏斗、温度计和氮气入口的500ml四口烧瓶中,加入100g丙二醇甲醚醋酸酯(PGMEA),充入氮气,搅拌条件下加热至70℃,分别滴加单体混 合物(配方见表1)和引发剂(偶氮二异庚腈)溶液,滴加时间控制在2h,滴加完成后,在此温度下保温4h,测定体系Mw达到要求后,降温即得丙烯酸树脂。根据不同单体组合,分别制备出了的丙烯酸树脂1-5和对比树脂,具体配方见表1。In a 500ml four-necked flask equipped with a stirring device, a condenser, a constant pressure dropping funnel, a thermometer and a nitrogen inlet, add 100g of propylene glycol methyl ether acetate (PGMEA), fill with nitrogen, and heat to 70°C under stirring. Drop the monomer mixture (see Table 1 for the formula) and the initiator (azobis-isoheptanonitrile) solution, and control the dripping time at 2h. After the dripping is completed, keep it at this temperature for 4h. After the Mw of the measuring system reaches the requirement, Acrylic resin is obtained when the temperature is lowered. According to different monomer combinations, acrylic resins 1-5 and comparative resins were prepared respectively, and the specific formulas are shown in Table 1.
表1Table 1
合成实施例2Synthesis Example 2
将一定量上述丙烯酸树脂1加入500ml反应四口瓶中,加热至110℃,待体系温度稳定后,加入0.5%(相对于树脂质量)的四丁基溴化铵和硅烷偶联剂3-(2,3-环氧丙氧)丙基三乙氧基硅烷(含有环氧基团),110℃保温反应2h开始测试体系环氧当量,当环氧当量>25000g/mol时,停止反应,降温,出料封存,即得有机硅烷改性丙烯酸树脂1,即改性树脂1。Add a certain amount of the above acrylic resin 1 into a 500ml reaction four-neck flask, heat it to 110°C, after the system temperature stabilizes, add 0.5% (relative to the resin mass) of tetrabutylammonium bromide and silane coupling agent 3-( 2,3-Glyoxypropoxy)propyltriethoxysilane (containing epoxy group), the epoxy equivalent of the system is measured after the temperature is maintained at 110°C for 2h. When the epoxy equivalent is greater than 25000g/mol, the reaction is stopped and the temperature is lowered. , Discharge and seal to obtain organosilane modified acrylic resin 1, namely modified resin 1.
采用上述方法,利用硅烷偶联剂对上述丙烯酸树脂2至5进行改性,制备出硅烷改性的丙烯酸树脂2至15,具体的硅烷偶联剂和改性树脂见下表2~表4。Using the above method, the acrylic resins 2 to 5 are modified with a silane coupling agent to prepare silane-modified acrylic resins 2 to 15. The specific silane coupling agent and modified resin are shown in Tables 2 to 4 below.
合成对比例1(对比例树脂1)Synthetic comparative example 1 (comparative example resin 1)
将一定量上述对比树脂预聚物加入500ml反应四口瓶中,加热至110℃,待体系温度稳定后,加入0.5%(相对于树脂质量)的四丁基溴化铵和甲基丙烯酸缩水甘油醚(GMA),110℃保温反应2h开始测试体系环氧当量,当环氧当量>25000g/mol时,停止反应,降温,出料封存,即得对比例树脂1。Add a certain amount of the above-mentioned comparative resin prepolymer into a 500ml reaction four-neck flask, heat it to 110°C, after the system temperature stabilizes, add 0.5% (relative to the resin mass) of tetrabutylammonium bromide and glycidyl methacrylate Ether (GMA), heat preservation and reaction at 110°C for 2h, start to test the epoxy equivalent of the system. When the epoxy equivalent is greater than 25000g/mol, stop the reaction, cool down, discharge and seal, and then obtain the comparative resin 1.
表2Table 2
表3table 3
表4Table 4
光固化树脂组合物评价Evaluation of light-curable resin composition
1.简单测评用光固化树脂组合物配制1. Preparation of light-curable resin composition for simple evaluation
配制示例性光固化树脂组合物,对本发明实施例给出的有机硅烷改性树脂的应用性能进行评价。优选对上述实施例中制备的改性树脂进行测试比较。参照表5中实施例1-15和比较例1-2所示配方,将原料按照如下比例混合均匀,形成光固化树脂组合物。An exemplary photocurable resin composition was prepared, and the application performance of the organosilane modified resin given in the examples of the present invention was evaluated. Preferably, the modified resin prepared in the above-mentioned embodiments is tested and compared. With reference to the formulations shown in Examples 1-15 and Comparative Examples 1-2 in Table 5, the raw materials were uniformly mixed in the following proportions to form a photocurable resin composition.
其中,光固化树脂先与部分溶剂混合后,再与其他组分混合。Among them, the light-curing resin is mixed with part of the solvent first, and then mixed with other components.
表5table 5
注:此处选择的碱溶性树脂II结构式如下图所示:Note: The structural formula of alkali-soluble resin II selected here is shown in the figure below:
选取改性树脂1与碱溶性树脂II的比例不同比例,按照表5中的质量配比制备实施例16至20的光固化树脂组合物,对应的光聚合性单体、引发剂、着色剂和溶剂与实施例1相同,进行比较,具体实施例见表6。Different ratios of modified resin 1 and alkali-soluble resin II were selected, and the photocurable resin compositions of Examples 16 to 20 were prepared according to the mass ratio in Table 5, and the corresponding photopolymerizable monomers, initiators, colorants, and The solvent is the same as in Example 1, for comparison, and specific examples are shown in Table 6.
表6Table 6
2、光固化树脂组合物应用性能评价2. Application performance evaluation of light-curable resin composition
使用旋涂机,将实施例1~20、比较例1和2的光固化树脂组合物,涂布在玻璃基板(100mm×100mm)上,在90℃下进行90秒预烘烤,形成膜厚1.0μm的涂膜。然后,使用镜面投影对准曝光器,将曝光间隙设为50μm,使用具有20μm的线状图案的负像掩模曝光隔离曝 光。曝光强度设为20、40、60、120mJ/cm
2 4个等级。将曝光后的样品涂膜在26℃的0.04质量%KOH水溶液中分别显影40s、60s、80s,再进行230℃30分钟后烘烤,形成线状图案,测试其图案特性,成膜残留率,检测其耐碱溶解性,耐溶剂性等性能。
Using a spin coater, the photocurable resin compositions of Examples 1-20 and Comparative Examples 1 and 2 were coated on a glass substrate (100mm×100mm), and pre-baked at 90°C for 90 seconds to form a film thickness 1.0μm coating film. Then, a mirror projection was used to align the exposure device, the exposure gap was set to 50 μm, and a negative image mask having a linear pattern of 20 μm was used to expose and isolate the exposure. The exposure intensity was set to 4 levels of 20, 40, 60, and 120mJ/cm 2. The exposed sample film was developed in a 0.04% by mass KOH aqueous solution at 26°C for 40s, 60s, and 80s, and then baked at 230°C for 30 minutes to form a linear pattern. The pattern characteristics and the residual rate of film formation were tested. Test its alkali solubility, solvent resistance and other properties.
同样地,隔着形成有2、5、10、20μm的线状图案的负像掩模,以50μm的曝光间隙,对涂膜照射紫外线。曝光量设为20mJ/cm
2。将曝光后的涂膜在26℃的0.04质量%KOH水溶液中显影后,在230℃下进行30min后烘烤,从而形成线状图案。利用光学显微镜观察所形成的图案,评价图案直线性及附着性。具体评价情况见下表7。另外对含有不同比例的改性树脂1和碱溶性树脂II的光刻胶树脂组合物应用效果进行评价,具体评价情况见表8。
Similarly, the coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative image mask formed with linear patterns of 2, 5, 10, and 20 μm. The exposure amount is set to 20mJ/cm 2 . After the exposed coating film was developed in a 0.04% by mass KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a linear pattern. The formed pattern was observed with an optical microscope, and the linearity and adhesion of the pattern were evaluated. The specific evaluation situation is shown in Table 7 below. In addition, the application effect of the photoresist resin composition containing the modified resin 1 and the alkali-soluble resin II in different proportions was evaluated, and the specific evaluation conditions are shown in Table 8.
评价标准:evaluation standard:
图案直线性:Pattern linearity:
○:图案线的边缘无锯齿;○: There is no jagged edge on the pattern line;
△:图案线的边缘有锯齿。△: The edge of the pattern line is jagged.
图案与基板的附着性:Adhesion between pattern and substrate:
○未从基板中剥落,形成线状图案;○Not peeled off from the substrate, forming a linear pattern;
△虽然形成了线状图案,但产生了图案缺损;△ Although a linear pattern is formed, there is a pattern defect;
╳从基板中剥落,没有形成线状图案。╳ Peel off from the substrate without forming a linear pattern.
表7Table 7
表8Table 8
以上检测结果显示,实施例2、实施例5、实施例9、实施例10、实施例13、实施例14等,在40mJ/cm
2曝光量时,已表现出较好的直线性,60mJ/cm
2曝光量时实施例均表现出较好的直线性,而比较例的直线性不好,存在边缘锯齿。附着性测试显示,2μm的线状图案,实施例1~15均已表现出一定的附着性;5μm~10μm线宽的图案的附着力明显较好,而比较例在2μm的线状图案有剥离,10μm的线状图案也有明显缺陷。
The above test results show, Example 2, Example 5, Example 9, Example 10, Example 13, Example 14 and the like, at 40mJ / cm 2 exposure, have demonstrated good linearity, 60mJ / The examples all showed good linearity at cm 2 exposure, while the linearity of the comparative example was not good, and there were jagged edges. The adhesion test showed that the 2μm linear pattern, Examples 1-15 have shown certain adhesion; the 5μm-10μm line width pattern has obviously better adhesion, while the comparative example has peeling off in the 2μm linear pattern , 10μm linear pattern also has obvious defects.
实施例16~20直线性比较看,40mJ曝光能量条件小,实施例18直线性较好,而实施例16、实施例17、实施例19、实施例20直线性稍有不足;附着力比较看,5μm的线状图案,实施例17、实施例18和实施例19均表现出较好的附着力,而实施例16和实施例20的附着性明显偏低。因此,综合比较可以看出,实施例18中的两种树脂配比是相对较为合适的配比。其他实施例均采用此比例进行应用性能测试。In comparison of the linearity of Examples 16-20, the 40mJ exposure energy condition is small, and the linearity of Example 18 is better, while the linearity of Example 16, Example 17, Example 19, and Example 20 is slightly insufficient; , With a linear pattern of 5 μm, Example 17, Example 18, and Example 19 all showed good adhesion, while the adhesion of Example 16 and Example 20 was significantly lower. Therefore, it can be seen from a comprehensive comparison that the ratio of the two resins in Example 18 is a relatively suitable ratio. In other embodiments, this ratio is used for application performance testing.
耐热性和耐碱溶解性评价:Evaluation of heat resistance and alkali resistance:
隔着形成有2、5、10、20μm的线状图案的负像掩模,以50μm的曝光间隙,对涂膜照射紫外线。曝光量设为20mJ/cm
2。将曝光后的涂膜在26℃的0.04质量%KOH水溶液中显影后,在230℃下进行30min后烘烤,从而形成线状图案。利用光学显微镜观察所形成的图案,评价耐热性(图案边缘与基板的接触角度)以及耐碱溶解性,从残膜率测定结果进行判断。具体 评价情况见下表9。另外对含有不同比例的改性树脂1和碱溶性树脂II的上述光固化树脂组合物进行了比较,选择较好的树脂配比,具体比较结果见表10。
The coating film was irradiated with ultraviolet rays with an exposure gap of 50 μm through a negative image mask formed with linear patterns of 2, 5, 10, and 20 μm. The exposure amount is set to 20mJ/cm 2 . After the exposed coating film was developed in a 0.04% by mass KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a linear pattern. The formed pattern was observed with an optical microscope, the heat resistance (the contact angle between the pattern edge and the substrate) and the alkali solubility were evaluated, and the determination was made from the measurement result of the residual film rate. The specific evaluation situation is shown in Table 9 below. In addition, the above-mentioned photocurable resin compositions containing modified resin 1 and alkali-soluble resin II in different proportions were compared, and a better resin ratio was selected. The specific comparison results are shown in Table 10.
评价标准如下The evaluation criteria are as follows
耐碱溶解性Alkali resistance
○残膜率≥95%○Remaining film rate≥95%
△95%>残膜率≥90%△95%>The residual film rate≥90%
╳残膜率<90%╳Remaining film rate <90%
耐热性Heat resistance
○图案边缘与基板接触角>45°○The contact angle between the pattern edge and the substrate>45°
△图案边缘与基板接触角40°-45°△The contact angle between the pattern edge and the substrate is 40°-45°
╳图案边缘与基板接触角<40°╳The contact angle between the pattern edge and the substrate <40°
表9Table 9
表10Table 10
从上述测试结果看,实施例1-15对应的光固化树脂组合物,均具有较好的耐碱溶解性;230℃后烘烤后,所得图案边缘与基板的接触角均>45°,耐热性较好,而比较例的接触角均<40℃,耐热性相对较差。From the above test results, it can be seen that the photocurable resin compositions corresponding to Examples 1-15 all have good alkali resistance; after 230°C post-baking, the contact angles between the edges of the resulting patterns and the substrate are all >45°, The heat resistance is better, and the contact angles of the comparative examples are all <40°C, and the heat resistance is relatively poor.
另外,对含有不同比例的改性树脂1和碱溶性树脂II的上述光固化树脂组合物进行比较可以看出,实施例17、实施例18、实施例19等均具有较好的耐碱溶解性和耐热性,特别是实施例18其耐碱溶解性和耐热性非常优异,因此,实施例18对应的改性树脂和碱溶性树脂II的比例是相对较好的比例条件,其他比较例均参考此比例进行组合物的配制和应用测评。In addition, a comparison of the above-mentioned photocurable resin composition containing modified resin 1 and alkali-soluble resin II in different proportions shows that Example 17, Example 18, Example 19, etc. all have good alkali solubility resistance. And heat resistance, especially Example 18 has excellent alkali solubility and heat resistance. Therefore, the ratio of modified resin and alkali-soluble resin II corresponding to Example 18 is a relatively good ratio condition. Other comparative examples All refer to this ratio for the preparation and application evaluation of the composition.
综上所述,本发明所提供的含有有机硅烷改性的光固化树脂及其组合物应用性能优异,具有较好的耐热性,较好的直线性和附着力,具有广阔的应用前景。In summary, the organic silane-modified photocurable resin and its composition provided by the present invention have excellent application performance, better heat resistance, better linearity and adhesion, and have broad application prospects.
从以上的描述中,本发明上述的实施例实现了如下技术效果:From the above description, the above-mentioned embodiments of the present invention achieve the following technical effects:
本申请中,具有上述特定结构式I的感光性树脂与碱溶性树脂配合使用制备出的光固化树脂组合物,具有较好的显影直线性,对基板附着力好,后烘烤耐热性好,耐碱溶解性较好。In this application, the photocurable resin composition prepared by using the photosensitive resin with the above-mentioned specific structural formula I and the alkali-soluble resin in combination has good linearity in development, good adhesion to the substrate, and good post-baking heat resistance. Good alkali resistance and solubility.
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
- 一种光固化树脂,其特征在于,所述光固化树脂具有结构式I所示结构:A light-curing resin, characterized in that the light-curing resin has a structure represented by structural formula I:其中,R 1表示C 6~C 20的环烷基、C 6~C 20的芳基中的任意一种; Wherein, R 1 represents any one of a C 6 ~C 20 cycloalkyl group or a C 6 ~C 20 aryl group;R 2、R 3、R 4、R 5相同或不同,且R 2、R 3、R 4、R 5各自独立的表示H、C 1~C 10的烷基、C 3~C 20的环烷基、C 6~C 20的芳基中的任意一种; R 2 , R 3 , R 4 , and R 5 are the same or different, and R 2 , R 3 , R 4 , and R 5 each independently represent H, C 1 ~C 10 alkyl, C 3 ~C 20 cycloalkane Any one of aryl groups, C 6 ~C 20 aryl groups;R 6具有-R 7-Si-(R 8)n 1(OR 9)n 2所示结构,R 7表示C 1~C 10的亚烷基、C 1~C 15的亚烷基烷氧基中的任意一种,各R 8各自独立地表示C 1~C 10的烷基、C 1~C 15的烷氧基中的任意一种,各R 9各自独立地表示氢、C 1~C 10的烷基中的任意一种,在R 8或R 9为多个的情况下,各R 8相同或不同,各R 9相同或不同,n 1和n 2为正整数且n 1+n 2=3; R 6 has a structure represented by -R 7 -Si-(R 8 )n 1 (OR 9 )n 2 , R 7 represents a C 1 ~C 10 alkylene group, a C 1 ~C 15 alkylene alkoxy group Each R 8 independently represents any one of a C 1 to C 10 alkyl group or a C 1 to C 15 alkoxy group, and each R 9 independently represents hydrogen, C 1 to C Any one of the alkyl groups of 10 , when R 8 or R 9 is more than one, each R 8 is the same or different, each R 9 is the same or different, n 1 and n 2 are positive integers and n 1 +n 2 = 3;x,y,z,n各自独立的表示整数,且x和n不为0。x, y, z, n each independently represent an integer, and x and n are not zero.
- 根据权利要求1所述的光固化树脂,其特征在于,所述R 1表示C 6~C 12的环烷基、C 6~C 12芳香基中的任意一种。 The photocurable resin according to claim 1, wherein the R 1 represents any one of a C 6 to C 12 cycloalkyl group and a C 6 to C 12 aromatic group.
- 根据权利要求1所述的光固化树脂,其特征在于,所述R 2、所述R 3、所述R 4、所述R 5相同,优选所述R 2、所述R 3、所述R 4、所述R 5为H、甲基、异丙基、环己基、苯基和苄基的任意一种。 The photocurable resin according to claim 1, wherein said R 2 , said R 3 , said R 4 , and said R 5 are the same, preferably said R 2 , said R 3 , and said R 4. The R 5 is any one of H, methyl, isopropyl, cyclohexyl, phenyl and benzyl.
- 根据权利要求1所述的光固化树脂,其特征在于,所述R 6中,所述R 7表示C 1~C 5的亚烷基、C 1~C 10的亚烷基烷氧基的任意一种,优选为C 1~C 5的烷基、C 3~C 5的亚烷基烷氧基中的任意一种;n 1为2,n 2为1,各所述R 8均表示C 1~C 5的烷基,C 1~C 10烷氧基中的任意一种,所述R 9表示C 1~C 5的烷基、C 1~C 10的烷氧基中的任意一种,优选为C 1~C 5的烷基、C 1~C 5烷氧基中的任意一种。 The photo-curable resin according to claim 1, wherein said R 6, said R 7 represents an optionally C 1 ~ C 5 alkylene group is, alkylene alkoxy C 1 ~ C 10 of One, preferably any one of a C 1 ~C 5 alkyl group and a C 3 ~C 5 alkylene alkoxy group; n 1 is 2, n 2 is 1, each of the R 8 represents C 1 to C 5 alkyl group, any one of C 1 to C 10 alkoxy group, said R 9 represents any one of C 1 to C 5 alkyl group or C 1 to C 10 alkoxy group , preferably C 1 ~ C 5 alkyl group, and any one of C 1 ~ C 5 alkoxy.
- 根据权利要求1所述的光固化树脂,其特征在于,所述光固化树脂的重均分子量为5000~15000,更优选为6000~10000。The photocurable resin according to claim 1, wherein the weight average molecular weight of the photocurable resin is 5,000 to 15,000, more preferably 6,000 to 10,000.
- 一种光固化树脂组合物,包括光固化丙烯酸酯类树脂、碱溶性树脂、光聚合性单体和引发剂,其特征在于,所述光固化丙烯酸酯类树脂为权利要求1至5中任一项所述的光固化树脂。A photocurable resin composition, comprising a photocurable acrylate resin, an alkali-soluble resin, a photopolymerizable monomer and an initiator, characterized in that the photocurable acrylate resin is any one of claims 1 to 5 The light-curable resin described in the item.
- 根据权利要求7所述的光固化树脂组合物,其特征在于,所述A选自如下基团中的任意一种: *表示酸酐可能的连接位置; 8. The photocurable resin composition according to claim 7, wherein the A is selected from any one of the following groups: * Indicates the possible connection position of acid anhydride;
- 根据权利要求6所述的光固化树脂组合物,其特征在于,所述光固化丙烯酸酯类树脂和所述碱溶性树脂的总质量份为10~50质量份,优选所述光固化丙烯酸酯类树脂和所述碱溶性树脂的总质量份为20~30质量份且所述光固化丙烯酸酯类树脂和所述碱溶性树脂质量比为7:10~8:10;所述光聚合性单体为1~30质量份,更优选15~25质量份;所述光聚合引发剂为1~5质量份,更优选1~3质量份。The photocurable resin composition according to claim 6, wherein the total mass parts of the photocurable acrylate resin and the alkali-soluble resin is 10-50 parts by mass, preferably the photocurable acrylate resin The total mass parts of the resin and the alkali-soluble resin is 20-30 parts by mass, and the mass ratio of the photocurable acrylate resin and the alkali-soluble resin is 7:10-8:10; the photopolymerizable monomer It is 1 to 30 parts by mass, more preferably 15 to 25 parts by mass; the photopolymerization initiator is 1 to 5 parts by mass, more preferably 1 to 3 parts by mass.
- 根据权利要求9所述的光固化树脂组合物,其特征在于,所述光固化树脂组合物还包括着色剂,所述着色剂为30~60质量份,优选40~50质量份。The photocurable resin composition according to claim 9, wherein the photocurable resin composition further comprises a colorant, and the colorant is 30-60 parts by mass, preferably 40-50 parts by mass.
- 一种黑色矩阵材料,包括光固化树脂组合物,其特征在于,所述光固化树脂组合物为权利要求6至10中任一项所述的光固化树脂组合物。A black matrix material, comprising a photocurable resin composition, characterized in that the photocurable resin composition is the photocurable resin composition according to any one of claims 6 to 10.
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