CN101349867B - Organic-inorganic compound sensitization resin composition and LCD element using sclerotium thereof - Google Patents
Organic-inorganic compound sensitization resin composition and LCD element using sclerotium thereof Download PDFInfo
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- CN101349867B CN101349867B CN2008101429199A CN200810142919A CN101349867B CN 101349867 B CN101349867 B CN 101349867B CN 2008101429199 A CN2008101429199 A CN 2008101429199A CN 200810142919 A CN200810142919 A CN 200810142919A CN 101349867 B CN101349867 B CN 101349867B
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- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Abstract
The invention relates to an organic-inorganic composite photosensitive resin combination and a liquid crystal display component comprising the hardened combination. The photosensitive resin combination comprises: a) colloidal state inorganic sol; b) acrylic copolymer; c) photoinitiator; d) polyfunctional monomer; e) silicon compound; and f) solvent. The organic-inorganic composite photosensitive resin combination achieves excellent low dielectric property, cohesive force, heat endurance, insulatibity, evenness and chemical resistance, is suitable imaging material for liquid crystal display component; the advantages of excellent dielectric constant, evenness, sensitivity, defective film rate and UV transmissivity of the composition play good roles while producing liquid crystal display components, so besides as a passivation organic insulation film in low dielectricity, the compositon also can be used as photoresistive resin in protective layer, a black matrix,, column divider or color filter. The composition also achieves the advantages of low dielectric property, high heat endurance and improved cohesive force.
Description
Technical field
The present invention relates to a kind of passivation (passivation) with the compound photosensitive resin composition of organic and inorganic and use the liquid crystal display cells of its hardenite.Relate in particular to a kind of photosensitive resin composition that has performances such as good low-dielectric, cohesive force, thermotolerance, insulativity, flatness and chemical resistance and be suitable as the image forming material of liquid crystal display cells; When making the organic insulating film of liquid crystal display cells; This photosensitive resin composition can have been given play to good low-k, moisture-proof, cohesive force and thermotolerance; Therefore not only be suitable as organic insulating film and use, can also be used for simultaneously protective layer used photoresistance resin, black matrix with photoresistance resin, column spacer with photoresistance resin or color filter with the photoresistance resin and strengthen thermotolerance and performance such as cohesive force.
Background technology
In general, to use maximum with organic insulator be SiO to element
2Because its insulation rate is high, can be formed at easily widely on the Si as baseplate material.Yet because it is a non-crystalline structure, specific inductive capacity is up to about 3.9, so its performance is not enough to become best low-k organic insulator.
Passivation needs lower specific inductive capacity with organic insulator, so can under thin thickness, reduce electric charge and move with reinforced insulation property, improves ON/OFF ratio (on-offratio), thereby promote the drive characteristic of TFT.
Currently be about 280 ℃ as passivation with the thermotolerance of the acrylic acid series organic insulating film of organic insulating film, this temperature is on the low side a bit, need possess the thermotolerance that can bear high temperature more than 300 ℃ for reliability, existing SiO
2Have with the acrylic acid series insulator that cost height, specific inductive capacity are high, thermotolerance is not enough, moisture-proof is low, a little less than the cohesive force and low and so on the problems of thermotolerance.
Summary of the invention
In order to solve the problems referred to above of prior art; The purpose of this invention is to provide a kind of compound photosensitive resin composition of organic and inorganic that has performance such as good low-dielectric, cohesive force, thermotolerance, insulativity, flatness and chemical resistance and be suitable as the image forming material of liquid crystal display cells, and use the liquid crystal display cells of its hardenite; During with organic and inorganic compound inslation film, this photosensitive resin composition can have been given play to good low-dielectric, moisture-proof, cohesive force and thermotolerance in the passivation of making liquid crystal display cells, so is applicable to that passivation uses dielectric film.
In order to solve above-mentioned problem, the compound photosensitive resin composition of organic and inorganic of the present invention comprises: a) colloidal state inorganics colloidal sol; B) acrylic acid series copolymer, this acrylic acid series copolymer is by i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri carry out copolyreaction with ii) more than one acrylic acid series unsaturated compound and form; C) light trigger; D) polyfunctional monomer, it is unsaturated link that this polyfunctional monomer has ethene; E) silicon based compound, this silicon based compound contains epoxy radicals or amido; And f) solvent.The present invention also provides the liquid crystal display cells of the hardenite that uses the compound photosensitive resin composition of above-mentioned organic and inorganic.
Above-mentioned a) colloidal state inorganics colloidal sol is through on colloid nano particle inorganics, adding the organosilane of 1-120 weight portion; Make organosilane and nano particle inorganics surface react and dewater, add organic solvent then and the reaction medium hydrophobization is made.Above-mentioned colloid nano particle inorganics is formed by hydrosol inorganics, said hydrosol inorganics be selected from by silicon dioxide, aluminium oxide, titania, zirconia, tin oxide, zinc paste, the inorganics that can react with organosilane, or the group formed of the above-mentioned inorganics that uses silicon dioxide to carry out surface modification at least a.
At this moment, on above-mentioned hydrosol inorganics, add above-mentioned organosilane, dewater and add the process of organic solvent and can once accomplish, also can carry out repeatedly by certain interval of time.
Preferably, above-mentioned organosilane has general formula R
1 0-3Si (OR
2)
1-4, wherein, R
1Be selected from least a in alkyl, phenyl, fluorine carbon alkyl, acryl, metering system aldehyde radical, propenyl, vinyl, the epoxy radicals, R
2Be selected from least a in methyl (methyl), ethyl (ethyl), isopropyl (iso-propyl), n-pro-pyl (n-propyl) or the normal-butyl (n-butyl), OR
2Be alkoxy, acetoxy group or oximido, colloidal state inorganics colloidal sol is 1 to 95 weight portion.
Also comprise; B) 100 parts by weight of acrylic based copolymers are by the i of 5 to 40 weight portions) ii) more than one the acrylic acid series unsaturated compound of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri and 5 to 95 weight portions carries out copolyreaction and forms; C) light trigger of 0.001 to 30 weight portion; D) polyfunctional monomer of 10 to 100 weight portions, this polyfunctional monomer has ethene property unsaturated link; E) the silicon based compound of 0.0001 to 5 weight portion, this silicon based compound comprises epoxy radicals or amido; And f) it is 10 to 50 weight % that solvent, the amount of solvent make the solid content in the photosensitive resin composition.
Preferably, being shaped as spherical and having the particle diameter of 1-100nm of above-mentioned colloidal state inorganics nano particle a) is perhaps for fibrous and have the particle diameter of 100-1000nm.The organosilane that the surface use of colloidal state inorganics nano particle contains reactive base carries out surface treatment, and the inorganics nano particle is stably evenly disperseed and the enhancing storage characteristics in organic solvent, can carry out chemical bond at molecular state and organic system resin.
Above-mentioned b) acrylic acid series copolymer is through i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri and ii) the acrylic acid series unsaturated compound under the condition that possesses solvent and polymerization initiator, carry out free radical reaction as monomer and process.
Above-mentioned b among the present invention) i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri can be selected from by unsaturated monocarboxylic, like acrylic acid and methacrylic acid etc.; Unsaturated dicarboxylic is like maleic acid, fumaric acid (fumaric acid), citraconic acid, first health acid (methaconic acid) and itaconic acid etc.; Or one or more potpourri in the group formed such as the acid anhydrides of unsaturated dicarboxylic, preferably, can obtain copolymerization property when using acrylic acid, methacrylic acid or maleic anhydride and for the dissolubility of alkaline aqueous solution developer solution.
Above-mentioned unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri should occupy 5 to 40 weight portions in whole monomer, 10 to 40 weight portions are then better.When being lower than 5 weight portions, its content will be not easy to be dissolved in alkaline aqueous solution, and then too high when its content is higher than 40 weight portions to the dissolubility of alkaline aqueous solution.
Above-mentioned b among the present invention) ii) the acrylic acid series unsaturated compound uses unsaturated compound and the ethylene series unsaturated compound that contains epoxy radicals.
The unsaturated compound that contains epoxy radicals can use glycidyl acrylate, GMA, α-Yi Jibingxisuan ethylene oxidic ester, α-n-propyl group glycidyl acrylate, α-n-butylacrylic acid ethylene oxidic ester, senecioate-methyl ethylene oxidic ester, methacrylic acid-Beta-methyl ethylene oxidic ester, senecioate-ethyl ethylene oxidic ester, methacrylic acid-β-ethyl ethylene oxidic ester, acrylic acid-3; 4-epoxy butyl ester, methacrylic acid-3; 4-epoxy butyl ester, acrylic acid-6; 7-epoxy heptyl ester, methacrylic acid-6; 7-epoxy heptyl ester, α-Yi Jibingxisuan-6; 7-epoxy heptyl ester, o-vinyl benzyl glycidol ether (o-vinylbenzyl glycidyl ether), m-vinyl benzyl glycidol ether or p-vinyl benzyl glycidol ether etc.; Can use above-claimed cpd separately, also can select two or more mixing to use.
The above-mentioned unsaturated compound that contains epoxy radicals uses GMA, methacrylic acid-Beta-methyl ethylene oxidic ester, methacrylic acid-6; When 7-epoxy heptyl, o-vinyl benzyl glycidol ether, m-vinyl benzyl glycidol ether or p-vinyl benzyl glycidol ether, help the thermotolerance that obtains copolymerization property and can improve figure.
Preferably, the above-mentioned unsaturated compound that contains epoxy radicals occupies 10 to 70 weight portions in whole monomer, and 20 to 60 weight portions are then better.Can reduce the thermotolerance of figure when its content is lower than 10 weight portions, then reduce the storage stability of multipolymer when its content is higher than 70 weight portions.
Above-mentioned ethylene series unsaturated compound can use the secondary butyl ester of methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, methacrylic acid, metering system tert-butyl acrylate, methyl acrylate, isopropyl acrylate (Isopropyl acrylate), cyclohexyl methacrylate, methacrylic acid 2-methylcyclohexyl ester, acrylic acid double cyclopentenyl ester, acrylic acid dicyclo amyl group ester (dicyclopentanyl acrylate), methacrylic acid double cyclopentenyl ester, methacrylic acid dicyclo amyl group ester, 1-adamantyl acrylic ester, 1-adamantyl methacrylate, methacrylic acid dicyclo amyl group oxygen ethyl ester (dicyclopentanyloxyethyl methacrylate), isobornyl methacrylate, cyclohexyl acrylate, 2-cyclohexyl methacrylate, acrylic acid dicyclo amyl group oxygen ethyl ester (dicyclopentanyloxyethylacrylate), IBOA, phenyl methacrylate, propenyl benzene acid benzyl ester, benzyl acrylate, 2-hydroxyethyl methacry-late, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, to methoxy styrene, 1; 3-butadiene, isoprene or 2; 3-dimethyl-1; The 3-butadiene; Can use above-claimed cpd separately, also can select two or more mixing to use.
Above-mentioned ethylene series unsaturated compound uses styrene, methacrylic acid dicyclo amyl group ester or during to methoxy styrene, helps obtaining copolymerization property and for the dissolubility of alkaline aqueous solution developer solution.
Above-mentioned ethylene series unsaturated compound should occupy 10 to 70 weight portions to whole monomer, and 20 to 50 weight portions are then better.Its content can improve the storage stability of acrylic acid series copolymer in above-mentioned scope the time, can also solve acrylic acid series copolymer is gone into alkaline aqueous solution developer solution etc. than indissoluble problems simultaneously.
Solvent when becoming acrylic acid series copolymer to above-mentioned monomer polymerization can use methyl alcohol; Tetrahydrofuran; Glycol monomethyl ether; Ethylene glycol monoethyl ether; The acetate EGME; Ethylene glycol ether; Methyl carbitol; Diethylene glycol one ether; Glycol dimethyl ether; Ethylene glycol diethyl ether; The Ethylene Glycol Methyl ether; Propylene glycol monomethyl ether; Dihydroxypropane single-ether; Propylene glycol propyl ether; The propylene glycol butyl ether; Propylene glycol methyl ether acetate; The propylene-glycol ethyl ether acetic acid esters; The propylene glycol propyl ether acetic acid esters; Propylene glycol butyl ether acetic acid esters; The methyl proxitol propionic ester; Propylene glycol ethylether propionic ester; Propylene glycol propyl ether propionic ester; Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol butyl ether propionic ester; The ethers of toluene, xylene, MEK, cyclohexanone, 4-hydroxyl 4-methyl 2 pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl glycollate, ethyl glycollate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-2-methyl methyl butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate or 3 butoxy butyl propionates and so on etc.; Can use above-claimed cpd separately, also can select two or more mixing to use.
Polymerization initiator when becoming acrylic acid series copolymer to above-mentioned monomer polymerization (polymerizationinitiator) can use radical polymerization initiator, specifically, can use 2; 2-azoisobutyronitrile, 2,2-azo two (2, the 4-methyl pentane nitrile), 2; 2-azo two (4-methoxyl 2; The 4-methyl pentane nitrile), 1,1-azo two (cyclohexane-1-nitrile) or dimethyl 2,2-azo-bis-iso-butyl etc.
Above-mentioned c among the present invention) light trigger can use the compound of Irgacure 369, Irgacur 65 1, Irgacure907, Darocur TPO, Irgacure 819, triazine system, styrax, acetophenone system, imidazoles system or xanthone system and so on.
Specifically, above-mentioned light trigger can use 2,4-two (trichloromethyl)-6-p-methoxyl-styrene-s-triazine, 2-p-methoxyl-styrene-4; 6-two (trichloromethyl)-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methyl naphthyl-6-triazine, Benzophenone, p-(lignocaine) Benzophenone, 2; 2-two chloro-4-metaphenoxy acetophenones, 2,2-diethoxy acetophenone, 2-dodecyl thioxanthones, 2,4-dimethyl thioxanthones, 2; 4-diethyl thioxanthone or 2,2-two-2-chlorphenyl-4,5; 4,5-tetraphenyl-2-1, compounds such as 2-diimidazole; Can use above-claimed cpd separately, also can select two or more mixing to use.
Preferably, with respect to 100 parts by weight of acrylic based copolymers, the content of above-mentioned light trigger is 0.001 to 30 weight portion, and 0.01 to 20 weight portion is then better.To make a very bad impression to residual film ratio because of muting sensitivity when its content is lower than 0.001 weight portion, and then influence storage stability when its content is higher than 30 weight portions, higher hardenability also can reduce the cohesive force of figure when developing.
Above-mentioned d among the present invention) the polyfunctional monomer with ethene property unsaturated link normally possesses the interlinkage monomer of the two keys of plural ethene system at least; Can use 1; 4-butanediol diacrylate, 1,3 butyleneglycol diacrylate, glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, triethylene glycol diacrylate, polyethyleneglycol diacrylate, double pentaerythritol methacrylate, bipentaerythrite triacrylate, bipentaerythrite diacrylate, sorbierite triacrylate (Sorbitol triacrylate), bisphenol a diacrylate derivant, bipentaerythrite polyacrylate or its methyl acrylic ester etc.
Preferably, with respect to 100 parts by weight of acrylic based copolymers, above-mentioned content with polyfunctional monomer of ethene property unsaturated link is 10 to 100 weight portions, and 10 to 60 weight portions are then better.When its content is lower than 10 weight portions, owing to the low hardenability with photosensitive resin is difficult to form contact hole and figure; When its content is higher than 100 weight portions, when developing, reduce the resolution of contact hole and figure because hardenability is too high.
Above-mentioned e) the silicon based compound that contains epoxy radicals or amido can use (3-diglycidyl propoxyl group) trimethoxy silane, (3-diglycidyl propoxyl group) triethoxysilane, (3-diglycidyl propoxyl group) methyl dimethoxysilane, (3-diglycidyl propoxyl group) dimethylethoxysilane, 3; 4-epoxy butyl trimethoxy silane, 3; 4-epoxy butyl triethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane or aminopropyl trimethoxysilane etc. can be used above-mentioned substance separately, also can select two or more mixing to use.
Preferably, with respect to 100 parts by weight of acrylic based copolymers, the above-mentioned content that contains the silicon based compound of epoxy radicals or amido is 0.0001 to 5 weight portion, and 0.005 to 2 weight portion is then better.To reducing the cohesive force between ITO electrode and the photosensitive resin, and heat-resistant quality also can weaken after sclerosis when its content was lower than 0.0001 weight portion; When its content is higher than 5 weight portions, the albinism of non-exposure portion will be occurred in developer solution inside, the transparent residual film (scum) of contact hole or figure will be occurred after the development.
Above-mentioned f among the present invention) solvent will can not cause the flatness and coating spot of dielectric film, thereby generate uniform graph outline (pattern profile).
Above-mentioned solvent can use ethanol classes such as methyl alcohol, ethanol; Ethers such as tetrahydrofuran; Gylcol ether such as glycol monomethyl ether, ethylene glycol monoethyl ether; Monoethylene glycol alkyl ether acetate esters such as acetate EGME, ethylene glycol ether; Diethylene glycol classes such as methyl carbitol, diethylene glycol one ether, diethylene glycol dimethyl ether; Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Propylene glycol alkyl ether acetic acid ester classes such as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester; Toluene, xylene etc. are aromatic hydrocarbon based; Ketones such as MEK, cyclohexanone, 4-hydroxyl 4-methyl 2 pentanone; Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl glycollate, ethyl glycollate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-2-methyl methyl butyrate, ester classes such as methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3 butoxy butyl propionates.
Preferably, above-mentioned solvent can be selected from have fine solubility, and each composition between the group formed of gylcol ether, vinyl alkyl ethers acetate esters and diethylene glycol the class reactive and generative capacity of filming in more than one.
Preferably; It is 10 to 50 weight % that above-mentioned solvent can make the solid content of associative perception photopolymer resin composition; Solid content should use the millipore filters (Milipore filter) of 0.1-0.2 μ m etc. to filter the back and use between the composition of above-mentioned scope, if make solid content between 15 to 40 weight % then better.Applied thickness was thin and make a very bad impression to applying flat board property when the solid content of above-mentioned entire combination thing was lower than 10 weight %, and applied thickness was thicker and in coating process, easily coating device is caused overload when its content was higher than 50 weight %.
Photosensitive resin composition of the present invention can add the adjuvant that thermal polymerization inhibitor and foam-breaking agent etc. possess compatibility as required in above-mentioned composition, also can add pigment according to purposes.For example; Black matrix as one of image forming material of TFT type liquid crystal display cells has added pigment with photoresistance and color filter with photoresistance in above-mentioned composition; The pigment of this moment can suitably be selected with the purposes of photoresistance with photoresistance and color filter according to black matrix, can use inorganic or organic pigment.
The present invention can also provide a kind of TFT type liquid crystal display cells that uses the hardenite of the compound photosensitive resin composition of above-mentioned organic and inorganic.
The figure method of formation of above-mentioned TFT type liquid crystal display cells is characterised in that; Use passivation with organic-inorganic photosensitive resin composition process organic insulating film, protective layer used photoresistance, black matrix with photoresistance, column spacer with photoresistance or color filter with photoresistance after during making TFT type liquid crystal display cells, use the compound photosensitive resin composition of above-mentioned organic and inorganic.
Illustrate the method for using the compound photosensitive resin composition of above-mentioned organic and inorganic to make the figure of TFT type liquid crystal display cells below.
At first, utilize technologies such as spraying process, roller coat (Roll coater) method or whirl coating to be coated in substrate surface to photosensitive resin composition of the present invention, remove solvent and form coated film through prebake (pre bake) operation.At this moment, above-mentioned prebake operation should be carried out in 70-110 ℃ temperature range 1-15 minute.
Then; Figure according to prior setting shines visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc. on the made above-mentioned coated film; And then use developer solution to carry out development treatment and remove unwanted part, can accomplish the setting figure.
Above-mentioned developer solution should use alkaline aqueous solution, more particularly, can use inorganic bases such as NaOH, potassium hydroxide and sodium carbonate; Primary amine classes such as n-propylamine; Secondary amine such as diethylamine, n-propylamine class; Tertiary amines such as trimethylamine, methyldiethanolamine, dimethylethanolamine, triethylamine; Alcaminess such as dimethyl ethanolamine, methyldiethanolamine, triethanolamine; Or the WS of quarternary ammonium salts such as TMAH, tetraethyl ammonium hydroxide etc.At this moment, above-mentioned developer solution uses after should being dissolved into the concentration of 0.1-10 weight % to alkali compounds, also can suitably add the water-miscible organic solvent and the surfactant of methyl alcohol and ethanol and so on.
After using above-mentioned developer solution to carry out development treatment; Utilize ultrapure water to clean 30-90 again and remove nonuseable part second; Dry the back and form figure; Light such as irradiation ultraviolet radiation on formed above-mentioned figure can form final graphics with 150-250 ℃ temperature to the heat treated that figure carried out 30-90 minute at the heating arrangement of baking oven and so on then.
The invention described above organic and inorganic compound inslation film has performances such as good low-dielectric, moisture-proof, cohesive force, thermotolerance, insulativity, flatness and chemical resistance, is suitable as the image forming material of liquid crystal display cells; Performances such as good low-dielectric, moisture-proof, cohesive force and thermotolerance can have been given play in the passivation of making liquid crystal display cells during with organic and inorganic compound inslation film; Therefore be applicable to that passivation use dielectric film, can also be used for protective layer used photoresistance resin, deceive matrix with photoresistance resin, column spacer with photoresistance resin or color filter with the photoresistance resin to improve performances such as thermotolerance and intensity.
The compound photosensitive resin composition of organic and inorganic of the present invention has good performances such as low dielectric property, thermotolerance, insulativity, flatness, chemical resistance and high rigidity, is suitable as the image forming material of liquid crystal display cells.When making the passivation dielectric film of liquid crystal display cells; Owing to possessed performances such as good hardness, thermotolerance, insulativity and flatness; Therefore can be used as the passivation dielectric film and use, can also be used for protective layer used photoresistance resin, black matrix with photoresistance resin, column spacer with photoresistance resin or color filter with the photoresistance resin to improve performances such as thermotolerance and hardness.
Embodiment
Below in conjunction with preferred embodiment the present invention is further specified, but following embodiment is merely the present invention for example, scope of the present invention does not receive the restriction of following embodiment.
First embodiment (preparation of inorganics colloidal sol)
Be adjusted to the acidity between pH3～5 to the colloidal state inorganics; Add 1～120 weight portion again by the organosilane of ethanol dilution; Be MTMS (MTMS) or vinyltrimethoxy silane (VTMS); Make organosilane and inorganics nanoparticle surface react and dewater, add organic solvent and make the reaction medium hydrophobization.
When react on the surface of the trimethoxy of MTMS and colloidal state inorganic particles, along with methyl is exposed to the surface and makes above-mentioned colloidal state inorganics become the form that can be distributed to the organic system resin, thus the hydrophobization degree that can regulate the inorganics surface.The OH base at the colloidal state inorganics interface of 3 trimethoxies of VTMS and above-mentioned hydrophobization carries out condensation reaction and vinyl is exposed, and the above-mentioned colloidal state inorganic particles of hydrophobization can form the colloidal state inorganics colloidal sol with vinyl or other reactive group.
Second embodiment (preparation of acrylic acid series copolymer)
In flask, add 2 of 10 weight portions with cooling tube and stirrer; The styrene of the GMA of the propylene glycol methyl ether acetate of 2 '-azo two (2, the 4-methyl pentane nitrile), 200 weight portions, the methacrylic acid of 20 weight portions, 35 weight portions, the methyl methacrylate of 15 weight portions and 30 weight portions also carries out stirring at leisure after the nitrogen displacement.Be heated to above-mentioned reaction solution and kept this temperature after 62 ℃ 5 hours and processed the polymer solution that comprises acrylic acid series copolymer.
Aforesaid propylene acid based copolymer is poured in the hexane of 5,000 weight portions and separates out the back isolated by filtration, add the propionic ester of 200 weight portions then and be heated to 30 ℃, solid concentration is 45 weight %, and the weight-average molecular weight of polymkeric substance is 11,000.At this moment, weight-average molecular weight is to use the conversion mean molecular weight of the polystyrene of GPC mensuration.
The 3rd embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The light trigger Irgacure 819 that comprises the polymer solution of aforesaid propylene acid based copolymer at 100 interior weight portions, 15 weight portions, as 40 weight portion double pentaerythritol methacrylates and 10 weight portion trimethylolpropane triacrylates, silicon based compound 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane of 1 weight portion and the silicon of 2 weight portions of polyfunctional monomer is that surfactant F171 mixes.Dissolving makes solid concentration become 35 weight % after said mixture adds diethylene glycol dimethyl ether.
Is the mixed weight ratio of the made inorganics colloidal sol of the aforesaid propylene processed acid based copolymer and first embodiment 95: 5.
Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, the viscosity of this moment is 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
The 4th embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The preparation method of acrylic acid series copolymer is identical with second embodiment, and the preparation method of inorganic sol is then identical with first embodiment.Acrylic acid series copolymer is 80: 20 with the mixed weight ratio of inorganic sol in the compound photosensitive resin composition of made organic and inorganic.Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, this moment, viscosity was 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
The 5th embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The preparation method of acrylic acid series copolymer is identical with second embodiment, and the preparation method of inorganic sol is then identical with first embodiment.Acrylic acid series copolymer is 60: 40 with the mixed weight ratio of inorganic sol in the compound photosensitive resin composition of made organic and inorganic.Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, this moment, viscosity was 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
The 6th embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The preparation method of acrylic acid series copolymer is identical with second embodiment, and the preparation method of inorganic sol is then identical with first embodiment.Acrylic acid series copolymer is 40: 60 with the mixed weight ratio of inorganic sol in the compound photosensitive resin composition of made organic and inorganic.Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, this moment, viscosity was 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
The 7th embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The preparation method of acrylic acid series copolymer is identical with second embodiment, and the preparation method of inorganic sol is then identical with first embodiment.Acrylic acid series copolymer is 20: 80 with the mixed weight ratio of inorganic sol in the compound photosensitive resin composition of made organic and inorganic.Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, this moment, viscosity was 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
The 8th embodiment (the compound photosensitive resin preparation of compositions of organic and inorganic)
The preparation method of acrylic acid series copolymer is identical with second embodiment, and the preparation method of inorganic sol is then identical with first embodiment.Acrylic acid series copolymer is 10: 90 with the mixed weight ratio of inorganic sol in the compound photosensitive resin composition of made organic and inorganic.Use the millipore filters of 0.2 μ m to filter removal of contamination behind the above-mentioned organic and inorganic composite resin composition of processing, this moment, viscosity was 15cps, can form 0.5～5.0 micron thickness according to coating speed when making film.
Use following method to assess the rerum natura that the compound photosensitive resin composition of the made organic and inorganic of above-mentioned the 3rd embodiment to the eight embodiment applies solution, table 1 is an assessment result.
Use the spin coated appearance to be coated to glass (glass) substrate to the made photosensitive resin composition solution of above-mentioned the 3rd embodiment to the eight embodiment, prebake formed film in 2 minutes on 90 ℃ hot plate then.
Intensity when using the prior figure cover of setting (pattem mask) the 365nm wavelength is 15mW/cm
2Ultraviolet ray be radiated at 6 seconds on the made above-mentioned film.Then, working concentration is that the tetramethylammonium hydroxide aqueous solution of 0.38 weight % developed 2 minutes under 25 ℃ of temperature, cleans 1 minute with ultrapure water again.
Intensity during then, the 365nm wavelength is 15mW/cm
2Ultraviolet ray be radiated at 34 seconds on the above-mentioned development figure, prebake is 3 minutes under 120 ℃ temperature, in baking oven, makes its sclerosis in 60 minutes and forms graphic films with the heating of 220 ℃ temperature.
A) graphic films that forms in the said determination process of thermotolerance-scrape finally films; Temperature when using thermogravimetric analyzer (TGA) gravimetry to reduce by 5 weight %; Temperature when weight reduces by 5 weight % be represent more than 300 ℃ the time very outstanding; Temperature is to represent more than 280 ℃ the time outstandingly, representes commonly in the time of more than 250 ℃, is lower than 250 ℃ and then representes bad.
B) hardness-use pencil hardness appearance is measured after on glass filming.Measuring method has been taked the film hardness mensuration based on pencil introduced among the ADTM D3363.
C) transmissivity-measure is above-mentioned a) time; Become 3 microns film to film thickness after the prebake and carry out visible light optical absorption spectra (spectrem) mensuration; Light transmission at the 400nm place was represented very outstanding greater than 98% o'clock; When 94-98%, represent outstandingly, when 92-94%, represent commonly, be lower than at 92% o'clock and then represent bad.
D) cohesive force-on Mo, Al and ito substrate, utilize 3M adhesive tape carries out tear tape test (Taping test) to accomplishing filming of final sclerosis.Be divided into back, 100 unit (cell) filming according to certain intervals and paste the 3M adhesive tape; Slowly open then, the residue element number is represented during greater than 95 very outstandingly in 100 unit, representes outstanding during greater than 90; 80 represent when above commonly, then represent bad when being lower than 80.
E) flatness-after coating on glass is filmed; Utilize the thickness measurement equipment of optical device and so on that about 100 point (point) is measured its thickness, its significant difference is lower than at 1% o'clock to be represented very outstandingly, is lower than at 2% o'clock and representes outstanding; Be lower than at 3% o'clock and represent common, surpass at 3% o'clock and represent bad.Can check through said method and to utilize the metallic compound dispersion that the ball comminutor processes with this patent and the deposition possibility of dispersion stabilization between the acrylic copolymer and metallic compound.
F) utilize computes after the static capacity of specific inductive capacity-Measurement of capacitor.After at first applying certain thickness thin dielectric film, utilize electric impedance analyzer measurement of electrostatic capacity, utilize following formula to calculate specific inductive capacity respectively then.
C (static capacity)=
ε
0(permittivity of vacuum) * ε
r(thin dielectric film relative dielectric constant) * A (useful area)/d (thin dielectric film thickness)
[table 1]
Above-mentioned table 1 has shown the characteristic of the compound photosensitive resin of processing according to the present invention of organic and inorganic.The 3rd embodiment to the eight embodiment have good heat endurance and hardness, and flatness and specific inductive capacity are excellent, and transmissivity and cohesive force are good.
The most important thing is,, therefore guaranteed to apply the storage stability of flatness and photoresist, use inorganic sol to process the compound photosensitive resin composition of the organic and inorganic with low-k owing to can stably mix the inorganic sol compound.
Hence one can see that, when the compound photosensitive resin composition of organic and inorganic of the present invention uses with the passivation dielectric film as TFT-LCD, can give play to very outstanding thermotolerance, excellent hardness, flatness and specific inductive capacity, good transmissivity and cohesive force.
Claims (10)
1. compound photosensitive resin composition of organic and inorganic, said composition comprises:
A) colloidal state inorganics colloidal sol, this colloidal state inorganics colloidal sol are to make inorganics surface-hydrophobicized and dewater, add organic solvent then and process through what on the colloid nano particle inorganics of 1 to 95 weight portion, add the 1-120 weight portion like the represented organosilane of Chemical formula 1, and colloid nano particle inorganics is formed by hydrosol nano particle inorganics; Said hydrosol nano particle inorganics is selected from by silicon dioxide; Aluminium oxide, titania, zirconia; Tin oxide; Zinc paste, at least a in the group that silicon dioxide, aluminium oxide, titania, zirconia, tin oxide and the zinc paste that perhaps uses silicon dioxide to carry out surface modification is formed
R
1 0-3Si(OR
2)
1-4
Chemical formula 1
R
1: be selected from least a in alkyl, phenyl, carbon fluorocarbon based, acryl, metering system aldehyde radical, propenyl, vinyl and the epoxy radicals,
R
2: be selected from least a in methyl, ethyl, isopropyl, n-pro-pyl or the normal-butyl,
OR
2: alkoxy, acetoxy group or oximido;
B) acrylic acid series copolymer; The amount of said acrylic acid series copolymer is 100 weight portions, and said acrylic acid series copolymer is by the i of 5 to 40 weight portions) ii) more than one the acrylic acid series unsaturated compound of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides or their potpourri and 5 to 95 weight portions carries out copolymerization and forms;
C) light trigger, the amount of said light trigger are 0.001 to 30 weight portion;
D) polyfunctional monomer, the amount of said polyfunctional monomer are 10 to 100 weight portions, and it is unsaturated link that said polyfunctional monomer has ethene;
E) silicon based compound, the amount of said silicon based compound are 0.0001 to 5 weight portion, and said silicon based compound contains epoxy radicals or amido; And
F) it is 10 to 50 weight % that solvent, the amount of said solvent make the solid content in the photosensitive resin composition.
2. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Above-mentioned b) unsaturated carboxylic acid i), unsaturated carboxylic acid anhydrides or their potpourri be selected from by acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, the acid of first health, itaconic acid, and the group formed of their acid anhydrides of unsaturated dicarboxylic in more than one.
3. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Above-mentioned b) ii) the unsaturated compound that contains epoxy radicals in the acrylic acid series unsaturated compound is selected from by glycidyl acrylate, GMA, α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, senecioate-methyl ethylene oxidic ester, methacrylic acid-Beta-methyl ethylene oxidic ester, senecioate-ethyl ethylene oxidic ester, methacrylic acid-β-ethyl ethylene oxidic ester, acrylic acid-3; 4-epoxy butyl ester, methacrylic acid-3; 4-epoxy butyl ester, acrylic acid-6; 7-epoxy heptyl ester, methacrylic acid-6; 7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, o-vinyl benzyl glycidol ether, m-vinyl benzyl glycidol ether, and the group formed of p-vinyl benzyl glycidol ether in more than one.
4. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Make above-mentioned b) acrylic acid series copolymer the time; At b) ii) add the ethylene series unsaturated compound of 10 to 70 weight portions in the acrylic acid series unsaturated compound in addition; This ethylene series unsaturated compound is selected from by the secondary butyl ester of methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, methacrylic acid, metering system tert-butyl acrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, acrylic acid double cyclopentenyl ester, acrylic acid dicyclo pentyl ester, methacrylic acid double cyclopentenyl ester, methacrylic acid dicyclo pentyl ester, acrylic acid 1-adamantane esters, methacrylic acid 1-adamantane esters, methacrylic acid dicyclo amyl group oxygen ethyl ester, isobornyl methacrylate, cyclohexyl acrylate, 2-cyclohexyl methacrylate, acrylic acid dicyclo amyl group oxygen ethyl ester, IBOA, phenyl methacrylate, propenyl benzene acid benzyl ester, benzyl acrylate, 2-hydroxyethyl methacry-late, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, to methoxy styrene, 1; 3-butadiene, isoprene, and 2; In the group that 3-dimethyl-1,3-butadiene is formed more than one.
5. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
The polystyrene conversion weight-average molecular weight of acrylic acid series copolymer above-mentioned b) is 6,000 to 90,000.
6. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Above-mentioned c) light trigger is selected from by Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure819,2,4-two (trichloromethyl)-6-p-methoxyl-styrene-s-triazine, 2-p-methoxyl-styrene-4,6-two (trichloromethyl)-s-triazine, 2; 4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methyl naphthyl-6-triazine, Benzophenone, p-(lignocaine) Benzophenone, 2,2-two chloro-4-metaphenoxy acetophenones, 2; 2-diethoxy acetophenone, 2-dodecyl thioxanthones, 2; 4-dimethyl thioxanthones, 2,4-diethyl thioxanthone and 2,2-two-2-chlorphenyl-4; 5; 4,5-tetraphenyl-2-1, more than one in the group that the 2-diimidazole is formed.
7. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Above-mentioned d) the ethene that has is that the polyfunctional monomer of unsaturated link is selected from by 1; 4-butanediol diacrylate, 1,3 butyleneglycol diacrylate, glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, triethylene glycol diacrylate, polyethyleneglycol diacrylate, double pentaerythritol methacrylate, bipentaerythrite triacrylate, bipentaerythrite diacrylate, sorbierite triacrylate, bisphenol a diacrylate derivant, bipentaerythrite polyacrylate, and the group formed of their methyl acrylic ester in more than one.
8. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
Above-mentioned e) the silicon based compound that contains epoxy radicals or amido is selected from by (3-diglycidyl propoxyl group) trimethoxy silane, (3-diglycidyl propoxyl group) triethoxysilane, (3-diglycidyl propoxyl group) methyl dimethoxysilane, (3-diglycidyl propoxyl group) dimethylethoxysilane, 3; 4-epoxy butyl trimethoxy silane, 3; 4-epoxy butyl triethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, and the group formed of aminopropyl trimethoxysilane in more than one.
9. the compound photosensitive resin composition of organic and inorganic according to claim 1 is characterized in that:
More than one the pigment that is added with thermal polymerization inhibitor, foam-breaking agent in this photosensitive resin composition in addition and from the group of forming by pigment, selects.
10. liquid crystal display cells is characterized in that:
Used the dielectric film that the adds silane-modified inorganic nano-particle hardenite with the photosensitive resin composition, said photosensitive resin composition is like any one the described organic and inorganic compound photosensitive resin composition of claim 1 in the claim 9.
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| KR1020070071201A KR100911889B1 (en) | 2007-07-16 | 2007-07-16 | Photosensitive resin composition with organic~inorganic hybrid and liquid display devices using |
| KR1020070071201 | 2007-07-16 | ||
| KR10-2007-0071201 | 2007-07-16 |
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| JP (1) | JP4961400B2 (en) |
| KR (1) | KR100911889B1 (en) |
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| KR101475780B1 (en) * | 2008-02-13 | 2014-12-23 | 주식회사 동진쎄미켐 | Organic-inorganic complex resin composition which is useful as a protecting layer |
| CN102031026B (en) * | 2009-09-28 | 2012-12-12 | 复旦大学 | Aqueous nano zirconia particle paint and method for preparing paint film thereof |
| JP5636839B2 (en) * | 2010-09-16 | 2014-12-10 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulating film, method for forming interlayer insulating film, and display element |
| JP5995963B2 (en) * | 2011-06-08 | 2016-09-21 | スリーエム イノベイティブ プロパティズ カンパニー | Photoresists containing polymer-linked nanoparticles |
| CN102294851A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | Hydrophobic scratch-resistant coating on organic polymer surface and preparation method thereof |
| CN103034056A (en) * | 2011-10-07 | 2013-04-10 | 住友化学株式会社 | Colored photosensitive resin composition |
| CN102643600B (en) * | 2012-04-18 | 2014-09-03 | 上海维凯化学品有限公司 | Ultraviolet light curing coating composition |
| TWI477556B (en) * | 2012-06-11 | 2015-03-21 | Chi Mei Corp | Curable resin composition, protective film and liquid crystal display device including the same |
| KR101329218B1 (en) * | 2012-10-22 | 2013-11-13 | (주)아이컴포넌트 | A optical transparent composite film for the use of display and manufacturing method thereof |
| KR102059489B1 (en) * | 2013-04-10 | 2019-12-26 | 주식회사 동진쎄미켐 | Negative photosensitive organic-inorganic hybrid insulator |
| WO2015033880A1 (en) * | 2013-09-04 | 2015-03-12 | 富士フイルム株式会社 | Resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
| JP6713320B2 (en) | 2016-03-31 | 2020-06-24 | 日揮触媒化成株式会社 | Surface-treated metal oxide sol |
| CN114397797A (en) * | 2022-01-11 | 2022-04-26 | 上海玟昕科技有限公司 | Negative photoresist composition containing nano particles |
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2008
- 2008-07-15 JP JP2008183905A patent/JP4961400B2/en not_active Expired - Fee Related
- 2008-07-16 TW TW097126860A patent/TWI392909B/en not_active IP Right Cessation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6183935B1 (en) * | 1998-01-07 | 2001-02-06 | Kansai Research Institute | Inorganic-containing photosensitive resin composition and method for forming inorganic pattern |
| WO2006065542A1 (en) * | 2004-12-13 | 2006-06-22 | General Electric Company | Compositions for articles comprising replicated microstructures |
| CN1900821A (en) * | 2005-07-19 | 2007-01-24 | 东进世美肯株式会社 | Organic inorganic composite photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI392909B (en) | 2013-04-11 |
| TW200916969A (en) | 2009-04-16 |
| CN101349867A (en) | 2009-01-21 |
| JP2009020520A (en) | 2009-01-29 |
| KR100911889B1 (en) | 2009-08-11 |
| KR20090007953A (en) | 2009-01-21 |
| JP4961400B2 (en) | 2012-06-27 |
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