CN100526981C - Pad for display panel, radiosensitive resin composition, and liquid crystal display device - Google Patents
Pad for display panel, radiosensitive resin composition, and liquid crystal display device Download PDFInfo
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- CN100526981C CN100526981C CNB2004100714718A CN200410071471A CN100526981C CN 100526981 C CN100526981 C CN 100526981C CN B2004100714718 A CNB2004100714718 A CN B2004100714718A CN 200410071471 A CN200410071471 A CN 200410071471A CN 100526981 C CN100526981 C CN 100526981C
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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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Materials For Photolithography (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a spacer for a display panel, the spacer capable of maintaining uniform gap width between substrates in any environment of normal temperature or high temperature, and always maintaining excellent display quality without influenced by temperature changes. The spacer for a display panel shows over 2.0*10<-4>/[deg.]C and <=8.0*10<-4>/[deg.]C coefficient of linear thermal expansion. The radiation-sensitive resin composition contains [A] a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride and (a2) an unsaturated compound except for the (a1) component, [B] a polyfunctional unsaturated monomer and [C] a radiation-sensitive polymerization initiator. An LCD comprising the spacer.
Description
Technical field
The present invention relates to pad, radiation-sensitive resin composition and the LCD of display panel.More specifically, the present invention relates to a kind of pad that is used for the display panel of display panels, touch panel etc., be used to form the radiation-sensitive resin composition of pad, and the LCD that comprises this pad.
Background technology
Up to now, have the pad particle of predetermined diameter such as beaded glass or plastic bead and be used for display panels to keep the gap width between two matrixes constant.Yet, owing to the pad particle is ejected on the matrix randomly, thereby when they are present in the effective pixel area, their imagings or scatter incident light, thereby the contrast of reduction display panels.
Therefore, form pad by photolithography.In this technology, matrix is applied by photosensitive resin, by predetermined mask exposure under UV radiation and develop to form point-like or strip pad.According to this technology, can form pad in the zone except effective pixel area, and can solve the problems referred to above that when spraying the pad particle, run into.In addition, because box gap (cell gap) can be controlled by the coating thickness of photosensitive resin in this technology, thereby the control gap width is to be easy to and to obtain high accuracy.
By keeping fixed numeric values in the gap width that under the normal temperature pad is clipped between the matrix that makes display panels between the matrix, the thickness of liquid crystal layer keeps constant between the matrix thus.Yet, annealing steps after injection in the display panels manufacture process and the encapsulated liquid crystals and the high temperature storage test that is used for assessing the display panels reliability, when display panels places high temperature following time, be filled in the liquid crystal generation thermal expansion between the matrix and because swelling pressure gap width changes, the thickness of matrix distortion and the liquid crystal layer part that becomes is inhomogeneous thus.Therefore, show that contrast becomes inhomogeneous and display quality worsens.Especially in having the large scale liquid crystal display panel of big matrix area, the distortion of the matrix that is caused by the thermal expansion of liquid crystal is tending towards remarkable.Because the size of the display panels used of TV is increasing, the inhomogeneous serious problems that will solve that more and more become of the demonstration contrast that causes by the liquid crystal thermal expansion.
Propose various suggestions and reduced the inhomogeneous of the demonstration contrast that causes by the liquid crystal thermal expansion.
JP-A 8-15708 (term used herein " JP-A " is meant " unexamined open Japanese patent application ") discloses a kind of method of utilizing a plurality of spherical washer, and the diameter of these pads is different with elasticity.About the process condition of assembling display panel, JP-A 2002-49041 discloses a kind of method of controlling the spherical washer diffuse density.JP-A 2001-147437 discloses the arrangement mode of column pad.
Yet, when display panels at high temperature when horizontal direction tilts because the spherical washer particle does not adhere to the surface of matrix, move into liquid crystal layer and unevenly distributing of particle, thereby produce uneven demonstration.Described column pad arrangement mode has limited the design freedom of panel, and owing to following design to display panels can become more and more diversified, thereby this is unsuitable.
Summary of the invention
The purpose of this invention is to provide the pad that is used for display panel, it has specific thermal linear expansion coefficient, can keep gap width between the matrix constant and can not be acted upon by temperature changes and guarantee excellent display quality all the time under normal temperature and the high temperature, and the LCD that is provided for forming the radiation-sensitive resin composition of pad and comprises this pad.
Other purpose of the present invention from the following description and advantage can be clearer.
According to the present invention, at first, above purpose of the present invention and advantage can be higher than 2.0 * 10 by thermal linear expansion coefficient
-4/ ℃ and 8.0 * 10
-4/ ℃ or lower display panel pad realize.
According to the present invention, secondly, above purpose of the present invention and advantage can realize by radiation-sensitive resin composition, this radiation-sensitive resin composition comprises [A] (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides and (a2) except multipolymer, [B] multifunctional unsaturated monomer and [C] radiosensitive polymerization initiating agent of the unsaturated compound of component (a1), and wherein the cured film of radiation-sensitive resin composition has and is higher than 2.0 * 10
-4/ ℃ and 8.0 * 10
-4/ ℃ or lower thermal linear expansion coefficient and radiation-sensitive resin composition be used to form the pad of the display panel described in the claim 1.
According to the present invention, the 3rd, above purpose of the present invention and advantage can realize that this LCD comprises display panel pad of the present invention by LCD.
To describe the present invention in detail below.
The display panel pad
The thermal linear expansion coefficient of display panel pad of the present invention is higher than 2.0 * 10
-4/ ℃ and 8.0 * 10
-4/ ℃ or lower, preferred (3.0 to 8.0) * 10
-4/ ℃, more preferably (4.0 to 8.0) * 10
-4/ ℃, preferred especially (5.0 to 8.0) * 10
-4/ ℃,
In the time of in its thermal linear expansion coefficient falls into above scope, display panel pad of the present invention can keep the gap width between the matrix constant under normal temperature and the high temperature, can not be acted upon by temperature changes and guarantee excellent display quality all the time, and can be advantageously used in display panels, the touch panel etc., not be subjected to the restriction of its shape and position and panel designs degree of freedom.
Radiation-sensitive resin composition
The material that is used to form display panel pad of the present invention is not restricted especially, as long as it has above thermal linear expansion coefficient and also can form the pad with reservation shape as the required intensity of pad, skin hardness, thermotolerance and chemical resistance.Preferred material is a radiation-sensitive resin composition, it comprise [A] (a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (hereinafter being called " sour unsaturated compound (a1) ") with (a2) except multipolymer (hereinafter being called " multipolymer [A] "), [B] multifunctional unsaturated monomer and [C] radiosensitive polymerization initiating agent of the unsaturated compound (hereinafter being called " other unsaturated compound (a2) ") of above component (a1), and have by the cured film that it obtains and to be higher than 2.0 * 10
-4/ ℃ and 8.0 * 10
-4/ ℃ or lower thermal linear expansion coefficient.
Multipolymer [A]
The example that is used for the sour unsaturated compound (a1) of multipolymer [A] comprises that unsaturated monocarboxylic is as (methyl) acrylic acid and corotonic acid; Unsaturated dicarboxylic such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And the acid anhydrides of these unsaturated dicarboxylics.
In these sour unsaturated compounds (a1), from copolyreaction and the preferred acrylic acid of viewpoint, methacrylic acid and the maleic anhydride that are easy to obtain.
Above sour unsaturated compound (a1) can use separately or use with the form of two or more potpourris.
The example that is used for other unsaturated compound (a2) of multipolymer [A] comprises that (methyl) alkyl acrylate is as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate; (methyl) acrylate cyclic ester is as (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, three ring [5.2.1.0
2.6] decane-8-base (methyl) acrylate, (methyl) acrylic acid 2-two cyclopentyl 2-ethoxyethyl acetates and (methyl) isobornyl acrylate; (methyl) acrylic acid aryl ester is as (methyl) phenyl acrylate and (methyl) benzyl acrylate; (methyl) hydroxyalkyl acrylate is as (methyl) acrylic acid 2-hydroxyl ethyl ester and (methyl) acrylic acid 2-hydroxypropyl acrylate; (methyl) acrylate that contains epoxide group is as (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy butyl ester, (methyl) acrylic acid 6,7-epoxy heptyl ester, (methyl) acrylic acid 2,3-epoxide ring pentyl ester and (methyl) acrylic acid 3,4-epoxy cyclohexyl; Unsaturated dicarboxylic diester such as diethyl maleate, DEF and diethyl itaconate; Unsaturated acyl group with imine moiety such as N-phenyl maleimide, N-benzyl maleimide and N-cyclohexyl maleimide; Vinyl nitrile compound is as (methyl) vinyl cyanide, α-chloroacrylonitrile and ethenylidene dintrile; The unsaturated acyl amines is as (methyl) acrylamide and N, N-dimethyl (methyl) acrylamide; Aromatic ethenyl compound such as styrene, α-methyl styrene ,-methyl styrene, right-methyl styrene, vinyltoluene and right-methoxy styrene; Indene derivative such as indenes and 1-methyl indenes; Conjugated diene compound is as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; And vinyl chloride, vinylidene chloride and vinyl-acetic ester.
In these other unsaturated compounds (a2), as (methyl) n-butyl acrylate, (methyl) acrylate cyclic ester is as three ring [5.2.1.0 from preferred (methyl) alkyl acrylate of the viewpoint of copolymerization
2.6] decane-8-base, (methyl) acrylic acid aryl ester is as (methyl) acrylic acid benzene methyl, and (methyl) acrylate that contains epoxide group is as (methyl) glycidyl acrylate, styrene and 1,3-butadiene.
Above other unsaturated compound (a2) can use separately or use with the form of two or more potpourris.
In the multipolymer [A] by derive preferred 5 to the 50 weight % of content of the repetitive that obtains of sour unsaturated compound (a1), preferred especially 10 to 40 weight %.When the content of this repetitive was lower than 5 weight %, the thermotolerance of pad, chemical resistance and skin hardness can worsen, and were higher than 50 weight % when this content, and the storage stability of composition can reduce.
The weight-average molecular weight with regard to polystyrene of multipolymer [A] (hereinafter being called " Mw ") is preferred 2000 to 500000, and more preferably 5000 to 100000.When the Mw of multipolymer [A] was lower than 2000, thermotolerance and skin hardness can be lower and when Mw was higher than 500000, development property can variation.
Multipolymer among the present invention [A] can use separately or use with the form of two or more potpourris.
By under the situation about existing at polymerization initiator in solvent polymeric acid unsaturated compound (a1) and other unsaturated compound (a2) can prepare multipolymer [A].
The example that is used to prepare the solvent of multipolymer [A] comprises that alcohol is as methyl alcohol and ethanol; Ether such as tetrahydrofuran are with diox; Glycol ether such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether and ethylene glycol mono-n-butyl ether; Ethylene glycol alkyl ether acetic acid esters such as Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, ethylene glycol n-propyl ether acetic acid esters and ethylene glycol n-butyl ether acetic acid ester; Diethylene glycol ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl-methyl ether; Diethylene glycol alkyl ether acetic acid esters such as diethylene glycol methyl ether acetic acid esters, diethylene glycol ethylether acetic acid esters, diethylene glycol n-propyl ether acetic acid esters and diethylene glycol n-butyl ether acetic acid esters; Propylene glycol such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether; Propylene glycol alkyl ether acetic acid ester such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol positive propyl ether acetic acid esters and propylene glycol n-butyl ether acetic acid esters; Propylene glycol alkyl ether propionic ester such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol positive propyl ether propionic ester and propylene glycol n-butyl ether propionic ester; Aromatic hydrocarbon such as toluene and dimethylbenzene; Ketone such as methyl ethyl ketone, cyclohexanone, 4-hydroxyl-4-methyl-2-pentanone and methyl isoamyl ketone; And other ester such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid n-propyl, the positive butyl ester of glycolic acid, the methoxyimino acetic acid methyl esters, the methoxyimino acetic acid ethyl ester, the methoxyimino acetic acid n-propyl, the positive butyl ester of methoxyimino acetic acid, the ethoxy methyl acetate, ethoxy ethyl acetate, the ethoxy n-propyl acetate, the ethoxy n-butyl acetate, the positive third fluoroacetic acid methyl esters, the positive third fluoroacetic acid ethyl ester, the positive third fluoroacetic acid n-propyl, the positive butyl ester of positive third fluoroacetic acid, positive fourth fluoroacetic acid methyl esters, positive fourth fluoroacetic acid ethyl ester, positive fourth fluoroacetic acid n-propyl, the positive positive butyl ester of fourth fluoroacetic acid, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propionic acid n-propyl, 2-methoxy n-butyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-ethoxy propionic acid n-propyl, 2-ethoxy n-butyl propionate, 2-positive third oxygen the methyl propionate, 2-positive third oxygen the ethyl propionate, 2-positive third oxygen propionic acid the n-propyl, 2-positive third oxygen the n-butyl propionate, the positive fourth oxygen of 2-methyl propionate, the positive fourth oxygen of 2-ethyl propionate, the positive fourth oxygen of 2-propionic acid n-propyl, the positive fourth oxygen of 2-n-butyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propionic acid n-propyl, 3-methoxy n-butyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy propionic acid n-propyl, 3-ethoxy n-butyl propionate, 3-positive third oxygen the methyl propionate, 3-positive third oxygen the ethyl propionate, 3-positive third oxygen propionic acid the n-propyl, 3-positive third oxygen the n-butyl propionate, 3-positive fourth oxygen methyl propionate, 3-positive fourth oxygen ethyl propionate, 3-positive fourth oxygen propionic acid n-propyl, 3-positive fourth oxygen n-butyl propionate, 2-hydroxyl-2-methylpropanoic acid methyl esters, 2-hydroxyl-2-methylpropanoic acid ethyl ester and 2-hydroxyl-3-methylbutanoic acid methyl esters.
These solvents can use separately or use with the form of two or more potpourris.
The polymerization initiator that is used for synthetic copolymer [A] can use general known radical polymerization initiator.The example of radical polymerization initiator comprises azo-compound as 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2,4-methyl pentane nitrile) and 2,2 '-azo two-(4-methoxy-2,4-methyl pentane nitrile); Organic peroxide such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pyvarate and 1,1 '-two (t-butyl peroxy) cyclohexane; Hydrogen peroxide; And the redox polymerization initiating agent that comprises above-mentioned a kind of superoxide and reductive agent.
These polymerization initiators can use separately or use with the form of two or more potpourris.
[B] multifunctional unsaturated monomer
Multifunctional unsaturated monomer is the monomer with two or more polymerizable unsaturated bonds.The preferred example of this multifunctional unsaturated monomer comprises multifunctional (methyl) acrylate with urethane bond.
In above multifunctional (methyl) acrylate, difunctionality (methyl) acrylate comprises ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, many ethylene glycol bisthioglycolates (methyl) acrylate, many propylene glycol two (methyl) acrylate and the full orange of two Phenoxyethanols (full orange) (methyl) acrylate.
The commercially available prod of two senses (methyl) acrylate comprises Aronix M-210,240 and 6200 (Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (Nippon Kayaku Co., Ltd.) and Biscoat 260,312 and 335HP (Osaka YukiKagaku Co., Ltd.), the commercially available prod with two senses (methyl) acrylate of urethane bond comprises Aronix M-1100,1200,1210,1310 and 1600 (Toagosei Chemical Industry Co., Ltd.'s), R-1000 series, 1204,1211 and 1213 (Dai-ichi Kogyo Seiyaku Co., Ltd.'s), and AH-60, AT-600 and UA-306H (Kyoeisha Kagaku Co., Ltd.'s).
Have 3 or more (methyl) acrylate of polyfunctionality comprise trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate and three [2-(methyl) acrylyl oxy-ethyl] phosphate.
Have 3 or more the commercially available prod of (methyl) acrylate of polyfunctionality comprise Aronix M-309,400,402,405,450,7100,8030,8060,1310,1600,1960,8100,8530,8560 and 9050, with Aronix TO-1450 (Toagosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 and MAX-3510 (Nippon Kayaku Co., Ltd.'s), and Biscoat 295,300,360,400, GPT and 3PA (Osaka Yuki Kagaku Co., Ltd.'s); Commercially available prod with trifunctional (methyl) acrylate of urethane bond comprises R-1000 series, 1301,1302,1303,1304,1306 and 1308 (Dai-ichi Kogyo Seiyaku Co., Ltd.'s); Have four senses of urethane bond or the commercially available prod of above (methyl) acrylate and comprise Aronix M-1960 (Toagosei Chemical IndustryCo., Ltd.'s), and R-1150 (Dai-ichi Kogyo Seiyaku Co., Ltd.'s).
Among the present invention, more than multifunctional unsaturated monomer can use separately or use with the form of two or more potpourris.Multifunctional unsaturated monomer preferably contain multifunctional (methyl) acrylate of being with urethane bond and more preferably with multifunctional (methyl) acrylate of urethane bond with not with the potpourri of multifunctional (methyl) acrylate of urethane bond.The multifunctional unsaturated monomer that contains multifunctional (methyl) acrylate of being with urethane bond by use can obtain having the radiation-sensitive resin composition of high thermal linear expansion coefficient.
In the multifunctional unsaturated monomer that contains multifunctional (methyl) acrylate, have preferred 10 to the 50 weight % of amount of multifunctional (methyl) acrylate of urethane bond, more preferably 15 to 50 weight %, preferred especially 25 to 50 weight % with urethane bond.When multifunctional (methyl) acrylate content of band urethane bond in described scope the time, light sensitivity, development and the intensity of the characteristic that can not weaken pad the time as exposure.
The radiosensitive polymerization initiating agent of-[C]-
The active specy that radiosensitive polymerization initiating agent reacts and can cause multifunctional unsaturated monomer [B] polymerization to produce radiation.
The preferred radiosensitive radical polymerization initiator of radiosensitive polymerization initiating agent.
More than the example of radiosensitive radical polymerization initiator comprise α-diketone such as benzyl and diacetyl; Acyloin class such as benzoin; Acyloin ether such as benzoin methyl ether, benzoin ethylether and benzoin isopropyl ether; Benzophenone such as thioxanthones, 2,4-diethyl thioxanthene, thioxanthene-4-sulfonic acid, benzophenone, 4,4 '-two (dimethylamino) benzophenone and 4,4 '-two (diethylamino) benzophenone; Acetophenones such as acetophenone, right-dimethylamino benzoylformaldoxime, 4-(α, α '-dimethoxy acetyl oxygen) benzophenone, 2,2 '-dimethoxy-2-phenyl acetophenone, to methoxy acetophenone, 2-methyl-2-beautiful jade generation-1-(4-methyl thio-phenyl)-1-acetone and 2-benzyl-2-dimethylamino-1-(4-beautiful jade is for phenyl)-butane-1-ketone; Quinone such as anthraquinone and 1,4-naphthoquinones; Halogen compounds such as phenacyl chloride, trisbromomethyl phenyl sulfone and three (trichloromethyl)-s-triazine; Acylphosphine oxide is as 2,4,6-trimethyl benzoin diphenyl phosphine oxide (2,4,6-trimethylbenzoildiphenyl phosphine oxide), two (2,6-veratroyl base)-2,4,4-tri-methyl-amyl phosphine oxide and two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; And superoxide such as di-tert-butyl peroxide.
The commercially available prod of radiosensitive radical polymerization initiator comprises IRGACURE-124,149,184,369,500,651,819,907,1000,1700,1800,1850 and 2959, and Darocur-1116,1173,1664,2959 and 4043 (Ciba Specialty Chemicals Co., Ltd,), KAYACURE-DETX ,-MBP,-DMBI ,-EPA and-OA (Nippon Kayaku Co., Ltd,), LUCIRINTPO (BASF Co., Ltd), VICURE-10 and 55 (STAUFFER Co., Ltd), TRIGGNALP1 (AKZO Co., Ltd,), SANDORAY 1000 (SANDOZ AG's), DEAP (APJOHN Co., Ltd,), and QUANTACURE-PDO ,-ITX and-EPD (WARD BLEKINSOP Co., Ltd).
These radiosensitive radical polymerization initiators can use separately or use with the form of two or more potpourris.
By using at least a radiation sensitizer can obtain the radiation-sensitive resin composition that has high sensitivity and seldom deactivated by contained oxygen in the air with above radiosensitive radical polymerization initiator.
Every kind of components contents in the radiation-sensitive resin composition of the present invention, multipolymer [A] based on 100 weight portions, preferred 10 to 150 weight portions of the amount of polyfunctional monomer [B], more preferably 20 to 120 weight portions, multipolymer [A] based on 100 weight portions, preferred 1 to 40 weight portion of the amount of radiation sensitive polymer initiating agent [C], more preferably 3 to 35 weight portions.
When polyfunctional monomer [B] content is less than 10 weight portions, be difficult to form the uniform film of thickness, and when its content during more than 150 weight portions, can reduce the adhesion of matrix.When the quantity of radiation sensitive polymer initiating agent [C] was lower than 1 weight portion, thermotolerance, skin hardness and chemical resistance can variation, and when this quantity during more than 40 weight portions, transparency can reduce.
-other adjuvant-
Radiation-sensitive resin composition of the present invention can contain other adjuvant such as surfactant and adhere to auxiliary agent, is restriction not damage purpose of the present invention.
Above surfactant is used to improve coating performance.
The above preferred fluoro-based surfactants of surfactant or silicone-based surfactants.
The fluoro-based surfactants preferably has the compound of fluoroalkyl group or fluorine alkylidene group in arbitrary position of its end, main chain and side chain.The example of fluoro-based surfactants comprises 1,1,2,2-tetrafluoro propyl group (1,1,2,2-tetrafluoro octyl group) ether, hexyl (1,1,2,2-tetrafluoro octyl group) ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro butyl) ether, six ethylene glycol bisthioglycolates (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3,3-hexafluoro decane, fluoro-alkyl benzene sulfonic acid sodium salt, the fluoro-alkyl sodium phosphate, fluoro-alkyl sodium carbonate, fluoro-alkyl polyoxyethylene ether, two glycerine four (fluoro-alkyl polyoxyethylene ether), the fluoro-alkyl ammonium iodide, fluoro-alkyl betaine, fluoro-alkyl polyoxyethylene ether, perfluoroalkyl poly oxyethanol, full fluoroalkane ester of alcoxyl acid and fluoro-base Arrcostab.
The commercially available prod of fluoro-based surfactants comprises BM-1000 and 1100 (BM CHEMIE., Ltd.), Megafac F142D, F172, F173, F178, F183, F191, F471 and F476 (Dainippon Inkand Chemicals, Inc.), Florade FC-170C, 171,430 and 431 (Sumitomo 3M Limited), Surflon S-112,113,131,141,145 and 382 and Surflon SC-101,102,103,104,105 and 106 (Ashi Glass Co., Ltd.), F Top EF301,303 and 352 (Shin Akita Kasei Co., Ltd's), and Futargent FT-100,110,140A, 150,250,251,300,310 and 400S andFutargent FTX-251 and, 218 (Neos Co., Ltd.'s).
The commercially available prod of above silicone-based surfactants comprises Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (Toray Dow Corning Silicone Co., Ltd.'s), and TSF-4300,4440,4445,4446,4452and4460 (GE Toshiba Silicone Co., Ltd.'s).
Other surfactant comprises non-ionic surfactant, and this ionic surfactant pack is drawn together polyoxyethylene alkyl ether such as polyoxyethylene laurel ether, polyoxyethylene 18 acyl ether and polyoxyethylene oleyl ethers; Polyoxyethylene aryl ether such as polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-nonyl phenyl ether; And polyoxyethylene dialkyl such as polyoxyethylene dilaurate and polyoxyethylene distearate; And the KP341 organic siloxane polymer (Shin-Etsu Chemical Co., Ltd.) and 57 and No. 95 (methyl) acrylic acid-base co-polymers of polyfluoride (polyflow) (Kyoeisha Kagaku Co., Ltd.).
These surfactants can use separately or use with the form of two or more potpourris.
Based on the multipolymer [A] of 100 weight portions, preferred 5 weight portions of the content of surfactant or still less, more preferably 2 weight portions or still less.When surface-active contents during more than 5 weight portions, film can roughening during coating.
More than the adhesion auxiliary agent is used to improve the adhesiveness to matrix.
The adhesion auxiliary agent preferably has the silane coupling agent of functional group, particularly has the silane coupling agent as the functional group of carboxylic group, methacryloyl group, isocyanate groups or epoxide group etc.The example that adheres to auxiliary agent comprises trimethoxy silicyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyl triacetyl oxosilane, vinyl trimethoxy silane, γ-isocyanide ester propyl-triethoxysilicane, γ-glycidoxy-propyltrimethoxy silane and β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
These adhesion auxiliary agents can use separately or use with the form of two or more potpourris.
Based on the multipolymer [A] of 100 weight portions, adhere to preferred 20 weight portions of content of auxiliary agent or still less, more preferably 15 weight portions or still less.When adhering to auxiliary agent content more than 20 weight portions, thermotolerance can reduce.
In the radiation-sensitive resin composition of the present invention, suitably select the quantity of multipolymer [A], multifunctional unsaturated monomer [B], radiosensitive polymerization initiating agent [C] and other adjuvant and these components to select thermal linear expansion coefficient with the cured film guaranteeing to obtain thus suitably for being higher than 2.0 * 10
-4/ ℃ and 8.0 * 10
-4/ ℃ or lower, preferred (3.0 to 8.0) * 10
-4/ ℃, more preferably (4.0 to 8.0) * 10
-4/ ℃, preferred especially (5.0 to 8.0) * 10
-4/ ℃.
The preparation of radiation-sensitive resin composition
Preferably, by with above multipolymer [A], multifunctional unsaturated monomer [B], radiosensitive polymerization initiating agent [C] and other optional adjuvant mixes and with these components dissolved in appropriate solvent, radiation-sensitive resin composition of the present invention is made as composition solution.
The above-mentioned solvent that is used to prepare above composition solution preferably can dissolve these components and not with these component reaction.
The example of solvent that the example of this solvent and those cited being used to prepare above-mentioned multipolymer [A] is identical.
In these solvents, from dissolubility, with the reactive of every kind of component and the preferred glycol ether of viewpoint, ethylene glycol alkyl ether acetic acid esters, diethylene glycol ether, propylene glycol alkyl ether acetic acid ester and other ester that form the simplification of coated film.
Above solvent can use separately or use with the form of two or more potpourris.
High boiling solvent can use with above solvent.
The example of high boiling solvent comprises N-NMF, N, N-dimethyl formamide, N-methyl formyl aniline, N-methylacetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzyl ethylether, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1-nonyl alcohol, phenmethylol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and benzyl cellulose acetic acid esters.
Above high boiling solvent can use separately or use with the form of two or more potpourris.
Was about 0.2 to 0.5 micron millipore filter filtration with opening diameter as the composition solution of above-mentioned preparation before using.
Form the method for display panel pad
Provide the description that forms the method for display panel pad of the present invention by radiation-sensitive resin composition of the present invention below.
At first above composition solution is applied on the surface of matrix to form coated film.
Composition solution can be coated with as injection, roller coat, rotary coating, rod by suitable mode and be coated with or ink-jet application.
Subsequently, this coated film prebake conditions is made solvent evaporation, thereby obtain there is not mobile film.
The prebake conditions condition with consumption and different, is generally 60 to 120 ℃ temperature and 10 to 600 seconds time according to the type of every kind of component.
Then, this film is exposed to pass a radiation to develop this film to remove unnecessary portions down and with developer with mask of predetermined pattern.
The radiation that is used to expose is visible radiation, UV radiation, far ultraviolet radiation, electron irradiation, X-radiation etc., and optimal wavelength is 190 to 450nm UV radiation.
Exposure preferred 100 is to 20000J/m
2, more preferably 150 to 10000J/m
2
Developer can be the aqueous alkali of following material: inorganic base such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammoniacal liquor; Primary amine such as ethylamine or n-pro-pyl amine; Secondary amine such as diethylamide or di-n-propyl amine; Tertiary amine such as triethylamine, methyl diethylamide or N-methyl pyrrolidone; Hydramine such as dimethylethanolamine or triethanolamine; Quaternary amine such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or choline; Perhaps cyclic amine such as pyrroles, piperidines, 1,8-diazabicylo [5.4.0]-7-undecylene or 1,5-diazabicylo [4.3.0]-5-nonene.
Above aqueous alkali can contain an amount of water-miscible organic solvent such as methyl alcohol or ethanol and surfactant.
Develop and preferably carried out at normal temperatures 30 to 180 seconds.
Development can be to stir to develop, flood or spray.
After the development,, and spray pressurized air or compressed nitrogen anhydrates so that obtain having the film of predetermined pattern to remove with the water rinse that flows 30 to 90 seconds.
Subsequently, with well heater such as hot plate or in 150 to 250 ℃ of heating films of baking oven, for example, heating is 5 to 30 minutes on hot plate, and heats 30 to 90 minutes in baking oven so that film solidifies, thereby obtains having the big pad of preboarding.
Embodiment
Embodiment
Provide the following examples further specifying the present invention, but restrictive anything but.
Synthetic embodiment 1
With 2 of 4 weight portions, the diethylene glycol ethyl-methyl ether of 2 '-azoisobutyronitrile (AIBN) and 200 weight portions injects the flask that is equipped with stirrer, further with 1 of 5 weight portions, the n-BMA of the benzyl methacrylate of the methacrylic acid of 3-butadiene, 18 weight portions, 40 weight portions and 37 weight portions injects flask, replace flask interior with nitrogen, stir these materials gently, the temperature of reactant solution is elevated to 80 ℃, kept 5 hours at this point, and then be elevated to 100 ℃ of continuation reactions 1 hour.Then, the temperature of reaction solution is reduced to the polymer solution (solids content=30.0 weight %s) of room temperature to obtain containing multipolymer [A].The Mw of this multipolymer is 27000.This multipolymer is labeled as multipolymer (A-1).
Synthetic embodiment 2
With 2 of 4 weight portions, the diethylene glycol ethyl-methyl ether of 2 '-azoisobutyronitrile (AIBN) and 200 weight portions injects the flask that is equipped with stirrer, further with 1,3-butadiene of 5 weight portions, the styrene of 5 weight portions, the methacrylic acid of 18 weight portions, the glycidyl methacrylate of 40 weight portions and three ring [5.2.1.0 of 32 weight portions
2.6] last of the ten Heavenly stems-8-base-methacrylate inject flask, replace flask interior with nitrogen, stir these materials gently, and the temperature of reactant solution is elevated to 80 ℃, kept 5 hours at this point, and then be elevated to 100 ℃ and continue reaction 1 hour.Then, the temperature of reaction solution is reduced to the polymer solution (solids content=29.8 weight %s) of room temperature to obtain containing multipolymer [A].The Mw of this multipolymer is 26000.This multipolymer is labeled as multipolymer (A-2).
Embodiment 1
(1) preparation of composition solution
With the multipolymer (A-1) of 100 weight portions (solids content) as component [A], the KAYARAD DPHA of 80 weight portions (Nippon Kayaku Co., Ltd.) and the R of 20 weight portions-1302 (Dai-ichi Kogyo Seiyaku Co., Ltd.) as component [B], 2-benzyl of 25 weight portions-2-dimethylamino-1-(4-beautiful jade is for phenyl)-fourth-1-ketone (Ciba Specialty Chemicals Co., Ltd. Irgacure 369) be dissolved in as component [C] that to make solids content in the propylene glycol methyl ether acetate be 35 weight %, gained solution opening diameter is that 0.2 micron millipore filter filters to make composition solution.
(2) formation of shim pattern
With spinner with above composition solution be applied to glass basis and in 80 ℃ on hot plate prebake conditions 3 minutes to form coated film.
Then coated film is exposed to that intensity is 100W/m in the air
2, wavelength is 365nm, passed a UV radiation with predetermined pattern (10 microns * 10 microns) mask following 30 seconds.Subsequently, in 25 ℃ coated film was developed 1 minute, thereby and obtain shim pattern (residue) to remove unnecessary portions with pure water rinsing coated film 1 minute with the aqueous solution of the Tetramethylammonium hydroxide of 0.2 weight %.Heating this shim pattern 60 minutes in 220 ℃ baking oven so that pattern cured thereby to obtain highly be 5 microns shim pattern.
(3) mensuration of thermal linear expansion coefficient
With spinner with above composition solution be applied to glass basis and in 80 ℃ on hot plate prebake conditions 3 minutes to form coated film.
Then this coated film is exposed to that intensity is 100W/m in the air
2, wavelength is following 30 seconds of 365nm UV radiation, with the tetramethylammonium hydroxide aqueous solution of 0.2 weight % in 25 ℃ of development coated film 1 minute, with pure water rinsing coated film 1 minute, thereby and in 220 ℃ baking oven heating made it to solidify in 60 minutes and obtain the film that is used to measure.
Be 2.5 ℃/minute with being equipped with programming rate, to measure temperature range be that the ellipsometer of 20 to 180 ℃ temperature change device is measured each and measured the variation in thickness of this film under temperature and map with respect to temperature, from linear-apporximation, obtain degree of tilt ε, thereby from following expression formula, obtain thermal linear expansion coefficient α.T represents the original depth of film, α=ε/T.
The thermal linear expansion coefficient of conventional gasket material is 2.0 * 10
-4/ ℃ or lower.We can say that the thermal linear expansion coefficient that is higher than this value is high.Measurement result is as shown in table 1.
(4) evaluation of gasket strength
The intensity of the shim pattern that obtains in (2) more than the tester (MCTM of Shimadzu Corporation-200) that contracts by minute-pressure under 25 ℃ measurement temperature is estimated.Utilizing diameter is that 50 microns flat impression meter is applied to load on the pad with fixing speed (2.65mN/ second), with measure that pad splits or breaking load when rupture and fracture deformation (remove with the height of pad the moment of rupturing the compression displacement gained numerical value and represent with %).Evaluation result is as shown in table 1.
(5) evaluation of hot crushing resistance
Estimate the hot crushing resistance of the shim pattern that obtains in above (2) by the minute-pressure tester (MCTM of Shimadzu Corporation-200) that contracts.Utilizing diameter at 160 ℃ is that 50 microns flat impression meter is applied to load on the pad with fixing speed (0.28mN/ second), and removes load when pad is compressed 0.75 micron, thereby obtains the coefficient of restitution according to following expression formula.
Coefficient of restitution (%)=(0.75-residual deformation) * 100/0.75
We can say when coefficient of restitution be 90% or when higher hot crushing resistance be gratifying.Evaluation result is as shown in table 1.
(6) evaluation of thermal dimensional stability
The shim pattern that obtains in the heating above (2) in 250 ℃ baking oven 60 minutes is to measure before the heating and the size change speed of film thickness afterwards.We can say when this value be 5% or more a hour thermal dimensional stability be gratifying.Evaluation result is as shown in table 1.
Embodiment 2
Prepare and estimate composition solution in the mode identical with embodiment 1, different is that the KAYARAD DPHA (Nippon Kayaku Co.Ltd.'s) of 70 weight portions and the R-1302 of 30 weight portions (Dai-ichi Kogyo Seiyaku Co., Ltd.'s) are used as component [B].Evaluation result is as shown in table 1.
Embodiment 3
Prepare and estimate composition solution in the mode identical with embodiment 1, different is as component [A] with multipolymer (A-2).Evaluation result is as shown in table 1.
Comparative Examples 1
Prepare and estimate composition solution in the mode identical with embodiment 1, different is multipolymer (A-2) as the KAYARAD DPHA (Nippon Kayaku Co., Ltd.'s) of component [A], 100 weight portions as component [B].Evaluation result is as shown in table 1.
Table 1
As mentioned above, according to the present invention, a kind of display panel pad is provided, it can keep the gap width between the matrix constant under normal temperature and the high temperature, can not be acted upon by temperature changes and guarantee excellent display quality all the time, be not limited to the design freedom of its shape and position and panel.Radiation-sensitive resin composition of the present invention has above characteristic and can form the display panel pad with superior physical properties such as intensity, hot crushing resistance and thermal dimensional stability etc.
Claims (3)
1, a kind of radiation-sensitive resin composition, it comprises the copolymer A of a1 unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides and the a2 unsaturated compound except component a1, multifunctional unsaturated monomer B and radiosensitive polymerization initiating agent C, and wherein the cured film of radiation-sensitive resin composition has 3.0 * 10
-4/ ℃ to 8.0 * 10
-4/ ℃ thermal linear expansion coefficient, and radiation-sensitive resin composition is used to form and has 3.0 * 10
-4/ ℃ to 8.0 * 10
-4/ ℃ the display panel pad of thermal linear expansion coefficient;
Wherein said a1 unsaturated carboxylic acid comprises and is selected from (methyl) acrylic acid unsaturated monocarboxylic; With the unsaturated dicarboxylic that is selected from maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And the unsaturated carboxylic acid anhydrides that is selected from the acid anhydrides of these unsaturated dicarboxylics;
The unsaturated compound of described a2 except component a1 comprises (methyl) alkyl acrylate, (methyl) acrylate cyclic ester, (methyl) acrylic acid aryl ester, (methyl) hydroxyalkyl acrylate, (methyl) acrylate that contains epoxide group, the unsaturated dicarboxylic diester, the unsaturated acyl group with imine moiety, vinyl nitrile compound, the unsaturated acyl amines, aromatic ethenyl compound, indene derivative, conjugated diene compound, vinyl chloride, vinylidene chloride and vinyl-acetic ester; With
Described multifunctional unsaturated monomer B comprises multifunctional (methyl) acrylate that can have urethane bond.
2, according to the radiation-sensitive resin composition of claim 1, wherein, based on the component A of 100 weight portions, the content of B component is 10 to 150 weight portions, and based on the total amount of compd B, B component contains multifunctional (methyl) acrylate that content is the band urethane bond of 10 to 50 weight %.
3, a kind of LCD comprises the display panel pad of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP167238/03 | 2003-06-12 | ||
| JP2003167238A JP4016893B2 (en) | 2003-06-12 | 2003-06-12 | Radiation sensitive resin composition and liquid crystal display element used for forming spacer for display panel |
| JP167238/2003 | 2003-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1573547A CN1573547A (en) | 2005-02-02 |
| CN100526981C true CN100526981C (en) | 2009-08-12 |
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|---|---|---|---|
| CNB2004100714718A Expired - Fee Related CN100526981C (en) | 2003-06-12 | 2004-06-11 | Pad for display panel, radiosensitive resin composition, and liquid crystal display device |
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| Country | Link |
|---|---|
| JP (1) | JP4016893B2 (en) |
| KR (1) | KR100874567B1 (en) |
| CN (1) | CN100526981C (en) |
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| CN101142516B (en) * | 2005-03-14 | 2011-08-24 | 富士通株式会社 | LCD device and method for manufacturing the same |
| TWI411877B (en) * | 2005-06-15 | 2013-10-11 | Jsr Corp | A photosensitive resin composition, a display panel spacer, and a display panel |
| JP2007033635A (en) * | 2005-07-25 | 2007-02-08 | Fujitsu Ltd | Liquid crystal display element and method for manufacturing the same |
| WO2007026629A1 (en) * | 2005-08-30 | 2007-03-08 | Kyocera Chemical Corporation | Photosensitive resin composition, spacer, color filter, and liquid crystal display device |
| WO2007105381A1 (en) * | 2006-03-13 | 2007-09-20 | Fujifilm Corporation | Photosensitive resin composition for photospacer, method for producing photospacer, substrate for liquid crystal display, liquid crystal display element, and liquid crystal display |
| JP4816917B2 (en) * | 2006-03-17 | 2011-11-16 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, spacer for liquid crystal display panel, method for forming spacer for liquid crystal display panel, and liquid crystal display panel |
| KR101241596B1 (en) | 2006-07-28 | 2013-03-08 | 코오롱인더스트리 주식회사 | Photoresist resin composition for column spacer |
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| JPH11133600A (en) | 1997-10-30 | 1999-05-21 | Jsr Corp | Radiation-sensitive resin composition for display panel spacer |
| JP2001154206A (en) * | 1999-11-25 | 2001-06-08 | Jsr Corp | Radiation sensitive resin composition for spacer, spacer and liquid crystal display element |
| JP4269480B2 (en) * | 2000-04-19 | 2009-05-27 | Ｊｓｒ株式会社 | Radiation sensitive resin composition |
| JP4660990B2 (en) * | 2001-07-17 | 2011-03-30 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, projection material and spacer formed therefrom, and liquid crystal display device comprising the same |
| JP2003066604A (en) * | 2001-08-28 | 2003-03-05 | Jsr Corp | Radiation sensitive resin composition for spacer, spacer and liquid crystal display element |
| JP3734436B2 (en) | 2001-09-19 | 2006-01-11 | 奇美実業股▲分▼有限公司 | Photosensitive resin composition for liquid crystal display spacers |
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| CN1573547A (en) | 2005-02-02 |
| KR20040107392A (en) | 2004-12-20 |
| SG120989A1 (en) | 2006-04-26 |
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| KR100874567B1 (en) | 2008-12-16 |
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