CN100538518C - Radiation-sensitive resin composition, display panel sept and display panel - Google Patents

Radiation-sensitive resin composition, display panel sept and display panel Download PDF

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CN100538518C
CN100538518C CNB2005100051131A CN200510005113A CN100538518C CN 100538518 C CN100538518 C CN 100538518C CN B2005100051131 A CNB2005100051131 A CN B2005100051131A CN 200510005113 A CN200510005113 A CN 200510005113A CN 100538518 C CN100538518 C CN 100538518C
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methyl
alkyl
sept
compound
phenyl
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CN1655060A (en
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一户大吾
岩渊智子
西尾寿浩
梶田彻
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/72—Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

Abstract

The invention provides a kind of radiation-sensitive resin composition, can verily reproduce the design size of mask pattern, and have good adhesiveness with substrate with high sensitivity, 1,500J/m 2Following exposure also can obtain desirable sept shape and thickness, in addition, can form all good display panel septs such as compressive strength and rub resistance.This radiation-sensitive resin composition contains: [A] (a1) unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides, (a2) contains the unsaturated compound of epoxy radicals and (a3) multipolymer of other unsaturated compound; [B] has the polymerizable compound of ethene unsaturated link; And [C] is with the radioactivity-sensitive polymerization initiator of the compound shown in following chemical formula (1) or (2) as neccessary composition.In the formula, R 1The expression alkyl or phenyl, R 2Expression hydrogen atom, alkyl or phenyl, R 3Expression hydrogen atom or alkyl.

Description

Radiation-sensitive resin composition, display panel sept and display panel
Technical field
The invention relates to radiation-sensitive resin composition, display panel sept and display panel, more particularly, the display panel that the invention relates to the radiation-sensitive resin composition that is fit to be used as the material that forms the sept that uses in the display panels such as display panels or contact type panel, is formed by said composition is with sept and display panel with this sept.
Background technology
In the past, in order to make the interval between two plate bases keep certain, in display panels, use uniformly-spaced thing particle of glass microballoon with regulation particle diameter or plastics microballon, but,, thereby form when having the sept particle in the zone phenomenon that is written into regard to origination interval thing particle when pixel because these sept particles are to be randomly dispersed on the transparency carrier such as glass substrate, perhaps incident light generation scattering, the problem that the contrast of liquid crystal panel reduces.
In order to address these problems, people adopt photoetching to form the method for sept.This method is, photosensitive polymer combination or radiation-sensitive resin composition (following these compositions are commonly referred to as " radiation-sensitive resin composition etc. ") are coated on the substrate, mask by regulation carries out ultraviolet isoradial exposure, video picture then, form the sept of point-like or striated, because only the regulation position beyond pixel forms the zone forms sept, thereby has solved the problems referred to above basically.
, form in the process of sept, for example adopt photoetching on employed substrates such as color filter, to form the occasion of sept, often use the proximity exposure machine in reality.When carrying out this proximity exposure, more satisfactory method is, at mask and formed and expose after between the substrate of tunicles such as radiation-sensitive resin composition certain interval being set, presses the pattern exposure of mask.Be full of air or nitrogen in this interval, the radioactive ray that see through the peristome (hyalomere) of mask spreads in this gap and broaden, thereby the exposure that reality occurs is than problems such as the design size of mask pattern are wide.
In order to address this problem; the inventor finds and points out in patent documentation 1; by using 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes) is as the Photoepolymerizationinitiater initiater of photosensitive polymer combination; even proximity exposure; also can verily reproduce the design size of mask pattern, in addition, can form the display panel sept of excellences such as intensity and thermotolerance.
Patent documentation 1: the spy opens the 2001-261761 communique
In addition, be accompanied by the maximization of display panel, require the control interval more accurately, if but the adhesiveness of tunicle that radiation-sensitive resin composition of being used by sept etc. forms and substrate is insufficient, then formed sept will move and departs from the origin-location from substrate, and the result can not keep at interval exactly.In addition, display panel develops in the direction towards the high apertureization of pixel, the result, and the area that can prepare the black matrix area of sept is also dwindling gradually.Thereby, require sept to have the higher transparency, like this,, also can not damage the tone of pixel even sept enters in the pixel region to a certain extent.
But, comprise described in the patent documentation 1, the radiation-sensitive resin composition etc. that in the past was used to form sept with the adhesiveness of substrate and transparent aspect still be not very satisfactory, press for the radiation-sensitive resin composition etc. that development and exploitation have these performances concurrently.
In recent years, based on the consideration of the large tracts of landization of display panel and aspect such as boost productivity, the mother glass substrate is also maximizing gradually.At in the past substrate size (under 680 * 880mm) the situation, compare with mask size, the size of substrate is little, thereby can adopt the mode of disposable exposure, but large substrate (for example 1,500 * 1, occasion 800mm), it almost is impossible wanting to make the mask size identical with this substrate size, thereby is difficult to adopt the mode of operation of disposable exposure.
As the Exposure mode that can adapt to large substrate, the someone has proposed the mode of exposure step by step.But, when adopting the substep Exposure mode, needing each time to carry out multiexposure, multiple exposure for a plate base, contraposition all needs the time with moving when exposing each time, thereby compares with disposable Exposure mode, and throughput may reduce.In addition, when adopting disposable Exposure mode, can allow 3,000J/m 2Exposure sensitivity, and when adopting the substep Exposure mode, require exposure sensitivity 1,500J/m 2Below.But when adopting the radiation-sensitive resin composition in the past be used to form sept etc., 1,500J/m 2Following exposure is difficult to fully form the shape and the thickness of sept.
Summary of the invention
Task of the present invention provides a kind of radiation-sensitive resin composition, can verily reproduce the design size of mask pattern with high sensitivity, and has good adhesiveness with substrate, even 1, and 500J/m 2Following exposure also can form the shape and the thickness of sept fully, in addition, can form the display panel sept of excellences such as compressive strength and rub resistance.
A first aspect of the present invention is radiation-sensitive resin composition (hereinafter to be referred as " radiation-sensitive resin composition "), it is characterized in that said composition contains:
[A] (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides, (a2) contains the ethene unsaturated compound of epoxy radicals and (a3) multipolymer of other ethene unsaturated compound;
[B] has the polymerizable compound of ethene unsaturated link; And
[C] is with the radioactivity-sensitive polymerization initiator of the compound shown in following chemical formula (1) or (2) as neccessary composition.
[Chemical formula 1]
Figure C200510005113D00071
[Chemical formula 2]
Figure C200510005113D00072
[in formula (1) and formula (2), each R 1The alkyl or phenyl of representing straight chain, side chain or the ring-type of carbon number 1-12 independently of one another, each R 2The alkyl or phenyl of representing straight chain, side chain or the ring-type of hydrogen atom, carbon number 1-12 independently of one another, each R 3The alkyl of representing straight chain, side chain or the ring-type of hydrogen atom or carbon number 1-12 independently of one another, each R 4, each R 5With each R 6The alkyl of representing straight chain, side chain or the ring-type of hydrogen atom or carbon number 1-6 independently of one another.But R 1, R 2, R 3, R 4, R 5And R 6The alkyl substituting group that also can be selected from respectively in alkoxy, phenyl and the halogen atom of straight chain, side chain or ring-type of carbon number 1-6 replace R 1And R 2The phenyl substituting group that also can be selected from respectively in alkoxy, phenyl and the halogen atom of straight chain, side chain or ring-type of alkyl, carbon number 1-6 of straight chain, side chain or the ring-type of carbon number 1-6 replace.]
A second aspect of the present invention is the display panel sept that is formed by above-mentioned radiation-sensitive resin composition.
A third aspect of the present invention is to have the display panel of above-mentioned display panel with sept.
Radiation-sensitive resin composition of the present invention can verily reproduce the design size of mask pattern with high sensitivity, and has good adhesiveness with substrate, 1, and 500J/m 2Following exposure also can obtain desirable sept shape and thickness, in addition, can form all good display panel septs such as compressive strength rub resistance.
Description of drawings
Fig. 1 is the figure that illustrates the pattern section shape.
Embodiment
Explain the present invention below.
＜radiation-sensitive resin composition 〉
Multipolymer [A]
[A] composition in the radiation-sensitive resin composition is to contain the ethene unsaturated compound (hereinafter to be referred as " unsaturated compound (a2) that contains epoxy radicals ") of epoxy radicals and (a3) multipolymer (hereinafter to be referred as " multipolymer [A] ") of other ethene unsaturated compound (hereinafter to be referred as " other unsaturated compound (a3) ") by (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides (hereinafter to be referred as " unsaturated carboxylic acid compounds (a1) "), (a2).
In each composition that constitutes multipolymer [A], described unsaturated carboxylic acid compounds (a1) for example can be enumerated: acrylic acid, methacrylic acid, citric acid, succinic acid-1 (2-acryloxy ethyl ester), succinic acid-1 (2-methacryloxy ethyl ester), fumaric acid-1 (2-acryloxy ethyl ester), fumaric acid-1 monocarboxylic acid classes such as (2-methacryloxy ethyl esters); Dicarboxylic acids classes such as maleic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid; The acid anhydride class of above-mentioned dicarboxylic acids etc.
In these unsaturated carboxylic acid compounds (a1),, preferentially select acrylic acid, methacrylic acid, maleic anhydride etc. for use from considering of copolymerization, gained multipolymer [A] for the dissolubility of aqueous alkali and the angle that obtains easily.
In multipolymer [A], unsaturated carboxylic acid compounds (a1) can be used singly or two or more kinds mixed.
In multipolymer [A], the containing ratio that derives from the repetitive of unsaturated carboxylic acid compounds (a1) is advisable at 5-50 weight %, preferably 10-40 weight %, preferably 15-30 weight %.In this case, when the containing ratio that derives from the repetitive of unsaturated carboxylic acid compounds (a1) was lower than 5 weight %, then the dissolubility for aqueous alkali was often lower, otherwise, when surpassing 40 weight %, resulting multipolymer may be excessive for the dissolubility of aqueous alkali.
In addition, the described unsaturated compound (a2) that contains epoxy radicals for example can be enumerated: glycidyl acrylate, acrylic acid 2-methyl ethylene oxidic ester, acrylic acid 3,4-epoxy radicals butyl ester, acrylic acid 6,7-epoxy radicals heptyl ester, acrylic acid 3,4-epoxy radicals cyclohexyl ester, glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 3,4-epoxy radicals butyl ester, methacrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 3, (methyl) acrylic acid epoxy base alkyl esters such as 4-epoxy radicals cyclohexyl ester; α-Yi Jibingxisuan ethylene oxidic ester, α-Yi Jibingxisuan 2-methyl ethylene oxidic ester, α-Yi Jibingxisuan 3,4-epoxy radicals butyl ester, α-Yi Jibingxisuan 6,7-epoxy radicals heptyl ester, α-Yi Jibingxisuan 3,4-epoxy radicals cyclohexyl ester, α-n-pro-pyl glycidyl acrylate, α-alpha-alkyl acrylic acid epoxy base alkyl esters such as normal-butyl glycidyl acrylate; Adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to unsaturated diglycidyl ethers such as vinyl benzyl glycidol ethers etc.
Contain in the unsaturated compound (a2) of epoxy radicals at these, consider from the angle of copolymerization and sept intensity, preferentially select glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 6 for use, 7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether etc.
In multipolymer [A], the unsaturated compound (a2) that contains epoxy radicals can use separately to mix more than a kind or 2 kinds and use.
In multipolymer [A], the containing ratio that derives from the repetitive of the unsaturated compound (a2) that contains epoxy radicals is advisable at 10-70 weight %, preferably 20-60 weight %, preferably 30-50 weight %.In this case, when the containing ratio that derives from the repetitive of the unsaturated compound (a2) that contains epoxy radicals was lower than 10 weight %, the compressive strength of resulting sept was often lower, otherwise, when surpassing 70 weight %, the storage stability of resulting multipolymer is often lower.
In addition, described other unsaturated monomer (a3) for example can be enumerated methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, the acrylic acid cyclohexyl ester, acrylic acid 2-methyl cyclohexyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, the metering system tert-butyl acrylate, the methacrylic acid cyclohexyl ester, (methyl) alkyl-acrylates such as methacrylic acid 2-methyl cyclohexyl ester; Acrylic acid three ring [5.2.1.0 2,6] decane-8-base, acrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) ethyl ester, isobornyl acrylate, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base, methacrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) other (methyl) acrylate ring type ester class such as ethyl ester, IBOMA; (methyl) acrylic acid aryl ester or aralkyl ester classes such as phenyl acrylate, benzyl acrylate, phenyl methacrylate, benzyl methacrylate; (methyl) acrylic acid hydroxyl alkane ester classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate; Acrylic acid assorted five rings ester or assorted six cyclic esters that contain oxygen atom such as acrylic acid tetrahydrofuran ester, tetrahydrofurfuryl acrylate, acrylic acid (oxinane-2-yl) methyl esters, methacrylic acid tetrahydrofuran ester, tetrahydrofurfuryl methacrylate, methacrylic acid (oxinane-2-yl) methyl esters (methyl); Unsaturated dicarboxylic dialkyl esters such as diethyl maleate, DEF, diethyl itaconate; Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrenes; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate dienes compound; Can enumerate vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc. in addition.
In these other unsaturated compound (a3), consider for the dissolubility aspect of aqueous alkali from copolymerization and gained multipolymer [A], preferentially select acrylic acid 2-methyl cyclohexyl ester, metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 for use 2,6] decane-8-base, tetrahydrofurfuryl methacrylate, styrene, to methoxy styrene, 1,3-butadiene etc.
In multipolymer [A], other unsaturated compound (a3) can use separately to mix more than a kind or 2 kinds and use.
In multipolymer [A], the containing ratio of repetitive that derives from other unsaturated compound (a3) is advisable at 10-70 weight %, preferably 20-50 weight %, preferably 30-50 weight %.In this case, when the containing ratio of repetitive that derives from other unsaturated compound (a3) was lower than 10 weight %, the storage stability of gained multipolymer was often lower, otherwise, when surpassing 70 weight %, the gained multipolymer is often lower for the dissolubility of aqueous alkali.
Multipolymer [A], have carboxyl and/or acid anhydride and epoxy radicals, the dissolubility that has appropriateness for aqueous alkali, simultaneously, even without also using special hardening agent, by heating it is solidified, the radiation-sensitive resin composition that contains this multipolymer is when using the imaging liquid that is made of aqueous alkali to carry out video picture, can not produce the remaining and film minimizing of video picture, can easily form the sept of predetermined pattern.
Multipolymer [A] for example can be by placing appropriate solvent with unsaturated carboxylic acid compounds (a1), the unsaturated compound (a2) that contains epoxy radicals and other unsaturated compound (a3), carries out polymerization and make in the presence of radical polymerization initiator.
The employed solvent of above-mentioned polymerization for example can be enumerated as follows:
Methyl alcohol, ethanol, n-propanol, isopropyl alcohol, benzylalcohol, 2-phenylethanol, 3-phenyl-alcohols such as 1-propyl alcohol;
Ethers such as tetrahydrofuran, diox;
Ethylene glycol one alkyl ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one n-propyl ether, ethylene glycol one n-butyl ether;
Ethylene glycol one alkyl ether esters of acrylic acids such as glycol monomethyl ether acrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol one n-propyl ether acrylate, ethylene glycol one n-butyl ether acrylate;
Diethylene glycol one alkyl ether esters of acrylic acids such as methyl carbitol acrylate, diethylene glycol one ether acrylate;
Ethylene glycol one alkyl ether propionic acid esters such as glycol monomethyl ether propionic ester, ethylene glycol monoethyl ether propionic ester, ethylene glycol one n-propyl ether propionic ester, ethylene glycol one n-butyl ether propionic ester;
Diethylene glycol alkyl ethers such as methyl carbitol, diethylene glycol one ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether;
Third ethylene glycol, one alkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol one n-propyl ether, propylene glycol one n-butyl ether;
Third ethylene glycol, one alkyl ether esters of acrylic acids such as the third glycol monomethyl ether acrylate, the third ethylene glycol monoethyl ether acrylate, third ethylene glycol, one n-propyl ether acrylate, third ethylene glycol, one n-butyl ether acrylate;
Third ethylene glycol, one alkyl ether propionic acid esters such as the third glycol monomethyl ether propionic ester, the third ethylene glycol monoethyl ether propionic ester, third ethylene glycol, one n-propyl ether propionic ester, third ethylene glycol, one n-butyl ether propionic ester;
Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;
Ketones such as methyl ethyl ketone, 2 pentanone, propione, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone;
2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxypropionic acid n-pro-pyl ester, 2-methoxypropionic acid n-butyl, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-propionic acid n-pro-pyl ester, 2-ethoxy-propionic acid n-butyl, 2-positive propoxy methyl propionate, 2-positive propoxy ethyl propionate, 2-positive propoxy propionic acid n-pro-pyl ester, 2-positive propoxy propionic acid n-butyl, 2-n-butoxy methyl propionate, 2-n-butoxy ethyl propionate, 2-n-butoxy propionic acid n-pro-pyl ester, 2-n-butoxy propionic acid n-butyl, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxypropionic acid n-pro-pyl ester, 3-methoxypropionic acid n-butyl, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid n-pro-pyl ester, 3-ethoxy-propionic acid n-butyl, 3-positive propoxy methyl propionate, 3-positive propoxy ethyl propionate, 3-positive propoxy propionic acid n-pro-pyl ester, 3-positive propoxy propionic acid n-butyl, 3-n-butoxy methyl propionate, 3-n-butoxy ethyl propionate, 3-n-butoxy propionic acid n-pro-pyl ester, alkoxypropan acid alkyl ester classes such as 3-n-butoxy propionic acid n-butyl;
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, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, the positive propoxy methyl acetate, positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, other ester class such as n-butoxy n-butyl acetate.
In these solvents, preferentially select diethylene glycol alkyl ether, propylene glycol one alkyl ether propionic acid ester, alkoxypropan acid alkyl ester class etc. for use.
Above-mentioned solvent can use separately to mix more than a kind or 2 kinds and use.
In addition, the employed radical polymerization initiator of above-mentioned polymerization has no particular limits, and for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivarate, 1, organic peroxides such as 1-two (tert-butyl hydroperoxide) cyclohexane; And hydrogen peroxide etc.In the occasion of using superoxide as radical polymerization initiator, also can and use reductive agent as the oxidation-reduction type initiating agent.
These radical polymerization initiators can use separately to mix more than a kind or 2 kinds and use.
The multipolymer that obtains like this [A] can be directly be used for preparing radiation-sensitive resin composition with the state of solution, also can separate to be used to prepare radiation-sensitive resin composition from solution.
The polystyrene conversion weight-average molecular weight (hereinafter to be referred as " Mw ") that adopts the multipolymer [A] that gel permeation chromatography (GPC) measures normally 2,000-100,000, preferably 5,000-50,000.The Mw of multipolymer [A] is lower than at 2,000 o'clock, and the video picture of gained tunicle and residual film ratio reduce, and the shape of pattern and thermotolerance may suffer damage, otherwise, surpassing at 100,000 o'clock, image resolution ratio reduces, and perhaps might damage the shape of pattern.
In the present invention, multipolymer [A] can use separately to mix more than a kind or 2 kinds and use.
Polymerizable compound [B]
[B] composition in the radiation-sensitive resin composition is the polymerizable compound (hereinafter to be referred as " polymerizable compound [B] ") with ethene unsaturated link.
Polymerizable compound [B] has no particular limits, and above (methyl) esters of acrylic acid of simple function, difunctionality or trifunctional has good polymerism, considers preferentially to select for use these compounds from the intensity angle that improves resulting sept.
Described simple function (methyl) esters of acrylic acid for example can be enumerated: acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, diethylene glycol one ether acrylate, diethylene glycol one ether methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid 3-methoxyl butyl ester, methacrylic acid 3-methoxyl butyl ester, fumaric acid (2-acryloxy ethyl) (2-hydroxypropyl) ester, fumaric acid (2-methacryloxyethyl) (2-hydroxypropyl) ester etc.
In addition, for example can enumerate as the commercial goods of simple function (methyl) esters of acrylic acid: ア ロ ニ ッ Network ス-101, ア ロ ニ ッ Network ス-111, ア ロ ニ ッ Network ス-114 (above product is that make in East Asia synthetic (strain)); KAYARAD TC-110S, KAYARADTC-120S (above product is Japanese chemical drug (strain) manufacturing); PVC ス コ-ト 158, PVC ス コ-ト 2311 (above product is Osaka organic chemistry industry (strain) manufacturing) etc.
Above-mentioned difunctionality (methyl) esters of acrylic acid for example can be enumerated: ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate, two (phenoxetol) fluorenes diacrylate, two (phenoxetol) fluorenes dimethylacrylate etc.
Commercial goods as difunctionality (methyl) esters of acrylic acid for example can be enumerated: ア ロ ニ ッ Network ス-210, ア ロ ニ ッ Network ス-240, ア ロ ニ ッ Network ス-6200 (above product is that make in East Asia synthetic (strain)); KAYARAD HDDA, KAYARAD HDDAHX-220, KAYARAD HDDA R-604 (above product is Japanese chemical drug (strain) manufacturing); PVC ス コ-ト 260, PVC ス コ-ト 312, PVC ス コ-ト 335HP (above product is Osaka organic chemistry industry (strain) manufacturing) etc.
(methyl) esters of acrylic acid that above-mentioned trifunctional is above for example can be enumerated: trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, three (2-acryloxy ethyl) phosphonate ester, three (2-methacryloxyethyl) phosphonate ester.As 9 officials can be above (methyl) esters of acrylic acid, can enumerate make the trifunctional that has 1 above hydroxyl in the compound that has alkylidene chain and ester ring type structure and contain 2 above isocyanate group and the molecule, 4 officials can or 5 officials can (methyl) acyclic compound react the quiet alkane acrylic ester compound that obtains etc.
Commercial goods as above (methyl) esters of acrylic acid of 3 officials energy for example can be enumerated: ア ロ ニ ッ Network ス M-309, ア ロ ニ ッ Network ス-400, ア ロ ニ ッ Network ス-405, ア ロ ニ ッ Network ス-450, ア ロ ニ ッ Network ス-7100, ア ロ ニ ッ Network ス-8030, ア ロ ニ ッ Network ス-8060, ア ロ ニ ッ Network ス TO-1450 (above product is that make in East Asia synthetic (strain)); KAYARAD TMPTA, KAYARAD DPHA, KAYARADDPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARADDPCA-120 (above product is Japanese chemical drug (strain) manufacturing); PVC ス コ-ト 295, PVC ス コ-ト 300, PVC ス コ-ト 360, PVC ス コ-ト GPT, PVC ス コ-ト 3PA, PVC ス コ-ト 400 (above product is Osaka organic chemistry industry (strain) manufacturing) can enumerate ニ ュ-Off ロ Application テ イ ア R-1150 (the first industrial pharmacy (strain) manufacturing), KAYARAD DPHA-40H (Japanese chemical drug (strain) manufacturing) etc. as the commercial goods of containing the urethane acrylate compounds.
In these simple functions, difunctionality or (methyl) esters of acrylic acid more than the 3 officials energy, preferentially select above (methyl) esters of acrylic acid of 3 officials energy for use, especially preferentially select trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate and dipentaerythritol acrylate for use.
In the present invention, polymerizable compound [B] can use separately to mix more than a kind or 2 kinds and use.
In radiation-sensitive resin composition, with respect to the multipolymer [A] of 100 weight portions, the consumption of polymerizable compound [B] is advisable at the 50-140 weight portion, preferably the 60-120 weight portion.In this case, the consumption of polymerizable compound [B] when using the imaging liquid that is made of aqueous alkali to carry out video picture, might produce video picture remnants during less than 50 weight portions, otherwise when its consumption surpassed 140 weight portions, the hardness of gained sept was often lower.
Polymerization initiator [C]
[C] composition in the radiation-sensitive resin composition; be with the O-acyl group oxime type carbazole compound (hereinafter to be referred as " carbazole compound (C1) ") shown in above-mentioned formula (1) or the formula (2) as neccessary composition, produce the radioactivity-sensitive polymerization initiator (hereinafter to be referred as " polymerization initiator [C] ") of spike that can initiated polymerization compound [B] polymerization when using visible light, ultraviolet ray, far ultraviolet, charged particle line, the exposure of X ray isoradial.
In formula (1) and formula (2), R 1, R 2And R 3The alkyl of straight chain, side chain or ring-type of carbon number 1-12 for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, base, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc. just.
In addition, R 4, R 5And R 6The alkyl of straight chain, side chain or ring-type of carbon number 1-6 for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, base, cyclopentyl, cyclohexyl etc. just.
With respect to R 1, R 2, R 3, R 4, R 5And R 6Each alkyl substituting group and with respect to R 1And R 2The substituting group of each phenyl in, alkoxy as straight chain, side chain or the ring-type of carbon number 1-6, for example methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc. be can enumerate, fluorine atom, chlorine atom etc. for example can be enumerated as halogen atom.
In addition, with respect to R 1And R 2The substituting group of each phenyl in, as the alkyl of straight chain, side chain or the ring-type of carbon number 1-6, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group etc.
In each alkyl and each phenyl, these substituting groups can exist more than 1 or more than a kind.
In formula (1) and formula (2), R 1Preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl etc., R 2Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-pentyl, base, n-heptyl, n-octyl etc. just, R 3Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc., R 4, R 5And R 6Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc.As preferred carbazole compound (C1); for example can enumerate 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-benzoic ether; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-pentane-1; 2-pentane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(1; 3, the 5-trimethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether etc.
In these carbazole compounds (C1), especially preferentially select 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl for use]-ethane-1-ketoxime-O-acetic acid esters.
In the present invention, carbazole compound (C1) can use separately to mix more than a kind or 2 kinds and use.
In addition, in photosensitive polymer combination, with carbazole compound (C1) can also and with other radioactivity-sensitive polymerization initiator (hereinafter to be referred as " other polymerization initiator ").
Described other polymerization initiator, preferably O-acyl group oxime type compound (hereinafter to be referred as " other O-acyl group oxime type polymerization initiator ").
Described other O-acyl group oxime type polymerization initiator; for example can enumerate: 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes), 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes), 1; 2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl group oxime), 1; 2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oximes), 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-methyl benzoyl oxime)) etc.
In these other O-acyl group oxime type polymerization initiator, particularly preferably be 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes).
Above-mentioned other O-acyl group oxime type polymerization initiator can use separately to mix more than a kind or 2 kinds and use.
In the present invention, by using carbazole compound (C1) or carbazole compound (C1) and other O-acyl group oxime type polymerization initiator, even 1,500J/m 2Following exposure, also can form high sensitivity and with the display panel sept of the good adhesion of substrate.
In radiation-sensitive resin composition, with respect to the polymerizable compound [B] of 100 weight portions, the total consumption of carbazole compound (C1) and other O-acyl group oxime type polymerization initiator is advisable at the 5-30 weight portion, preferably the 5-20 weight portion.In this case, when this total consumption was lower than 5 weight portions, when using the imaging liquid video picture that is made of aqueous alkali, the residual film ratio was often lower, otherwise when surpassing 30 weight portions, unexposed position often reduces for the dissolubility of this imaging liquid.
In addition; with carbazole compound (C1) and other O-acyl group oxime type polymerization initiator and time spent; total amount with respect to carbazole compound (C1) and other O-acyl group oxime type polymerization initiator; the usage ratio of other O-acyl group oxime type polymerization initiator is advisable below 50 weight %, preferably 1-30 weight %.In this case, when the usage ratio of other O-acyl group oxime type polymerization initiator surpassed 50 weight %, the pattern form of resulting sept might suffer damage.
In addition; as other polymerization initiator beyond other the O-acyl group oxime type polymerization initiator; for example can enumerate diimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthones compound, phosphine compound, compound in triazine class etc., wherein preferentially select acetophenone compounds and diimidazole compounds for use.
Above-mentioned acetophenone compounds for example can be enumerated alpha-hydroxy ketones, alpha-amido ketone compounds etc.
Above-mentioned alpha-hydroxy ketones for example can be enumerated 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxy-cyclohexyl phenyl ketone etc.; Above-mentioned alpha-amido ketone compounds for example can be enumerated 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone etc.
In addition, as the acetophenone compounds beyond alpha-hydroxy ketones and the alpha-amido ketone compounds, for example can enumerate 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.
These acetophenone compounds can use separately to mix more than a kind or 2 kinds and use.
In the present invention, by using the polymerization initiator of acetophenone compounds, can further improve the shape of sensitivity, resulting sept and compressive strength etc. as other.
Diimidazole compounds recited above for example can be enumerated: 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole etc.
In these diimidazole compounds, preferentially select 2,2 '-two (2-chlorphenyl)-4,4 ', 5 for use, 5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole particularly preferably is, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Above-mentioned diimidazole compounds can use separately to mix more than a kind or 2 kinds and use.
In the present invention, by using the polymerization initiator of diimidazole compounds, can further improve the adhesiveness of sensitivity, image resolution ratio and resulting sept and substrate as other.
In addition, in the occasion of using the diimidazole compounds as other polymerization initiator,, can and use aromatics (hereinafter to be referred as " sensitizer that contains dialkyl amido ") with dialkyl amido in order to make its sensitization.
The described sensitizer that contains dialkyl amido, for example can enumerate 4,4 '-two (dimethylamino) Benzophenone, 4,4 '-two (lignocaine) Benzophenone, (dimethylamino)-ethyl benzoate, to lignocaine ethyl benzoate, p-(dimethylamino)-benzoic acid isopentyl ester, to lignocaine isoamyl benzoate etc.
Contain in the sensitizer of dialkyl amido at these, preferably 4,4 '-two (lignocaine) Benzophenone.
The above-mentioned sensitizer that contains dialkyl amido can use separately to mix more than a kind or 2 kinds and use.
With respect to the multipolymer [A] of 100 weight portions, the consumption that contains the sensitizer of dialkyl amido is advisable at the 0.1-50 weight portion, preferably the 1-20 weight portion.In this case, when the consumption that contains the sensitizer of dialkyl amido was lower than 0.1 weight portion, film may take place the gained sept reduced, and perhaps pattern form suffers damage, otherwise when surpassing 50 weight portions, the pattern form of sept may suffer damage.
In addition, as other polymerization initiator and with diimidazole compounds and the sensitizer that contains dialkyl amido, can add sulfur alcohol compound as the compound of supplying with hydrogen.The diimidazole compounds is contained the sensitizer sensitizing of dialkyl amido and is ftractureed, and produces imidazole radical, but may not have high polymerization energy of initiation this moment, and resulting sept forms unfavorable shapes such as back taper mostly.This problem can be eased by add sulfur alcohol compound in the system of diimidazole compounds and the sensitizer coexistence that contains dialkyl amido.That is, by supplying with hydroperoxyl radical by mercaptan compound to imidazole radical, imidazole radical is transformed into neutral imidazoles, produces the composition of the sulphur free radical with high polymerization energy of initiation, thereby makes the shape of sept form more satisfactory positive taper.
Described mercaptan compound for example can be enumerated: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-aromatics such as 5-methoxyl benzo imidazoles; 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid n-octyl, can enumerate 3 as the compound more than the difunctionality, 6-Er Evil-1, hot two mercaptan of 8-, pentaerythrite four (mercaptoacetate), pentaerythrite four fatty compounds such as (3-mercaptopropionic acid esters) etc.
These mercaptan compounds can use separately to mix more than a kind or 2 kinds and use.
With respect to the carbazole compound (C1) of 100 weight portions, the consumption of sulfur alcohol compound is advisable at the 0.1-50 weight portion, preferably the 1-20 weight portion.When the consumption of sulfur alcohol compound was lower than 0.1 weight portion, the film that the gained sept may take place reduced, and perhaps damages the shape of pattern, otherwise when surpassing 50 weight portions, the pattern form of sept may suffer damage.
In radiation-sensitive resin composition, with respect to all polymerization initiators of 100 weight portions, the usage ratio of other polymerization initiator is advisable below 100 weight portions, below preferred 80 weight portions, preferably below 60 weight portions.When the usage ratio of other polymerization initiator surpassed 100 weight portions, Expected Results of the present invention may suffer damage.
Adjuvant
In case of necessity, in the scope of not damaging effect of the present invention, for example can in radiation-sensitive resin composition, add surfactant, adhesive aid, preserving stabilizer, thermotolerance improving agent etc.
Above-mentioned surfactant is the composition that is used for improving coating performance, can enumerate fluorine type surfactant and silicone surfactant as preferred surfactants.
Fluorine type surfactant recited above is preferentially selected for use and is not being held, the compound that has fluoroalkyl and/or fluorine alkylidene at least one position in main chain and the side chain, for example: 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-pro-pyl) ether, 1,1,2,2-tetrafluoro-n-octyl (base just) ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro-normal-butyl) ether, six ethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, six propylene glycol two (1,1,2,2-tetrafluoro-normal-butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, perfluor n-dodecane sodium sulfonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine n-dodecanes, 1,1,2,2,3,3-hexafluoro n-decane, and fluoroalkyl benzene sodium sulfonate class, fluoroalkyl Alendronate class, fluoroalkyl carboxylic acid sodium class, the fluoroalkyl polyethenoxy ether class, two glycerine four (fluoroalkyl polyoxyethylene ether) class, fluoroalkyl ammonium iodide class, the fluoroalkyl betaines, the fluoroalkyl polyethenoxy ether class, perfluoroalkyl poly oxyethanol class, perfluoroalkyl alcoxylates class, fluorine is an alkyl ether etc.
In addition, commercial goods as fluorine type surfactant, for example can enumerate: BM-1000, BM-1100 (above product is that BM CHEMIE company makes), メ ガ Off ア ッ Network F142D, メ ガ Off ア ッ Network F172, メ ガ Off ア ッ Network F173, メ ガ Off ア ッ Network F183, メ ガ Off ア ッ Network F178, メ ガ Off ア ッ Network F191, メ ガ Off ア ッ Network F471, メ ガ Off ア ッ Network F476 (above product is big Japanese ink chemical industry (strain) manufacturing), Off ロ ラ-De FC-170C, Off ロ ラ-De FC-171, Off ロ ラ-De FC-430, Off ロ ラ-De FC-431 (above product is the manufacturing of Sumitomo ス リ-エ system (strain)), サ-Off ロ Application S-112, サ-Off ロ Application S-113, サ-Off ロ Application S-131, サ-Off ロ Application S-141, サ-Off ロ Application S-145, サ-Off ロ Application S-382, サ-Off ロ Application SC-101, サ-Off ロ Application SC-102, サ-Off ロ Application SC-130, サ-Off ロ Application SC-104, サ-Off ロ Application SC-105, サ-Off ロ Application SC-106 (above product is Asahi Glass (strain) manufacturing), エ Off ト ッ プ EF301, エ Off ト ッ プ EF303, エ Off ト ッ プ EF352 (above product is that new autumn fields changes into (strain) manufacturing), Off -ジ エ Application ト FT-100, Off -ジ エ Application ト FT-110, Off -ジ エ Application ト FT-140A, Off -ジ エ Application ト FT-150, Off -ジ エ Application ト FT-250, Off -ジ エ Application ト FT-251, Off -ジ エ Application ト FTX-251, Off -ジ エ Application ト FTX-218, Off -ジ エ Application ト FTX-300, Off -ジ エ Application ト FTX-310, Off -ジ エ Application ト FTX-400S (above product is that (strain) ネ オ ス makes) etc.
Silicone surfactant recited above, for example can enumerate with following trade name product sold: ト-レ シ リ コ-Application DC3PA, ト-レ シ リ コ-Application DC7PA, ト-レ シ リ コ-Application SH11PA, ト-レ シ リ コ-Application SH21PA, ト-レ シ リ コ-Application SH28PA, ト-レ シ リ コ-Application SH29PA, ト-レ シ リ コ-Application SH30PA, ト-レ シ リ コ-Application SH-190, ト-レ シ リ コ-Application SH-193, ト-レ シ リ コ-Application SZ-6032, ト-レ シ リ コ-Application SF-8428, ト-レ シ リ コ-Application DC-57, ト-レ シ リ コ-Application DC-190 (above product is the manufacturing of eastern レ ダ ウ コ-ニ Application グ シ リ コ-Application (strain)), TSF-4300, TSF-4440, TSF-4445, TSF-4446, TSF-4452, TSF-4460 (above product is the シ リ of GE Toshiba コ-Application (strain) manufacturing).
In addition, as the surfactant beyond above-mentioned, for example can enumerate: polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Non-ionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate; Can enumerate KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), Port リ Off ロ-No.57, Port リ Off ロ-No.95 (above product is common prosperity society chemistry (strain) manufacturing) etc. as commercially available commodity.
These surfactants can use separately to mix more than a kind or 2 kinds and use.
With respect to the multipolymer [A] of 100 weight portions, the use level of surfactant is advisable below 5 weight portions, preferably below 2 weight portions.In this case, when the use level of surfactant surpasses 5 weight portions, often be easy to generate during coating film coarse.
Adhesive aid recited above is the adhering composition that is used for further improving with substrate, and preferred adhesive aid can be enumerated the functional silanes coupling agent.
Functional silanes coupling agent recited above; for example can enumerate: silane coupling agent with carboxyl, methacryl, vinyl, isocyanate group, epoxy radicals isoreactivity functional group; more particularly; can enumerate trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.
These adhesive aids can use separately to mix more than a kind or 2 kinds and use.
With respect to the multipolymer [A] of 100 weight portions, the use level of adhesive aid is advisable below 20 weight portions, preferably below 10 weight portions.In this case, if the use level of adhesive aid surpasses 20 weight portions, when then using the imaging liquid video picture that constitutes by aqueous alkali, often be easy to generate video picture remnants.
Preserving stabilizer recited above for example can be enumerated: sulphur, benzoquinones class, hydroquinones, polyoxy compounds, amine, nitro nitroso compound etc., more particularly, can enumerate 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.
These preserving stabilizers can use separately to mix more than a kind or 2 kinds and use.
With respect to the multipolymer [A] of 100 weight portions, the use level of preserving stabilizer is advisable below 3.0 weight portions, preferably below 0.5 weight portion.In this case, when the use level of storage stability surpassed 3.0 weight portions, sensitivity reduced, and the pattern form of gained sept may suffer damage.
Thermotolerance improving agent recited above for example can be enumerated N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound, be had the compound of 2 above epoxy radicals etc.
N-recited above (alkoxy methyl) glycoluril compounds for example can be enumerated: N, N, N, N-four (methoxy) glycoluril, N, N, N, N-four (ethoxyl methyl) glycoluril, N, N, N, N-four (n-propoxymethyl) glycoluril, N, N, N, N-four (isopropoxy methyl) glycoluril, N, N, N, N-four (n-butoxy methyl) glycoluril, N, N, N, N-four (tert-butoxy methyl) glycoluril etc., wherein, preferentially select N for use, N, N, N-four (methoxy) glycoluril.
N-recited above (alkoxy methyl) melamine compound for example can be enumerated: N, N, N, N, N, N-six (methoxy) melamine, N, N, N, N, N, N-six (ethoxyl methyl) melamine, N, N, N, N, N, N-six (n-propoxymethyl) melamine, N, N, N, N, N, N-six (isopropoxy methyl) melamine, N, N, N, N, N, N-six (n-butoxy methyl) melamine, N, N, N, N, N, N-six (tert-butoxy methyl) melamine etc., wherein, preferentially select N for use, N, N, N, N, N-six (methoxy) melamine.
In addition, as the commercial goods of N-(alkoxy methyl) melamine compound, for example can enumerate ニ カ ラ ッ Network N-2702, ニ カ ラ ッ Network MW-30M (above product be three and ケ ミ カ Le (strain) make) etc.
Compound with 2 above epoxy radicals recited above, for example can enumerate as follows: ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerine diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, hydrogenation bisphenol A diglycidyl ether, bisphenol A diglycidyl ether etc.
In addition, as the commercial goods of compound, for example can enumerate エ Port ラ イ ト 40E, エ Port ラ イ ト 100E, エ Port ラ イ ト 200E, エ Port ラ イ ト 70P, エ Port ラ イ ト 200P, エ Port ラ イ ト 400P, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 1600, エ Port ラ イ ト 3002, エ Port ラ イ ト 4000 (above product is common prosperity society chemistry (strain) manufacturing) with 2 above epoxy radicals.
These thermotolerance improving agents can use separately to mix more than a kind or 2 kinds and use.
Composition solution
Radiation-sensitive resin composition normally is dissolved in multipolymer [A], polymerizable compound [B], polymerization initiator constituents such as [C] in the appropriate solvent when reality is used, and makes composition solution.
Be used to prepare the solvent of above-mentioned composition solution, can use and uniform dissolution to constitute each composition of radiation-sensitive resin composition, do not react and to have appropriate volatile solvent with each composition, as the example of such solvent, can enumerate with about making the same solvent of the illustrated solvent of polymeric part of multipolymer [A].
In these solvents, dissolving power from each composition, with the reactivity of each composition be easy to form the tunicle equal angles and consider, preferentially select alcohols for use, ethylene glycol one alkyl ether acetate esters, diethylene glycol one alkyl ether acetate esters, the diethylene glycol alkyl ether, propylene glycol one alkyl ether acetate esters, alkoxypropan acid alkyl ester classes etc. are especially preferentially selected phenmethylol for use, 2 phenylethyl alcohol, 3-phenyl-1-propyl alcohol, ethylene glycol one n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol ethyl-methyl ether, the Glycol Monomethyl ether acetic acid esters, propylene glycol monoethyl ether acetic acid esters etc.
Above-mentioned solvent can use separately to mix more than a kind or 2 kinds and use.
In addition, when the preparation composition solution, can also and use high boiling solvent with above-mentioned solvent.
Described high boiling solvent for example can be enumerated: N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, the basic just ether of benzylisoeugenol, two, acetonyl acetone, isophorone, sour, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol one phenyl ether acetic acid esters etc.
These high boiling solvents can use separately to mix more than a kind or 2 kinds and use.
Zhi Bei composition solution as required, for example can also use with the filtration backs such as millipore filter of aperture 0.2-0.5 μ m like this.
The composition of preferred radiation-sensitive resin composition of the present invention more specifically for example can be enumerated following (1)-(5).
(1) composition described below, promptly, in the various compositions that constitute multipolymer [A], unsaturated carboxylic acid compounds (a1) is by acrylic acid, the potpourri more than a kind or 2 kinds in methacrylic acid and the maleic anhydride constitutes, the unsaturated compound (a2) that contains epoxy radicals is by glycidyl methacrylate, methacrylic acid 6,7-epoxy radicals heptyl ester, adjacent vinyl benzene methyl glycidyl ether, between vinyl benzene methyl glycidyl ether and the potpourri more than a kind or 2 kinds in the vinyl benzene methyl glycidyl ether constituted, other unsaturated compound (a3) is by acrylic acid 2-methyl cyclohexyl ester, the metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base, tetrahydrofurfuryl acrylate, styrene, the potpourri more than a kind or 2 kinds in methoxy styrene and the 1,3-butadiene is constituted.
(2) composition of above-mentioned (1), in multipolymer [A], the containing ratio that derives from the repetitive of unsaturated carboxylic acid compounds (a1) is 5-40 weight %, 10-30 weight % preferably, the containing ratio that derives from the repetitive of the unsaturated compound (a2) that contains epoxy radicals is 10-70 weight %, 20-60 weight % preferably, the containing ratio of repetitive that derives from other unsaturated compound (a3) is 10-70 weight %, preferably 20-50 weight %.
(3) composition of above-mentioned (1) or (2), wherein polymerizable compound [B] is above (methyl) esters of acrylic acid of simple function, difunctionality or trifunctional, preferably above (methyl) esters of acrylic acid of trifunctional particularly preferably is the potpourri more than a kind or 2 kinds in trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate and the dipentaerythritol acrylate.
(4) each described composition in above-mentioned (1)-(3), wherein, polymerization initiator [C] also contains the potpourri more than a kind or 2 kinds of other O-acyl group oxime type polymerization initiator.
(5) each described composition in above-mentioned (1)-(4), wherein, multipolymer [A] with respect to 100 weight portions, the consumption of polymerizable compound [B] is the 50-140 weight portion, 60-120 weight portion preferably, with respect to the polymerizable compound [B] of 100 weight portions, the consumption of polymerization initiator [C] is the 5-30 weight portion, preferably the 5-20 weight portion.
This radiation-sensitive resin composition is particularly suitable for being used as display panel spacer material such as formation liquid crystal panel or contact type panel.
The display panel sept
When usability radiation resin composite formation display panel is used sept, composition solution is coated on the surface of substrate, prebake is removed solution then, forms tunicle.
The coating process of composition solution, the method that for example can adopt spraying process, rolling method, spin-coating method (centrifugal rubbing method), narrow slit rubbing method, excellent knife coating, the ink-jet method etc. of winding the line to suit is especially preferentially selected spin-coating method, narrow slit rubbing method for use.
The condition of prebake was normally cured under 70-90 ℃ 1-15 minute according to the kind of each constituent and proportioning etc. and different.
Then, the mask by predetermined pattern exposes to the tunicle through prebake, makes it polymerization, use the imaging liquid video picture, removes unwanted part, the formation pattern.
The employed radioactive ray that expose can suitably be selected visible light, ultraviolet ray, far ultraviolet, charged particle line, X ray isoradial for use, preferentially select the radioactive ray of wavelength in the 190-450nm scope for use.
The method of video picture for example can be any in flow liquid method, infusion process, the spray process etc., and the time of video picture is 30-180 second at normal temperatures normally.
Above-mentioned imaging liquid for example can use: inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Primary amine such as ethamine, n-propylamine class; Secondary amine such as diethylamine, di-n-propylamine class; Tertiary amines such as trimethylamine, methyl-diethyl-amine, ethyl dimethylamine, triethylamine; Tertiary alkanol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; Pyrroles, piperidines, N-methyl piperidine, N-crassitude, 1,8-diazabicylo [5.4.0]-7-undecylene, 1,5-diazabicylo [4.3.0]-alicyclic tertiary amines such as 5-nonene; Pyridine, trimethylpyridine, lutidines, quinoline are treated aromatic tertiary amine; The aqueous solution (aqueous alkali) of alkali compounds such as quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide.
In addition, in above-mentioned aqueous alkali, can also add water-miscible organic solvent and/or surfactants such as amount of methanol, ethanol.
After the video picture, for example clean 30-90 second by flowing water, remove unwanted part, jet then pressurized air or compressed nitrogen carry out drying, form the pattern of regulation.
Subsequently, use heating arrangements such as electric hot plate or baking oven, with the temperature of this pattern in regulation, for example 150-250 ℃ is heated official hour down, on electric hot plate, for example heated 5-30 minute, in baking oven, for example heated 30-90 minute, and can obtain needed sept (curing after hereinafter this heating being called).
Radiation-sensitive resin composition of the present invention can verily reproduce the design size of mask pattern with high sensitivity, and has good adhesiveness with substrate, 1, and 500J/m 2Following exposure also can obtain desirable sept shape and thickness, in addition, can form all good display panel septs such as compressive strength rub resistance.
Embodiment
Enumerate embodiment below and further specifically describe embodiments of the present invention, but the invention is not restricted to these embodiment.
Synthesis example 1
In the flask that has cooling tube and stirrer, pack 2 into, 2 '-azo two (2, the 4-methyl pentane nitrile) 5 weight portions and diethylene glycol methyl ethyl ether 200 weight portions, methacrylic acid 18 weight portions of then packing into, glycidyl methacrylate 40 weight portions, styrene 5 weight portions and methacrylic acid three ring [5.2.1.0 2,6] decane-8-base 32 weight portions, with reinstalling 1,3-butadiene 5 weight portions behind the nitrogen replacement, one side stirs one side lentamente makes the temperature of solution rise to 70 ℃, keep this temperature 5 hours and made it polymerization, obtain the solution (Gu shape branch concentration=33.0 weight %) of multipolymer [A].The Mw of this multipolymer [A] is 11,000.If this multipolymer [A] is " multipolymer [A-1] ".
Synthesis example 2
In the flask that has cooling tube and stirrer, pack 2 into, 2 '-azo two (2, the 4-methyl pentane nitrile) 7 weight portions and diethylene glycol methyl ethyl ether 200 weight portions, methacrylic acid 18 weight portions of then packing into, glycidyl methacrylate 20 weight portions, styrene 5 weight portions, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base 32 weight portions and tetrahydrofurfuryl methacrylate 25 weight portions, stirring one side lentamente with one side behind the nitrogen replacement makes the temperature of solution rise to 70 ℃, keep this temperature to make it polymerization in 5 hours, obtain the solution (Gu shape branch concentration=33.4 weight %) of multipolymer [A].The Mw of this multipolymer [A] is 9,000.If this multipolymer [A] is " multipolymer [A-2] ".
Embodiment 1
The preparation composition solution
Will be as the solution of the multipolymer [A-1] of [A] composition by the amount that is equivalent to multipolymer [A-1] 100 weight portions (Gu shape branch); dipentaerythritol acrylate (trade name KAYARAD DPHA as [B] composition; Japan's chemical drug (strain) manufacturing) 1-[9-ethyl-6-(2-the methyl benzoyl)-9.H.-carbamyl-3-yl of 80 weight portions and conduct [C] composition]-ethane-1-ketoxime-O-acetic acid esters (trade name CGI-242; チ バ ス ペ シ ャ リ テ イ-ケ ミ カ Le ズ company manufacturing) 8 weight portions are dissolved in the propylene glycol monomethyl ether acetic acid esters; make solid shape branch concentration reach 35 weight %; millipore filter with aperture 0.2 μ m filters then, makes composition solution (hereinafter to be referred as " composition (S-1) ").
Form sept
Use centrifugal coating machine coating composition solution (S-1) on alkali-free glass substrate, then on electric hot plate in 90 ℃ of following prebake 3 minutes, form the tunicle of thickness 6.0 μ m.
Then, by the mask of the square pattern of residual 10 μ m,, use the exposure intensity of wavelength 365nm to be 300W/m with the exposure interval of 150 μ m 2Ultraviolet ray the gained tunicle is exposed.Use 0.05 weight % potassium hydroxide aqueous solution 25 ℃ of following video pictures 60 seconds then, clean 1 minute with pure water.Put it into then in the baking oven, after under 150 ℃, cured 120 minutes, form the sept of predetermined pattern.
Then resulting sept is carried out various evaluations by following standard, evaluation result is shown among the table 2-1.
(I) evaluation of sensitivity
For resulting pattern, reach exposure more than 90% as sensitivity with the residual film ratio after the video picture (thickness after the video picture * 100/ initial film thickness, below identical), sensitivity is 1,500J/m 2Be good when following.
(II) evaluation of image resolution ratio
For resulting pattern, be that the minimum pattern size of the exposure more than 90% is estimated according to residual film ratio after the video picture.Pattern dimension is more little, and pattern resolution is good more.
(III) evaluation of pattern form
Use the section shape of sem observation gained pattern, be equivalent to a certain evaluation the among the A-C shown in Fig. 1 according to its shape.At this moment, shown in A, pattern edge is the occasion of positive taper, and picture shape is good, shown in B, pattern edge is vertical occasion, pattern form still can, shown in C, pattern edge is that back taper is (in section shape, the limit on film surface is than the del of the length of side of substrate one side) occasion, the possibility that pattern is peeled off when follow-up friction treatment is very high, thereby pattern form is bad.
(IV) evaluation of compressive strength
Use miniature compression test (trade name MCTM-200, (strain) Shimadzu Seisakusho Ltd. make) to measure the compressive strength of gained pattern.Specifically, the plane pressure head of use diameter 50 μ m applies the load of 10mN under 23 ℃ temperature, measures the deflection of this moment, and this is worth when 0.55 μ m is following, shows that compressive strength is good.
(V) evaluation of rub resistance
Use the liquid crystal orientation film coating on the substrate that has formed sept, to be coated with AL3046 (trade name, JSR (strain) make) as aligning agent for liquid crystal with printing machine, then 180 ℃ dry 1 hour down, the alignment agent of formation thickness 0.05 μ m is filmed.
Use has the rubbing machine of roller of the cloth of the polyamide system of twining, and under roller revolution 500rpm, the objective table translational speed 1cm/ condition of second, this is filmed carry out friction treatment, has or not according to pattern and is pruned or peel off and estimate.
(VI) adhering evaluation
Except not using the pattern mask, operate equally with the occasion of above-mentioned formation sept, be formed for estimating adhering cured film.
Then, in the tack test of JIS K-5400 (1900) 8.5, carry out 8.52 the lattice adhesive tape method of drawing test, estimate according to residual lattice number in per 100 lattice.
Embodiment 2-18
[A] composition, [B] composition and [C] composition are as shown in table 1-1, and in addition operation similarly to Example 1 prepares each composition solution, forms sept, carries out various evaluations, and evaluation result is shown among the table 2-1.
Embodiment 19
Similarly to Example 3 [A] composition, [B] composition and [C] composition are dissolved in the diethylene glycol ethyl-methyl ether, make solid shape branch concentration reach 17.5 weight %, millipore filter with aperture 0.2 μ m filters then, makes composition solution (hereinafter to be referred as " composition (S-19) ").
Use composition (S-19) to replace composition (S-1), adopt the narrow slit coating machine to replace centrifugal coating machine to be coated with, in addition operation similarly to Example 1 forms sept, carries out various evaluations, and evaluation result is shown among the table 2-1.
Embodiment 20
Similarly to Example 5 [A] composition, [B] composition and [C] composition are dissolved in the potpourri of diethylene glycol ethyl-methyl ether/benzylalcohol=90/10 (weight ratio), make solid shape branch concentration reach 15 weight %, millipore filter with aperture 0.2 μ m filters then, makes composition solution (hereinafter to be referred as " composition (S-20) ").
Use composition (S-20) to replace composition (S-1), adopt the narrow slit coating machine to replace centrifugal coating machine to be coated with, in addition operation similarly to Example 1 forms sept, carries out various evaluations, and evaluation result is shown among the table 2-1.
Comparative example 1-10
[A] composition, [B] composition and polymerization initiator are as shown in table 1-2, and in addition operation similarly to Example 1 prepares each composition solution, forms sept, carries out various evaluations, and evaluation result is shown among the table 2-2.
In table 1-1 and table 1-2, the various compositions beyond [A] composition are as described below.
[B] composition
B-1: dipentaerythritol acrylate (trade name KAYARAD DPHA, Japanese chemical drug (strain) are made)
B-2: trade name KAYARAD DPHA-40H (Japanese chemical drug (strain) manufacturing)
Polymerization initiator
C-1:1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-second-1-ketoxime-O-acetic acid esters (trade name CGI-242, チ バ ス ペ シ ャ Le テ イ-ケ ミ カ Le ズ company makes)
γ-1:1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes (trade name CGI-124, チ バ ス ペ シ ャ Le テ イ-ケ ミ カ Le ズ company makes)
γ-2:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (trade name イ Le ガ キ ュ ア 907, チ バ ス ペ シ ャ Le テ イ-ケ ミ カ Le ズ company makes)
γ-3:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (trade name イ Le ガ キ ュ ア 369, チ バ ス ペ シ ャ Le テ イ-ケ ミ カ Le ズ company makes)
γ-4:2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole
γ-5:4,4 '-two (lignocaine) Benzophenone
γ-6:2-mercaptobenzothiazoler
Table 1-1
Figure C200510005113D00351
Table 1-2
Table 2-1
The kind of composition Sensitivity (J/m 2) Image resolution ratio (μ m) Pattern form Compressive strength (μ m) Rub resistance Adhesiveness
Embodiment 1 S-1 1,500 10 B 0.51 Do not have 100
Embodiment 2 S-2 1,300 8 B 0.52 Do not have 100
Embodiment 3 S-3 1,300 10 A 0.32 Do not have 100
Embodiment 4 S-4 1,200 8 A 0.32 Do not have 100
Embodiment 5 S-5 1,000 10 B 0.48 Do not have 100
Embodiment 6 S-6 800 8 B 0.52 Do not have 100
Embodiment 7 S-7 800 10 A 0.25 Do not have 100
Embodiment 8 S-8 800 8 A 0.27 Do not have 100
Embodiment 9 S-9 700 8 A 0.28 Do not have 100
Embodiment 10 S-10 800 12 A 0.28 Do not have 100
Embodiment 11 S-11 700 10 A 0.27 Do not have 100
Embodiment 12 S-12 700 12 A 0.25 Do not have 100
Embodiment 13 S-13 600 10 A 0.26 Do not have 100
Embodiment 14 S-14 900 8 A 0.28 Do not have 100
Embodiment 15 S-15 800 8 A 0.27 Do not have 100
Embodiment 16 S-16 800 8 A 0.25 Do not have 100
Embodiment 17 S-17 700 8 A 0.26 Do not have 100
Embodiment 18 S-18 600 8 A 0.26 Do not have 100
Embodiment 19 S-19 1,300 10 A 0.33 Do not have 100
Embodiment 20 S-20 1,000 10 B 0.55 Do not have 100
Table 2-2
The kind of composition Sensitivity (J/m 2) Image resolution ratio (μ m) Pattern form Compressive strength (μ m) Rub resistance Adhesiveness
Comparative example 1 S-1 3000 8 C 0.57 Have 80
Comparative example 2 S-2 2700 10 A 0.36 Do not have 100
Comparative example 3 S-3 2500 8 A 0.32 Do not have 100
Comparative example 4 S-4 2200 10 B 0.48 Do not have 100
Comparative example 5 S-5 2000 8 B 0.56 Do not have 100
Comparative example 6 S-6 1800 10 A 0.27 Do not have 100
Comparative example 7 S-7 1600 8 A 0.29 Do not have 100
Comparative example 8 S-8 1700 8 A 0.29 Do not have 100
Comparative example 9 S-9 1600 12 A 0.29 Do not have 100
Comparative example 10 S-10 1700 8 A 0.27 Do not have 100

Claims (3)

1. radiation-sensitive resin composition is characterized in that, said composition contains:
[A] ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides, contain the ethene unsaturated compound of epoxy radicals and the multipolymer of other ethene unsaturated compound;
[B] has the polymerizable compound of ethene unsaturated link; And
[C] with the radioactivity-sensitive polymerization initiator of the compound shown in following chemical formula (1) or (2) as neccessary composition,
[Chemical formula 1]
Figure C200510005113C00021
[Chemical formula 2]
Figure C200510005113C00022
In formula (1) and formula (2), each R 1The alkyl or phenyl of representing straight chain, side chain or the ring-type of carbon number 1-12 independently of one another, each R 2The alkyl or phenyl of representing straight chain, side chain or the ring-type of hydrogen atom, carbon number 1-12 independently of one another, each R 3The alkyl of representing straight chain, side chain or the ring-type of hydrogen atom or carbon number 1-12 independently of one another, each R 4, each R 5With each R 6The alkyl of representing straight chain, side chain or the ring-type of hydrogen atom or carbon number 1-6 independently of one another, R 1, R 2, R 3, R 4, R 5And R 6Alkyl or be not substituted, the substituting group that perhaps is selected from alkoxy, phenyl and the halogen atom of straight chain, side chain or ring-type of carbon number 1-6 replaces R 1And R 2Phenyl or be not substituted, the substituting group that perhaps is selected from alkoxy, phenyl and the halogen atom of straight chain, side chain or ring-type of alkyl, carbon number 1-6 of straight chain, side chain or the ring-type of carbon number 1-6 replaces.
2. the display panel sept that forms by the described radiation-sensitive resin composition of claim 1.
3. have the display panel of the described display panel of claim 2 with sept.
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CI01 Publication of corrected invention patent application

Correction item: Abstract

Correct: Agent. In the formula, R 1 represents an alkyl group

False: Agent. R 1 represents alkyl

Number: 33

Page: 252

Volume: 21

CI02 Correction of invention patent application

Correction item: Abstract

Correct: Agent. In the formula, R 1 represents an alkyl group

False: Agent. R 1 represents alkyl

Number: 33

Page: The title page

Volume: 21

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