CN1797196A - Photosensitive resin composites, spacer for display panel and display panel - Google Patents
Photosensitive resin composites, spacer for display panel and display panel Download PDFInfo
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- CN1797196A CN1797196A CN 200510138088 CN200510138088A CN1797196A CN 1797196 A CN1797196 A CN 1797196A CN 200510138088 CN200510138088 CN 200510138088 CN 200510138088 A CN200510138088 A CN 200510138088A CN 1797196 A CN1797196 A CN 1797196A
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Abstract
To provide a photosensitive resin composition solution for spacer formation giving an even film uniform in thickness and suitable for a slit die coater method in which a reduced-pressure drying step is carried out in a short time. The photosensitive resin composition comprises (A) a copolymer of at least one selected from the group consisting of ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides, an epoxy group-containing ethylenically unsaturated compound, and another ethylenically unsaturated compound different from those, (B) a polymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, wherein a solid concentration X (wt.%) and a viscosity Y (mPa s) at 25[deg.]C satisfy relationships of LogY<=0.04X-0.08 (1), LogY>=0.04X-0.50 (2), LogY>=0.30 (3) and LogY<=1.08 (4).
Description
Technical field
The present invention relates to photosensitive polymer combination, display panel sept and display panel.More specifically, the display panel that relate to the photosensitive polymer combination that is suitable as the material of used sept in the display panels such as being used to form display panels or touch panel, is formed by said composition is with sept and display panel with this sept.
Background technology
In display panels, in order to make 2 gaps (box gap) between substrate keep certain, used uniformly-spaced particle of beaded glass with regulation particle diameter, plastic bead in the past, but, because these spacer particles are dispersed on the transparency carrier such as glass substrate randomly, if thereby pixel forms the zone and have spacer particle, just have the problem that contrast that spacer particle produces reflection phenomenon (writing り Write body Now resembles), incident light generation scattering, liquid crystal panel reduces.
Therefore, in order to address these problems, begin to adopt the method that forms sept by photoetching.This method is a photosensitive resin coating composition on substrate, mask by regulation carries out ultraviolet exposure, develops then, forms the sept of point-like or strip, because only the regulation position beyond pixel forms the zone forms sept, thereby can address the above problem basically.In addition, according to this method,, also has the advantage of control enclosure gap width easily by the coating film thickness of sense of control photosensitive resin composition.
But in the manufacturing of display panels, from the viewpoint of enhancing productivity, adapting with large-scale picture, substrate size constantly maximizes.The size of substrate has been passed through the first generation of 300mm * 400mm, the second generation of 370mm * 470mm, the third generation of 620mm * 750mm, the 4th generation of 960mm * 1100mm, and the 5th generation of 1100mm * 1300mm is just becoming present main flow.And then substrate size the 6th generation of 1500mm * 1850mm, the 7th generation of 1850mm * 2100mm occur will further maximizing from now on.
When substrate size is small-sized, for example be 370mm * 470mm or when following, photosensitive polymer combination drops in substrate center, and is coated with by spin-coating method.In the method, there is following shortcoming: in coating, need a large amount of photosensitive polymer combination solution, thereby can not adapt to more large-scale substrate.
When substrate size is 960mm * 1100mm or when following, in order to save photosensitive polymer combination solution, usually by slit rotary process (ス リ Star ト ﹠amp; ス ピ Application method) is coated with.This method be from gap nozzle with the photosensitive polymer combination solution coat to real estate, form uniformly by rotary plate then and film.Though this method has the effect of saving solution, but be difficult to adapt to the substrate size after the 5th generation.
Under such background, be accompanied by the maximization of substrate size, begin to utilize slit die spreader (ス リ Star ト ダ イ コ one one) to be coated with.But, in the situation of slit die spreader,, become important for the viscosity of photosensitive polymer combination solution, the control of solid component concentration (TSC) in order to obtain good filming.If viscosity, TSC are too high, then produce disconnected liquid phenomenon from gap nozzle, the inhomogeneous of strip appears.In addition, if viscosity is low excessively, then the thickness of substrate end occurs inhomogeneous.If TSC is low, then the strength of fluid in the photosensitive polymer combination solution raises, thus in the drying under reduced pressure operation after painting process essential time elongated.From the viewpoint of enhancing productivity, the increase of drying under reduced pressure activity time is undesirable.
From these reasons, in slit die spreader method, need a kind of uniform film thickness strongly, do not have sept formation photosensitive polymer combination solution inhomogeneous and that the drying under reduced pressure activity time is short.
Summary of the invention
Therefore, problem of the present invention is to provide a kind of and is suitable for uniform film thickness, do not have the sept of inhomogeneous and the slit die spreader method that the drying under reduced pressure activity time is short to form and uses photosensitive polymer combination solution.
According to the present invention, the first aspect of above-mentioned problem realizes by a kind of photosensitive polymer combination (below, be called " photosensitive polymer combination (I) "), it is characterized in that comprising:
At least a, (a2) that [A] (a1) is selected from ethene unsaturated carboxylic acid and ethene unsaturated carboxylic acid anhydrides comprise the ethene unsaturated compound of epoxy radicals and (a3) be different from the multipolymer of (a1) and other ethene unsaturated compounds (a2),
[B] have the ethene unsaturated link polymerizable compound and
[C] Photoepolymerizationinitiater initiater,
And
Viscosity when solid component concentration and 25 ℃ satisfies the relation of following formula (1)～(4):
Log Y≤0.04X-0.08 (1)
Log Y≥0.04X-0.50 (2)
Log Y≥0.30 (3)
Log Y≤1.08 (4)
Wherein, X is solid component concentration (weight %), the viscosity when Y is 25 ℃ (mPas).
According to the present invention, the second aspect of above-mentioned problem realizes with sept (expression パ ネ Le ス ペ one サ one) by the display panel that is formed by photosensitive polymer combination (I).
According to the present invention, the third aspect of above-mentioned problem realizes with the display panel of sept by having above-mentioned display panel.
Description of drawings
Fig. 1 is the section shape synoptic diagram of spacer patterns (spacer pattern).
Embodiment
Below the present invention will be described in detail.
Photosensitive polymer combination (I)
-multipolymer [A]-
The composition [A] of photosensitive polymer combination (I) comprise the ethene unsaturated compound of epoxy radicals by (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides, (a2) and (a3) be different from (a1) composition and (a2) multipolymer of other ethene unsaturated compounds of composition (being called " multipolymer [A] " hereinafter) constitute.
In each composition that constitutes multipolymer [A], as (a1) ethene unsaturated carboxylic acid and/or ethene unsaturated carboxylic acid anhydrides (following these are referred to as " unsaturated carboxylic acid class monomer (a1) "), can enumerate for example acrylic acid, methacrylic acid, crotonic acid, succinic acid-2-methacryloxy ethyl ester, hexahydrobenzene dioctyl phthalate-monocarboxylic acids such as 2-methacryloxy ethyl ester; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The acid anhydrides of above-mentioned dicarboxylic acids etc.
In these unsaturated carboxylic acid class monomers (a1), from copolyreaction, resulting multipolymer to the dissolubility of alkaline aqueous solution and the viewpoint that obtains easily, preferred acrylic acid, methacrylic acid, maleic anhydride etc.
In photosensitive polymer combination (I), unsaturated carboxylic acid class monomer (a1) can use separately, perhaps uses mixing more than 2 kinds or 2 kinds.
In multipolymer [A], the containing ratio that derives from the repetitive of unsaturated carboxylic acid class monomer (a1) is preferably 5～50 weight %, and more preferably 10～40 weight % are preferably 15～30 weight % especially.If derive from the containing ratio less than 5 weight % of the repetitive of unsaturated carboxylic acid class monomer (a1), then there is tendency to the dissolubility reduction of alkaline aqueous solution, on the other hand, if surpass 50 weight %, then there be the possibility excessive to the dissolubility of alkaline aqueous solution.
In addition, the ethene unsaturated compound (being called " monomer (a2) that comprises epoxy radicals " hereinafter) that comprises epoxy radicals as (a2), can enumerate for example glycidyl acrylate, acrylic acid-2-methyl ethylene oxidic ester, acrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, acrylic acid-3, acrylic acid epoxy Arrcostabs such as 4-epoxy cyclohexyl; Glycidyl methacrylate, methacrylic acid-2-methyl ethylene oxidic ester, methacrylic acid-3,4-epoxy butyl ester, methacrylic acid-6,7-epoxy heptyl ester, methacrylic acid-3, methacrylic acid epoxy alkyl esters such as 4-epoxy cyclohexyl; α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-Yi Jibingxisuan-6, alpha-alkyl acrylic acid epoxy Arrcostabs such as 7-epoxy heptyl ester; Adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to glycidyl ethers such as vinyl benzyl glycidol ethers.
Comprise in the monomer (a2) of epoxy radicals at these, viewpoint from copolyreaction and sept intensity, preferable methyl glycidyl acrylate, methacrylic acid-2-methyl ethylene oxidic ester, methacrylic acid-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether etc.
In photosensitive polymer combination (I), the monomer (a2) that contains epoxy radicals can use separately, perhaps uses mixing more than 2 kinds or 2 kinds.
In multipolymer [A], the containing ratio that derives from the repetitive of the monomer (a2) that contains epoxy radicals is preferably 10～70 weight %, and more preferably 20～60 weight % are preferably 30～50 weight % especially.If derive from the containing ratio less than 10 weight % of the repetitive of the monomer (a2) that contains epoxy radicals, the tendency that then has the intensity reduction of the sept that obtains, on the other hand, if surpass 70 weight %, then there is the tendency of the storage stability reduction of the multipolymer that obtains.
And then, as (a3) other ethene unsaturated compounds (abbreviating " other monomer (a3) " hereinafter as), can enumerate for example alkyl acrylate such as methyl acrylate, isopropyl acrylate; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate; Cyclohexyl acrylate, acrylic acid-2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0
2,6] decane-8-base ester, acrylic acid-2-(three ring [5.2.1.0
2,6] decane-8-base oxygen base) acrylate ring type esters such as ethyl ester, isobornyl acrylate; Cyclohexyl methacrylate, methacrylic acid-2-methyl cyclohexane ester, methacrylic acid three ring [5.2.1.0
2,6] decane-8-base ester, methacrylic acid-2-(three ring [5.2.1.0
2,6] decane-8-base oxygen base) methacrylic acid ester ring type esters such as ethyl ester, isobornyl methacrylate; Acrylic acid aryl ester or aralkyl esters such as phenyl acrylate, acrylic acid benzyl ester; Metering system such as phenyl methacrylate, benzyl methacrylate acid aryl ester or aralkyl ester; Dicarboxylic acids dialkyls such as diethyl maleate, DEF, diethyl itaconate; Methacrylic acid-2-hydroxy methacrylate, methacrylic acid-methacrylic acid hydroxyl Arrcostabs such as 2-hydroxy propyl ester; Methacrylic acid tetrahydro furfuryl ester, methacrylic acid tetrahydrofuran ester, methacrylic acid oxinane-2-methyl esters etc. contain unsaturated five Yuans or the six element heterocycle methacrylates of an oxygen atom; 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 also has vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc. in addition.
In these other monomers (a3), from copolyreaction and the multipolymer that obtains deliquescent viewpoint, preferred acrylic acid-2-methylcyclohexyl ester, metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 to alkaline aqueous solution
2,6] decane-8-base ester, styrene, to methoxy styrene, methacrylic acid tetrahydro furfuryl ester, 1,3-butadiene etc.Particularly when using 1,3-butadiene, can obtain better development, so more preferably.
In photosensitive polymer combination (I), other monomers (a3) can use separately, or use mixing more than 2 kinds or 2 kinds.
In multipolymer [A], the containing ratio that derives from the repetitive of other monomers (a3) is preferably 10～70 weight %, and more preferably 20～60 weight % are preferably 30～50 weight % especially.At this moment, if derive from the containing ratio less than 10 weight % of the repetitive of other monomers (a3), then there is the tendency of the multipolymer storage stability reduction that obtains, on the other hand, if surpass 70 weight %, the tendency that then exists the multipolymer that obtains that the dissolubility of alkaline aqueous solution is reduced.
Multipolymer [A] has carboxyl and/or acid anhydride and epoxy radicals, and alkaline aqueous solution is had appropriate solubleness, simultaneously, even also do not use special hardening agent, also can easily make it to solidify by heating.Therefore, the photosensitive polymer combination (I) that contains this multipolymer does not produce when developing and develops residual and the film loss, and can easily form the sept of predetermined pattern.
Multipolymer [A] for example can by with unsaturated carboxylic acid class monomer (a1), the monomer (a2) that contains epoxy radicals and other monomers (a3) in appropriate solvent, in the presence of radical polymerization initiator, carry out polymerization and prepare.
As the solvent that in the preparation of multipolymer [A], uses, can enumerate for example alcohol, ether, glycol ether, ethylene glycol alkyl ether acetic acid esters, diethylene glycol, dipropylene glycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.
As the object lesson of these solvents, can be listed below respectively:
As alcohol, can enumerate for example methyl alcohol, ethanol, phenmethylol, 2-phenylethanol, 3-phenyl-1-propyl alcohol etc.;
As ethers, can enumerate for example tetrahydrofuran etc.;
As glycol ether, can enumerate for example glycol monoethyl ether, ethylene glycol monoethyl ether etc.;
As ethylene glycol alkyl ether acetic acid esters, can enumerate for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.;
As diethylene glycol, can enumerate for example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.;
As dipropylene glycol, can enumerate for example dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl-methyl ether etc.;
As propylene-glycol monoalky lether, can enumerate for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate for example propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.;
As propylene glycol alkyl ether propionic ester, can enumerate for example propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
As aromatic hydrocarbons, can enumerate for example toluene, dimethylbenzene etc.;
As ketone, can enumerate for example MEK, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone etc.;
As ester, can enumerate for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid propyl ester, the Methoxy acetic acid butyl ester, the ethoxy methyl acetate, the ethoxy ethyl acetate, the ethoxy propyl acetate, the ethoxy butyl acetate, the propoxyl group methyl acetate, the propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy methyl acetate, the butoxy ethyl acetate, the butoxy propyl acetate, the butoxy butyl acetate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, esters such as 3-butoxy butyl propionate.
Wherein, preferred ethylene glycol alkyl ether acetic acid esters, diethylene glycol, dipropylene glycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, wherein, preferred especially diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, methyl proxitol, methyl proxitol acetate.
Above-mentioned solvent can use separately, or uses mixing more than 2 kinds or 2 kinds.
In addition, as the radical polymerization initiator that uses in the above-mentioned polymerization, there is no particular limitation, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl-2, the 4-methyl pentane nitrile), 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; Hydrogen peroxide etc.In addition, when with superoxide during, can also and be used as the oxidation-reduction type initiating agent with itself and reductive agent as radical polymerization initiator.
These radical polymerization initiators can use separately, also can use mixing more than 2 kinds or 2 kinds.
The multipolymer that obtains like this [A] can directly be used to prepare radiation sensitive resin composition with solution state, is used to prepare radiation sensitive resin composition after also can separating from solution.
The polystyrene conversion weight-average molecular weight (hereinafter referred to as " Mw ") that multipolymer [A] is measured by gel permeation chromatography (GPC) is preferably 2,000～100,000, and more preferably 5,000～50,000, be preferably 5,000～10,000 especially.At this moment, if Mw less than 2,000 then has the reduction such as development, residual film ratio of resulting tunicle, or the possibility that suffers damage such as pattern form, thermotolerance, on the other hand, if surpass 100,000, then there is coating to worsen, or the possibility that suffers damage of development.
-polymerizable compound [B]-
[B] composition of photosensitive polymer combination (I) is polymerizable compound with ethene unsaturated link (below, be called " polymerizable compound [B] ").
As polymerizable compound [B], not special the qualification, good or improve the viewpoint of the intensity of the sept that obtains, preferred simple function, difunctionality or trifunctional or above (methyl) acrylate from polymerism.
As above-mentioned simple function (methyl) acrylate, can enumerate for example 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid-3-methoxyl butyl ester, methacrylic acid-3-methoxyl butyl ester, phthalic acid-2-acryloxy ethyl-2-hydroxy propyl ester, phthalic acid-2-methacryloxyethyl-2-hydroxy propyl ester etc.In addition, as commercially available product, can also enumerate for example ア ロ ニ Star Network ス M-101, ア ロ ニ Star Network ス M-111, ア ロ ニ Star Network ス M-114 (East Asia synthetic (strain) makes); KAYARAD TC-110S, KAYARAD TC-120S (Japanese chemical drug (strain) manufacturing); PVC ス コ one ト 158, PVC ス コ one ト 2311 (Osaka organic chemistry industry (strain) manufacturing) etc.
In addition, as above-mentioned difunctionality (methyl) acrylate, can enumerate for example glycol diacrylate, ethylene glycol bisthioglycolate (methacrylate), diethylene glycol diacrylate, diethylene glycol two (methacrylate), tetraethylene glycol diacrylate, TEG two (methacrylate), 1, the 6-hexanediyl ester, 1,6-hexanediol two (methacrylate), 1,9-nonanediol diacrylate, 1,9-nonanediol two (methacrylate), two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes two (methacrylate) etc.In addition, as commercially available product, can enumerate for example ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (East Asia synthetic (strain) makes); KAYARADHDDA, KAYARAD HX-220, KAYARAD R-604 (Japanese chemical drug (strain) manufacturing); PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (Osaka organic chemistry industry (strain) manufacturing) etc.
And then, as above-mentioned trifunctional or above (methyl) acrylate, can enumerate for example trimethylolpropane triacrylate, trimethylolpropane tris (methacrylate), pentaerythritol triacrylate, pentaerythrite three (methacrylate), tetramethylol methane tetraacrylate, pentaerythrite four (methacrylate), dipentaerythritol five acrylate, dipentaerythritol five (methacrylate), dipentaerythritol acrylate, dipentaerythritol six (methacrylate), three (2-acryloxy ethyl) phosphate, three (2-methacryloxyethyl) phosphate etc.
Particularly as nine senses or above (methyl) acrylate, can enumerate make comprise 1 or 1 above hydroxyl in the compound that has alkylidene straight chain and alicyclic structure and comprise 2 or 2 above isocyanate group and the molecule trifunctional, four senses and face can the urethane acrylate compound that obtains of (methyl) acrylate compounds reaction.
As above-mentioned commercially available product, can enumerate for example ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, ア ロ ニ Star Network ス TO-1450 (East Asia synthetic (strain) makes); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (Japanese chemical drug (strain) manufacturing); PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (Osaka organic chemistry industry (strain) manufacturing) etc.The commercially available product of nine functional groups or above polyfunctional group urethane acrylate can for example be enumerated) ニ ユ one Off ロ Application テ イ ア R-1150 (above make), KAYARADDPHA-40H (above make) etc. by Japanese chemical drug (strain) by the-industrial pharmacy (strain).
In these simple functions, difunctionality, trifunctional or above (methyl) acrylate, more preferably trifunctional or above (methyl) acrylate, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate and dipentaerythritol acrylate.
Above-mentioned simple function, difunctionality, trifunctional or above (methyl) acrylate can use separately, perhaps will be used in combination more than 2 kinds or 2 kinds.
In photosensitive polymer combination (I), with respect to the multipolymer [A] of 100 weight portions, the use amount of polymerism thing [B] is preferably 50～250 weight portions, more preferably 100～200 weight portions.At this moment, if use amount less than 50 weight portions of polymerization rerum natura compound [B] then may produce when developing and develop residually, in addition-aspect,, then exist the adaptation of the sept that obtains that the tendency of reduction is arranged if surpass 250 weight portions.
-Photoepolymerizationinitiater initiater [C]-
Photoepolymerizationinitiater initiater described in the present invention is meant by exposing with visible light, ultraviolet ray, far ultraviolet, charged particle beam, X ray etc., the composition of the spike of the polymerization that generation can initiated polymerization compound [B].
With respect to the polymerizable compound [B] of 100 weight portions, the use amount of Photoepolymerizationinitiater initiater [C] is preferably 5～30 weight portions in the photosensitive polymer combination (I), more preferably 5～20 weight portions.At this moment, when use amount less than 5 weight portions of Photoepolymerizationinitiater initiater [C], the tendency that exists the residual film ratio when developing to reduce on the other hand, if surpass 30 weight portions, then exists in the tendency that unexposed portion when developing reduces the dissolubility of alkaline-based developer.
In addition, in photosensitive polymer combination (I), can also with at least a kind other Photoepolymerizationinitiater initiater and Photoepolymerizationinitiater initiater [C] and use.
As Photoepolymerizationinitiater initiater [C], can enumerate for example O-acyl group oxime ester compound, bisglyoxaline compounds, benzoin compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones (multinuclear キ ノ Application based compound), xanthone compounds, phosphine compound, compound in triazine class etc.
Concrete example as O-acyl group oxime ester compound; 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-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether etc.In addition; for example can also 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.
Wherein, preferred especially 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters, 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oximes).These Photoepolymerizationinitiater initiaters can use more than 2 kinds or 2 kinds simultaneously.
By using these Photoepolymerizationinitiater initiaters, can obtain having good susceptibility, the sept of adaptation.
As above-mentioned acetophenone compounds, for example can enumerate alpha-hydroxy ketones, alpha-amido ketone compounds, and other compound.
As the concrete example of above-mentioned alpha-hydroxy ketones, can enumerate 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-hydroxycyclohexylphenylketone etc.Concrete example as above-mentioned alpha-amido ketone compounds, can enumerate 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone etc.As the concrete example of in addition compound, can enumerate 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone etc.
These acetophenone compounds can use separately, also can use mixing more than 2 kinds or 2 kinds.
By using these acetophenone compounds, can further improve susceptibility, sept shape and compression strenght.
As the concrete example of above-mentioned bisglyoxaline compounds, can enumerate
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-bisglyoxaline,
2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-carbethoxy phenyls)-1,2 '-bisglyoxaline,
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In above-mentioned bisglyoxaline compounds, preferred 2,2 '-diimidazole (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
Above-mentioned bisglyoxaline compounds can use separately or use mixing more than 2 kinds or 2 kinds.
By using these bisglyoxaline compounds, can further improve susceptibility, image definition and adaptation.
In addition, for the sensitization united imidazole, can use aliphatics or aromatic series compounds with dialkyl amido.
Concrete example as above-mentioned sensitizer, can enumerate for example N methyldiethanol amine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester etc.In these sensitizers, preferred 4,4 '-two (diethylamino) benzophenone.
These sensitizers can use separately or will use together more than 2 kinds or 2 kinds.
With respect to 100 weight portions [A], the use amount of sensitizer is preferably 0.1～50 weight portion, more preferably the ratio of 1～20 weight portion.
When quantity not sufficient 0.1 weight portion of sensitizer, then there be the film loss or the not good tendency of pattern form of gained sept, in addition,, there is the not good tendency of pattern form equally if surpass 50 weight portions.
When using united imidazole, can also further use sulfur alcohol compound as the hydrogen supplying compound.Benzophenone compound by having dialkyl amido is the united imidazole sensitization, the united imidazole cracking, thus produce imidazole radical.At this moment, scarcely show high free radical polymerization initiating power, and form trapezoidal (contrary テ one パ shape) this not preferred shape.This problem can be eased by add sulfur alcohol compound [C-5] in the system of united imidazole and the benzophenone compound coexistence with dialkyl amido.By providing hydroperoxyl radical to imidazole radical, produce neutral imidazoles and compound with sulphur free radical of high polymerization initiating power by mercaptan compound.Form than falling trapezoidal preferred trapezoid like this.
With respect to 100 weight portion compounds [A], the usage ratio of above-mentioned sulfur alcohol compound is preferably 0.1～50 weight portion, more preferably the ratio of 1～20 weight portion.When quantity not sufficient 0.1 weight portion of sulfur alcohol compound, then there be the film loss or the not good tendency of pattern form of gained sept, in addition,, then there is the not good tendency of pattern form equally if surpass 50 weight portions.
As its concrete example, can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxyl benzo thiazole, 2-sulfydryl-fragrant same clan mercaptan such as 5-methoxyl benzo imidazoles; The single mercaptan of aliphatics such as 3-mercaptopropionic acid, 3-mercapto-propionate, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid monooctyl ester.As difunctionality or above aliphatics mercaptan, can enumerate 3,6-two oxa-s-1, hot two mercaptan of 8-, pentaerythrite four (mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester) etc.
-adjuvant-
As required, in the scope of not damaging the desirable effect of the present invention, can also in photosensitive polymer combination (I), cooperate mentioned component adjuvant in addition.
For example, in order to improve coating, can the matching surface activating agent.This surfactant can preferably use fluorine class surfactant and siloxane type surfactants.
As fluorine class surfactant, can preferably use endways, the compound that has fluoroalkyl or fluorine alkylidene at least one position of main chain and side chain as its concrete example, can enumerate 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro butyl) ether, six ethylene glycol (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, the perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3,3-hexafluoro decane, the fluoro-alkyl benzene sulfonic acid sodium salt, the fluoro-alkyl Alendronate, the fluoro-alkyl carboxylic acid sodium, the fluoro-alkyl polyoxyethylene ether, two glycerine four (fluoro-alkyl polyoxyethylene ether), iodate fluoro-alkyl ammonium, the fluoro-alkyl betaine, the fluoro-alkyl polyoxyethylene ether, the perfluoroalkyl poly oxyethanol, the perfluoroalkyl alkoxide, fluorine class alkyl ether etc.
In addition, as their commercially available product, can enumerate for example BM-1000, BM-1100 (above) by the manufacturing of BM CHEMIE company, メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network F178, メ ガ Off ア Star Network F191, メ ガ Off ア Star Network F471, メ ガ Off ア Star Network F476 (above) by big Japanese イ Application キ chemical industry (strain) manufacturing, Off ロ ラ one De FC 170C, FC-171, FC-430, FC-431 (above) by the manufacturing of Sumitomo ス リ one エ system (strain), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (above) by Asahi Glass (strain) manufacturing, エ Off ト Star プ EF 301, エ Off ト Star プ EF 303, エ Off ト Star プ EF 352 (above change into (strain) make) by new autumn fields, Off one ジ エ Application ト FT-100, Off one ジ エ Application ト FT-110, Off one ジ エ Application ト FT-140A, Off one ジ エ Application ト FT-150, Off one ジ エ Application ト FT-250, Off one ジ エ Application ト FT-251, Off one ジ エ Application ト FKI-251, Off one ジ エ Application ト FYX-218, Off one ジ エ Application ト FT-300, Off one ジ エ Application ト FT-310, Off one ジ エ Application ト FT-400S (above) etc. by (strain) ネ オ ス manufacturing.
In addition, as siloxane type surfactants, can enumerate for example with ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (above) by eastern レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) manufacturing, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, the TSF-4452 commercially available products of trade name such as (above) by GE Toshiba シ リ コ one Application (strain) manufacturing.
In addition, as the surfactant beyond above-mentioned, can enumerate for example polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base 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 such as polyoxyethylene dilaurate, polyoxyethylene distearate, or, can enumerate KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), Port リ Off ロ one No.57,95 (common prosperity society chemistry (strain) manufacturing) etc. as commercially available product.
These surfactants can use separately, also can use mixing more than 2 kinds or 2 kinds.
With respect to the multipolymer [A] of 100 weight portions, the use level of surfactant is preferably 5 weight portions or following, more preferably 2 weight portions or following.At this moment, if the use level of surfactant surpasses 5 weight portions, then when coating, exist to be easy to generate the tendency that film is chapped.
In addition, for the adaptation of further raising, can cooperate bonding auxiliary agent with matrix.
As above-mentioned bonding auxiliary agent; preferred functional silanes coupling agent; as the example; can enumerate and have carboxyl; methacryl; isocyanate group; the silane coupling agent of epoxy radicals isoreactivity functional group; more specifically; can enumerate the trimethoxysilyl benzoic acid; γ-methacryloxypropyl trimethoxy silane; vinyltriacetoxy silane; vinyltrimethoxy silane; γ-isocyanato-propyl-triethoxysilicane; γ-glycidoxypropyltrime,hoxysilane; 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.
These bonding auxiliary agents can use separately or use mixing more than 2 kinds or 2 kinds.
With respect to 100 weight portion multipolymers [A], the use level of bonding auxiliary agent is preferably 20 weight portions or following, more preferably 10 weight portions or following.At this moment, if the use level of bonding auxiliary agent surpasses 20 weight portions, then exist to be easy to generate the residual tendency of developing.
Can add other adjuvant.Can add for the purpose that improves storage stability etc.Particularly, can enumerate sulphur, quinones, hydroquinones, polyoxygenated compound (Port リ オ キ シ compound), amine, nitro nitroso compound.As its concrete example, can enumerate 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.With respect to 100 weight portion multipolymers [A], these adjuvants preferably use 3.0 weight portions or following, more preferably use 0.001～0.5 weight portion.When surpassing 3.0 weight portions, can not obtain sufficient susceptibility, pattern form worsens.
In addition, in order to improve thermotolerance, can add N-(alkoxy methyl) glycoluril compounds, N-(alkoxy methyl) melamine compound and in 1 molecule, have 2 officials can or the compound of above epoxy radicals.As the concrete example of above-mentioned N-(alkoxy methyl) glycoluril compounds, can enumerate 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.In these materials, preferred especially N, N, N, N-four (methoxy) glycoluril.As the concrete example of above-mentioned N-(alkoxy methyl) melamine compound, can enumerate for example 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.In these materials, preferred especially N, N, N, N, N, N-six (methoxy) melamine.As their commercially available product, for example can enumerate ニ カ ラ Star Network N-2702, MW-30M (above by three and ケ ミ カ Le (strain) make) etc.As in 1 molecule, have 2 officials can or the compound of above epoxy radicals, can enumerate for example 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, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether etc.As their concrete example of commercially available product, 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 40E, エ Port ラ イ ト 1500NP, エ Port ラ イ ト 1600, エ Port ラ イ ト 80MF, エ Port ラ イ ト 100MF, エ Port ラ イ ト 4000, エ Port ラ イ ト 3002 (above make) etc. by common prosperity society chemistry (strain).These compounds can use separately, perhaps two or more are used in combination.
Composition solution
During usability photosensitive resin composition (I), normally polymkeric substance [A], polymerizable compound [B], Photoepolymerizationinitiater initiater constituents such as [C] are dissolved in the appropriate solvent, are mixed with composition solution.
As the solvent that in the preparation of above-mentioned composition solution, uses, use each composition that can uniform dissolution constitutes photosensitive polymer combination (I), and not with the solvent of each composition reaction.
As such solvent, can enumerate the cited identical solvent of solvent that can be used for preparing above-mentioned multipolymer [A] with conduct.
In these solvents, from the dissolubility of each composition, with the reactivity of each composition, the viewpoints such as easy degree of filming and forming, preferred for example alcohol, glycol ether, ethylene glycol alkyl ether acetic acid esters, ester and the diethylene glycol of using.Wherein, especially preferably use for example phenmethylol, 2-phenylethanol, 3-phenyl-1-propyl alcohol, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
And then, in order to improve the inner evenness of thickness, can also and use above-mentioned solvent and high boiling solvent.As can and the high boiling solvent of usefulness, can enumerate for example N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters etc.Wherein, preferred N-Methyl pyrrolidone, gamma-butyrolacton, N,N-dimethylacetamide.
Can use the aperture as required is that for example the millipore filter about 0.2～0.5 μ m etc. filters the composition solution for preparing like this, and then supplies with and use.
Viscosity when the solid component concentration of photosensitive polymer combination of the present invention (I) and 25 ℃ must satisfy the relation of following formula (1)～(4).
Log Y≤0.04X-0.08 (1)
Log Y≥0.04X-0.50 (2)
Log Y≥0.30 (3)
Log Y≤1.08 (4)
Wherein, X is solid component concentration (weight %), and Y is the viscosity (mPas) of said composition in the time of 25 ℃.
LogY less than 0.30 viscosity under, when being coated with by the slit die spreader, the thickness of filming of substrate end becomes inhomogeneous, in addition, LogY greater than 1.08 viscosity under, produce disconnected liquid from gap nozzle easily.The generation of disconnected liquid can cause producing the striped inequality, and is therefore not preferred.
In addition, when LogY＞0.04X-0.08, the solid component concentration deficiency, the drying of filming needs long-time, and production efficiency reduces, so not preferred.When LogY＜0.04X-0.50, pattern form becomes trapezoidal easily, so not preferred.
Photosensitive polymer combination (I) is particularly suitable as the material with sept such as the display panel that forms liquid crystal panel or touch panel.
The display panel sept
When usability photosensitive resin composition (I) formation display panel was used sept, after composition solution was coated on substrate surface, except that desolvating, formation was filmed by prebake.
As the coating process of composition solution, for example can adopting, spraying process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, rod are coated with suitable method such as method, ink-jet application method, especially preferably method of spin coating, slit die rubbing method.
In addition, the condition of prebake is generally and is carrying out about 1～15 minute under 70～90 ℃ according to the kind of each constituent, cooperation ratio etc. and different.
Then, the mask by predetermined pattern develops with developer solution then to through the filming to expose and make its polymerization of prebake, removes unwanted part, thereby forms pattern.
As the ray that uses in the exposure, can suitably select visible light, ultraviolet ray, far ultraviolet, charged particle beam, X ray, but optimal wavelength is at the ray of 190～450nm scope.
As developing method, can be any of liquid flow method (liquid contain り method), infusion process, spray process etc. for example, development time is generally 30～180 seconds.
As above-mentioned developer solution, can use for example inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate (メ ケ イ acid Na ト リ ウ system), ammoniacal liquor; Primary amine such as ethamine, n-propylamine class; Secondary amine such as diethylamine, di-n-propylamine class; Tertiary amines such as trimethylamine, methyl diethylamide, ethyl dimethyl amine, triethylamine; Alkanol tertiary 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; Aromatic tertiary amines such as pyridine, trimethylpyridine, lutidines, quinoline; The aqueous solution of alkali compounds such as quaternary ammonium salt such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.
In addition, in the aqueous solution of above-mentioned alkali compounds, can also add water-miscible organic solvent and/or surfactants such as amount of methanol, ethanol.
After the development, carry out for example 30～90 seconds washing by for example flowing water washing, remove unwanted part, blowing compressed air or compressed nitrogen carry out drying then, thereby form the pattern of regulation.
Then, can pass through heating arrangements such as heating plate, baking oven in set point of temperature, for example under 150～250 ℃ with this pattern heat treated official hour, heat treated is for example 5～30 minutes on heating plate, heat treated is for example 30～90 minutes in baking oven, can obtain the purpose sept.
Photosensitive polymer combination of the present invention (I) provides a kind of is not had safety issue to biosome, and large substrate also had good coating, can form can be with the design size of high sensitivity faithful reappearance mask pattern, and good with the adaptation of substrate, and also good display panel such as intensity, thermotolerance is with the photosensitive polymer combination of sept.
Embodiment
Below, by embodiment and comparative example the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
Synthesis example 1
In the flask that condenser pipe, stirrer are housed, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 224 weight portion diethylene glycol methyl ethyl ethers, then add 15 weight portion methacrylic acids, 30 weight portion glycidyl methacrylate, 8 parts by weight of styrene, 44 weight portion methacrylic acids, three ring [5.2.1.0
2,6] decane-8-base ester, behind nitrogen replacement, add 5 weight portion 1,3-butadienes, Yi Bian slowly stir,, keep this temperature to carry out polymerization in 4 hours Yi Bian make the temperature of solution rise to 70 ℃, obtain the solution of multipolymer [A-1].
The solid component concentration of this solution is 29.1 weight %, and the Mw of multipolymer [A-1] is 10,000.
Synthesis example 2
In the flask that condenser pipe, stirrer are housed, add 7 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 255 weight portion diethylene glycol methyl ethyl ethers, then add 15 weight portion methacrylic acids, 30 weight portion glycidyl methacrylate, 8 parts by weight of styrene, 47 weight portion methacrylic acids, three ring [5.2.1.0
2,6] decane-8-base ester, behind nitrogen replacement, add 5 weight portion 1,3-butadienes, Yi Bian slowly stir,, keep this temperature to carry out polymerization in 4 hours Yi Bian make the temperature of solution rise to 70 ℃, obtain the solution of multipolymer [A-2].
The solid component concentration of this solution is 29.0 weight %, and the Mw of multipolymer [A-2] is 5,000.
Synthesis example 3
In the flask that condenser pipe, stirrer are housed, add 2 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 150 weight portion diethylene glycol methyl ethyl ethers, then add 15 weight portion methacrylic acids, 30 weight portion glycidyl methacrylate, 8 parts by weight of styrene, 44 weight portion methacrylic acids, three ring [5.2.1.0
2,6] decane-8-base ester, behind nitrogen replacement,,, keep this temperature to carry out polymerization in 7 hours Yi Bian make the temperature of solution rise to 70 ℃ Yi Bian slowly stir, obtain the solution of multipolymer [A-3].
The solid component concentration of this solution is 37.8 weight %, and the Mw of multipolymer [A-3] is 50,000.
Synthesis example 4
In the flask that condenser pipe, stirrer are housed, add 3.5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 180 weight portion diethylene glycol methyl ethyl ethers, then add 15 weight portion methacrylic acids, 30 weight portion glycidyl methacrylate, 8 parts by weight of styrene, 44 weight portion methacrylic acids, three ring [5.2.1.0
2,6] decane-8-base ester, behind nitrogen replacement,,, keep this temperature to carry out polymerization in 5 hours Yi Bian make the temperature of solution rise to 70 ℃ Yi Bian slowly stir, obtain the solution of multipolymer [A-4].
The solid component concentration of this solution is 34.0 weight %, and the Mw of multipolymer [A-4] is 30,000.
Synthesis example 5
In the flask that condenser pipe, stirrer are housed, add 5 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile), 224 weight portion diethylene glycol methyl ethyl ethers, then add 15 weight portion methacrylic acids, 30 weight portion glycidyl methacrylate, 8 parts by weight of styrene, 44 weight portion methacrylic acids, three ring [5.2.1.0
2,6] decane-8-base ester, behind nitrogen replacement,,, keep this temperature to carry out polymerization in 4 hours Yi Bian make the temperature of solution rise to 70 ℃ Yi Bian slowly stir, obtain the solution of multipolymer [A-5].
The solid component concentration of this solution is 29.7 weight %, and the Mw of multipolymer [A-5] is 10,000.
Embodiment 1
The preparation of composition solution
The solution of the multipolymer [A-1] that 100 weight portions (solid constituent) are obtained as the synthesis example 1 of multipolymer [A], 100 weight portions are as the KAYARAD DPHA (Japanese chemical drug (strain) manufacturing) of polymerizable compound [B], 15 weight portions are as the 2-benzyl-2-N of Photoepolymerizationinitiater initiater [C], N-dimethylamino-1-(4-morpholino phenyl)-1-butanone (trade name " IRGACURE 369 ", チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ company makes) mix, be dissolved in the diethylene glycol methyl ethyl ether as solvent, make that solid component concentration is 25.5 weight %, using the aperture then is that the PTFE filtrator of 0.2 μ m filters, preparation composition solution (S-1).
(I) evaluation of drying under reduced pressure (VCD) time
On the chromium film forming glass of 550 * 650mm, use slit die spreader (TR632105-CL, chemical industry (strain) manufacturing is answered in Tokyo) coating composition prepared solution, make the thickness after the curing reach 4 μ m and 1.5 μ m.Measure the decompression degree reaches 0.5Torr from normal pressure time then.VCD time weak point is favourable.
(II) evaluation of coating (the outstanding vestige (substrate is held げ ピ ン Trace on the Chi) of substrate protuberance)
On the chromium film forming glass of 550 * 650mm, use slit die spreader coating composition prepared solution.Be decompressed to 0.5Torr and carry out drying, on heating plate, filmed with formation in 2 minutes 100 ℃ of following prebake, then further at 2000J/m
2Exposure under expose, form 4 μ m, and the film of 1.5 μ m at the upper surface of chromium film forming glass.
Use sodium vapor lamp irradiation film surface, and confirm the coated thin film surface by range estimation.Can know the situation of confirming the outstanding vestige of substrate protuberance for *, the situation that can confirm a little is △, the situation that almost can not confirm is zero, can not confirms that the situation of the outstanding vestige of any substrate protuberance is ◎.
(III) evaluation of coating (homogeneity)
Use the pin contact to measure machine (Japanese vacuum technique (strain) system Dektak OSP-1100) and measure the thickness of filming on the chromium film forming glass of making by said method.
Calculate homogeneity from the thickness of 9 measuring points.If the short-axis direction with substrate is that X, long axis direction are Y, then (X[mm], Y[mm]) of 9 measuring points is respectively (275,20), (275,30), (275,60), (275,100), (275,325), (275,550), (275,590), (275,620), (275,630).
As inhomogeneity calculating formula, represent with following mathematical expression (3).The FT of following mathematical expression (3) (X, Y) max is the maximal value in the thickness of 9 measuring points, FT (X, Y) min is the minimum value in the thickness of 9 measuring points, (X, Y) avg is the mean value of the thickness of 9 measuring points to FT.Be ◎ when lack of uniformity 2%, when being zero, 3～5% 2～3% the time be △, 5% or above for *.
Homogeneity (%)={ FT (X, Y) max-FT (X, Y) min} * 100/{2 * FT (X, Y) avg} (3)
(IV) evaluation of pattern form
Use spinner on alkali-free glass substrate, be coated with above-mentioned composition solution, then under 90 ℃ on heating plate prebake 3 minutes, the formation thickness is filming of 1.5 μ m.
Then to the mask of resulting tunicle by the square residual pattern of 10 μ m, under 365nm with 200W/m
2Intensity carry out 10 seconds of ultraviolet ray irradiation.Use the potassium hydroxide aqueous solution of 0.05 weight % to develop for 60 seconds down at 25 ℃ then, use pure water to clean afterwards 1 minute, further in baking oven, heating formed sept in 120 minutes under 150 ℃.
The section shape of the spacer patterns that the use sem observation obtains, its result meets any of the A～C shown in Fig. 1 with its shape and is illustrated in the table 1.When the pattern edge as A or B was situation along trapezoidal or vertical configuration, pattern form was good.Shown in C, when forming the shape of trapezoidal (in section shape, the limit on film surface is longer than the limit of substrate-side, is upside-down triangle shape),, therefore be considered as such shape bad because the possibility that pattern is peeled off in polishing operation subsequently is very big.
(V) mensuration of viscosity
Use E type viscosity meter (eastern machine industry (strain) is made, VISCONIC ELD.R) under 25 ℃, to measure.
(VI) mensuration of solid component concentration
The accurate about 0.3g composition solution of weighing in aluminum dish adds about 1g diethylene glycol dimethyl ether, then under 175 ℃ on heating plate drying 60 minutes, obtain solid component concentration from the weight of drying front and back.
Embodiment 2～11, comparative example 1～5
Except using kind as described in Table 1, amount conduct [A] composition～[C] composition, other and embodiment 1 same compositions formulated solution, formation is filmed, and estimates.The addition of [B]～[C] is the weight ratio with respect to 100 weight portion multipolymers [A].
In table 1, the abbreviation of composition is expressed as follows compound.
(B-1): dipentaerythritol acrylate
(KAYARAD DPHA (Japanese chemical drug (strain) manufacturing))
(B-2): KAYARAD DPHA-40H (Japanese chemical drug (strain) manufacturing)
(C-1): 2-benzyl-2-N, N-dimethylamino-1-(4-morpholino phenyl)-1-butanone
(チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company makes, and IRGACURE 369)
(C-2): 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone
(チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company makes, IRGACURE907)
(C-3) 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline
(C-4): 4,4 '-two (diethylamino) benzophenone
(C-5): 2-mercaptobenzothiazole
In the table 1, "-" mark represents not add this composition.
Table 1
| Component list | Embodiment | Comparative example | ||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 1 | 2 | 3 | 4 | 5 | |||
| [A] composition | A-1 | 100 | 100 | 100 | 100 | 50 | - | - | - | 100 | 100 | 100 | - | - | - | 100 | - | |
| A-2 | - | - | - | - | 50 | 100 | 100 | - | - | - | - | - | - | - | - | 50 | ||
| A-3 | - | - | - | - | - | - | - | - | - | - | - | 100 | 50 | - | - | - | ||
| A-4 | - | - | - | - | - | - | - | - | - | - | - | - | 50 | 100 | - | - | ||
| A-5 | - | - | - | - | - | - | - | 100 | - | - | - | - | - | - | - | - | ||
| [B] composition | B-1 | 100 | 100 | 100 | 150 | 100 | 100 | 150 | 100 | 150 | - | 150 | 100 | 100 | 100 | 100 | 150 | |
| B-2 | - | - | - | - | - | - | - | - | - | 100 | - | - | - | - | - | - | ||
| [C] composition | C-1 | 15 | 5 | 5 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | |
| C-2 | 10 | |||||||||||||||||
| C-3 | 7 | |||||||||||||||||
| C-4 | 2 | |||||||||||||||||
| C-5 | 1 | |||||||||||||||||
| Solvent | 567 | 567 | 567 | 563 | 567 | 567 | 563 | 526 | 451 | 567 | 887 | 720 | 720 | 720 | 366 | 366 | ||
| Viscosity (mPas) | 7.5 | 7.5 | 7.5 | 7.5 | 6.0 | 5.0 | 5.0 | 8.0 | 11.0 | 8.0 | 3.0 | 13.0 | 11.0 | 9.0 | 14.0 | 5.0 | ||
| Solid component concentration (weight %) | 25.5 | 25.5 | 25.5 | 30.0 | 25.5 | 25.5 | 30.0 | 27.0 | 35.0 | 25.5 | 21.0 | 21.0 | 21.0 | 21.0 | 35.0 | 35.0 | ||
| Assessment item | Thickness | |||||||||||||||||
| The VCD time (second) | 4μm | 20 | 20 | 20 | 16 | 20 | 20 | 16 | 19 | 14 | 20 | 24 | 24 | 24 | 24 | 14 | 14 | |
| The outstanding vestige of substrate protuberance | △ | △ | △ | ○ | △ | △ | ○ | △ | ○ | △ | × | × | × | × | ○ | ○ | ||
| Homogeneity | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | △ | △ | △ | ◎ | △ | △ | △ | × | ○ | ||
| The VCD time (second) | 1.5μm | 11 | 11 | 11 | 8 | 11 | 11 | 8 | 10 | 7 | 11 | 13 | 13 | 13 | 13 | 7 | 7 | |
| The outstanding vestige of substrate protuberance | ○ | ○ | ○ | ◎ | ○ | ○ | ◎ | ○ | ◎ | ○ | △ | △ | △ | △ | ◎ | ◎ | ||
| Homogeneity | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | △ | △ | △ | ◎ | △ | △ | △ | × | ○ | ||
| Pattern form | A | B | B | A | A | A | A | A | A | A | A | A | A | A | A | C | ||
Claims (4)
1, a kind of photosensitive polymer combination is characterized in that comprising:
At least a, (a2) that [A] (a1) is selected from ethene unsaturated carboxylic acid and ethene unsaturated carboxylic acid anhydrides comprise the ethene unsaturated compound of epoxy radicals and (a3) be different from the multipolymer of (a1) and other ethene unsaturated compounds (a2),
[B] have the ethene unsaturated link polymerizable compound and
[C] Photoepolymerizationinitiater initiater,
And
Viscosity satisfies the relation of following formula (1)～(4) when solid component concentration and 25 ℃:
Log Y≤0.04X-0.08 (1)
Log Y≥0.04X-0.50 (2)
Log Y≥0.30 (3)
Log Y≤1.08 (4)
Wherein, X is solid component concentration (weight %), and Y is the viscosity (mPas) under 25 ℃.
2, photosensitive polymer combination as claimed in claim 1, it is used to use the slit die spreader to be coated with.
3, a kind of display panel sept that forms by the described photosensitive polymer combination of claim 1.
4, a kind of display panel with the described display panel of claim 3 with sept.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004347962 | 2004-12-01 | ||
| JP2004347962 | 2004-12-01 | ||
| JP2005073765 | 2005-03-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1797196A true CN1797196A (en) | 2006-07-05 |
Family
ID=36818311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510138088 Pending CN1797196A (en) | 2004-12-01 | 2005-12-01 | Photosensitive resin composites, spacer for display panel and display panel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1797196A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215369B (en) * | 2008-01-16 | 2010-04-07 | 京东方科技集团股份有限公司 | Optical cured resin, photosensitive resin composition and preparation method thereof |
| CN101105625B (en) * | 2006-07-10 | 2011-11-09 | 富士胶片株式会社 | Light solidifying composition and pattern forming method using the same |
| CN102243396A (en) * | 2011-06-30 | 2011-11-16 | 深超光电（深圳）有限公司 | LCD (liquid crystal display) panel and manufacturing method thereof |
| CN102681343A (en) * | 2011-03-08 | 2012-09-19 | 住友化学株式会社 | Colored photosensitive resin composition |
| CN103034058A (en) * | 2011-10-03 | 2013-04-10 | Jsr株式会社 | Coloring composition, color filter and display device |
| CN109445193A (en) * | 2018-02-13 | 2019-03-08 | 京东方科技集团股份有限公司 | A kind of display panel of horizontal electric field type, its production method and display device |
| US11126042B2 (en) | 2018-02-13 | 2021-09-21 | Beijing Boe Display Technology Co., Ltd. | Horizontal electric field type display panel, method of manufacturing the same, and display device |
-
2005
- 2005-12-01 CN CN 200510138088 patent/CN1797196A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101105625B (en) * | 2006-07-10 | 2011-11-09 | 富士胶片株式会社 | Light solidifying composition and pattern forming method using the same |
| CN101215369B (en) * | 2008-01-16 | 2010-04-07 | 京东方科技集团股份有限公司 | Optical cured resin, photosensitive resin composition and preparation method thereof |
| CN102681343A (en) * | 2011-03-08 | 2012-09-19 | 住友化学株式会社 | Colored photosensitive resin composition |
| CN102243396A (en) * | 2011-06-30 | 2011-11-16 | 深超光电（深圳）有限公司 | LCD (liquid crystal display) panel and manufacturing method thereof |
| CN103034058A (en) * | 2011-10-03 | 2013-04-10 | Jsr株式会社 | Coloring composition, color filter and display device |
| CN109445193A (en) * | 2018-02-13 | 2019-03-08 | 京东方科技集团股份有限公司 | A kind of display panel of horizontal electric field type, its production method and display device |
| US11126042B2 (en) | 2018-02-13 | 2021-09-21 | Beijing Boe Display Technology Co., Ltd. | Horizontal electric field type display panel, method of manufacturing the same, and display device |
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