CN1760757A - Radioactivity sensitive resin composition - Google Patents
Radioactivity sensitive resin composition Download PDFInfo
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- CN1760757A CN1760757A CNA2005101137411A CN200510113741A CN1760757A CN 1760757 A CN1760757 A CN 1760757A CN A2005101137411 A CNA2005101137411 A CN A2005101137411A CN 200510113741 A CN200510113741 A CN 200510113741A CN 1760757 A CN1760757 A CN 1760757A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/039—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种感放射线性树脂组合物，其为含有具有硬化性的碱可溶性树脂(A)、醌二叠氮基化合物(B)、溶剂(C)和硅氧烷系表面活性剂(D)的感放射线性树脂组合物，其中，硅氧烷系表面活性剂(D)为含有HLB值为1以上9以下的硅氧烷系表面活性剂(D1)、和HLB值超过9的硅氧烷系表面活性剂(D2)的硅氧烷系表面活性剂。A radiation-sensitive resin composition comprising a curable alkali-soluble resin (A), a quinonediazide-based compound (B), a solvent (C) and a siloxane-based surfactant (D). A radioactive resin composition, wherein the siloxane-based surfactant (D) contains a siloxane-based surfactant (D1) with an HLB value of 1 to 9 and a siloxane-based surface active agent with an HLB value exceeding 9. The siloxane-based surfactant of the active agent (D2).
Description
Technical field
The present invention relates to radiation-sensitive resin composition.
Background technology
Radiation-sensitive resin composition is as being used to form with for example: the material of the hardening resin figure headed by the diffuse reflector that uses in thin film transistor (TFT) (the following TFT that the is designated as sometimes) dielectric film of type liquid crystal indicator, the dielectric film of organic EL display, the reflection-type TFT substrate, the diaphragm of solid-state imager (the following CCD that is designated as sometimes) etc. is useful (with reference to No. 2933879 communique of Jap.P.).At this, the dielectric film of TFT is required that following performance is arranged, in order to obtain more high performance TFT substrate, the step discrepancy in elevation planarization (with reference to Japanese kokai publication hei 9-244009 communique) of substrates such as the TFT element that will on substrate, form.
In addition, be accompanied by the maximization of the base plate glass size that in recent years TFT substrate uses in making, the painting method of composition is also by become the method that does not make the substrate rotation and applied by seam shape nozzle from spin coating method.In coating unit with seam shape nozzle, material as nozzle uses stainless steel (with reference to TOHKEMY 2001-162204 communique, TOHKEMY 2003-211053 communique, Japanese kokai publication hei 8-173875 communique), but, require radiation-sensitive resin composition good to the wetting state of stainless steel substrate in order to use these coating units to apply.
It is good to the wetting state of stainless steel substrate that the inventor finds to contain the radiation-sensitive resin composition of 2 kinds of silicone type surface active agents.
Summary of the invention
The object of the present invention is to provide the radiation-sensitive resin composition good to the wetting state of stainless steel substrate.
That is, the invention provides aspect, following [1]～[8]:
[1]. a kind of radiation-sensitive resin composition, it has indurative alkali soluble resin (A) for containing, the radiation-sensitive resin composition of quinone diazido compound (B), solvent (C) and silicone type surface active agent (D), wherein, silicone type surface active agent (D) for containing HLB value be more than 1～silicone type surface active agent (D1) below 9 and HLB value be above the silicone type surface active agent of 9 silicone type surface active agent (D2).
[2] .[1] described composition, wherein, has indurative alkali soluble resin (A) for containing multipolymer by the formation unit (a2) that constitutes unit (a1) and derive by the unsaturated compound with hardening group [but not being unsaturated carboxylic acid] of unsaturated carboxylic acid derivative.
[3] .[2] described composition, wherein, the hardening group that constitutes in the unit (a2) is an oxetanyl.
[4] .[1]～[3] any described composition, wherein, have indurative alkali soluble resin (A) and also contain and constitute unit (a3), described formation unit (a3) is to be selected from by what the carboxylate with the two keys of alkene was derived to constitute unit (a31), constituted unit (a32), constituted unit (a33) and constituted at least a kind of unit (a34) by what N-substituted maleimide amines was derived by what the vinyl cyanide based compound was derived by what the aromatics with polymerism carbon-to-carbon unsaturated bond was derived.
[5] .[1]～[4] any described composition, wherein, surfactant (D1) is the poly alkylene glycol modified siloxane.
[6] .[1]～[5] any described composition, wherein, surfactant (D2) is the poly alkylene glycol modified siloxane.
[7] .[1]～[6] any described composition, wherein, with respect to radiation-sensitive resin composition, in massfraction, the content of silicone type surface active agent (D) is 1～1000ppm.
[8] .[1]～[7] any described composition, wherein, with respect to the total amount of silicone type surface active agent (D), in massfraction, the content of surfactant (D1) is 50～90 quality %.
[9] .[1]～[8] any described composition, it is applied to have the coating unit of seam shape nozzle.
[10]. a kind of transparent hard resin figure, it is formed by any described composition in [1]～[9].
[11]. a kind of display device, it has [10] described transparent hard resin figure.
Embodiment
Radiation-sensitive resin composition of the present invention has indurative alkali soluble resin (A) for containing, the radiation-sensitive resin composition of quinone diazido compound (B), solvent (C) and silicone type surface active agent (D), wherein, this silicone type surface active agent (D) for containing HLB value be more than 1～silicone type surface active agent (D1) below 9 and HLB value be above the silicone type surface active agent of 9 silicone type surface active agent (D2).
Has an indurative alkali soluble resin (A) as what use among the present invention, the preferred multipolymer that contains by the formation unit (a2) that constitutes unit (a1) and derive by the unsaturated compound with hardening group (wherein, removing unsaturated carboxylic acid) of unsaturated carboxylic acid derivative that uses.
As above-mentioned unsaturated carboxylic acid, for example can enumerate unsaturated carboxylic acid that has 1 or 2 above carboxyl in unsaturated monocarboxylic acid, the unsaturated dicarboxylic acid equimolecular etc.
As this unsaturated carboxylic acid, can enumerate acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc. particularly.
As above-mentioned unsaturated compound with hardening group (wherein, remove unsaturated carboxylic acid) (methyl) glycidyl acrylate for example arranged, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, (methyl) acrylic acid 3-methyl-3,4-epoxy radicals butyl ester, (methyl) acrylic acid 3-ethyl-3,4-epoxy radicals butyl ester, (methyl) acrylic acid 4-methyl-4,5-epoxy radicals amyl group ester, (methyl) acrylic acid 2,3-epoxy radicals cyclohexyl methyl ester, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl ester, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, 2-vinyl cyclohexene oxide, 3-vinyl cyclohexene oxide, 4-vinyl cyclohexene oxide etc. contains the unsaturated compound of epoxy radicals;
3-(methyl) acrylic methyl oxetanes, 3-methyl-3-(methyl) acrylic methyl oxetanes, 3-ethyl-3-(methyl) acrylic methyl oxetanes, 2-phenyl-3-(methyl) acrylic methyl oxetanes, 2-trifluoromethyl-3-(methyl) acrylic methyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acrylic methyl oxetanes, 3-methyl-3-(methyl) acrylic ethyl oxetanes, 3-methyl-3-(methyl) acrylic ethyl oxetanes, 2-phenyl-3-(methyl) acrylic ethyl oxetanes, 2-trifluoromethyl-3-(methyl) acrylic ethyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acrylic ethyl oxetanes etc. contains the unsaturated compound of oxetanyl etc.
Among this, preferred 3-(methyl) the acrylic methyl oxetanes that uses, 3-methyl-3-(methyl) acrylic methyl oxetanes, 3-ethyl-3-(methyl) acrylic methyl oxetanes, 2-phenyl-3-(methyl) acrylic methyl oxetanes, 2-trifluoromethyl-3-(methyl) acrylic methyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acrylic methyl oxetanes, 3-methyl-3-(methyl) acrylic ethyl oxetanes, 3-methyl-3-(methyl) acrylic ethyl oxetanes, 2-phenyl-3-(methyl) acrylic ethyl oxetanes, 2-trifluoromethyl-3-(methyl) acrylic ethyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acrylic ethyl oxetanes etc. contains the unsaturated compound of oxetanyl, more preferably uses 3-ethyl-3-methacrylic acid ylmethyl oxetanes.
Use comprises the alkali soluble resin of the unsaturated compound that contains oxetanyl, during the preparation radiation-sensitive resin composition, has the tendency of bin stability excellence, and is therefore preferred.
In above-mentioned multipolymer, can also contain at least a kind the formation unit (a3) that constitutes unit (a34) of deriving as the unsaturated link cracking that is selected from the maleimide compound that constitutes unit (a33) and replace by N-that constitutes unit (a32), derives by the vinyl cyanide based compound that constitutes unit (a31), derives by aromatic ethenyl compound of deriving by carboxylate with the two keys of alkene with polymerism carbon-to-carbon unsaturated bond.
As the carboxylate with the two keys of alkene of the above-mentioned formation unit (a31) of deriving, for example can enumerate esters of unsaturated carboxylic acids such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate or (methyl) acrylic acid two cyclopentyl esters, (methyl) phenyl acrylate, diethyl maleate, DEF, diethyl itaconate;
Unsaturated carboxylic acid aminoalkyl esters such as (methyl) acrylic-amino ethyl ester;
Vinyl carboxylates such as vinyl acetate, propionate etc.
As the aromatic ethenyl compound with polymerism carbon-to-carbon unsaturated bond of the above-mentioned formation unit (a32) of deriving, for example, can enumerate aromatic ethenyl compound etc.As this aromatic ethenyl compound, for example, can enumerate styrene, α-Jia Jibenyixi, vinyltoluene etc.
As the vinyl cyanide based compound of the above-mentioned formation unit (a33) of deriving, for example, can enumerate vinyl cyanide based compounds such as vinyl cyanide, methacrylonitrile, alpha-chloro (methyl) vinyl cyanide etc.
The maleimide compound that replaces as the N-of the above-mentioned formation unit (a34) of deriving; for example; can enumerate N-methyl maleimide; the N-ethyl maleimide; the N-butyl maleimide; N-cyclohexyl maleimide; N-benzyl maleimide; N-phenylmaleimide; N-(4-acetylphenyl) maleimide; N-(2; 6-diethyl phenyl) maleimide; N-(4-dimethylamino-3,5-dinitrophenyl) maleimide; N-succinimide base-3-maleimide ベ Application ソ エ one ト; N-succinimide base-3-maleimide Block ロ ヒ オ ネ one ト; N-succinimide base-4-maleimide Block チ レ one ト; N-succinimide base-6-maleimide カ Block ロ エ one ト; N-(1-phenylamino naphthyl-4)-maleimide; N-[4-(2-benzoxazolyl) phenyl] maleimide; N-(9-acridinyl) maleimide etc.
Use separately can be distinguished in this formation unit, also can make up more than 2 kinds and use.
Constitute unit (a1) and (wherein by unsaturated carboxylic acid derivative containing by unsaturated compound with hardening group, remove unsaturated carboxylic acid) in the multipolymer of the formation unit (a2) of deriving, total mole number with respect to the formation unit of multipolymer, constitute preferred 5～50 moles of % of ratio of unit (a1), more preferably 15～40 moles of %, with respect to the total mole number of the formation unit of multipolymer, the ratio that constitutes unit (a2) is preferred 95～50 moles of %, more preferably 85～60 moles of %.
In above-mentioned multipolymer, constitute unit (a1) and the ratio that constitutes unit (a2) when above-mentioned scope, when figure forms developer solution is shown suitable dissolution velocity, and the figure that obtains exists also and shows high indurative tendency, therefore preferred.
Except that constituting unit (a1) and formation unit (a2), contain the multipolymer that constitutes unit (a1) and constitute unit (a2) and also can contain other any composition of formation unit conduct.The formation unit that multipolymer contains other is during as composition arbitrarily, formation unit with respect to multipolymer is overall, the ratio that constitutes unit (a1) is preferably 5～50 moles of %, more preferably 15～40 moles of %, with respect to the formation unit of multipolymer, the ratio that constitutes unit (a2) is preferably 95～5 moles of %, more preferably 85～15 moles of %, preferred 0.1～90 mole of % of the ratio of other formation unit, more preferably 5～80 moles of %.
Constitute unit (a1) and the multipolymer that constitutes unit (a2) as containing, for example, can enumerate 3-ethyl-3-methacrylic acid ylmethyl oxetanes/benzyl methacrylate/methacrylic acid copolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/benzyl methacrylate/methacrylic acid/styrol copolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/styrol copolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/cyclohexyl methacrylate multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/methylmethacrylate copolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/methyl methacrylate/styrol copolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/methacrylic acid tertiary butyl ester multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/isobornyl methacrylate multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/benzyl acrylate multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/cyclohexyl acrylate multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/isobornyl acrylate multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/methacrylic acid two cyclopentyl ester multipolymers, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/acrylic acid tertiary butyl ester multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/phenyl maleimide multipolymer, 3-ethyl-3-methacrylic acid ylmethyl oxetanes/methacrylic acid/cyclohexyl maleimide copolymer etc.
As standard, use gel permeation chromatography to try to achieve to contain the weight-average molecular weight that constitutes unit (a1) and the multipolymer that constitutes unit (a2) to be preferably 2,000～100 with polystyrene, 000, more preferably 2,000～50,000, further preferred 3,000～20,000.Weight-average molecular weight is when above-mentioned scope, and the residual film ratio while when keeping developing, existence can obtain the tendency of high developing powder, and is therefore preferred.
With respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content that containing in the radiation-sensitive resin composition of the present invention constitutes unit (a1) and the multipolymer that constitutes unit (a2) is preferably 50～90%, and more preferably 60～90%.
As the quinone diazido compound (B) that uses among the present invention, for example, can enumerate 1,2-benzoquinones diazido sulphonic acid ester, 1,2-naphthoquinones diazido sulphonic acid ester, 1,2-benzoquinones diazido sulfonamide, 1,2-naphthoquinones diazido sulfonamides etc.
As the instantiation of quinone diazido compound (B), can enumerate 2,3,4-trihydroxy benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,3,4-trihydroxy benzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,4,6-trihydroxy benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,4,6-trihydroxy benzophenone-1,1 of 2-naphthoquinones diazido-trihydroxy Benzophenones such as 5-sulphonic acid ester, 2-naphthoquinones diazido sulphonic acid ester;
2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,3,4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,3,4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl benzophenone-1,1 of 2-naphthoquinones diazido-tetrahydroxybenzophenone classes such as 5-sulphonic acid ester, 2-naphthoquinones diazido sulphonic acid ester;
2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,1 of 2-naphthoquinones diazido-pentahydroxybenzophenone classes such as 5-sulphonic acid ester, 2-naphthoquinones diazido sulphonic acid ester;
2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones diazido-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,1 of 2-naphthoquinones diazido-hexahydroxy Benzophenones such as 5-sulphonic acid ester, 2-naphthoquinones diazido sulphonic acid ester;
Two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones diazido-4-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones diazido-5-sulphonic acid ester, two (p-hydroxybenzene) methane-1,2-naphthoquinones diazido-4-sulphonic acid ester, two (p-hydroxybenzene) methane-1,2-naphthoquinones diazido-5-sulphonic acid ester, 1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones diazido-4-sulphonic acid ester, 1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones diazido-5-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-naphthoquinones diazido-4-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,2 '-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,2 '-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones diazido-5-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones diazido-4-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones diazido-5-sulphonic acid ester, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones diazido-5-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones diazido-4-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-and 2-hydroxy phenyl methane-1,2-naphthoquinones diazido-5-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones diazido-4-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones diazido-5-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-naphthoquinones diazido-4-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,1 of 2-naphthoquinones diazido-(polyhydroxy phenyl) paraffinic such as 5-sulphonic acid ester, 2-naphthoquinones diazido sulphonic acid ester etc.
Above-mentioned quinone diazido compound (B) can be distinguished use separately, also can make up more than 2 kinds and use.
With respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content of the quinone diazido compound (B) among the present invention is preferably 2～50%, and more preferably 5～40%.When quinone diazido compound (B) content is above-mentioned scope, because the dissolution velocity difference of unexposed and exposure portion becomes big, existence can highly keep the developing tendency of residual film ratio, therefore preferred.
As the solvent that uses among the present invention (C), for example can enumerate ethylene glycol monoalkyl ether classes such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-propyl ether, glycol monomethyl isopropyl ether, glycol monomethyl n-butyl ether, glycol monomethyl sec-butyl ether, glycol monomethyl tertbutyl ether, glycol monomethyl n-pentyl ether, glycol monomethyl n-hexyl ether, glycol monomethyl n-heptyl ether, glycol monomethyl n-octyl ether;
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol di ether, the diglycol Di Iso Propyl Ether, the diglycol di-n-butyl ether, diglycol di-secondary butyl ether, the diglycol di-tert-butyl ether, diglycol two n-pentyl ethers, the diglycol methyl ethyl ether, diglycol methyl n-propyl ether, the diglycol methyl isopropyl ether, diglycol methyl n-butyl ether, diglycol methyl sec-butyl ether, the diglycol methyl tert-butyl ether, diglycol methyl n-pentyl ether, diglycol ethyl n-propyl ether, diglycol ethyl isopropyl ether, the diglycol ethyl n-butyl ether, diglycol ethyl sec-butyl ether, the diglycol ethyl tert-butyl ether (ETBE), diglycol ethyl n-pentyl ether, diglycol n-pro-pyl isopropyl ether, diglycol n-pro-pyl n-butyl ether, diglycol n-pro-pyl sec-butyl ether, diglycol n-pro-pyl tertbutyl ether, diglycol n-pro-pyl n-pentyl ether, diglycol isopropyl n-butyl ether, diglycol isopropyl sec-butyl ether, diglycol isopropyl tertbutyl ether, diglycol isopropyl n-pentyl ether, diglycol normal-butyl sec-butyl ether, diglycol normal-butyl tertbutyl ether, diglycol normal-butyl n-pentyl ether, diglycol sec-butyl tertbutyl ether, diglycol dialkyl ethers such as diglycol sec-butyl n-pentyl ether;
Ethylene glycol such as methylcellosolve acetate, ethyl cellosolve acetate alkyl ether acetate esters;
Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters;
Benzene,toluene,xylene, etc. arene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine;
Ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, 2-hydroxy-methyl isobutyl acid, ethyl lactate, butyl lactate, butyl acetate, pentyl acetate, methyl pyruvate, 1,3 butylene glycol diacetate esters etc.
Can use above-mentioned solvent (C) separately, also can make up more than 2 kinds and use.
Wherein, preferably use diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol methyl ethyl ether, 3-ethoxyl ethyl propionate, ethyl lactate, butyl lactate, butyl acetate, during combination solvent (C), these solvents of preferred compositions also use.
As the preferred compositions of solvent, for example can enumerate diethylene glycol dimethyl ether and 3-ethoxyl ethyl propionate, diethylene glycol dimethyl ether and ethyl lactate, diethylene glycol dimethyl ether and butyl lactate, diethylene glycol dimethyl ether and butyl acetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate, diethylene glycol diethyl ether and ethyl lactate, diethylene glycol diethyl ether and butyl lactate, diethylene glycol diethyl ether and butyl acetate, diglycol methyl ethyl ether and 3-ethoxyl ethyl propionate, diglycol methyl ethyl ether and ethyl lactate, diglycol methyl ethyl ether and butyl lactate, diglycol methyl ethyl ether and butyl acetate, 3-ethoxyl ethyl propionate and ethyl lactate, 3-ethoxyl ethyl propionate and butyl lactate, 3-ethoxyl ethyl propionate and butyl acetate;
Diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl lactate, diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl acetate,
Diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl lactate/butyl acetate.
More preferably use diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl lactate, diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl acetate, especially preferably use diglycol methyl ethyl ether/3-ethoxyl ethyl propionate/butyl lactate/butyl acetate.
With respect to radiation-sensitive resin composition, in massfraction, preferred 50～95 quality % of the content of solvent (C), more preferably 70～90 quality %.
When being applied to only to have the coating unit of the operation that applies from seam shape nozzle, in benchmark same as described above, preferred 75～90 quality % of the content of solvent (C).In addition, be applied to except that the operation that applies from seam shape nozzle, when having the coating unit of operation of the substrate rotation that makes application composition, in benchmark same as described above, preferred 65～80 quality % of the content of solvent (C).
When the content of solvent (C) is in aforementioned range, have to form the few tendency of filming of unevenness, so preferred.
The silicone type surface active agent that uses among the present invention (D) contains the HLB value and is more than 1～and silicone type surface active agent (D1) and HLB value below 9 surpass 9 silicone type surface active agent (D2).
At this, the HLB value is specifically measured by the following method.
With the 0.5g surfactant dissolves in 5mL ethanol.Drip 2% phenol solution, the addition (mL) during with the liquid muddiness is recorded as turbidity A.Calculate HLB value (the western youth of reference: surfactant brief guide/industry books Co., Ltd.) by HLB=0.89 * (turbidity A)+1.11.
Can set multiple HLB with the ratio of the ethylene oxide/propylene oxide in polyethers import volume or the polyethers,, preferably use polyether modified silicon oil therefore as silicone type surface active agent of the present invention (D).
As the HLB value is～silicone type surface active agent (D1) below 9 for example to enumerate FS1265, SH710, SH203, BY16-880, SH3775, SH3748, SH3749, SF8410, SF8421, SH8400, SH28PA (eastern レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) system) etc. more than 1.
Surpass 9 silicone type surface active agent (D2) as the HLB value, for example can enumerate SH3771M, SH3746 (eastern レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) system); PS558 (United Chemical Technologies, inc corporate system); Q2-5211 (DowCorning Corp corporate system); SILWET408, L-7210, L-7200 (more than be the OSiSpecialties corporate system) etc.
With respect to radiation-sensitive resin composition, in massfraction, the preferred 1～1000ppm of content of silicone type surface active agent (D), more preferably 10～500ppm, further preferred 50～300ppm.The content of silicone type surface active agent (D) is when above-mentioned scope, and existence can form the few tendency of filming of unevenness, and is therefore preferred.
In addition, with respect to total effective dose of silicone type surface active agent (D), in massfraction, preferred 50～90 quality % of the content of the silicone type surface active agent of 1≤HLB≤9 (D1).
In radiation-sensitive resin composition of the present invention, also can contain polymerization initiator (F), polyphenol compound (G), crosslinking chemical (H), polymerizable monomer (I), silane coupling agent (J) etc. as other compositions.
As above-mentioned polymerization initiator (F), for example can enumerate salt as the light cationic polymerization initiators.Salt constitutes by kation with from lewis acidic negative ion.
As above-mentioned kation, can enumerate diphenyl iodine particularly, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to the octadecyl phenyl) iodine, two (to octyloxyphenyl) iodine, two (to octadecane oxygen base phenyl) iodine, phenyl (to octadecane oxygen base phenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, triphenylsulfonium, three (p-methylphenyl) sulfonium, three (p-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (to tert-butyl-phenyl) sulfonium, three (to cyano-phenyl) sulfonium, three (rubigan) sulfonium, dimethyl (methoxyl) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxyl group) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluorine methoxyl) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromine propoxyl group) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium, dimethyl (three (trichloromethyl) methyl) sulfoniums etc. are preferably enumerated two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium, three (to tert-butyl-phenyl) sulfonium etc.
From lewis acidic negative ion, can enumerate hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate, four (pentafluorophenyl group) borate etc. as above-mentioned particularly, preferably enumerate hexafluoro antimonate, four (pentafluorophenyl group) borate.
Can the above-mentioned kation of combination in any and from lewis acidic negative ion.
Instantiation as the light cationic polymerization initiators can be enumerated diphenyl iodine hexafluorophosphate, two (p-methylphenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, two (to octyl phenyl) iodine hexafluorophosphate, two (to the octadecyl phenyl) iodine hexafluorophosphate, two (to octyloxyphenyl) iodine hexafluorophosphate, two (to octadecane oxygen base phenyl) iodine hexafluorophosphate, phenyl (to octadecane oxygen base phenyl) iodine hexafluorophosphate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, methyl naphthalene iodide hexafluorophosphate, ethyl naphthalene iodide hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (p-methylphenyl) sulfonium hexafluorophosphate, three (p-isopropyl phenyl) sulfonium hexafluorophosphate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, three (to cyano-phenyl) sulfonium hexafluorophosphate, three (rubigan) sulfonium hexafluorophosphate, dimethyl naphthyl sulfonium hexafluorophosphate, diethyl naphthyl sulfonium hexafluorophosphate, dimethyl (methoxyl) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxyl group) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluorine methoxyl) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromine propoxyl group) sulfonium hexafluorophosphate, dimethyl (4-cyano group butoxy) sulfonium hexafluorophosphate, dimethyl (8-nitro octyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluorophosphate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluorophosphate, diphenyl iodine hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, two (to octyl phenyl) iodine hexafluoro arsenate, two (to the octadecyl phenyl) iodine hexafluoro arsenate, two (to octyloxyphenyl) iodine hexafluoro arsenate, two (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, methyl naphthalene iodide hexafluoro arsenate, ethyl naphthalene iodide hexafluoro arsenate, the triphenylsulfonium hexafluoro arsenate, three (p-methylphenyl) sulfonium hexafluoro arsenate, three (p-isopropyl phenyl) sulfonium hexafluoro arsenate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, three (to cyano-phenyl) sulfonium hexafluoro arsenate, three (rubigan) sulfonium hexafluoro arsenate, dimethyl naphthyl sulfonium hexafluoro arsenate, diethyl naphthyl sulfonium hexafluoro arsenate, dimethyl (methoxyl) sulfonium hexafluoro arsenate, dimethyl (ethoxy) sulfonium hexafluoro arsenate, dimethyl (propoxyl group) sulfonium hexafluoro arsenate, dimethyl (butoxy) sulfonium hexafluoro arsenate, dimethyl (octyloxy) sulfonium hexafluoro arsenate, dimethyl (octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (isopropoxy) sulfonium hexafluoro arsenate, dimethyl (tert-butoxy) sulfonium hexafluoro arsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoro arsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoro arsenate, dimethyl (fluorine methoxyl) sulfonium hexafluoro arsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoro arsenate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro arsenate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro arsenate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro arsenate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro arsenate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro arsenate, diphenyl iodine hexafluoro antimonate, two (p-methylphenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, two (to octyl phenyl) iodine hexafluoro antimonate, two (to the octadecyl phenyl) iodine hexafluoro antimonate, two (to octyloxyphenyl) iodine hexafluoro antimonate, two (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, methyl naphthalene iodide hexafluoro antimonate, ethyl naphthalene iodide hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (p-methylphenyl) sulfonium hexafluoro antimonate, three (p-isopropyl phenyl) sulfonium hexafluoro antimonate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, three (to cyano-phenyl) sulfonium hexafluoro antimonate, three (rubigan) sulfonium hexafluoro antimonate, dimethyl naphthyl sulfonium hexafluoro antimonate, diethyl naphthyl sulfonium hexafluoro antimonate, dimethyl (methoxyl) sulfonium hexafluoro antimonate, dimethyl (ethoxy) sulfonium hexafluoro antimonate, dimethyl (propoxyl group) sulfonium hexafluoro antimonate, dimethyl (butoxy) sulfonium hexafluoro antimonate, dimethyl (octyloxy) sulfonium hexafluoro antimonate, dimethyl (octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (isopropoxy) sulfonium hexafluoro antimonate, dimethyl (tert-butoxy) sulfonium hexafluoro antimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro antimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoro antimonate, dimethyl (fluorine methoxyl) sulfonium hexafluoro antimonate, dimethyl (2-ammonia ethoxy) sulfonium hexafluoro antimonate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro antimonate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro antimonate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro antimonate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro antimonate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro antimonate, diphenyl iodine four (pentafluorophenyl group) borate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, two (to octyl phenyl) iodine four (pentafluorophenyl group) borate, two (to the octadecyl phenyl) iodine four (pentafluorophenyl group) borate, two (to octyloxyphenyl) iodine four (pentafluorophenyl group) borate, two (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, phenyl (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, methyl naphthalene iodide four (pentafluorophenyl group) borate, ethyl naphthalene iodide four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (p-methylphenyl) sulfonium four (pentafluorophenyl group) borate, three (p-isopropyl phenyl) sulfonium four (pentafluorophenyl group) borates, three (2, the 6-3,5-dimethylphenyl) sulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate, three (to cyano-phenyl) sulfonium four (pentafluorophenyl group) borate, three (rubigan) sulfonium four (pentafluorophenyl group) borate, dimethyl naphthyl sulfonium four (pentafluorophenyl group) borate, diethyl naphthyl sulfonium four (pentafluorophenyl group) borate, dimethyl (methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (ethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (tert-butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclopentyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclohexyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (fluorine methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-chloroethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (3-bromine propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (4-cyano group butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (8-nitro octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-hydroxyl isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (three (trichloromethyl) methyl) sulfonium four (pentafluorophenyl group) borates etc. are preferably enumerated two (p-methylphenyl) iodine hexafluorophosphates, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, two (p-methylphenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, the triphenylsulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.
Wherein, preferred pair (p-methylphenyl) iodine hexafluoro antimonates that use, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate.
When using polymerization initiator (F), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content of polymerization initiator is preferably 0.01～10 quality %, more preferably 0.1～5 quality %.When the content of polymerization initiator (F) is above-mentioned scope, the setting rate in the time of can improving thermmohardening, the reduction of the resolution when suppressing thermmohardening, and then there is the tendency that improves in the solvent resistance of cured film, therefore preferred.
As above-mentioned polyphenol compound (G), for example can enumerate the compound of the phenol hydroxyl that has in the molecule more than 2 etc.
As polyphenol compound (G), for example can enumerate polyatomic phenols such as the trihydroxy Benzophenones identical, tetrahydroxybenzophenone class, pentahydroxybenzophenone class, hexahydroxy Benzophenones, (polyhydroxy phenyl) paraffinic etc. with record in quinone diazido compound.
In addition, as above-mentioned polyphenol compound (G), for example can enumerate is the polymkeric substance of starting monomer at least with the hydroxy styrenes.
As above-mentioned polyphenol compound (G), can enumerate resin that polymerization hydroxy styrenes such as polycarboxylated styrene, hydroxystyrene/methyl methacrylate multipolymer, hydroxy styrenes/methacrylic acid cyclohexyl ester multipolymer, hydroxy styrenes/styrol copolymer, hydroxy styrenes/alkoxystyrene multipolymer obtain etc. particularly, and then, can enumerate by at least a compound that is selected from phenol, cresols class and pyrocatechol and be selected from aldehydes and novolac resin that the compound more than a kind of ketone obtains through polycondensation etc.
When using above-mentioned polyphenol compound (G), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, preferred 0.01～40 quality % of the content of polyphenol compound, more preferably 0.1～25 quality %.When the content of polyphenol compound (G) is above-mentioned scope, there is the tendency that resolution improves, transmission of visible light does not reduce, therefore preferred.
(H) for example can enumerate methylol compound etc. as above-mentioned crosslinking chemical.
As above-mentioned methylol compound, for example can enumerate alkoxy methyl amino resins such as alkoxy methyl melamine resin, alkoxy methyl urea resin etc.
Wherein, as the alkoxy methyl melamine resin, for example can enumerate methoxy melamine resin, ethoxyl methyl melamine resin, propoxyl group methylated melamines resin, butoxymethyl melamine resin etc.; As the alkoxy methyl urea resin, for example can enumerate methoxy urea resin, ethoxyl methyl urea resin, propoxyl group methylate urea resin, butoxymethyl urea resin etc.Above-mentioned crosslinking chemical (H) can be distinguished use separately, also can make up more than 2 kinds and use.
When using crosslinking chemical (H), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content of crosslinking chemical is preferably 0.01～15 quality %.When the content of crosslinking chemical was above-mentioned scope, the transmission of visible light of the film that obtains increased, and improved as the performance of hardening resin figure, and is therefore preferred.
As above-mentioned polymerizable monomer (I), for example can enumerate by the heating can carry out free radical polymerization polymerizable monomer, can carry out the polymerizable monomer of cationic polymerization etc.Among them, preferred use can be carried out the polymerizable monomer of cationic polymerization.
As the above-mentioned polymerizable monomer that can carry out free radical polymerization, for example can enumerate compound with polymerism carbon-to-carbon unsaturated bond, can be the polymerizable monomer of simple function, also can be the above polyfunctional polymerizable monomers such as polymerizable monomer of dual functional polymerizable monomer or trifunctional.
As the polymerizable monomer of simple function, for example can enumerate acrylic acid nonyl phenyl carbitol ester, methacrylic acid nonyl phenyl carbitol ester, acrylic acid 2-hydroxyl-3-benzene oxygen propyl diester, methacrylic acid 2-hydroxyl-3-benzene oxygen propyl diester, acrylic acid 2-ethylhexyl carbitol ester, methacrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, N-vinyl pyrrolidone etc.
Polymerizable monomer as two simple functions, for example can enumerate 1,6-hexanediyl ester, 1, two (acryloxy ethyl) ethers of 6-hexanediol dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bisphenol-A, 3-methyl pentanediol diacrylate, 3-methyl pentanediol dimethylacrylate etc.
In addition, as the polymerizable monomer more than three simple functions, for example can enumerate trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, pentaerythrite five acrylate, pentaerythrite pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate etc.
In above-mentioned polymerizable monomer, preferably use the above polymerizable monomer of difunctionality or trifunctional.Specifically, preferably use tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc.More preferably use dipentaerythritol acrylate.In addition, also the polymerizable monomer of difunctionality or polymerizable monomer more than the trifunctional and simple function can be used in combination.
As the polymerizable monomer that can carry out cationic polymerization, for example can enumerate the polymerizable monomer of the functional group of cationically polymerizables such as having vinyl ether group, propenyl ether, epoxy radicals, oxetanyl.As the compound that contains vinyl ether group, for example can enumerate triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl etc., as the compound that contains the propenyl ether, for example can enumerate 4-(1-propenyl oxygen ylmethyl)-1,3-dioxolanes-2-ketone etc., as the compound that contains epoxy radicals, for example can enumerate bisphenol A type epoxy resin, the phenol novolac epoxy resin, the cresols novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hetero ring type epoxy resin etc., as the compound that contains oxetanyl, for example can enumerate two [3-(3-ethyl oxetanyl) methyl] ethers, 1, two [3-(the 3-ethyl oxetanyl) methoxyl] benzene of 4-, 1, two [3-(the 3-ethyl oxetanyl) methoxyl] methylbenzene of 4-, 1, two [3-(the 3-ethyl oxetanyl) methoxyl] cyclohexanes of 4-, 1, two [3-(the 3-ethyl oxetanyl) methoxyl] methylcyclohexanes of 4-, 3-(3-ethyl oxetanyl) methylates novolac resin etc.
When using above-mentioned polymerizable monomer (I), polymerizable monomer (I) can be distinguished use separately, also can make up more than 2 kinds and use.With respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content of polymerizable monomer (I) is generally 0.1～20 quality %.
As above-mentioned silane coupling agent (J), for example can enumerate methyltrimethoxy silane, methyl triethoxysilane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl three (2-methoxy ethoxy) silane, 3-chloropropyl-trimethoxy silane, 3-chloropropyl methyl-dichlorosilane, 3-chloropropyl methyl-dimethoxy silane, 3-chloropropyl methyl-diethoxy silane, 3-glycidoxy propyl group-trimethoxy silane, 3-glycidoxy propyl group-triethoxysilane, 3-glycidoxy propyl group methyl-dimethoxy silane, 3-sulfydryl propyl group-trimethoxy silane, 3-methacryloxypropyl-trimethoxy silane, 3-methacryloxypropyl methyl-dimethoxy silane, 2-(3,4-epoxy radicals cyclohexyl) ethyl-trimethoxy silane, N-2-(N-vinyl benzyl amino-ethyl)-3-aminopropyl-trimethoxy silane hydrochloride, hexamethyldisilazane, diamino silanes, triamido propyl group-trimethoxy silane, 3-aminopropyl-trimethoxy silane, 3-aminopropyl-triethoxysilane, 3-aminopropyl methyl-diethoxy silane, 3-aminopropyl-three (2-methoxy ethoxy ethoxy) silane, 3-(2-amino-ethyl)-3-aminopropyl-trimethoxy silane, 3-(2-amino-ethyl)-3-aminopropyl methyl-dimethoxy silane, 3-urea groups propyl group-trimethoxy silane, 3-urea groups propyl group-triethoxysilane, N-amino-ethyl-3-aminopropyl-trimethoxy silane, N-amino-ethyl-3-aminopropyl methyl-dimethoxy silane, N-methyl-3-aminopropyl-trimethoxy silane, N-phenyl-3-aminopropyl-trimethoxy silane etc.
Wherein, preferably use the silane coupling agent that has epoxy radicals in its structure.
As the silane coupling agent that has epoxy radicals in above-mentioned its structure, for example can enumerate 3-glycidoxy propyl group-trimethoxy silane, 3-glycidoxy propyl group-triethoxysilane, 3-glycidoxy propyl group methyl-dimethoxy silane, 2-(3,4-epoxy radicals cyclohexyl) ethyl-trimethoxy silane, preferred 2-(3, the 4-epoxy radicals cyclohexyl) ethyl-trimethoxy silane etc. that uses has the silane coupling agent of ester ring type epoxy radicals.
With respect to radiation-sensitive resin composition, in massfraction, the content of silane coupling agent (J) is preferably 0.01～10 quality %, more preferably 0.1～2 quality %, further preferred 0.2～1 quality %.When the content of silane coupling agent is above-mentioned scope, when using radiation-sensitive resin composition of the present invention to form the hardening resin figure, owing to improve the transmission of visible light of this hardening resin figure, except improving the transparency, improve the tack of this hardening resin figure and base material, so preferred.
In radiation-sensitive resin composition of the present invention, as required, can also contain other compositions, for example various adjuvants such as antioxidant, dissolution inhibitor, sensitizer, ultraviolet light absorber, light stabilizer, cohesiveness modifying agent, electron donor.
Radiation-sensitive resin composition of the present invention can be prepared as follows, and for example mixed dissolution has the solution of the solvent (C) with indurative alkali soluble resin (A), the solution that is dissolved with the solvent (C) of quinone diazido compound (B), silicone type surface active agent (D).In addition, after the mixing, and then can also add solvent (C), or can also to add fluorine as required be surfactant (E).And then after solution mixed, preferred solids removed by filtration material for example preferably used below the 3 μ m of aperture, and preferred 0.1 μ m is above～and filter about 2 μ m are following filters.For the used solvent of above-mentioned each composition, can be identical, if the solvent that dissolves each other, also can be inequality.
In order to use radiation-sensitive resin composition of the present invention to form transparent hard resin figure, for example, form the layer that is made of radiation-sensitive resin composition of the present invention on substrate, after by mask above-mentioned layer irradiation radioactive ray being exposed, developing gets final product.
For example can enumerate transparent glass plate etc. as substrate.On aforesaid substrate, also can form circuit such as TFT or CCD, color filter etc.
The preferred coating unit with seam shape nozzle that uses of layer that is made of radiation-sensitive resin composition applies.As coating unit, for example can enumerate slit coater, die coater, curtain stream coating machine etc. with seam shape nozzle.
After the coating, heat behind heat drying (prebake conditions) or the drying under reduced pressure,, form the radiation-sensitive resin composition layer of solvent minimizing by removing part or all of volatile ingredients such as desolvating.In addition, the thickness of this radiation-sensitive resin composition layer for example is about 1.5 μ m～5 μ m.
Then, by mask the radiation-sensitive resin composition layer is shone radioactive ray.The figure of mask can suit according to the purpose figure of hardening resin figure to select.For example use the light of g line, i line etc. as radioactive ray.The radioactive ray preference shines as using mask aligner or stepping exposure device (ス テ Star パ) etc., with the irradiation abreast generally at the radiation-sensitive resin composition layer.
Develop after the exposure in this wise.For example develop and to be undertaken by the method that makes the radiation-sensitive resin composition layer contact developer solution after the exposure.Usually use aqueous alkali as developer solution.Usually use the aqueous solution of alkali compounds as aqueous alkali, alkali compounds can be an inorganic alkaline compound, also can be organic basic compound.
As inorganic alkaline compound, for example can enumerate NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammonia etc.
As organic basic compound, for example can enumerate tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethylammonium, monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, monoethanolamine etc.
Above-mentioned alkali compounds can be distinguished use separately, also can make up more than 2 kinds and use.
Per 100 mass parts developer solutions contain alkali compounds 0.01～10 mass parts usually, preferred 0.1～5 mass parts.
Developer solution can also contain surfactant.As this surfactant, for example can enumerate nonionic is that surfactant, kation are that surfactant, negative ion are surfactant etc.
As nonionic is surfactant, for example can enumerate polyoxyethylene derivs such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
As kation is surfactant, for example can enumerate quaternary ammonium salts such as amine salt, lauryl trimethyl ammonium chloride such as stearic amine hydrochloride etc.
As negative ion is surfactant, for example can enumerate sulfuric acid high alcohol ester salt such as lauryl alcohol sodium sulfovinate, sulfuric acid oleyl alcohol ester sodium; Alkyl sulfate such as lauryl sodium sulfate, ammonium lauryl sulfate; Alkyl aryl sulfonates such as neopelex, dodecyl sodium naphthalene sulfonate etc.
These surfactants can be distinguished use separately, also can make up more than 2 kinds and use.
In addition, developer solution can also contain organic solvent.As above-mentioned organic solvent, for example can enumerate water-miscible organic solvents such as methyl alcohol, ethanol etc.
In order to make radiation-sensitive resin composition layer contact developer solution, for example the substrate that is formed with the radiation-sensitive resin composition layer can be impregnated in the developer solution.By developing, among the radiation-sensitive resin composition layer, when exposing before, be dissolved in developer solution by the radiation exposure zone of radiation exposure, the non-irradiated radioactive ray of radioactive ray not irradiation area are insoluble to developer solution and residual, form figure.
Therefore radiation-sensitive resin composition of the present invention contains quinone diazido compound (B), even the radiation-sensitive resin composition layer is short duration of contact with developer solution, also dissolve easily in the radiation exposure zone, removes.In addition, owing to contain quinone diazido compound (B), even therefore radiation-sensitive resin composition layer and developer solution are long duration of contact, radioactive ray not irradiation area can not be dissolved in the developer solution yet and disappear.
Back washing and drying usually develops.After the drying, so to the gained figure all or part of the irradiation radioactive ray.At this, preferred ultraviolet ray of the radioactive ray of irradiation or far ultraviolet, the exposure of the unit area preferably exposure when exposing before is many.
The figure of Xing Chenging is considered from the angle of the thermotolerance that improves the hardening resin figure, solvent resistance etc. like this, and then preferably carries out heat treated (back baking).By comprehensive method of having shone the substrate heating behind the radioactive ray being heated with heating arrangements such as hot plate, Network リ one Application baking ovens.Heating-up temperature is generally 150 ℃～250 ℃, preferred 180 ℃～240 ℃.Be generally 5 minutes heat time heating time～120 minutes, preferred 15 minutes～90 minutes.Make the figure sclerosis by heating, form the hardening resin figure.
The present invention can provide the radiation-sensitive resin composition good to the stainless steel substrate wetting state.Therefore, radiation-sensitive resin composition of the present invention can make the coating of the coating unit with seam shape nozzle improve.
The hardening resin figure that uses radiation-sensitive resin composition of the present invention to form is preferably used as the diffuse reflector that uses in the dielectric film that for example constitutes TFT type base stage, organic EL, photospacer, the reflection-type TFT substrate, the liquid crystal aligning hardening resin figure with the diaphragm of projection, CCD etc.
Embodiment
Below, illustrate in greater detail the present invention according to embodiment, but not being implemented example, the present invention do not limit.
Production Example 1: Resin A 1
In the 300mL four neck flasks that stirring machine, condenser pipe and thermometer are housed, adding is as the ethyl lactate 36g of solvent and 3-ethoxyl ethyl propionate 146g, as the azoisobutyronitrile 2.2g of polymerization initiator and following monomer, flow down at nitrogen, keeping internal temperature is 100～110 ℃, stir simultaneously and reacted in 3 hours, obtain containing the solution of Resin A 1.The polystyrene conversion weight-average molecular weight of this Resin A 1 is 7,900.
Methacrylic acid 10.8g
3-ethyl-3-methacrylic acid ylmethyl oxetanes 36.9g
N-cyclohexyl maleimide 31.4g
[mensuration of polystyrene conversion weight-average molecular weight (Mw)]
Adopt the GPC method, measure by following condition.
Device: HLC-8120GPC (eastern ソ one (strain) system)
Post: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)
Column temperature: 40 ℃
Solvent: THF
Flow velocity: 1.0mL/ minute
Sample size: 50 μ L
Detecting device: RI
Measure sample solution concentration: 0.6 quality % (solvent: THF)
Proofread and correct and use standard substance: TSK polystyrene standard (TSK STANDARDPOLYSTYRENE) F-40, F-4, F-1, A-2500, A-500 (eastern ソ one (strain) system)
[surfactant HLB pH-value determination pH example]
With the 0.5g surfactant dissolves in 5mL ethanol.Drip 2% phenol solution, the addition (mL) during with the liquid muddiness is recorded as turbidity A.Calculate HLB value (the western youth of reference: surfactant brief guide/industry books Co., Ltd.) by HLB=0.89 * (turbidity A)+1.11.
Embodiment 1
With following each composition after mixing under 23 ℃, overall with respect to composition, as the HLB value be more than 1～silicone type surface active agent (D1) composition below 9 adds SH8400 (HLB value=8.0, polyether modified silicon oil: SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) is made) 200ppm; Overall with respect to composition, add SH 3746 (HLB value=14.0, polyether modified silicon oil: SHIN-ETSU HANTOTAI's シ リ コ one Application (strain) system) 100ppm as the HLB value for silicone type surface active agent (D2) composition above 9.
Teflon system core strainer by aperture 1.0 μ m carries out pressure filtration, obtains radiation-sensitive resin composition 1 as filtrate.The content of the solvent in the radiation-sensitive resin composition that obtains (C) is 72.5%, and solvent composition is than being ethyl lactate: 3-ethoxyl ethyl propionate: butyl acetate: propylene glycol monomethyl ether=16: 60: 20: 4.
Solution 333 mass parts that contain Resin A 1 (are divided conversion with solid shape: 100 mass parts)
Compound 20 mass parts by formula (1) expression
ァ デ カ オ プ ト マ one SP-172 (light cationic polymerization catalyst: rising sun electrochemical industry (strain) system) 2 mass parts
サ Application エ イ De SI-100L (hot cationic polymerization catalyst: three new chemical industry (strain) system) 2 mass parts
KBM-303 (silane coupling agent: β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, SHIN-ETSU HANTOTAI's chemical industry (strain) system) 3 mass parts
Ethyl lactate 8.1 mass parts
3-ethoxyl ethyl propionate 16.2 mass parts
Butyl acetate 67 mass parts
13.4 parts of propylene glycol monomethyl ether
(in the formula, Q
4Expression is by the represented substituting group of formula (1-1).)
Comparative example 1
Except that not using the SH3746, carry out identical operations with embodiment 1, obtain radiation-sensitive resin composition 2.
Comparative example 2
Except that the consumption with SH8400 becomes 300ppm, does not use the SH3746, carry out identical operations with embodiment 1, obtain radiation-sensitive resin composition 3.
＜mobile mensuration example 〉
At horizontally disposed SUS630 plate (size: 100mm * 200mm * 10mm, surfaceness: the unidirectional microgroove finishing suitable) with JIS B065912.5-S, from crust formula suction pipe (5-3/4 ": Off イ Star シ ヤ one corporate system) drip the radiation-sensitive resin composition that obtains 10 μ L the foregoing descriptions and the comparative example; after the dropping, this SUS630 plate erect be vertical direction immediately.At this moment, the microgroove of plate is perpendicular to the dropping direction of liquid.
Flow when stopping until said composition, measure the distance that this radiation-sensitive resin composition flows, as mobile distance.Measurement result is as shown in table 1.
In addition, during liquid flow, carry out following evaluation: stop more than 10 seconds at liquid on the microgroove, the flowing of liquid temporarily stops being designated as flowability *; Liquid do not stop and flow smoothly flowability is designated as zero.Think, mobile good, also good to the wetting state of stainless steel substrate.
Result of determination is as shown in table 1.
Table 1
| Embodiment 1 | Comparative example 1 | Comparative example 2 | ||
| (D1) composition | SH8400 (HLB value=8.0) | 200 | 200 | 300 |
| (D2) composition | SH3746 (HLB value=14.0) | 100 | ||
| Evaluation | Distance flows | 78 | 75 | 74 |
| Mobile | ○ | × | × |
Claims (11)
1. radiation-sensitive resin composition, it has indurative alkali soluble resin (A) for containing, the radiation-sensitive resin composition of quinone diazido compound (B), solvent (C) and silicone type surface active agent (D), wherein, silicone type surface active agent (D) for containing HLB value be more than 1～silicone type surface active agent (D1) below 9 and HLB value be above the silicone type surface active agent of 9 silicone type surface active agent (D2).
2. the described composition of claim 1, wherein, has indurative alkali soluble resin (A) for containing multipolymer by the formation unit (a2) that constitutes unit (a1) and derive by the unsaturated compound with hardening group [but not being unsaturated carboxylic acid] of unsaturated carboxylic acid derivative.
3. the described composition of claim 2, wherein, the hardening group that constitutes in the unit (a2) is an oxetanyl.
4. any described composition of claim 1～3, wherein, have indurative alkali soluble resin (A) and also contain and constitute unit (a3), described formation unit (a3) is to be selected from by what the carboxylate with the two keys of alkene was derived to constitute unit (a31), constituted unit (a32), constituted unit (a33) and constituted at least a kind of unit (a34) by what N-substituted maleimide amines was derived by what the vinyl cyanide based compound was derived by what the aromatics with polymerism carbon-to-carbon unsaturated bond was derived.
5. any described composition of claim 1～4, wherein, surfactant (D1) is the poly alkylene glycol modified siloxane.
6. any described composition of claim 1～5, wherein, surfactant (D2) is the poly alkylene glycol modified siloxane.
7. any described composition of claim 1～6, wherein, with respect to radiation-sensitive resin composition, in massfraction, the content of silicone type surface active agent (D) is 1～1000ppm.
8. any described composition of claim 1～7, wherein, with respect to the total amount of silicone type surface active agent (D), in massfraction, the content of surfactant (D1) is 50～90 quality %.
9. any described composition of claim 1～8, it is applied to have the coating unit of seam shape nozzle.
10. transparent hard resin figure, it is formed by any described composition of claim 1～9.
11. a display device, it has the described transparent hard resin of claim 10 figure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004300160 | 2004-10-14 | ||
| JP2004-300160 | 2004-10-14 | ||
| JP2004300160 | 2004-10-14 |
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| Publication Number | Publication Date |
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| CN1760757A true CN1760757A (en) | 2006-04-19 |
| CN1760757B CN1760757B (en) | 2010-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005101137411A Expired - Fee Related CN1760757B (en) | 2004-10-14 | 2005-10-14 | Radioactivity sensitive resin composition |
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| Country | Link |
|---|---|
| KR (1) | KR20060052212A (en) |
| CN (1) | CN1760757B (en) |
| TW (1) | TW200622486A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286218A (en) * | 2006-09-04 | 2011-12-21 | Jsr株式会社 | Pigment resin composition, resin composition for ink jet mode color filter, color filter and liquid crystal display device |
| CN102352122A (en) * | 2006-09-04 | 2012-02-15 | Jsr株式会社 | Pigment-resin composition, resin composition for ink-jet type color filter, the ink-jet type color filter and liquid crystal display device |
| TWI425315B (en) * | 2007-01-18 | 2014-02-01 | Jsr Corp | Sensitive radiation linear resin composition, interlayer insulating film and microlens, and the like |
| CN101910943B (en) * | 2007-12-25 | 2015-03-25 | 旭化成电子材料株式会社 | Layered photosensitive-resin product |
| CN105842990A (en) * | 2015-02-04 | 2016-08-10 | 东友精细化工有限公司 | Photosensitive resin composition, photocurable pattern formed from the same and image display device comprising the pattern |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU661438B1 (en) * | 1994-01-25 | 1995-07-20 | Morton International, Inc. | Waterborne photoresists having polysiloxanes |
| JP2000267270A (en) * | 1999-03-19 | 2000-09-29 | Clariant (Japan) Kk | Photosensitive resin composition for roll coating and roll coating method |
| US6984476B2 (en) * | 2002-04-15 | 2006-01-10 | Sharp Kabushiki Kaisha | Radiation-sensitive resin composition, forming process for forming patterned insulation film, active matrix board and flat-panel display device equipped with the same, and process for producing flat-panel display device |
-
2005
- 2005-10-07 TW TW094135105A patent/TW200622486A/en unknown
- 2005-10-12 KR KR1020050095942A patent/KR20060052212A/en not_active Abandoned
- 2005-10-14 CN CN2005101137411A patent/CN1760757B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286218A (en) * | 2006-09-04 | 2011-12-21 | Jsr株式会社 | Pigment resin composition, resin composition for ink jet mode color filter, color filter and liquid crystal display device |
| CN102352122A (en) * | 2006-09-04 | 2012-02-15 | Jsr株式会社 | Pigment-resin composition, resin composition for ink-jet type color filter, the ink-jet type color filter and liquid crystal display device |
| TWI425315B (en) * | 2007-01-18 | 2014-02-01 | Jsr Corp | Sensitive radiation linear resin composition, interlayer insulating film and microlens, and the like |
| CN101910943B (en) * | 2007-12-25 | 2015-03-25 | 旭化成电子材料株式会社 | Layered photosensitive-resin product |
| CN105842990A (en) * | 2015-02-04 | 2016-08-10 | 东友精细化工有限公司 | Photosensitive resin composition, photocurable pattern formed from the same and image display device comprising the pattern |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060052212A (en) | 2006-05-19 |
| CN1760757B (en) | 2010-11-10 |
| TW200622486A (en) | 2006-07-01 |
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