CN1760756A - Radioactivity sensitive resin composition - Google Patents

Radioactivity sensitive resin composition Download PDF

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Publication number
CN1760756A
CN1760756A CNA2005101137290A CN200510113729A CN1760756A CN 1760756 A CN1760756 A CN 1760756A CN A2005101137290 A CNA2005101137290 A CN A2005101137290A CN 200510113729 A CN200510113729 A CN 200510113729A CN 1760756 A CN1760756 A CN 1760756A
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China
Prior art keywords
sulfonium
dimethyl
phenyl
solvent
methyl
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Chinese (zh)
Inventor
八子由子
武部和男
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CN1760756A publication Critical patent/CN1760756A/en
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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
    • 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
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • 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
    • 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
    • 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
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • 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
    • 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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (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

The radiation-sensitive resin composition contains an alkali-soluble resin (A) having curability, a quinonediazido compound (B) and a solvent (C), wherein butyl lactate is contained as the solvent (C).

Description

Radiation-sensitive resin composition
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 transparent hard resin figure headed by the diffuse reflector that uses in the organic EL dielectric film that uses in the dielectric film of thin film transistor (TFT) (the following TFT that is designated as sometimes) type liquid crystal indicator, the 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 Japanese kokai publication hei 9-152625 communique).
But, in the developing procedure when usability radiation resin composite formation transparent hard resin figure, have the situation that figure is peeled off that takes place, wish that therefore exploitation can obtain the radiation-sensitive resin composition of the difficult figure of peeling off.
The inventor finds that the radiation-sensitive resin composition that comprises the solvent that contains butyl lactate can obtain the difficult figure of peeling off.
Summary of the invention
The object of the present invention is to provide when development transparent hard resin figure the difficult radiation-sensitive resin composition of peeling off of figure.
That is, the invention provides aspect, following [1]～[9]:
[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) and solvent (C), and wherein solvent (C) is the solvent that contains butyl lactate.
[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, solvent (C) is for containing at least a kind the organic solvent being selected from diethylene glycol dimethyl ether, diglycol methyl ethyl ether, propylene glycol methyl ether acetate, 3-ethoxyl ethyl propionate, ethyl lactate, butyl acetate and gamma-butyrolacton and the solvent of butyl lactate.
[6] .[1]～[5] any described composition, wherein, with respect to solvent (C), in massfraction, the content of butyl lactate is 1～30 quality %.
[7]. a kind of transparent hard resin figure, it is formed by any described composition in [1]～[6].
[8]. a kind of manufacture method of transparent hard resin figure, wherein on substrate, apply any described composition in [1]～[6], except that after desolvating, by mask irradiation radioactive ray, then with after the aqueous alkali development and forming compulsory figure, to the irradiation of the figure on substrate radioactive ray.
[9] .[8] described manufacture method, wherein, behind the irradiation of the figure on substrate radioactive ray, and then heating.
Description of drawings
Fig. 1 uses radiation-sensitive resin composition of the present invention for expression and forms the mode chart of the operation of transparent hard resin figure.
The explanation of symbol
1: the radiation-sensitive resin composition layer
11: irradiation area not
12: irradiation area
2: substrate
3: mask
4: radioactive ray
5: the resin figure
6: transparent hard resin figure
Embodiment
Below describe the present invention in detail.
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) and solvent (C), and wherein solvent (C) is the solvent that contains butyl lactate.
Has an indurative alkali soluble resin (A) as what use among the present invention, the preferred multipolymer that constitutes unit (a2) that constitutes unit (a1) and derive (wherein, being derivatized to the unsaturated compound that constitutes unit (a2) is not unsaturated carboxylic acid) that contains by unsaturated carboxylic acid derivative that uses by unsaturated compound with hardening group.
Constitute the unsaturated carboxylic acid of unit (a1) as above-mentioned deriving, for example can enumerate the unsaturated carboxylic acid that has one or more carboxyls in unsaturated monocarboxylic acid or the unsaturated dicarboxylic acid equimolecular etc.
As this unsaturated carboxylic acid, for example can enumerate acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.
Unsaturated compound as the above-mentioned formation unit (a2) of deriving with sclerosis group, (methyl) glycidyl acrylate is 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.
Constitute the unsaturated compound with sclerosis base of unit (a2) as deriving, preferably use the above-mentioned unsaturated compound that contains oxetanyl, especially preferably use 3-ethyl-3-methacrylic acid ylmethyl oxetanes.
As constituting unit (a2), use the alkali soluble resin that comprises the unsaturated compound that contains oxetanyl, during the preparation radiation-sensitive resin composition, there is the tendency of bin stability excellence in said composition, and is therefore preferred.
In the used in the present invention alkali soluble resin with hardening group (A), as the multipolymer composition, can also contain at least a kind the formation unit (a3) that constitutes unit (a34) that constitutes unit (a33) and derive that constitutes unit (a32), derives by the vinyl cyanide based compound that constitutes unit (a31), derives by aromatics of deriving by carboxylate with the two keys of alkene as being selected from by the maleimide compound that N-replaces with polymerism carbon-to-carbon unsaturated bond.
Constitute the carboxylate with the two keys of alkene of unit (a31) as 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, (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.
Constitute the aromatics with polymerism carbon-to-carbon unsaturated bond of unit (a32) as deriving, for example, can enumerate aromatic ethenyl compound etc.As this aromatic ethenyl compound, for example, can enumerate styrene, α-Jia Jibenyixi, vinyltoluene etc.
Constitute the vinyl cyanide based compound of unit (a33) as deriving, for example, can enumerate vinyl cyanide, methacrylonitrile, alpha-chloro (methyl) vinyl cyanide etc.
The maleimide compound that the N-that constitutes unit (a34) as deriving replaces; 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 ゾ エ one ト; N-succinimide base-3-maleimide プ ロ ピ オ ネ one ト; N-succinimide base-4-maleimide Block チ レ one ト; N-succinimide base-6-maleimide カ プ ロ エ one ト; N-(1-phenylamino naphthyl-4)-maleimide; N-[4-(2-benzoxazolyl) phenyl] maleimide; N-(9-acridinyl) maleimide etc.
Constitute unit (a1), (a2), (a31), (a32), (a33) and (a34) separately,, also can make up multiple use by the constituting the unit and can use separately of the above-mentioned compound deriving that exemplifies.
In the multipolymer that constitutes unit (a2) that constitutes unit (a1) and derive that contains by unsaturated carboxylic acid derivative by above-mentioned unsaturated compound with hardening group, with respect to the overall molal quantity in the formation unit of multipolymer, the content that constitutes unit (a1) is 5～50 moles of %, preferred 15～40 moles of %, with respect to the overall molal quantity in the formation unit of multipolymer, the content that constitutes unit (a2) is 95～50 moles of %, preferred 85～60 moles of %.
In composition of the present invention, the content of formation unit (a1) in the multipolymer and formation unit (a2) is when above-mentioned scope, from developer solution is shown that suitable dissolution velocity and high indurative angle are preferred.
In composition of the present invention, alkali soluble resin (A) is when containing the multipolymer that constitutes unit (a1) and formation unit (a2), except that constituting unit (a1) and constituting the unit (a2), also can contain other any composition of formation unit conduct.The formation unit that multipolymer contains other is during as composition arbitrarily, and with respect to the formation unit of above-mentioned multipolymer, the content of other formation unit constitutes the overall mol ratio in unit with respect to multipolymer and is preferably 0.1～90 mole of %, 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, or 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.When weight-average molecular weight was aforementioned range, there was the tendency that can obtain high developing powder simultaneously in the residual film ratio when keeping developing, and is therefore preferred.
With respect to the solid shape branch of radiation-sensitive resin composition, the content that containing in the radiation-sensitive resin composition of the present invention constitutes the multipolymer of unit (a1) and formation unit (a2) is preferably 50～90 quality %, more preferably 60～90 quality %.
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 sulfonamide 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, quinone diazido compound (B) content 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.
The solvent that uses among the present invention (C) is for containing the solvent of butyl lactate.Use contains the solvent of butyl lactate, when forming figure, has the tendency that improves tack, and is therefore preferred.
In solvent (C), preferred butyl lactate mixes with the organic solvent that is generally used for radiation-sensitive resin composition.
As this organic solvent, for example can enumerate ethylene glycol monoalkyl ether classes such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether;
Diglycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol dipropyl ether or diglycol dibutyl ethers, diglycol methyl ethyl ether, diglycol methyl isopropyl 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;
Arenes such as benzene,toluene,xylene;
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, methyl lactate, ethyl lactate, 2-hydroxy-methyl isobutyl acid, butyl acetate, pentyl acetate, isoamyl acetate, methyl pyruvate;
Cyclic ester classes such as gamma-butyrolacton etc.
As the solvent that preferred and butyl lactate are used in combination, can enumerate diethylene glycol dimethyl ether, diglycol methyl ethyl ether, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, ethyl lactate, butyl acetate, gamma-butyrolacton.
With respect to solvent (C), in massfraction, the content of butyl lactate is preferably 1～100 quality %, more preferably 1～50 quality %, further preferred 1～30 quality %.When forming figure, there is the tendency that improves tack in the content of butyl lactate when above-mentioned scope, therefore preferred.
With respect to radiation-sensitive resin composition, in massfraction, the content of solvent (C) is preferably 50～95 quality %, more preferably 65～90 quality %.The content of solvent (C) is when above-mentioned scope, and existence can form the tendency of the good film of flatness, and is therefore preferred.
In the radiation-sensitive resin composition of the present invention, except that containing alkali soluble resin (A), quinone diazido compound (B) and solvent (C), also can contain polymerization initiator (D), polyphenol compound (E), crosslinking chemical (F), polymerizable monomer (G) etc.
As above-mentioned polymerization initiator (D), for example can enumerate salt as cationic polymerization initiators etc.This 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 (fluoro 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) sulfonium etc.
Preferred cation is enumerated two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium, three (to tert-butyl-phenyl) sulfonium.
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 or four (pentafluorophenyl group) borate.
Can combination in any use above-mentioned kation and from lewis acidic negative ion.
Instantiation as light cationic polymerization initiators (D) 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-chloroethoxy) 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) borate etc.
Wherein, preferred pair (p-methylphenyl) iodine hexafluorophosphates that use, (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, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate more preferably uses two (p-methylphenyl) iodine hexafluoro antimonates, (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 containing polymerization initiator (D), 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 (D) 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 (E), can enumerate the compound of the phenol hydroxyl that has in the molecule more than 2, be the polymkeric substance that obtains of starting monomer or novolac resin etc. with the hydroxy styrenes at least.
As the compound that has the phenol hydroxyl more than 2 in the above-mentioned molecule, for example can enumerate the trihydroxy Benzophenones that in the explanation of quinone diazido compound, exemplifies, tetrahydroxybenzophenone class, pentahydroxybenzophenone class, hexahydroxy Benzophenones, (polyhydroxy phenyl) paraffinic etc.
In addition, as the instantiation that with the hydroxy styrenes is the polymkeric substance that obtains of starting monomer at least, 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.
And then, as above-mentioned novolac resin, for example can enumerate the resin that obtains through polycondensation by at least a compound that is selected from phenol, cresols class and pyrocatechol and the compound more than a kind that is selected from aldehydes and ketone etc.
When containing above-mentioned polyphenol compound (E), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, preferred 0.1～40 quality % of the content of polyphenol compound, more preferably 0.1～25 quality %.When the content of polyphenol compound (E) is above-mentioned scope, there is the tendency that resolution improves, transmission of visible light does not reduce, therefore preferred.
(F) 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 or 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.In addition, as the alkoxy methyl urea resin, can enumerate methoxy urea resin, ethoxyl methyl urea resin, propoxyl group methylate urea resin, butoxymethyl urea resin etc.Above-mentioned crosslinking chemical can be distinguished use separately, also can make up more than 2 kinds and use.
When using crosslinking chemical (F), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, the content of crosslinking chemical is preferably 0.1～15 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 transparent hard resin figure, and is therefore preferred.
As above-mentioned polymerizable monomer (G), 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.As preferred polymerizable monomer (G), can enumerate the polymerizable monomer that can carry out 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 etc.This compound with polymerism carbon-to-carbon unsaturated bond can be the polymerizable monomer of simple function, also can be dual functional polymerizable monomer, can also be the polymerizable monomer of multifunctional (more than the 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.
As dual functional polymerizable monomer, 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 polyfunctional polymerizable monomer, 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 compound with polymerism carbon-to-carbon unsaturated bond, preferably use difunctionality or polyfunctional polymerizable monomer.Specifically, preferably use tetramethylol methane tetraacrylate, dipentaerythritol acrylate.More preferably use dipentaerythritol acrylate.
In addition, also the polymerizable monomer of difunctionality or polyfunctional polymerizable monomer and simple function can be used in combination.
As the polymerizable monomer that can carry out cationic polymerization, for example can enumerate the monomer etc. of the functional group of cationically polymerizables such as having vinyl ether group, propenyl ether, epoxy radicals, oxetanyl.
As the above-mentioned monomer that contains vinyl ether group, for example can enumerate triethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl etc.
As the above-mentioned monomer that contains the propenyl ether, for example can enumerate 4-(1-propenyl oxygen ylmethyl)-1,3-dioxolanes-2-ketone etc.
As the above-mentioned compound that contains epoxy radicals, for example can enumerate bisphenol A type epoxy resin, phenol novolac epoxy resin, cresols novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, hetero ring type epoxy resin etc.
As the above-mentioned compound that contains oxetanyl, for example can enumerate two [3-(3-ethyl oxetanyl) methyl] ethers, 1, two [3-(the 3-ethyl oxetanyl) methoxyl] benzene, 1 of 4-, two [3-(the 3-ethyl oxetanyl) methoxyl] methylbenzene, 1 of 4-, two [3-(the 3-ethyl oxetanyl) methoxyl] cyclohexanes, 1 of 4-, two [3-(the 3-ethyl oxetanyl) methoxyl] methylcyclohexanes of 4-, 3-(3-ethyl oxetanyl) methylates novolac resin etc.
Can distinguish and use above-mentioned polymerizable monomer (G) separately, also can make up more than 2 kinds and use.When containing polymerizable monomer (G), with respect to the solid shape branch of radiation-sensitive resin composition, in massfraction, its content is preferably 0.1～20 quality %.
In radiation-sensitive resin composition of the present invention, as required, can also contain other compositions, for example various adjuvants such as surfactant, 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 mixes the solution that above-mentioned alkali soluble resin (A) is dissolved in the solution of solvent (C) and quinone diazido compound (B) is dissolved in solvent (C).In addition, the liquid after the preparation, and then can also mix and add solvent (C).Solution preferably removes by filter solid shape matter after mixing.Above-mentioned filtration preferably uses the filter of aperture 3 μ m following (more preferably about 0.1 μ m～2 μ m) to filter.With respect to above-mentioned alkali soluble resin (A) or quinone diazido compound (B), used solvent (C) can be identical, also can be inequality.In addition, if the solvent that dissolves each other also can use multiple solvent (C).
When using radiation-sensitive resin composition of the present invention to form transparent hard resin figure, for example, go up layer (1) [with reference to Fig. 1 (a)] that formation comprises radiation-sensitive resin composition of the present invention at substrate (2), to above-mentioned layer (1) irradiation radioactive ray (4) exposure backs [with reference to Fig. 1 (b)], [with reference to Fig. 1 (c)] can develop by mask (3).
For example can enumerate transparent glass plate etc. as substrate (2).On aforesaid substrate, also can form circuit such as TFT or CCD or color filter etc.
The layer (1) that comprises radiation-sensitive resin composition for example can form by radiation-sensitive resin composition being coated to method on the substrate (2) etc.Apply and for example can be undertaken by spin coating method, curtain coating cladding process, rolling method, slit-spin coating method, slot coated method etc.After the coating, heat behind heat drying (prebake conditions) or the drying under reduced pressure, volatilize, form radiation-sensitive resin composition layer (1) by making volatile ingredients such as solvent.Wherein, heating-up temperature is generally 70～200 ℃, preferred 80～130 ℃.The radiation-sensitive resin composition layer (1) that forms contains volatile ingredient hardly.In addition, the thickness of above-mentioned radiation-sensitive resin composition layer (1) is about 1.5 μ m～5 μ m.
Afterwards, by mask (3) radiation-sensitive resin composition layer (1) is shone radioactive ray (4).The figure of mask (3) can suit according to the targeted graphical shape of resin figure to select.For example use the light of g line, i line etc. as radioactive ray.Radioactive ray for example preferably use mask aligner or stepping exposure device (ス テ Star パ) (not shown) etc. to shine, with irradiation abreast on the overall or part of radiation-sensitive resin composition layer.By the irradiation radioactive ray, can carry out mask (3) and radiation-sensitive resin composition layer (1) position alignment exactly like this.
Develop after the above-mentioned exposure.Develop and for example the radiation-sensitive resin composition layer (1) after the exposure can be waited and carries out by パ パ De Le method, infusion process, spray process.Usually use aqueous alkali as developer solution.As the aqueous solution of aqueous alkali use alkali compounds, 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 use separately, also can make up more than 2 kinds and use.With respect to developer solution, in massfraction, the content of the alkali compounds in the developer solution is preferably 0.01～10 quality %, more preferably 0.1～5 quality %.
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 alkyl aryl sulfonates such as alkyl sulfates such as sulfuric acid high alcohol ester salt, lauryl sodium sulfate, ammonium lauryl sulfate, neopelex, dodecyl sodium naphthalene sulfonate such as lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate etc.
These surfactants can 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.
By developing, among the radiation-sensitive resin composition layer (1), be dissolved in developer solution by the radiation exposure zone (12) of radiation exposure when exposing before, the non-irradiated radioactive ray of radioactive ray not irradiation area (11) are insoluble to developer solution and residual, form resin figure (5).
Radiation-sensitive resin composition of the present invention contains quinone diazido compound (B), even therefore radiation-sensitive resin composition layer (1) is short duration of contact with developer solution, irradiation area (12) is dissolving easily also, removes.In addition, owing to contain quinone diazido compound (B), even therefore radiation-sensitive resin composition layer (1) is long duration of contact with developer solution, irradiation area (11) can not be dissolved in the developer solution yet and disappears.
Common washing and drying after alkali develops.After the drying, so to gained resin figure (5) all or part of the irradiation radioactive ray.At preferred ultraviolet ray of the radioactive ray of this irradiation or far ultraviolet, the exposure of the unit area preferably exposure when exposing before is many.
The resin figure (5) of Xing Chenging is considered from the angle of the thermotolerance that improves the transparent hard resin figure (6) that finally obtains or solvent resistance etc. like this, further preferably carries out heat treated (back baking).By adopt heating arrangements such as hot plate or Network リ one Application baking oven to TBI the method for the substrate heating behind the radioactive ray heat.Heating-up temperature is generally 150 ℃～250 ℃, preferred about 180 ℃～240 ℃.Be generally 5 minutes heat time heating time～120 minutes, preferred about 15 minutes～90 minutes.Make the figure sclerosis by heating, form transparent hard resin figure (6).
The transparent hard resin figure of Xing Chenging is to the tack height of ground like this.Therefore, when using radiation-sensitive resin composition of the present invention, can high productivity form the transparent hard resin figure of high finished product rate.
The transparent hard resin figure that uses radiation-sensitive resin composition of the present invention to obtain for example is preferably used as the TFT substrate, the dielectric film of organic EL, the diaphragm of 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
In the 200mL four neck flasks that stirring machine, condenser pipe and thermometer are housed, add following raw material, flow down at nitrogen, four neck flasks are immersed oil bath, keeping the flask interior temperature is 85～95 ℃, stirs simultaneously and reacts in 3 hours, obtains Resin A 1.The polystyrene conversion weight-average molecular weight of this Resin A 1 is 8,000.
Methacrylic acid 6.8g
N-cyclohexyl maleimide
14.2g
3-ethyl-3-methacrylic acid ylmethyl oxetanes 17.8g
Ethyl lactate 90.7g
Azoisobutyronitrile 1.1g
About the polystyrene conversion weight-average molecular weight of this Resin A 1, measure under the following conditions.
Device: HLC-8120GPC (eastern ソ-(strain) system)
Post: TSK-GELG2000HXL, TSK-GELG4000HXL (series connection)
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0mL/ minute
Sample size: 50 μ L
Detecting device: RI
Measure sample solution concentration: 0.6 quality % (solvent: tetrahydrofuran)
Proofread and correct and use standard substance: TSK polystyrene standard (TSK STANDARDPOLYSTYRENE) F-40, F-4, F-1, A-2500, A-500 (eastern ソ-(strain) system)
Embodiment 1
Under 23 ℃, with Resin A 1 (100 mass parts), by compound (22 mass parts), (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate (the Rhodorsil Photoinitiator2074 of following formula (1) expression; ロ-デ イ ア corporate system) after (2 mass parts), 3-ethoxyl ethyl propionate (285 mass parts), butyl acetate (34 mass parts) and butyl lactate (17 mass parts) mix, teflon system core strainer by aperture 1.0 μ m carries out pressure filtration, obtains radiation-sensitive resin composition 1.
Figure A20051011372900221
At transparent glass substrate (#1737; コ-ニ Application グ corporate system) on, rotation applies the above-mentioned radiation-sensitive resin composition that obtains 1, uses Network リ one Application baking oven to heat 3 minutes (prebake conditions) down at 100 ℃, forms the thick radiation-sensitive resin composition layer (1) of 3 μ m [with reference to Fig. 1 (a)].Film thickness uses film thickness meter (DEKTAK3; (strain) ULVAC system) measures.
Afterwards, use contact alignment device (M-2Li; ミ カ サ (strain) system), (intensity under the wavelength 365nm benchmark is 250mJ/cm by mask (3) the radiation-sensitive resin composition layer (1) that obtains to be shone radioactive ray (4) 2), [with reference to Fig. 1 (b)] exposes.
After the exposure, dipping develops for 70 seconds in 23 ℃ 0.4 quality % tetramethylammonium hydroxide aqueous solution, then with ultrapure water washing, drying.Do not see after development and peel off that tack is good.
After resin figure (5) drying after the development, use contact alignment device (M-2Li; ミ カ サ (strain) system) (intensity under the wavelength 365nm benchmark is 300mJ/cm to its all irradiation radioactive ray 2), heating is 30 minutes in 220 ℃ Network リ, one Application baking oven, forms transparent hard resin figure (6) [with reference to Fig. 1 (c)].
The thickness (T1) of the transparent hard resin figure (6) that obtains uses the film thickness meter to measure, and this thickness is 2.5 μ m.
Use microspectrophotometer (OSP-200; オ リ Application パ ス optics industry (strain) system) measures transmission of visible light.Under wavelength 400～750nm, the light average transmittance of the per 1 μ m of the hardening resin film that obtains is 99.6%, shows high transparent, does not see painted.
Embodiment 2
Except that using 3-ethoxyl ethyl propionate (151 mass parts), diglycol methyl ethyl ether (151 mass parts), butyl acetate (17 mass parts) and butyl lactate (17 mass parts), carry out same operation with embodiment 1, the filtrate that obtains after the pressure filtration as radiation-sensitive resin composition.
Carry out 1 identical operations with embodiment, the result obtains the transparent hard resin figure (6) that thickness (T1) is 2.5 μ m, and the tack after it develops is good, does not see and peels off.Light transmittance is shown as 99.6%.
Comparative example 1
Except that using diglycol methyl ethyl ether (287 mass parts), butyl acetate (32 mass parts), carry out same operation with embodiment 1, the filtrate that obtains after the pressure filtration is radiation-sensitive resin composition.
Carry out 1 identical operations with embodiment, the result is that tack is poor, films after the development and peels off, and does not obtain resin figure (5).

Claims (9)

1. radiation-sensitive resin composition, it has indurative alkali soluble resin (A) for containing, the radiation-sensitive resin composition of quinone diazido compound (B) and solvent (C), and wherein solvent (C) is the solvent that contains butyl lactate.
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, solvent (C) is for containing at least a kind the organic solvent being selected from diethylene glycol dimethyl ether, diglycol methyl ethyl ether, propylene glycol methyl ether acetate, 3-ethoxyl ethyl propionate, ethyl lactate, butyl acetate and gamma-butyrolacton and the solvent of butyl lactate.
6. any described composition of claim 1～5, wherein, with respect to solvent (C), in massfraction, the content of butyl lactate is 1～30 quality %.
7. transparent hard resin figure, it is formed by any described composition of claim 1～6.
8. the manufacture method of a transparent hard resin figure, wherein on substrate, apply any described composition of claim 1～6, except that after desolvating, by mask irradiation radioactive ray, then with after the aqueous alkali development and forming compulsory figure, to the irradiation of the figure on substrate radioactive ray.
9. the described manufacture method of claim 8 wherein, behind the irradiation of the figure on substrate radioactive ray, and then heats.
CNA2005101137290A 2004-10-14 2005-10-14 Radioactivity sensitive resin composition Pending CN1760756A (en)

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