CN1975574B - Radiation sensitive resin composition - Google Patents
Radiation sensitive resin composition Download PDFInfo
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- CN1975574B CN1975574B CN2006101604841A CN200610160484A CN1975574B CN 1975574 B CN1975574 B CN 1975574B CN 2006101604841 A CN2006101604841 A CN 2006101604841A CN 200610160484 A CN200610160484 A CN 200610160484A CN 1975574 B CN1975574 B CN 1975574B
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- resin 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
- G03F7/022—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
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention provides a radiate sensitive resin composition, including soda soluble solidifiedness resin (A), quinine diazido-compound (B), cation photopolymerization initiator of anion of anion containing anion from onium cation and formula (1) and anion in formula (2), and solvent (H), wherein R<1>-R<3>, R<11> and R<33> independently represent linear perfluoroalkyl having 1-20 carbon atoms, or branched chain perfluoroalkyl that have 3-20 carbon atoms, or cyclic perfluoroalkyl having 3-20 carbon atoms, or perfluoroaryl having 6-20 carbon atoms, each of group -O-, and -N(R)-, or -SO2- can inserts the carbon atom of above groups (R represents hydrogen atom or the alkyl that has 1-4 carbon atoms), each two of R<11> , R<33> and R<1>-R<3> may bind each other to form ring structure and one or two ring structures may form heterocyclic ring.
Description
Technical field
The present invention relates to a kind of radiation-sensitive resin composition.
Background technology
Radiation-sensitive resin composition can be as the material that forms the transparent cured resin pattern, and the latter for example is used for the thin film transistor (TFT) (hereinafter referred to as TFT) that uses at film transistor type LCD and display of organic electroluminescence with dielectric film, the diffusion reflector that uses be used for the organic light-emitting device dielectric film in the reflection-type TFT substrate.In order to obtain brighter display image, need the TFT dielectric film that visible light is had more high-transmission rate at this.For improving the throughput rate of TFT substrate, need good solvent resistance, the radioactive ray that are used to form dielectric film are had hypersensitivity and high resolving power.
The example of known photosensitive resin composition comprise based on the multipolymer of acrylate or based on the multipolymer of oxetanes as adhesive resin, photosensitizer and Photoepolymerizationinitiater initiater (referring to the open 2001-281853 of Jap.P., the 2nd page, hurdle 2-25 is capable on a left side, open 2003-156843 of Jap.P. and the open 2003-330170 of Jap.P.).As everyone knows, the multipolymer of oxygen heterocycle butane can get (referring to the open 2000-239648 of Jap.P., the 5th page, right hurdle the 38th walks to the 6th page, and left hurdle the 1st row and the 7th page of left hurdle the 3rd walk to right hurdle the 34th row) via cationic polymerization.
The example of known cationic polymerization initiators comprises that to contain hexafluoro-phosphate radical anionic
Salt
(referring to the open H9-304931 of Jap.P., the 2nd page of left hurdle 2-30 is capable).
Yet the pattern that is formed by the radiation-sensitive resin composition that comprises adhesive resin, photosensitizer and Photoepolymerizationinitiater initiater is still remaining improvement aspect the transparency, solvent resistance and the resolution.
The inventor has formed the resin combination of pattern and has studied to having the problems referred to above hardly, find to contain to comprise
The pattern that the resin combination of kation and certain anionic polymerization initiator forms has the excellent transparency, solvent resistance and resolution.
Summary of the invention
The object of the present invention is to provide a kind of radiation-sensitive resin composition, it can produce the pattern with the excellent transparency, solvent resistance and resolution.
That is, the invention provides following [1]-[7].
[1]. a kind of radiation-sensitive resin composition, it comprises alkali-soluble curable resin (A), quinone di-azido compound (B), contains
Kation and be selected from negative ion that formula (1) provides and anionic cationic polymerization initiators (C) that formula (2) provides, and solvent (H),
R wherein
1-R
3, R
11And R
33Representative independently of one another have 1-20 carbon atom the straight chain perfluoroalkyl, have 3-20 carbon atom the side chain perfluoroalkyl, have the ring-type perfluoroalkyl of 3-20 carbon atom or have the perfluor aryl of 6-20 carbon atom, group-O-,-N (R)-or-SO
2-in any can insert between the carbon atom of above-mentioned each group (R represents hydrogen atom or has the alkyl of 1-4 carbon atom) R
11And R
33Or R
1-R
3In any two can form heterocycle in conjunction with forming ring structure and one or two ring structure.
[2]. according to the radiation-sensitive resin composition of [1], wherein
Kation is to be selected from iodine
At least a kation with sulfonium.
[3]. according to the radiation-sensitive resin composition of [1] or [2], wherein alkali-soluble curable resin (A) be comprise derived from unsaturated carboxylic acid structural unit (a1) and derived from the multipolymer of the structural unit (a2) of the unsaturated compound with oxetanyl (but except unsaturated carboxylic acid).
[4]. according to [1] to [3] any one radiation-sensitive resin composition, wherein alkali-soluble curable resin (A) comprises at least a structural unit (a3) that is selected from following: the structural unit of derived from carboxylic acid ester (a31), derived from the structural unit (a34) of the structural unit (a32) of aromatic vinyl compound, the maleimide compound that replaces derived from the structural unit (a33) of cyano group vinyl compound with derived from N-.
[5]. according to [1] to [4] any one radiation-sensitive resin composition, wherein the mass content of alkali-soluble curable resin (A) is 50-90%, the mass content of quinone di-azido compound (B) is 5-40%, the mass content of cationic polymerization initiators (C) is 0.01-10%, based on the solids content of radiation-sensitive resin composition.
[6]. a kind of by the solidified resin pattern that forms according to [1] to [5] any one radiation-sensitive resin composition.
[7]. a kind of method of producing solidified resin pattern, by being administered to substrate according to [1] to [5] any one radiation-sensitive resin composition, shine by mask with radiant rays after removing solvent, develop to form pattern with alkaline aqueous solution subsequently, use the whole zone of pattern on the irradiation with radiation substrate then.
Description of drawings
Fig. 1 is that expression uses this radiation-sensitive resin composition to form the synoptic diagram of the method for solidified resin pattern.
[symbol description]
1: the radiation-sensitive resin composition layer
2: substrate
3: mask
4: radiant rays
5: resin pattern
6: solidified resin pattern
11: radioactive ray are irradiation area not
12: the radiation exposure zone
Embodiment
The example of the alkali-soluble curable resin (A) that uses in the radiation-sensitive resin composition of the present invention preferably includes the structural unit (a1) that comprises derived from unsaturated carboxylic acid and derived from the multipolymer of the structural unit (a2) (unsaturated compound that produces structural unit (a2) must not be a unsaturated carboxylic acid) of the unsaturated compound with curable group.
The example that produces the unsaturated carboxylic acid of structural unit (a1) comprises: for example in molecule, contain the unsaturated carboxylic acid of one or more hydroxy-acid groups, for example, undersaturated monocarboxylic acid or undersaturated dicarboxylic acid.
The example of described unsaturated carboxylic acid comprises acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid.
Has the curable group, the unsaturated compound example that produces structural unit (a2) comprises: the unsaturated compound that contains epoxy radicals is (methyl) glycidyl acrylate for example, (methyl) acrylic acid Beta-methyl ethylene oxidic ester, (methyl) propenoic acid beta-ethyl ethylene oxidic ester, (methyl) acrylic acid 3-methyl-3,4-epoxy butyl ester, (methyl) acrylic acid 3-ethyl-3,4-epoxy butyl ester, (methyl) acrylic acid 4-methyl-4,5-epoxy pentyl ester, (methyl) acrylic acid 2,3-epoxycyclohexyl methyl esters, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters, neighbour-vinyl benzyl glycidol ether, between-the vinyl benzyl glycidol ether, right-the vinyl benzyl glycidol ether, 2-vinyl cyclohexene oxygen, 3-vinyl cyclohexene oxygen, the unsaturated compound of 4 vinyl cyclohexene oxygen etc. and oxygen heterocycle butane group is 3-(methyl) acryloyl-oxy methyl oxetanes for example, 3-methyl-3-(methyl) acryloyl-oxy methyl oxetanes, 3-ethyl-3-(methyl) acryloyl-oxy methyl oxetanes, 2-phenyl-3-(methyl) acryloyl-oxy methyl oxetanes, 2-trifluoromethyl-3-(methyl) acryloyl-oxy methyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acryloyl-oxy methyl oxetanes, 3-methyl-3-(methyl) acrylyl oxy-ethyl oxetanes, 2-phenyl-3-(methyl) acrylyl oxy-ethyl oxetanes, 2-trifluoromethyl-3-(methyl) acrylyl oxy-ethyl oxetanes, 2-pentafluoroethyl group-3-(methyl) acrylyl oxy-ethyl oxetanes etc.
Example with unsaturated compound curable group, generation structural unit (a2) preferably includes the above-mentioned unsaturated compound of oxygen heterocycle butane group.The especially preferred example that contains the unsaturated compound of oxetane groups is 3-ethyl-3-acryloyl-oxy methyl oxetanes.
When the unsaturated compound that comprises the oxygen heterocycle butane group when use prepares radiation-sensitive resin composition as the alkali soluble resin that has the curable group and produce the unsaturated compound of structural unit (a2), then be preferred, because above-mentioned radiation-sensitive resin composition is often more stable aspect storage.
Alkali-soluble curable resin (A) in the radiation-sensitive resin composition of the present invention can also comprise at least a be selected from following structural unit (a3) but as the copolymerization component: the structural unit of derived from carboxylic acid ester (a31), derived from the structural unit (a34) of the structural unit (a32) of aromatic compounds, the maleimide compound that replaces derived from the structural unit (a33) of cyano group vinyl compound with derived from N-with polymerizable carbon-to-carbon unsaturated bond.
The example that produces the carboxylate of structural unit (a31) comprises: esters of unsaturated carboxylic acids, as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid two cyclopentyl esters etc., unsaturated carboxylic acid aminoalkyl ester is as (methyl) acrylic acid ammonia ethyl ester etc.; And vinyl carboxylates, as vinyl acetate, propionate etc.
The example that produces the aromatic compounds with polymerizable carbon-to-carbon unsaturated bond of structural unit (a32) comprises, for example aromatic vinyl compound.The example of aromatic vinyl compound comprises for example styrene, α-Jia Jibenyixi, vinyltoluene etc.
The example that produces the cyano group vinyl compound of structural unit (a33) comprises for example vinyl cyanide, methacrylonitrile, α-chlorine (methyl) vinyl cyanide etc.
The example that produces the N-substituted maleimide amines of structural unit (a34) comprises for example 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-succinimido-3-maleimide benzoic ether; N-succinimido-3-maleimide propionic ester; N-succinimido-4-maleimide butyric ester; N-succinimido-6-maleimide capronate; N-(1-anilino-naphthyl-4)-maleimide; N-[4-(2-benzo
The azoles base) phenyl] maleimide, N-(9-acridinyl) maleimide etc.
In this manual, (methyl) acrylate refers to be selected from least a of acrylate and methacrylate, and the meaning of (methyl) acryloxy is also same as described above.
Structural unit (a1) derived from unsaturated carboxylic acid, structural unit (a2) derived from unsaturated compound with curable group, the structural unit of derived from carboxylic acid ester (a31), structural unit (a32) derived from aromatic compounds with polymerizable carbon-to-carbon unsaturated bond, the structural unit (a34) of the maleimide compound that replaces derived from the structural unit (a33) of cyano group vinyl compound with derived from N-can be used in combination with one or more unit derived from above-claimed cpd separately.
In the structural unit (a1) and multipolymer that comprise derived from unsaturated carboxylic acid derived from the structural unit (a2) of unsaturated compound with curable group, total mole number based on the structural unit of multipolymer, proportion of composing derived from the last unit (a1) of unsaturated carboxylic acid is preferably 5 to 50 moles of %, more preferably 15 to 40 moles of %.
Based on the total mole number of the structural unit of multipolymer, be preferably 95 to 50 moles of % derived from the ratio of the structural unit (a2) of unsaturated compound, more preferably 85 to 60 moles of % with curable group.
When in structural unit recited above (a1) and described in the above each scope of ratio (a2), then be preferred, because can obtain the suitable dissolution velocity and the high curing performance of developer.
When this multipolymer comprised structural unit (a3), based on the total mole number of above copolymer structure unit, the ratio of structural unit (a3) was preferably 0.1 to 90 mole of %, more preferably 5 to 80 moles of %.
Contain structural unit (a1) and comprise: 3-ethyl-3-methacryloxy methyl oxetanes/benzyl methacrylate/methacrylic acid copolymer for example derived from the example of the multipolymer of the structural unit (a2) of unsaturated compound with curable group derived from unsaturated carboxylic acid, 3-ethyl-3-methacryloxy methyl oxetanes/benzyl methacrylate/methacrylic acid/styrol copolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/styrol copolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/cyclohexyl methacrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/methylmethacrylate copolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/methyl methacrylate/styrol copolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/metering system tert-butyl acrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/IBOMA multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/benzyl acrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/cyclohexyl acrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/isobornyl acrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/methacrylic acid two cyclopentyl ester multipolymers, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/tert-butyl acrylate multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/phenyl Maleimide multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/cyclohexyl Maleimide multipolymer etc.
Based on the polystyrene calibration standards thing, contain structural unit (a1) and be generally 2 derived from the weight-average molecular weight of the multipolymer of the structural unit (a2) of unsaturated compound with curable group derived from unsaturated carboxylic acid, 000 to 100,000, be preferably 2,000 to 50,000, more preferably 3,000 to 20,000.In the time of in based on the described in the above scope of the weight-average molecular weight of polystyrene calibration standards thing, then be preferred, in development, keep residual film ratio simultaneously because often obtain high developing powder.
Based on the solids content of radiation-sensitive resin composition, the content that has the alkali soluble resin (A) of curable group in the radiation-sensitive resin composition of the present invention is preferably 50 to 90 quality %, more preferably 60 to 90 quality %.
The massfraction of the component beyond herein, the solids content of radiation-sensitive resin composition refers to desolventize in the gross mass of radiation-sensitive resin composition.
The example of the quinone di-azido compound that adopts in the radiation-sensitive resin composition of the present invention (B) comprises 1 of trihydroxy benzophenone for example, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide and 1,2-naphthoquinones two nitrine sulfonamide etc.
The example of quinone di-azido compound (B) comprises 1 of trihydroxy benzophenone for example, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide and 1,2-naphthoquinones two folded Clofenamides are as 2,3,4-trihydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4-trihydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,4,6-trihydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,4,6-trihydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.; 1 of tetrahydroxybenzophenone, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide, with 1,2-naphthoquinones two nitrine sulfonamide are as 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2 ', 4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3 ', 4,2 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.; 1 of pentahydroxybenzophenone, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide and 1,2-naphthoquinones two nitrine sulfonamide are as 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.; 1 of hexahydroxy benzophenone, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide and 1,2-naphthoquinones two nitrine sulfonamide are as 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.; 1 of (polyhydroxy phenyl) alkane, 2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonamide, with 1,2-naphthoquinones two nitrine sulfonamide, as two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (right-hydroxy phenyl) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (right-hydroxy phenyl) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 1,1,1-three (right-hydroxy phenyl) ethane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 1,1,1-three (right-hydroxy phenyl) ethane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2 '-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2 '-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.
Each quinone di-azido compound recited above (B) can be used in combination separately or with two or more.Based on the solids content of radiation-sensitive resin composition, the content of the quinone di-azido compound in the radiation-sensitive resin composition of the present invention (B) is preferably 2 to 50 quality %, more preferably 5 to 40 quality %.When in the described in the above scope of the content of quinone di-azido compound (B), then be preferred, because the difference of the solubleness between exposed portion and the unexposed portion improves, thereby the residual film ratio after developing is often higher.
The anionicsite of used cationic polymerization initiators (C) is provided by following formula (1) or (2) in the radiation-sensitive resin composition of the present invention.
R wherein
1-R
3, R
11And R
33Representative independently of one another have 1-20 carbon atom the straight chain perfluoroalkyl, have 3-20 carbon atom the side chain perfluoroalkyl, have the ring-type perfluoroalkyl of 1-20 carbon atom or have the perfluor aryl of 6-20 carbon atom.Group-O-,-N (R)-or-SO
2-in any can insert between the carbon atom of above-mentioned each group.Herein, R represents hydrogen atom or has the alkyl of 1-4 carbon atom.R in the formula (1)
1-R
3Any two, and formula (2) in R
11And R
33Respectively can be in conjunction with forming ring.One or two unit in the described structure can form heterocycle.
Example with straight chain perfluoroalkyl of 1-20 carbon atom comprises for example trifluoromethyl, pentafluoroethyl group, seven fluoro-n-pro-pyls, nine fluoro-normal-butyls, 11 fluoro-n-pentyls, 13 fluoro-n-hexyls, 15 fluoro-n-heptyls, 17 fluoro-n-octyls, 19 fluoro-n-nonyls, the positive decyl of 21 fluoro-, perfluor-positive undecyl, perfluor-positive dodecyl, perfluor-positive tritriacontyl, perfluor-positive tetradecyl, perfluor-positive pentadecyl, perfluor-positive hexadecyl, perfluor-positive heptadecyl, perfluor-positive octadecyl, perfluor-positive nonadecyl, perfluor-positive 20 bases etc., preferred trifluoromethyl, pentafluoroethyl group, seven fluoro-n-pro-pyls, nine fluoro-normal-butyls etc.
Example with side chain perfluoroalkyl of 3-20 carbon atom comprises for example seven fluorine isopropyls, nine fluoro-sec-butyls, the nine fluoro-tert-butyl groups, perfluor-2-methyl hexyl, perfluor-uncle's octyl group etc., preferred seven fluorine isopropyls, nine fluoro-sec-butyls, the nine fluoro-tert-butyl groups, perfluor-2-methyl hexyl etc.
Example with ring-type perfluoroalkyl of 3-20 carbon atom comprises for example perfluor cyclopropyl, perfluorocyclobutanearyl, perfluor cyclopentyl, perfluor cyclohexyl, perfluor suberyl, perfluor ring octyl group etc., preferred perfluor cyclopentyl, perfluor cyclohexyl, perfluor suberyl, perfluor ring octyl group etc.
Example with perfluor aryl of 6-20 carbon atom comprises for example perfluorophenyl, perfluor naphthyl, perfluor anthryl etc., preferred perfluorophenyl, perfluor naphthyl etc.
The example that has the alkyl of 1-4 carbon atom among the R comprises for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc.
The anionic example that formula (1) provides comprises:
Three (trifluoromethane sulfonyl group) methide,
Three (hexafluoroethane sulfonyl) methide,
Three (perfluoropropane sulfonyl) methide,
Three (perfluorinated butane sulfonyl) methide,
Three (perflenapent sulfonyl) methide,
Three (perflexane sulfonyl) methide,
Three (PF 5070 sulfonyl) methide,
Three (PFO sulfonyl) methide,
Three (Perfluorononane sulfonyl) methide,
Three (perfluoro decane sulfonyl) methide,
Three (perfluor undecane sulfonyl) methide,
Three (perfluor dodecane sulfonyl) methide,
Three (perfluor cyclohexane sulfonyl) methide,
Three (the different propane sulfonyl of perfluor) methide,
Three (perfluor-2-ethyl hexane sulfonyl) methide,
Two (trifluoromethane sulfonyl group) perfluorinated butane sulfonyl methide,
Two (trifluoromethane sulfonyl group) perflexane sulfonyl methide,
Two (trifluoromethane sulfonyl group) PFO sulfonyl methide,
Perfluor-N, two (trifluoromethane sulfonyl group) sulfonyl methides of N-dimethylamino ethane sulfonyl,
Two (trifluoromethane sulfonyl group) methides of perfluor morpholinyl ethane sulfonyl,
Two (trifluoromethane sulfonyl group) methides of perfluor methyl butyl ether sulfonyl,
The negative ion that formula (3) and (4) provide.
The negative ion example that formula (2) provides comprises:
Two (trifluoromethane sulfonyl group) imines,
Two (hexafluoroethane sulfonyl) imines,
Two (perfluoropropane sulfonyl) imines,
Two (perfluorinated butane sulfonyl) imines,
Two (perflenapent sulfonyl) imines,
Two (perflexane sulfonyl) imines,
Two (PF 5070 sulfonyl) imines,
Two (PFO sulfonyl) imines,
Two (Perfluorononane sulfonyl) imines,
Two (perfluoro decane sulfonyl) imines,
N-trifluoromethane sulfonyl group perfluorinated butane sulfonyl imines and
The negative ion that formula (5) and (6) provide.
Wherein, preferred example comprises:
Three (trifluoromethane sulfonyl group) methide,
Three (hexafluoroethane sulfonyl) methide,
Three (perfluoropropane sulfonyl) methide,
Three (perfluorinated butane sulfonyl) methide,
Two (trifluoromethane sulfonyl group) imines,
Two (hexafluoroethane sulfonyl) imines,
Two (perfluoropropane sulfonyl) imines,
Two (perfluorinated butane sulfonyl) imines, etc.
Above negative ion can be used in combination separately or with two or more.
R
4-I+R
6(8)
R in formula (7) and (8)
4-R
6Representative independently of one another can be by the phenyl of at least one atom or group replacement, and this atom or group are selected from halogen atom such as fluorine, chlorine, bromine or iodine atom, have the alkyl of 1-18 carbon atom, the alkoxy with 1-18 carbon atom, the alkyl-carbonyl with 2-18 carbon atom, the alkoxy carbonyl with 2-18 carbon atom, carboxyl, sulfydryl, cyano group, hydroxyl and nitro; The naphthyl that can be replaced by at least one atom or group, this atom or group be selected from halogen atom such as fluorine, chlorine, bromine or iodine atom, have the alkoxy of 1-12 carbon atom, have 2-12 carbon atom alkyl-carbonyl, have alkoxy carboxyl, carboxyl, sulfydryl, cyano group, hydroxyl and the nitro of 2-12 carbon atom; Can be by the straight chained alkyl with 1-18 carbon atom of at least one atom or group replacement, this atom or group are selected from halogen atom such as fluorine, chlorine, the bromine or iodine atom, carboxyl, sulfydryl, cyano group, hydroxyl, nitro, phenyl and alkyl with 1-12 carbon atom, can be by the branched alkyl with 3-18 carbon atom of at least one atom or group replacement, this atom or group are selected from halogen atom such as fluorine, chlorine, the bromine or iodine atom, carboxyl, sulfydryl, cyano group and nitro, or can be by the naphthenic base with 3-18 carbon atom of at least one atom or group replacement, this atom or group are selected from halogen atom such as fluorine, chlorine, the bromine or iodine atom, carboxyl, sulfydryl, cyano group and nitro.
Example with alkyl of 1-18 carbon atom comprises for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive undecyl, positive dodecyl, positive tritriacontyl, positive tetradecyl, positive pentadecyl, positive hexadecyl, positive heptadecyl, positive octadecyl, positive nonadecyl, positive 20 bases etc., preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl and the tert-butyl group.
Example with alkoxy of 1-18 carbon atom comprises for example methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, just own oxygen base, positive heptan the oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems the oxygen base, n-decyloxy, positive 11 oxygen bases, positive ten dioxy bases, positive 13 oxygen bases, positive 14 oxygen bases, positive 15 oxygen bases, positive 16 oxygen bases, positive 17 oxygen bases, positive 18 oxygen bases, positive 19 oxygen bases, positive 20 oxygen bases etc., preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.
Example with alkyl-carbonyl of 2-18 carbon atom comprises for example acetyl group; the ethyl carbonyl; the n-pro-pyl carbonyl; the isopropyl carbonyl; the normal-butyl carbonyl; the isobutyl carbonyl; the sec-butyl carbonyl; tert-butyl group carbonyl; the n-pentyl carbonyl; the n-hexyl carbonyl; the n-heptyl carbonyl; the n-octyl carbonyl; the n-nonyl carbonyl; positive decyl carbonyl; positive undecyl carbonyl; positive dodecyl carbonyl; positive tritriacontyl carbonyl; positive tetradecyl carbonyl; positive pentadecyl carbonyl; positive hexadecyl carbonyl; positive heptadecyl carbonyl; positive octadecyl carbonyl; positive nonadecyl carbonyl; positive 20 basic carbonyls etc., preferred acetyl group; the ethyl carbonyl; the n-pro-pyl carbonyl; the isopropyl carbonyl; the normal-butyl carbonyl; the isobutyl carbonyl; sec-butyl carbonyl and tert-butyl group carbonyl.
Example with alkoxy carbonyl of 2-18 carbon atom comprises for example methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the n-butoxy carbonyl, isobutoxy carbonyl, the sec-butoxy carbonyl, tert-butoxycarbonyl, the n-pentyloxy carbonyl, positive hexyloxy carbonyl, positive heptan oxygen base carbonyl, the n-octyloxy carbonyl, positive ninth of the ten Heavenly Stems oxygen base carbonyl, the n-decyloxy carbonyl, positive 11 oxygen base carbonyls, positive ten dioxy base carbonyls, positive 13 oxygen base carbonyls, positive 14 oxygen base carbonyls, positive 15 oxygen base carbonyls, positive 16 oxygen base carbonyls, positive 17 oxygen base carbonyls, positive 18 oxygen base carbonyls, positive 19 oxygen base carbonyls, positive 20 oxygen base carbonyls etc., preferred methoxycarbonyl, ethoxy carbonyl, the positive propoxy carbonyl, isopropoxy carbonyl, the n-butoxy carbonyl, isobutoxy carbonyl, sec-butoxy carbonyl and tert-butoxycarbonyl.
The example of the phenyl that can replace by at least one atom or group comprise phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-n-pro-pyl phenyl, 3-n-pro-pyl phenyl, 4-n-pro-pyl phenyl,
Base, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl etc., preferred 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-hydroxy phenyl, 3-hydroxy phenyl and 4-hydroxy phenyl.
The example of the naphthyl that can be replaced by at least one atom or group comprises naphthyl, fluoronaphthalene base, chloronaphthyl, methylnaphthyl, bromonaphthalene base, methyl naphthyl, ethyl naphthyl, n-pro-pyl naphthyl, dimethyl naphthyl, hydroxyl naphthyl etc., preferable methyl naphthyl and hydroxyl naphthyl.
The example of the straight chained alkyl with 1-18 carbon atom that can be replaced by at least one atom or group comprises methyl fluoride, difluoromethyl, trifluoromethyl, ethyloic, carboxyethyl, the carboxylic butyl, carboxylic 20 bases, mercapto methyl, mercaptoethyl, the sulfydryl butyl, sulfydryl 20 bases, cyano methyl, cyano ethyl, the cyano group butyl, cyano group 20 bases, the nitro methyl, nitro-ethyl, the nitro butyl, nitro 20 bases, hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxyl 20 bases, benzyl, 2-aminomethyl phenyl methyl, 3-aminomethyl phenyl methyl, 4-aminomethyl phenyl methyl, the 2-fluorophenyl methyl, the 3-Chlorophenylmethyl, 4-hydroxy phenyl methyl, phenylethyl etc., preferred benzyl, 2-aminomethyl phenyl methyl, 3-aminomethyl phenyl methyl and 4-aminomethyl phenyl methyl.
The example of the branched alkyl with 3-18 carbon atom that can be replaced by at least one atom or group comprises fluorine isopropyl, perfluor isopropyl, perfluor isobutyl, carboxyl isopropyl, carboxyl isobutyl, sulfydryl isopropyl, sulfydryl isobutyl, cyano group isopropyl, cyano group isobutyl, nitro isopropyl, nitro isobutyl, hydroxyl isopropyl, hydroxyl isobutyl etc., preferably fluorine isopropyl, perfluor isopropyl, perfluor isobutyl, hydroxyl isopropyl and hydroxyl isobutyl.
The example of the naphthenic base with 3-18 carbon atom that can be replaced by at least one atom or group comprises fluorine cyclopentyl, perfluor cyclopentyl, perfluor cyclohexyl, carboxyl cyclopentyl, carboxyl cyclohexyl, sulfydryl cyclopentyl, sulfydryl cyclohexyl, cyano group cyclopentyl, cyanocyclohexanoic base, nitro cyclopentyl, nitrocyclohex base, hydroxycyclopent base, hydroxy-cyclohexyl etc., preferably fluorine cyclopentyl, perfluor cyclopentyl, perfluor cyclohexyl, hydroxycyclopent base and hydroxy-cyclohexyl.
Formula (7) provides
Cation examples comprises triphenylsulfonium, three (4-tolyl) sulfonium, three (4-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (right-cyano-phenyl) sulfonium, three (4-chlorphenyl) sulfonium, diphenyl (4-hydroxy phenyl) sulfonium, aminomethyl phenyl (4-hydroxy phenyl) sulfonium, dibenzyl phenyl sulfonium, dibenzyl (4-hydroxy phenyl) sulfonium, benzyl methyl (4-hydroxy phenyl) sulfonium, benzyl methyl (4-acetoxyl group phenyl) sulfonium, methyl (4) (2-aminomethyl phenyl) 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 (uncle-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) sulfonium etc.Preferred triphenylsulfonium, three (right-tolyl) sulfonium, benzyl methyl (right-hydroxy phenyl) sulfonium, benzyl methyl (right-the acetoxyl group phenyl) sulfonium, methyl (right-hydroxy phenyl) (neighbour-aminomethyl phenyl) sulfonium, more preferably three (right-tolyl) sulfonium, benzyl methyl (right-hydroxy phenyl) sulfonium and benzyl methyl (right-the acetoxyl group phenyl) sulfonium.
Formula (8) provides
Cationic example comprises: diphenyl iodine
, two (4-tolyl) iodine
, two (4-tert-butyl-phenyl) iodine
, two (4-n-octyl phenyl) iodine
, two (4-octadecyl phenyl) iodine
, two (4-n-octyloxy phenyl) iodine
, two (4-n-octadecane oxygen base phenyl) iodine
, phenyl (4-n-octadecane oxygen base phenyl) iodine
, (4-tolyl) (4-isopropyl phenyl) iodine
, phenyl (4-hydroxy phenyl) iodine
, phenylbenzyl iodine
, benzyl (4-hydroxy phenyl) iodine
, preferred diphenyl iodine
With two (4-tert-butyl-phenyl) iodine
More than
Kation can be used in combination separately or with two or more.
Should
The above cationic any combination that above negative ion that salt can provide with formula (1) or (2) and formula (7) or (8) provide is used.
Based on the solids content of radiation-sensitive resin composition, the content of cationic polymerization initiators (C) is preferably 0.01 to 10 quality %, more preferably 0.1 to 5 quality %.When in the described in the above scope of the content of cationic polymerization initiators (C), then be preferred, because the decline of resolution often is inhibited after solidifying.
Radiation-sensitive resin composition of the present invention comprises solvent (H).
The example of solvent (H) comprises for example ethylene glycol monoalkyl ether, as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether etc.; The diglycol dialkyl ether is as diethylene glycol dimethyl ether, diethyl carbitol, diglycol dipropyl ether, diethylene glycol dibutyl ether, diglycol ethyl methyl ether, diglycol methyl isopropyl ether etc.; Ethylene glycol alkyl ether acetic acid esters is as methylcellosolve acetate, ethyl cellosolve acetate etc.; Propylene glycol alkyl ether acetic acid ester is as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters etc.; Aromatic hydrocarbon, as benzene,toluene,xylene,
Deng; Ketone is as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexyl ketone etc.; Alcohols is as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.; The ester class is as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, butyl acetate, pentyl acetate, isoamyl acetate, methyl pyruvate etc. and cyclic ester such as gamma-butyrolacton.
Preferred examples of solvents comprises diglycol ethyl methyl ether, 2-hydroxy-methyl isobutyl acid, ethyl lactate, propylene glycol methyl ether acetate, 3-ethoxyl ethyl propionate and gamma-butyrolacton.
Solvent (H) can use separately or be used in combination with two or more.
The preferred 50-95 quality of the content % of the solvent of radiation resin combination (H), more preferably 60-90 quality %.
Except alkali-soluble curable resin (A), quinone di-azido compound (B) and cationic polymerization initiators (C), radiation-sensitive resin composition of the present invention can optionally contain radiosensitizing agent (D), polyhydroxy phenol (E), crosslinking chemical (F) and polymerisable monomer (G).
The example of radiosensitizing agent (D) comprises for example aphthols, as the 1-naphthols, beta naphthal, 1, the 2-dihydroxy naphthlene, 1, the 3-dihydroxy naphthlene, 1, the 4-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 1, the 7-dihydroxy naphthlene, 1, the 8-dihydroxy naphthlene, 2, the 3-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 4-methoxyl-1-naphthols etc., with the thioxanthene ketone, thioxanthones for example, the 2-isopropyl thioxanthone, the 4-isopropyl thioxanthone, 2, the 3-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones, 2-cyclohexyl thioxanthones, 4-cyclohexyl thioxanthones etc.
Especially preferred 1-naphthols, beta naphthal, 4-methoxyl-1-naphthols and 2, the 4-diethyl thioxanthone.
When containing radiosensitizing agent (D), based on the solids content of radiation resin combination, the amount of radiosensitizing agent (D) is 0.1-10 quality %, more preferably 0.1-5 quality %.When the amount of radiosensitizing agent (D) is in above scope, then be preferred, because the degraded of cationic polymerization initiators obtains promoting, the decline of solidifying back resolution is prevented, and the gained coat film will not be reduced to the level that has problems in actual applications to visible light transmittance.
Polyhydroxy phenol (E) preferably has the compound of two or more phenolic hydroxyl groups in the molecule.
The example of above-mentioned polyhydroxy phenol comprises for example trihydroxy benzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane etc., as describing as an example in the quinone di-azido compound (B).
The example of polyhydroxy phenol (E) comprises that by hydroxy styrenes at least be the polymkeric substance that starting monomer obtains.The example of polyhydroxy phenol (E) comprises the hydroxy styrenes polymer resin, as polycarboxylated styrene, hydroxystyrene/methyl methacrylate multipolymer, hydroxy styrenes/cyclohexyl methacrylate multipolymer, hydroxy styrenes/styrol copolymer, hydroxy styrenes/alkoxystyrene multipolymer etc., and be selected from compound in phenol, cresols class and the pyrocatechol and one or more are selected from the phenolic novolac that the compound in aldehydes and the ketone obtains by polycondensation is at least a.
When containing above polyhydroxy phenol (E), its content is preferably 0.1 to 40 quality % based on the solids content of radiation-sensitive resin composition, is preferably 1 to 25 quality %.When in the described in the above scope of the content of polyhydroxy phenol, then be preferred, because the transmission of visible light of gained film often can not descend.
The example of above crosslinking chemical (F) comprises for example methylol compound etc.
The example of methylol compound comprises for example alkoxy methyl amino resins, as alkoxy methyl melamine resin class, alkoxy methyl urea resin class etc.The example of alkoxy methyl melamine resin class comprises methoxy melamine resin, ethoxyl methyl melamine resin, propoxyl group methylated melamine resin, butoxymethyl melamine resin etc., and the example of alkoxy methyl urea resin class for example comprises methoxy urea resin, ethoxyl methyl urea resin, propoxyl group methylate urea resin, butoxymethyl urea resin etc.Can be separately or two or more be used in combination crosslinking chemical recited above.
When containing above crosslinking chemical (F), its content is preferably 0.1 to 15 quality % based on the solids content of radiation-sensitive resin composition.When in the described in the above scope of the content of crosslinking chemical, then be preferred, because the transmission of visible light of gained film often can not descend.
The embodiment of above polymerisable monomer (G) comprises, for example, can carry out the hot polymerisable monomer and the polymerisable monomer that can carry out cationic polymerization of free radical polymerization, preferably can carry out the polymerisable monomer of cationic polymerization.
The example that can carry out the polymerisable monomer of free radical polymerization comprises the compound that for example has the polymerizable carbon-to-carbon unsaturated bond, and can be simple function polymerisable monomer or multifunctional polymerisable monomer such as difunctionality polymerisable monomer or three or multifunctional polymerisable monomer.
The example of simple function polymerisable monomer comprises for example nonyl phenyl carbitol acrylate, nonyl phenyl carbitol methacrylate, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid 2-hydroxyl-3-phenoxy group propyl ester, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone etc.
The example of difunctionality polymerisable monomer for example comprises 1,6-hexanediyl ester, 1, two (acryloxy ethyl) ether 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.
Three or the example of multifunctional polymerisable monomer comprise 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 the superincumbent polymerisable monomer, preferably use difunctionality or three or multifunctional polymerisable monomer.
Preferred embodiment comprises tetramethylol methane tetraacrylate and dipentaerythritol acrylate, more preferably dipentaerythritol acrylate.Can also with difunctionality three or multifunctional polymerisable monomer and simple function polymerisable monomer be used in combination.
The example that can carry out the polymerisable monomer of cationic polymerization comprises the polymerisable monomer that for example has cationic polymerizable functional group, as has the polymerisable monomer of vinyl ether, propenyl ether or oxetanyl.
Examples for compounds with vinyl ether group comprises for example triethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl etc.The examples for compounds that contains the propenyl ether comprises for example 4-(1-propenyloxy group methyl)-1,3-dioxolanes-2-ketone etc., the examples for compounds that contains oxetanyl comprises for example two { 3-(3-ethyl oxetanyl) methyl } ether, 1,4-two { 3-(3-ethyl oxetanyl) methoxyl } benzene, 1,4-two { 3-(3-ethyl oxetanyl) methoxyl } methylbenzene, 1,4-two { 3-(3-ethyl oxetanyl) methoxyl } cyclohexane, 1,4-two { 3-(3-ethyl oxetanyl) methoxyl } methylcyclohexane, 3-(3-ethyl oxetanyl) methylates novolac resin etc.
Above polymerisable monomer (G) can be used in combination separately or with two or more.Based on the solids content of radiation-sensitive resin composition, the consumption of polymerisable monomer is preferably 0.1 to 20 quality %.
If desired, radiation-sensitive resin composition of the present invention can also further contain various adjuvants, as surfactant, antioxidant, dissolution inhibitor, ultraviolet light absorber, tackifier, electron donor etc.
Radiation-sensitive resin composition of the present invention for example can prepare by following method: mixed be dissolved in the solvent (H) comprise derived from unsaturated carboxylic acid structural unit (a1) and derived from multipolymer (A) solution of the structural unit (a2) of the unsaturated compound with curable group (but except unsaturated carboxylic acid), be dissolved in the solution of the quinone di-azido compound (B) in the solvent (H) and be dissolved in the solution of the cationic polymerization initiators (C) in the solvent (H).
Each solvent can be identical or different.Radiosensitizing agent, polyhydroxy phenol, crosslinking chemical and polymerisable monomer, adjuvant etc. can further add the mixed solution of above gained.Can after mixed, further add solvent (H).After mixed, preferably remove solid constituent by filtering, for example, using the aperture is common 3 μ m or following, the filtrator of preferred 0.1-2 μ m filters.The used separately solvent of above component can be identical or different, as long as it is compatible.
Use radiation-sensitive resin composition of the present invention to prepare solidified resin pattern, for example go up and form layer (1) (Fig. 1 (a)) that comprises radiation-sensitive resin composition of the present invention at substrate (2), shine described layer (1) (Fig. 1 (b)) with exposure by mask (3) with radiant rays (4), develop then (Fig. 1 (c)).
The example of substrate (2) comprises transparency glass plate, silicon wafer etc., and resin substrate is polycarbonate, polyester, aromatic poly amide, polyamide-imide, poly-imines substrate etc. for example.On above-mentioned substrate, can be pre-formed TFT circuit, color filter etc.
Can for example form the layer that comprises this radiation-sensitive resin composition by go up coating radiation-sensitive resin composition (1) at substrate (2).Coating process comprises: for example spin coating, curtain coating, roller coat, slit and spin-coating method or slot coated method.After coating, heating is with the evaporating volatile component, as solvent etc., to form radiation-sensitive resin composition layer (1) after the substrate that is coated with of heating and drying (prebake) or the vacuum drying.Heating-up temperature is generally 70-200 ℃, preferred 80-130 ℃.Described radiation-sensitive resin composition layer (1) contains volatile constituent usually hardly.The thickness of radiation-sensitive resin composition layer (1) is generally 1.5-5 μ m.
Then, shine described radiation-sensitive resin composition layer (1) by mask (3) with radiant rays (4).Mask pattern (3) can suitably be selected to mate required pattern structure.The example of used radiant rays comprises light beam such as g or i line.Preference carries out the irradiation of radiant rays as using mask aligner or stepper (not shown), make this radiation-sensitive resin composition layer (1) on whole zone by parallel radiation.This irradiation with radiation makes mask (3) accurately aim at radiation-sensitive resin composition layer (1).
Behind irradiation with radiation, development radiation-sensitive resin composition layer (1).Exposure back radiation-sensitive resin combination layer (1) carries out as paddle development, immersion development or spray developing method.Used developer is generally alkaline aqueous solution.The example of alkaline aqueous solution comprises for example aqueous solution of alkali compounds, and alkali compounds can be inorganic alkaline compound or organic basic compound.
The example of above inorganic alkaline compound comprises for example 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.
The example of above organic basic compound comprises for example tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethylammonium, single methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc.
Alkali compounds recited above can use separately or two or more are used in combination.In developer, based on the developer of 100 mass parts, the content of alkali compounds is generally 0.01 to 10 mass parts, is preferably 0.1 to 5 mass parts.
Developer can also contain surfactant.The example of surfactant comprises for example nonionic, kation or anionic surfactant.
The example of non-ionic surfactant comprises for example polyoxyethylene deriv, as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether etc., oxygen ethene/oxypropylene segmented copolymer, D-sorbite fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
The example of cationic surfactant comprises for example amine salt, as stearic amine salt alkoxide, quaternary ammonium salt such as lauryl trimethyl ammonium chloride.
The example of anionic surfactant comprises for example higher alcohol sulfate, as sldium lauryl sulfate, oleyl alcohol sodium sulphate etc., alkyl sulfate is as NaLS, Texapon Special etc., or alkyl aryl sulfonate, as neopelex, dodecyl sodium naphthalene sulfonate etc.Use these surfactants separately or with two or more.
Developer can contain organic solvent.The example of organic solvent comprises for example water-miscible organic solvent, as methyl alcohol, ethanol etc.
In above-mentioned exposure, developing causes in the radiation-sensitive resin composition layer (1) dissolving through the radiant rays exposure area (12) of irradiation with radiation, and be not exposed to the territory, radiant rays non-exposed area (11) of radiant rays thus not being developed the agent dissolving keeps and forms resin pattern (5).
After the alkaline solution development, wash the substrate and the drying of exposure usually with water.After the drying, the part or all of zone of the resin pattern that obtains with irradiation with radiation (5) again.The light source that described radiant rays is used preferably contains the light source of 300 to 450nm wavelength radiation lines.
For improving the thermotolerance and the solvent resistance of the resin pattern (5) that forms thus, preferably resin pattern is heat-treated (afterwards baking and banking up with earth) again.Heat treatment method preferably adopts after irradiation resin pattern (5) whole or a part of zone, the method that substrate is heated by the heating arrangement as hot plate or ultra-clean baking oven (clean oven).Heating-up temperature is preferably 150 ℃ to 250 ℃, more preferably 180 ℃ to 240 ℃.Be preferably 5 minutes to 120 minutes heat time heating time, more preferably 15 minutes to 90 minutes.Heat treated makes resin pattern (5) solidify, thereby forms solidified resin pattern (6).
The solidified resin pattern of Xing Chenging (6) is applicable to for example as the solidified resin pattern of forming the TFT substrate thus.
According to the present invention, the solidified resin pattern that can obtain to have non-coloring almost, visible light be had high-transmission rate and enough solvent resistance.Also can obtain to have the solidified resin pattern of good geometry.
Embodiment
With embodiment is that the present invention is described on the basis in more detail, and still self-evident is the restriction that scope of the present invention is not subjected to these embodiment.
Synthetic embodiment 1
In the 200mL four neck flasks that are equipped with stirrer, condenser and thermometer, the raw material below adding.Under nitrogen atmosphere, four neck flasks are immersed oil bath and kept the flask interior temperature at 85-95 ℃ in 3 hours simultaneously, to obtain Resin A 1 to stir.Based on the polystyrene calibration standards thing, the weight-average molecular weight that obtains this Resin A 1 by gel permeation chromatography (GPC) is 15000.
Methacrylic acid 7.3g
Cyclohexyl methacrylate 12.5g
3-ethyl-3-methacryloxy methyl oxetanes 17.8g
2-hydroxy-methyl isobutyl acid 87.6g
Azoisobutyronitrile 0.9g
The gpc measurement condition of the weight-average molecular weight of above binder polymer is as follows:
Instrument: HLC-8120GPC type (Tosoh Corp.)
Post: TSK-GEL G2000HXL and the series connection of TSK-GEL G4000HXL post
Column temperature: 40 ℃
Solvent: tetrahydrofuran (THF)
Flow velocity: 1.0ml/ minute
Sample concentration: 0.6 quality % (solvent THF)
Injection volume: 50 μ l
Detecting device: refractive index (RI)
The polystyrene that molecular weight calibration is used: (Tosoh Corp.)
Synthetic embodiment 2
In the 200mL four neck flasks that are equipped with stirrer, condenser and thermometer, the raw material below adding.Under nitrogen atmosphere, four neck flasks are immersed oil bath and kept the flask interior temperature at 85-95 ℃ in 3 hours simultaneously, to obtain Resin A 2 to stir.Based on the polystyrene calibration standards thing, the weight-average molecular weight of this Resin A 2 is 8000.
Methacrylic acid 6.8g
N-cyclohexyl maleimide 14.2g
3-ethyl-3-methacryloxy methyl oxetanes 17.8g
Ethyl lactate 90.7g
Azoisobutyronitrile 1.1g
Embodiment 1
The compound (22 mass parts) that provides 23 ℃ of mixed Resin A 1 (100 mass parts), as the formula (9) of quinone di-azido compound (B) as alkali-soluble curable resin (A), as two (4-tert-butyl-phenyl) iodine of cationic polymerization initiators (C)
Three (trifluoromethane sulfonyl group) methide (2 mass parts) and as the 2-hydroxy-methyl isobutyl acid (302 mass parts) of solvent (H); under pressure, be that the teflon core strainer of 1.0 μ m filters then, to obtain radiation-sensitive resin composition 1 as mother liquor by the aperture.
On 4 inches silicon wafers (2), the radiation-sensitive resin composition 1 that spin coating obtains above uses electric hot plate 2 minutes (baking and banking up with earth in advance) of 100 ℃ of heating, to form the thick radiation-sensitive resin composition layer (1) of 2.6 μ m (Fig. 1 (a)).Use film thickness instrument (Lambda Ace; DainipponScreen MFG C0.Ltd.) measures the thickness of this film.
Afterwards, use i line stepper (NSR-1755i7A type; Nikon Corp., NA=0.5], shine this radiation-sensitive resin composition layer (1) (Fig. 1 (b)) with exposure with radiant rays (4) by mask (3).Used mask (3) is the mask that is used to form the resin pattern (5) of the contact hole with 9 μ m live width 3 μ m at interval.
After the exposure, the substrate that exposes was developed for 70 seconds with tetramethyl ammonium hydroxide aqueous solution (containing 0.2 mass parts tetramethyl ammonium hydroxide in the solution of 100 mass parts) is middle at 23 ℃, use the ultrapure water cleaning, drying subsequently.Effective sensitivity is 135mJ/cm
2, prerequisite is that the effective sensitivity in the developing pattern is the exposure that forms in the mask exposure of contact hole that diameter is 3 μ m.After the drying, use deep ultraviolet (DUV) lamp (Model UXM-501MD; Ushio Inc.) (throughput based on wavelength 313nm is 300mJ/cm to the whole area illumination radiant rays of resin pattern (5)
2), in the ultra-clean baking oven, heated 30 minutes down in 220 ℃, form solidified resin pattern (6) (Fig. 1 (c)).
Using film thickness gauge to measure the thickness (T1) of the solidified resin pattern (6) that obtains, is 2.0 μ m.
Use microspectrophotometer (Model 0SP-200; Olympus Corp.) is determined at transparent glass substrate (Grade #1737; Corning Inc.) on, except not exposing by stepper, the cured resin film that forms according to said method is to visible light transmittance.Use film thickness gauge (Model DEKTAK3; ULVAC Inc.) measures thickness.Per 1 μ m gained cured resin film thickness is 99.6% in the average light transmissivity of wavelength 400-750nm, has shown high transparent, and non-coloring.The substrate that is formed with solidified resin pattern on it is flooded 30 minutes with the test solvent resistance in N-Methyl pyrrolidone (in 23 ℃).Before and after dipping, do not find to change, demonstrated good solvent resistance.
Embodiment 2
Except using three (4-tert-butyl-phenyl) sulfonium three (trifluoromethane sulfonyl group) methides, obtain radiation-sensitive resin composition 2 in the mode identical with embodiment 1 as the cationic polymerization initiators (C).
Except adopting radiation-sensitive resin composition 2 to replace the radiation-sensitive resin composition 1, adopt the mode identical on substrate, to form solidified resin pattern (6) with embodiment 1.Adopt 100mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m.The transmissivity that records this solidified resin pattern by the mode identical with embodiment 1 has shown 99.6% high transparent.Now do not examine painted.Be presented at the not variation of dipping front and back coated film with solvent resistance test identical among the embodiment 1.
Embodiment 3
Except using two (4-tert-butyl-phenyl) iodine
Two (trifluoromethane sulfonyl group) imines obtains radiation-sensitive resin composition 3 in the mode identical with embodiment 1 as cationic polymerization initiators (C) in addition.
Except adopting radiation-sensitive resin composition 3 to replace the radiation-sensitive resin composition 1, adopt the mode identical on substrate, to form solidified resin pattern (6) with embodiment 1.Adopt 120mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m.The transmissivity that records this solidified resin pattern by the mode identical with embodiment 1 has shown 99.5% high transparent.Do not observe painted.Be presented at the not variation of dipping front and back coated film with solvent resistance test identical among the embodiment 1.
Except using three (4-tert-butyl-phenyl) sulfonium two (trifluoromethane sulfonyl group) imines, obtain radiation-sensitive resin composition 4 in the mode identical with embodiment 1 as the cationic polymerization initiators (C).
Except adopting radiation-sensitive resin composition 4 to replace the radiation-sensitive resin composition 1, adopt the mode identical on substrate, to form solidified resin pattern (6) with embodiment 1.Adopt 110mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m.The transmissivity that records this solidified resin pattern by the mode identical with embodiment 1 has shown 99.6% high transparent.Do not observe painted.Be presented at the not variation of dipping front and back coated film with solvent resistance test identical among the embodiment 1.
Embodiment 5
Except using Resin A 2, obtain radiation-sensitive resin composition 5 in the mode identical with embodiment 1 as the alkali soluble resin (A).
Except adopting radiation-sensitive resin composition 5 to replace the radiation-sensitive resin composition 1, adopt the mode identical on substrate, to form solidified resin pattern (6) with embodiment 1.Adopt 120mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m.The transmissivity that records this solidified resin pattern by the mode identical with embodiment 1 has shown 99.7% high transparent.Do not observe painted.Be presented at the not variation of dipping front and back coated film with solvent resistance test identical among the embodiment 1.
Comparative example 1
Except not using cationic polymerization initiators (C), obtain radiation-sensitive resin composition 6 in the mode identical with embodiment 1.
Except adopting radiation-sensitive resin composition 6 to replace the radiation-sensitive resin composition 1, adopt the operation identical with embodiment 1.Adopt 100mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m, but this pattern melts in thermal treatment, does not form solidified resin pattern (6).The transmissivity that records by the mode identical with embodiment 1 is 99.6%.Do not observe painted.When carry out with embodiment 1 in during the test of identical solvent resistance, find that thickness increases by 6% behind dipping.
Comparative example 2
Except using three (4-tert-butyl-phenyl) sulfonium hexafluorophosphate, obtain radiation-sensitive resin composition 7 in the mode identical with embodiment 1 as the cationic polymerization initiators (C).
Except adopting radiation-sensitive resin composition 7 to replace the radiation-sensitive resin composition 1, adopt the operation identical with embodiment 1.Adopt 100mJ/cm
2Effective sensitivity differentiate the contact hole pattern of 3 μ m, but this pattern melts in thermal treatment, does not form solidified resin pattern (6).The transmissivity that records by the mode identical with embodiment 1 is 99.3%.Do not observe variable color.When carry out with embodiment 1 in during the test of identical solvent resistance, coated film does not show variation before and after the dipping.
Industrial applicability
Radiation-sensitive resin composition of the present invention is applicable to the formation solidified resin pattern; it comprises for TFT substrate and organic electroluminescent device and is used for the dielectric film of display element of liquid crystal display and the diaphragm of charge-coupled image sensor (CCD) that it consists of image device.
Claims (7)
1. radiation-sensitive resin composition, it comprises alkali-soluble curable resin (A), quinone di-azido compound (B), contains
Kation and be selected from negative ion that formula (1) provides and anionic cationic polymerization initiators (C) that formula (2) provides, and solvent (H),
R wherein
1-R
3, R
11And R
33Representative independently of one another have 1-20 carbon atom the straight chain perfluoroalkyl, have 3-20 carbon atom the side chain perfluoroalkyl, have the ring-type perfluoroalkyl of 3-20 carbon atom or have the perfluor aryl of 6-20 carbon atom, group-O-,-N (R)-or-SO
2-in any can insert between the carbon atom of above-mentioned each group, wherein R represents hydrogen atom or has the alkyl of 1-4 carbon atom, R
11And R
33Or R
1-R
3In any two can form heterocycle in conjunction with forming ring structure and one or two ring structure.
2. according to the radiation-sensitive resin composition of claim 1, wherein
Kation is to be selected from iodine
At least a kation with sulfonium.
3. according to the radiation-sensitive resin composition of claim 1 or 2, wherein alkali-soluble curable resin (A) be comprise derived from unsaturated carboxylic acid structural unit (a1) and derived from the multipolymer of the structural unit (a2) of unsaturated compound with oxetanyl, the described unsaturated compound of the described structural unit (a2) of wherein deriving does not comprise unsaturated carboxylic acid.
4. according to the radiation-sensitive resin composition of claim 1 or 2, wherein alkali-soluble curable resin (A) comprises at least a structural unit (a3) that is selected from following: the structural unit of derived from carboxylic acid ester (a31), derived from the structural unit (a34) of the structural unit (a32) of aromatic vinyl compound, the maleimide compound that replaces derived from the structural unit (a33) of cyano group vinyl compound with derived from N-.
5. according to the radiation-sensitive resin composition of claim 1 or 2, wherein the content of alkali-soluble curable resin (A) is 50-90 quality %, the content of quinone di-azido compound (B) is 5-40 quality %, the content of cationic polymerization initiators (C) is 0.01-10 quality %, based on the solid content meter of described radiation-sensitive resin composition.
6. one kind by the patterning cured resin that forms according to any one radiation-sensitive resin composition of claim 1 to 5.
7. method of producing the patterning cured resin, by being coated on the substrate according to any one radiation-sensitive resin composition of claim 1 to 5, shine it with radiant rays by mask after removing solvent, develop to form pattern with alkaline aqueous solution subsequently, use the whole zone of the above pattern of irradiation with radiation substrate then.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005-345224 | 2005-11-30 | ||
| JP2005345224 | 2005-11-30 | ||
| JP2005345224A JP2007148208A (en) | 2005-11-30 | 2005-11-30 | Radiation-sensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1975574A CN1975574A (en) | 2007-06-06 |
| CN1975574B true CN1975574B (en) | 2011-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101604841A Expired - Fee Related CN1975574B (en) | 2005-11-30 | 2006-11-28 | Radiation sensitive resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP2007148208A (en) |
| KR (1) | KR20070056988A (en) |
| CN (1) | CN1975574B (en) |
| TW (1) | TW200720844A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4564977B2 (en) * | 2007-04-05 | 2010-10-20 | 東京応化工業株式会社 | Photosensitive resin composition, method for producing resist pattern, laminate, and device |
| JP5137673B2 (en) * | 2008-04-26 | 2013-02-06 | 日本化薬株式会社 | Photosensitive resin composition for MEMS and cured product thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437015A2 (en) * | 1990-01-08 | 1991-07-17 | Hoechst Celanese Corporation | Positive working, peel developable, colour proofing system having two photosensitive layers |
| CN1501167A (en) * | 2002-10-24 | 2004-06-02 | 住友化学工业株式会社 | Radiation-sensitive resin composition |
| CN1542548A (en) * | 2002-11-01 | 2004-11-03 | 住友化学工业株式会社 | Radiation-sensitive resin composition |
| CN1550893A (en) * | 2003-03-25 | 2004-12-01 | 住友化学工业株式会社 | Solidified resin pattern forming method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2187046A1 (en) * | 1996-10-03 | 1998-04-03 | Alain Vallee | Sulfonylimides and sulfonylmethylides, use thereof as photoinitiators |
| JP4199958B2 (en) * | 2002-06-03 | 2008-12-24 | Ｊｓｒ株式会社 | Radiation sensitive resin composition |
| JP2004139070A (en) * | 2002-09-27 | 2004-05-13 | Sumitomo Chem Co Ltd | Radiation-sensitive resin composition |
| JP4148098B2 (en) * | 2002-10-24 | 2008-09-10 | 住友化学株式会社 | Radiation sensitive resin composition |
| US6777460B2 (en) * | 2002-12-23 | 2004-08-17 | 3M Innovative Properties Company | Curing agents for cationically curable compositions |
| JP2005265866A (en) * | 2003-03-25 | 2005-09-29 | Sumitomo Chemical Co Ltd | Method of forming hardening resin pattern |
-
2005
- 2005-11-30 JP JP2005345224A patent/JP2007148208A/en active Pending
-
2006
- 2006-11-23 TW TW095143325A patent/TW200720844A/en unknown
- 2006-11-28 KR KR1020060118239A patent/KR20070056988A/en not_active Application Discontinuation
- 2006-11-28 CN CN2006101604841A patent/CN1975574B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0437015A2 (en) * | 1990-01-08 | 1991-07-17 | Hoechst Celanese Corporation | Positive working, peel developable, colour proofing system having two photosensitive layers |
| CN1501167A (en) * | 2002-10-24 | 2004-06-02 | 住友化学工业株式会社 | Radiation-sensitive resin composition |
| CN1542548A (en) * | 2002-11-01 | 2004-11-03 | 住友化学工业株式会社 | Radiation-sensitive resin composition |
| CN1550893A (en) * | 2003-03-25 | 2004-12-01 | 住友化学工业株式会社 | Solidified resin pattern forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070056988A (en) | 2007-06-04 |
| JP2007148208A (en) | 2007-06-14 |
| TW200720844A (en) | 2007-06-01 |
| CN1975574A (en) | 2007-06-06 |
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