CN1716094B - Radiation sensitive resin composition - Google Patents
Radiation sensitive resin composition Download PDFInfo
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- CN1716094B CN1716094B CN2005100791719A CN200510079171A CN1716094B CN 1716094 B CN1716094 B CN 1716094B CN 2005100791719 A CN2005100791719 A CN 2005100791719A CN 200510079171 A CN200510079171 A CN 200510079171A CN 1716094 B CN1716094 B CN 1716094B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A radiation sensitive resin combination contains alkali-soluble resin (A) with hardenability, quinone diazide (B), solvent (C) and silane coupling agent (D).
Description
Technical field
The present invention relates to a kind of radiosensitive (radiation sensitive) resin combination.
Background technology
Radiation-sensitive resin composition can be as forming the material that the hardening resin pattern is used; described material typically be included in thin-layer transistor (below; be called TFT in some cases) the TFT dielectric film that uses in the type LCD, the diffusion reflector that in the reflection-type TFT substrate, uses, organic EL dielectric film, stereocamera (solid camera) element (below; be called CCD in some cases) in diaphragm etc. (referring to; Jap.P. No.2933879; the 2nd page; hurdle, a left side, the 22nd to 25 row).Require the hardening resin pattern to have high transmittance for visible light, with obtain brighter display image (referring to, Jap.P. No.2933879, the 3rd page, left hurdle, the 13rd to 14 row).
But, visible light is not had enough transmittances by approval by the hardening resin pattern that uses traditional radiation-sensitive resin composition to form.
Summary of the invention
An object of the present invention is to provide a kind of radiation-sensitive resin composition, it can form the hardening resin pattern with high transmittance under the wavelength of 400nm.
The inventor a kind ofly to have as mentioned above the radiation-sensitive resin composition of problem hardly and studies in order to find, found that: a kind of radiation-sensitive resin composition that comprises silane coupling agent forms the hardening resin pattern with high transmittance under the wavelength of 400nm, thereby has finished the present invention.
That is, the invention provides following [1] to [13].
[1] a kind of radiation-sensitive resin composition, it comprises alkali soluble resins that (A) have hardening capacity, (B) quinone two nitrine (quinonediazide) compound, (C) solvent and (D) silane coupling agent.
[2] according to the composition of [1], wherein silane coupling agent (D) has epoxy radicals in its structure.
[3] according to the composition of [1] or [2], wherein the content of silane coupling agent (D) is 0.01 to 10 weight % based on radiation-sensitive resin composition.
[4] according to [1] to [3] any one composition, wherein solvent (C) comprises the compound that selects free style (1) and at least a solvent in the ethyl lactate:
R
1-COO-R
2 (1)
(wherein, R
1Expression contains the alkyl of 1 to 4 carbon atom, R
2Expression contains the alkyl of 3 to 10 carbon atoms).
[5] composition of basis [4], wherein R
1Expression contains the straight chained alkyl of 1 or 2 carbon atom, and R
2Expression contains the straight chained alkyl of 4 to 8 carbon atoms or contains the branched alkyl of 4 to 8 carbon atoms.
[6] according to [1] to [5] any one composition, wherein the content of solvent (C) is 50 to 80 weight % based on radiation-sensitive resin composition.
[7] according to [4] to [6] any one composition, the content of the compound of its Chinese style (1) based on the solvent total amount by weight mark count 10 to 90 weight %.
8 according to [4] to [7] any one composition, and wherein the content of ethyl lactate is 5 to 50 weight % based on the solvent total amount.
[9] according to [1] to [8] any one composition, the alkali soluble resins (A) that wherein has hardening capacity be comprise derived from unsaturated carboxylic acid component units (a1) and derived from the multipolymer of the component units (a2) of the unsaturated compound (except that unsaturated carboxylic acid) that contains the group that hardens.
[10] according to the composition of [9], wherein in the component units (a2) derived from the unsaturated compound (except that unsaturated carboxylic acid) that contains the group that hardens, the sclerosis group is oxetanyl (oxetanylgroup).
[11] according to the composition of [9] or [10], the alkali soluble resins (A) that wherein has hardening capacity is also to comprise at least a multipolymer that is selected from the component units (a3) in following: the component units (a34) that the unsaturated link of the component units of derived from carboxylic acid ester (a31), the maleimide compound that replaces derived from the component units (a33) of the component units (a32) of aromatic vinyl compound, derived from ethylene base cyanogen compound with by fracture N-is derived.
[12] a kind of by the hardening resin pattern that forms according to [1] to [11] any one composition.
[13] a kind of display that comprises according to the hardening resin pattern of [12].
The alkali soluble resins with hardening capacity (A) that uses among preferred the present invention for comprise derived from unsaturated carboxylic acid component units (a1) and derived from the multipolymer of the component units (a2) of the unsaturated compound (except that unsaturated carboxylic acid) that contains the group that hardens.
As for unsaturated carboxylic acid recited above, that mentions has: the unsaturated carboxylic acid that contains one or more carboxyls in molecule, for example, undersaturated monocarboxylic acid, undersaturated dicarboxylic acid etc., its instantiation comprises acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.
Example with unsaturated compound (except that unsaturated carboxylic acid) of sclerosis group recited above comprises: the unsaturated compound that contains epoxy radicals, as (methyl) glycidyl acrylate, (methyl) acrylic acid (Beta-methyl diglycidyl) ester, (methyl) acrylic acid (β-ethyl diglycidyl) ester, (methyl) acrylic acid (3-methyl-3,4-epoxy fourth) ester, (methyl) acrylic acid (3-ethyl-3,4-epoxy fourth) ester, (methyl) acrylic acid (4-methyl-4,5-epoxy penta) ester, (methyl) acrylic acid (2,3-epoxycyclohexyl first) ester, (methyl) acrylic acid (3,4-epoxycyclohexyl first) ester, 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, 4 vinyl cyclohexene oxygen etc.; The unsaturated compound of oxygen heterocycle butane group is as 3-(methyl) acryloyl-oxy methyl oxetanes, 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, 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.
The preferred unsaturated compound that uses the oxygen heterocycle butane group, as 3-(methyl) acryloyl-oxy methyl oxetanes, 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) 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. more preferably use 3-ethyl-3-acryloyl-oxy methyl oxetanes.
When the alkali soluble resins that comprises the unsaturated compound of oxygen heterocycle butane group when use prepares radiation-sensitive resin composition, the trend of excellent storage stability occurring having, is preferred.
Multipolymer among the present invention can also comprise at least a component units (a3) that is selected from following: the component units (a34) that the unsaturated link of the component units of derived from carboxylic acid ester (a31), the maleimide compound that replaces derived from the component units (a33) of the component units (a32) of aromatic vinyl compound, derived from ethylene base cyanogen compound with by fracture N-is derived.
The example of the carboxylate with the two keys of alkene derived from (a31) recited above comprises: esters of unsaturated carboxylic acids, as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid (2-hydroxyl second) ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Isobornyl, (methyl) acrylic acid two ring penta (dicyclopentanyl) esters, (methyl) phenyl acrylate, diethyl maleate, DEF, diethyl itaconate etc.; Unsaturated carboxylic acid aminoalkyl ester is as (methyl) acrylic acid ammonia ethyl ester etc.; Vinyl carboxylates is as vinyl acetate, propionate etc.
The example of the aromatic compounds with polymerizable carbon-to-carbon unsaturated bond derived from (a32) recited above comprises aromatic vinyl compound etc.The example of aromatic vinyl compound comprises styrene, α-Jia Jibenyixi, vinyltoluene etc.
The example of the vinyl cyanide compound derived from (a33) recited above comprises vinyl cyanide compound, as vinyl cyanide, methacrylonitrile, α-chlorine (methyl) vinyl cyanide etc.
The example of the N-substituted maleimide amines derived from (a34) recited above comprises 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-benzoxazolyl) phenyl] maleimide; N-(9-acridinyl) maleimide etc.
These substituting groups can use separately or two or more are used in combination.
In the component units (a1) and multipolymer that comprise derived from unsaturated carboxylic acid derived from the component units (a2) of the unsaturated compound (except that unsaturated carboxylic acid) that contains the group that hardens, total mole number based on the component units of multipolymer, (a1) proportion of composing is generally 5 to 50 moles of %, be preferably 15 to 40 moles of %, and total mole number based on the component units of multipolymer, (a2) proportion of composing is generally 95 to 50 moles of %, is preferably 85 to 60 moles of %.
In described multipolymer in the above, (a1) and the described in the above scope of proportion of composing (a2) in the time, have such trend: promptly having the performance that dissolution velocity that is suitable for developer and the pattern that obtains also have high sclerosis in pattern forms, is preferred.
Comprise in the present invention (a1) and multipolymer (a2) can comprise as any component except that (a1) and other component units (a2).When multipolymer comprises other component units of any component of conduct, total mole number based on the component units of multipolymer, (a1) proportion of composing is generally 5 to 50 moles of %, be preferably 15 to 40 moles of %, based on same standard, (a2) proportion of composing is generally 95 to 5 moles of %, is preferably 85 to 15 moles of %.In addition, when multipolymer comprised other component units, based on same standard, its ratio was preferably 0.01 to 90 mole of %, more preferably 5 to 15 moles of %.
The example that comprises (a1) and multipolymer (a2) in the present invention comprises: 3-ethyl-3-methacryloxy methyl oxetanes/benzyl methacrylate/methacrylic acid copolymer, 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/methacrylic acid uncle-butyl ester multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/methacrylic acid Isobornyl 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/acrylic acid Isobornyl multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/methacrylic acid two ring pentyl ester multipolymers, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/acrylic acid uncle-butyl ester multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/phenyl Maleimide multipolymer, 3-ethyl-3-methacryloxy methyl oxetanes/methacrylic acid/cyclohexyl Maleimide multipolymer etc.
According to the GPC method, the weight-average molecular weight that, comprises (a1) and multipolymer (a2) among the present invention based on the polystyrene calibration standard is generally 2,000 to 100,000, is preferably 2,000 to 50,000, and 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 standard, trending towards obtaining high developing powder and keep the film remaining proportion simultaneously in development, is preferred.
Based on the solid constituent in the radiation-sensitive resin composition, the content that comprises (a1) and multipolymer (a2) in the radiation-sensitive resin composition among the present invention is generally 50 to 90 weight %, is preferably 60 to 90 weight %.
The example of the quinone di-azido compound among the present invention (B) comprises 1,2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonic acid amides, 1,2-naphthoquinones two nitrine sulfonic acid amides etc.
Its instantiation comprises 1 of trihydroxy benzophenone, and 2-naphthalene quinone di-azide sulfonic acid ester is 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-naphthalene quinone di-azide sulfonic acid ester is 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-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.;
1 of pentahydroxybenzophenone, 2-naphthalene quinone di-azide sulfonic acid ester, 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-naphthalene quinone di-azide sulfonic acid ester, as 2,4,6,3 ', 4 ', 5 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester etc.;
1 of (polyhydroxy phenyl) alkane, 2-naphthalene quinone di-azide sulfonic acid ester, 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 (fravane)-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.
Be used alone or in combination two or more quinone di-azido compounds recited above (B).Based on the solid constituent of radiation-sensitive resin composition, the content of the quinone di-azido compound among the present invention is generally 2 to 50 weight %, is preferably 5 to 40 weight %.When in the described in the above scope of the content of quinone di-azido compound, the difference by the dissolution velocity between unexposed portion and the exposed portion improves, and it is high that development film reservation ratio is tended to keep, and is preferred.
Radiation-sensitive resin composition of the present invention comprises solvent (C).Preferred solvent (C) comprises the compound and the ethyl lactate of formula (1).
R
1-COO-R
2 (1)
(wherein, R
1Expression contains the alkyl of 1 to 4 carbon atom, R
2Expression contains the alkyl of 3 to 10 carbon atoms).
R
1Instantiation comprise methyl, ethyl, propyl group and butyl.In them, that preferably mentions has a straight chained alkyl that contains 1 to 3 carbon atom, and specifically mention methyl, ethyl and just-propyl group arranged, that more preferably mentions has a straight chained alkyl that contains 1 or 2 carbon atom, that mentions especially has: methyl and ethyl.
Preferred R
2Comprise the straight chained alkyl that contains 4 to 8 carbon atoms or contain the branched alkyl of 4 to 8 carbon atoms that mentions especially is just having-butyl, just-hexyl, just-heptyl, just-octyl group, isobutyl, the second month in a season-amyl group and isopentyl.
The instantiation of formula (1) compound comprise acetate just-pentyl ester, the acetate second month in a season-pentyl ester, isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, propionic acid just-butyl ester, the propionic acid isobutyl, propionic acid just-pentyl ester, the propionic acid second month in a season-pentyl ester, isoamyl propionate, hexyl propionate, heptyl propionate, octyl propionate, butyric acid just-butyl ester, isobutyl isobutyrate (IBIB), butyric acid just-pentyl ester, the butyric acid second month in a season-pentyl ester, isoamyl butyrate, n-hexyl butyrate, amyl butyrate, the different monooctyl ester of butyric acid, butyric acid just-butyl ester, isobutyl isobutyrate, isobutyric acid just-pentyl ester, the isobutyric acid second month in a season-pentyl ester, isoamyl isobutyrate, the own ester of isobutyric acid, the isobutyric acid heptyl ester, isobutyric acid octyl group etc., preferably mention have acetate just-pentyl ester, the acetate second month in a season-pentyl ester, isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, propionic acid just-butyl ester, isobutyl propionate, propionic acid just-pentyl ester, the propionic acid second month in a season-pentyl ester, isoamyl propionate, hexyl propionate, heptyl propionate and octyl propionate, and more preferably mention have acetate just-pentyl ester, the acetate second month in a season-pentyl ester, isoamyl acetate, propionic acid just-butyl ester, isobutyl propionate, propionic acid just-pentyl ester, the propionic acid second month in a season-pentyl ester and isoamyl propionate.
Be used alone or in combination described formula (1) compound above two or more.
Above described formula (1) compound and ethyl lactate can use with other solvent is mixed.
Can be comprised ethylene glycol monoalkyl ether by the example of the mixed top described solvent that uses, as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether etc.;
Diglycol dioxane ether is as diethylene glycol dimethyl ether, diethyl carbitol, diglycol dipropyl ether, diethylene glycol dibutyl 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 is as benzene,toluene,xylene etc.;
Ketone is as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexyl ketone etc.;
Alcohols is as ethanol, propyl alcohol, butanols, amylalcohol, cyclohexanol, 1,2 ethylene glycol, glycerine etc.;
Cyclic ethers is as ethylene carbonate, propylene carbonate, butylene carbonic ester etc.;
The ether-ether class is as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters etc.
The example of the silane coupling agent that uses in the radiation-sensitive resin composition of the present invention (D) comprises methyl trimethoxy oxygen base monosilane, methyl-triethoxysilane, vinyl trichlorosilane, the vinyl trimethoxy monosilane, the vinyl triethoxyl monosilane, vinyl triacetyl oxygen base monosilane, vinyl three (2-methoxy ethoxy) monosilane, 3-chloropropyl-trimethoxy monosilane, 3-chloropropyl methyl-dichlorosilane, 3-chloropropyl methyl-dimethoxy monosilane, 3-chloropropyl methyl-diethoxy monosilane, 3-glycidoxy propyl group-trimethoxy monosilane, 3-glycidoxy propyl group-triethoxy-silicane, 3-glycidoxy propyl group methyl-dimethoxy monosilane, 3-sulfydryl propyl group-trimethoxy monosilane, 3-methacryloxypropyl-trimethoxy monosilane, 3-methacryloxypropyl methyl-dimethoxy monosilane, 2-(3,4-ethoxy cyclohexyl) ethyl trimethoxy monosilane, N-2-(N-vinyl benzyl amino-ethyl)-3-aminopropyl-trimethoxy monosilane hydrochloride, hexamethyldisilazane, the diamido monosilane, triamido propyl group-trimethoxy monosilane, 3-aminopropyl-trimethoxy monosilane, 3-aminopropyl-triethoxy-silicane, 3-aminopropyl methyl-diethoxy monosilane, 3-aminopropyl-three (2-methoxy ethoxy) monosilane, 3-(2-amino-ethyl)-3-aminopropyl-trimethoxy monosilane, 3-(2-amino-ethyl)-3-aminopropyl methyl-dimethoxy monosilane, 3-uride propyl group-trimethoxy monosilane, 3-uride propyl group-triethoxy-silicane, N-amino-ethyl-3-aminopropyl-trimethoxy monosilane, N-amino-ethyl-3-aminopropyl methyl-dimethoxy monosilane, N-methyl-3-aminopropyl-trimethoxy monosilane, N-phenyl-3-aminopropyl-trimethoxy monosilane etc.
In the middle of them, preferably use the silane coupling agent that in its structure, has epoxy radicals.As for the silane coupling agent that in its structure, has epoxy radicals recited above, for example, that mentions has: 3-glycidoxy propyl group-trimethoxy monosilane, 3-glycidoxy propyl group-triethoxy-silicane, 3-glycidoxy propyl group methyl-dimethoxy monosilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy monosilane etc., that more preferably mentions has a silane coupling agent with alicyclic epoxy base, as 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy monosilane etc.
Based on radiation-sensitive resin composition, the content of preferred silane coupling agent (D) is 0.01 to 10 weight %, and more preferably 0.1 to 2 weight % is preferably 0.2 to 1 weight % again.In the described in the above scope of the content of preferred silane coupling agent, when using radiation-sensitive resin composition of the present invention to form the hardening resin pattern, transparency is owing to the visible transmission of hardening resin pattern tends to improve than improving, in addition, improved the close adhesion of hardening resin pattern and base material.
Radiation-sensitive resin composition of the present invention can comprise (E) polymerization initiator as other component, (F) polyphenol compound, (G) crosslinking chemical and (H) polymerisable monomer.
As for polymerization initiator (E), that mentions has salt as cationic polymerization initiators.Salt is made up of the kation and the lewis acidic negative ion in place of deriving.
Cationic instantiation recited above comprises diphenyl iodonium, two (right-tolyl) iodine, two (right-the tert-butyl phenyl) iodine, two (right-octyl phenyl) iodine, two (right-the octadecyl phenyl) iodine, two (right-octyloxyphenyl) iodine, two (right-octadecane oxygen base phenyl) iodine, phenyl (right-octadecane oxygen base phenyl) iodine, (right-tolyl) (right-isopropyl phenyl) iodine, triphenylsulfonium, three (right-tolyl) sulfonium, three (right-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (right-the tert-butyl phenyl) sulfonium, three (right-cyano-phenyl) sulfonium, three (right-chlorphenyl) sulfonium, dimethyl (dimethoxy) 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) etc., and preferably mention two (right-tolyl) iodine arranged, (right-tolyl) (right-isopropyl phenyl) iodine, two (right-the tert-butyl phenyl) iodine, triphenylsulfonium, three (right-the tert-butyl phenyl) sulfonium etc.
The lewis acidic anionic instantiation of deriving recited above comprises hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate, four (pentafluorophenyl group) borate etc., and preferably mention hexafluoro antimonate and four (pentafluorophenyl group) borate arranged.
Can the combination in any kation recited above and the lewis acidic negative ion of deriving.
When using polymerization initiator (E), its content is generally 0.01 to 10 weight % based on the solid constituent of radiation-sensitive resin composition, is preferably 0.1 to 8 weight %.When in the described in the above scope of the content of polymerization initiator (E), by improving the setting rate of thermmohardening, tend to suppress the reduction of the resolution of thermmohardening, in addition, tend to improve the solvent resistance of cured film, be preferred.
As for polyphenol compound (F), that mentions has a compound that contains two or more phenolic hydroxyls in the molecule.The example of polyphenol compound recited above comprises polyhydric phenol, and as trihydroxy benzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane etc., they are mentioned in quinone di-azido compound equally.
As for polyphenol compound recited above (F), mention to have by at least a hydroxy styrenes be the polymkeric substance that raw material obtains.As for polyphenol compound (F), that mentions especially has: the resin that obtains by the polymerization hydroxy styrenes, and as polycarboxylated styrene, hydroxystyrene/methyl methacrylate multipolymer, hydroxy styrenes/cyclohexyl methacrylate multipolymer, hydroxy styrenes/styrol copolymer, hydroxy styrenes/alkoxystyrene.In addition, can also use by polycondensation is at least a and be selected from compound in phenol, cresols class and the catechol and one or more are selected from the novolac that the compound in aldehydes and the ketone obtains.
When using polyphenol compound recited above (F), its content is generally 0.01 to 40 weight % based on the solid constituent of radiation-sensitive resin composition, is preferably 0.1 to 25 weight %.When in the described in the above scope of the content of polyphenol compound (F), resolution is tended to improve and the visible transmission ratio tends to not show and descends, and is preferred.
As for crosslinking chemical (G), mention methylol compound etc.
As for methylol compound recited above, that mentions has: the alkoxy methyl resin, and as alkoxy methyl melamine resin, alkoxy methyl urea resin etc.Herein, as for the alkoxy methyl melamine resin, that mentions has methoxy melamine resin, ethoxyl methyl melamine resin, propoxyl group methylated melamine resin, a butoxymethyl melamine resin etc., as for the alkoxy methyl urea resin, that mentions has methoxy urea resin, ethoxyl methyl urea resin, propoxyl group methylate urea resin, a butoxymethyl urea resin etc.Can be separately or two or more be used in combination crosslinking chemical recited above.
When using crosslinking chemical (C), its content is generally 0.01 to 15 weight % based on the solid constituent of radiation-sensitive resin composition, is preferably 1 to 10 weight %.When in the described in the above scope of the content of crosslinking chemical, the visible transmission ratio that obtains film is improved, and has improved the performance as the hardening resin pattern, is preferred.
As for polymerisable monomer (H), for example, having by heating of mentioning can be carried out the polymerisable monomer of free radical polymerization and can carry out the polymerisable monomer of cationic polymerization, and that preferably mentions has a polymerisable monomer that can carry out cationic polymerization.
As for the polymerisable monomer that can carry out free radical polymerization recited above, for example, that mentions has a compound that contains the polymerizable carbon-to-carbon unsaturated bond, and can use the simple function polymerisable monomer, can also use multifunctional polymerisable monomer, as difunctionality polymerisable monomer or three or multifunctional polymerisable monomer etc.
The example of simple function polymerisable monomer comprises nonyl phenyl carbitol acrylate, nonyl phenyl carbitol methacrylate, acrylic acid (2-hydroxyl-3-phenoxy group third) ester, methacrylic acid (2-hydroxyl-3-phenoxy group third) ester, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, acrylic acid (2-hydroxyl second) ester, methacrylic acid (2-hydroxyl second) ester, N-vinylpyrrolidone etc.
The example of difunctionality polymerisable monomer comprises 1,6-hexanediyl ester, 1, two (acryloxy ethyl) ether of 6-dimethacrylate (1, the 6-hexanediol) ester, 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 described polymerisable monomer, preferably use difunctionality or three or multifunctional polymerisable monomer in the above.Particularly, preferred tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc. more preferably use dipentaerythritol acrylate.Can also allow with difunctionality three or multifunctional polymerisable monomer and simple function polymerisable monomer be used in combination.
As for the polymerisable monomer that can carry out cationic polymerization, for example, that mentions has a polymerisable monomer that contains cationic polymerizable functional group, as has a vinyl ether group, the propenyl ether, epoxy radicals, the polymerisable monomer of oxetanyl etc., and the instantiation that contains the compound of vinyl ether group comprises triethylene glycol diethyl alkene ether, 1,4-cyclohexanedimethanol diethyl alkene ether, 4-hydroxybutyl ethyl alkene ether, dodecyl ethyl alkene ether etc., the instantiation that contains the compound of propenyl ether comprises 4-(1-propenyloxy group methyl)-1,3-dioxolanes-2-ketone etc., the instantiation that contains the compound of epoxy radicals comprises bisphenol A type epoxy resin, phenol novolac-type epoxy resin, cresols novolac-type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, the heterocyclic ring epoxy resins, and the instantiation that contains the compound of oxetanyl comprises 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, two 1.4-{ 3-(3-ethyl oxetanyl) methoxyl } methylcyclohexane, 3-(3-ethyl oxetanyl) methylates novolac resin etc.
When using polymerisable monomer recited above (H), separately or two or more be used in combination them.Based on the solid constituent of radiation-sensitive resin composition, polymerisable monomer (H) content is generally 0.1 to 20 weight %.
Hardenable resin composition of the present invention is contained at least aly to be selected from siloxy group surfactant, fluorine based surfactant and to contain surfactant in the siloxy group surfactant of fluorine atom.
Above described siloxy group surfactant comprise trade name: Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA and SH30PA (by Toray SiliconeK.K preparation); Trade name: Polyether-modified Silicon Oil SH8400 (by Toray SiliconeK.K. preparation); Trade name: KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (by Shin-Etsu Silicone K.K. preparation); Trade name: TSF400, TSF401, TSF410, TSP4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSP4460 (by GEToshiba Silicone K.K. preparation) etc.
Above described fluorine based surfactant comprise Florad FC430 and FC431 (by the Sumitomo3M preparation); Megafack (trade name) F142D, F171, F172, F173, F177, F183 and R30 are (by Dainippon Ink ﹠amp; Chemicals Inc. preparation); Eftop (trade name) EF301, EF303, EF351 and EF352 (by Shin Akita Kasei K.K. preparation);
Surfron (trade name) S381, S382, SC101 and SC105 (Asahi Glass Co., Ltd.);
Trade name: E1830, E5844 (by Daikin Fine Chemical Laboratory K.K. preparation); Trade name: BM-1000 and BM-1100 (by BM Chemie preparation) etc.
The siloxy group surfactant that contains fluorine atom comprises that Megafack (trade name) R08, BL20, F475, F477 and F443 are (by Dainippon Ink; Chemicals Inc. preparation) etc.
Can be separately or two or more be used in combination these surfactants.
In addition, in hardenable resin composition of the present invention, can use other surfactant together, as acryloyl group polymer-matrix surfactant and polyvinyl based surfactants etc.
Acryloyl group polymer-matrix surfactant comprises (trade name) OX-880, OX-881, OX883, OX-70, OX-77, OX-77HF, OX-60, OX-710, OX-720, OX-740, OX-750, OX-8040,1970,230, L-1980-50, L-1982-50, L-1983-50, L-1984-50, L-1985-50, LAP-10, LAP-20, LAP-30 and LHP-95 (by Kusumoto Chemicals preparation); Trade name: BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 and BYK-390 (by BYK Chemie Japan preparation); Efka (trade name) LP3778 (by Efka Chemicals preparation) etc.
The polyvinyl based surfactants comprises Disperon (trade name) 1922,1927,1950,1951, P-410, P-410HF, P-420, P-425, PD-7 and LHP-90 (by Kusumoto Chemicals preparation) etc.
If desired, radiation-sensitive resin composition of the present invention can also further contain other component, as various adjuvants, as antioxidant, dissolution inhibitor, sensitizer, ultraviolet light absorber, light stabilizer, gluing improver, electron donor etc.
Radiation-sensitive resin composition of the present invention can prepare by following method: mixed by dissolving in solvent (C) have solution that the alkali soluble resins (A) of hardening capacity obtains, by in solvent (C), dissolving solution that quinone di-azido compound (B) obtains and by in solvent (C), dissolving the solution that decomposition silane coupling agent (D) obtains.After mixed, can further add solvent (C).In addition, preferably after mixed solution, remove solid constituent by filtering, for example, preferably using the aperture is 3 μ m or following, and preferred 0.1 μ m or above and 2 μ m or following filtrator filter.Above the described solvent that is used for different component can be identical or different, precondition is that they are compatible.
Using radiation-sensitive resin composition to form in the hardening resin pattern, for example on substrate, form the layer of making by radiation-sensitive resin composition, expose recited above layer by mask with irradiation with radiation, develop then to obtain resin pattern, it is obtained the hardening resin pattern by thermal treatment.
As for substrate, for example, that mentions has a transparency glass plate etc.On the described substrate, can form TFT or CCD circuit etc., color filter etc. in the above.
Can form the layer of forming by radiation-sensitive resin composition by following method, for example, the method by on substrate, being coated with radiation-sensitive resin composition etc.Coating is to be undertaken by for example following method: spin-coating method, stream casting coating process, rolling method, slit and spin-coating method, slot coated method, mould are coated with method, curtain flow coat cloth method etc.After coating,,, test the chamber floor to form radiation-sensitive resin composition as solvent etc. by heated drying (prebake), vacuum drying or by two kinds of methods are used the vaporization volatile constituent together.The thickness of radiation-sensitive resin composition layer is generally 3 to 5 μ m.
Then, by mask irradiation with radiation sensitive resin composition.Mask pattern is suitably selected according to the pattern of the needs of hardening resin pattern.As for radiant rays, for example, use light beam such as g line, i line etc.Preferably the irradiation with radiant rays is to use mask aligner, steeper etc. to carry out.
Behind irradiation with radiation, development radiation-sensitive resin composition layer.Undertaken to develop by the back radiation-sensitive resin combination that exposes as stirring (paddle) method, dipping method or spraying method etc.
As for developer, use alkaline aqueous solution usually.As for alkaline aqueous solution, use the aqueous solution of alkali compounds, alkali compounds can be inorganic alkaline compound or organic basic compound.
The example of inorganic alkaline compound comprises 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 organic basic compound comprises tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethylammonium, single methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc.Independent use or two or more are used in combination alkali compounds recited above.In developer, based on the developer of 100 weight portions, the use amount of alkali compounds is 0.01 to 10 weight portion, is preferably 0.1 to 5 weight portion.
Developer can also contain surfactant.The example of surfactant comprises non-ionic surfactant, cationic surfactant, anionic surfactant etc.
The example of non-ionic surfactant comprises polyoxyethylene deriv, as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether etc. and oxygen ethene/oxypropylene segmented copolymer, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty ester, glycerin fatty ester, polyoxyethylene fatty ester, polyoxyethylene alkyl amine etc.
The example of cationic surfactant comprises amine salt, as stearmide hydrochloride etc., quaternary ammonium salt such as lauryl trimethyl ammonium chloride etc.
The example of anionic surfactant comprises higher alcohol sulfate, as sldium lauryl sulfate, oleyl alcohol sodium sulphate etc., alkyl sulfate is as NaLS, Texapon Special etc., alkyl aryl sulfonate is as neopelex, dodecyl sodium naphthalene sulfonate etc.Separately or two or more use these surfactants.
Developer can contain organic solvent.As for organic solvent recited above, that mentions has a water-miscible organic solvent, as methyl alcohol, ethanol etc.
By developing, the radiation-sensitive resin composition layer be dissolved in the developer with the irradiation with radiation zone of irradiation with radiation in advance and the non-irradiation area of radiant rays of irradiation with radiation of no use is not retained in the developer with dissolving, with the formation resin pattern.
After the alkaline development, wash this layer and drying usually with water.After the drying, the part or all of surface of the resin pattern that obtains with irradiation with radiation again.The power supply of using as for this radiant rays, the preferred use has the light source that wavelength is 330 to 380nm radiant rays.
Consider the thermotolerance that obtains the hardening resin pattern, solvent resistance etc., preferably the resin pattern that therefore forms is heat-treated (afterwards baking and banking up with earth) again.Heating means by adopting firing equipment such as electric hot plate, cleaning stove (clean oven) etc. are to heating with the substrate behind the irradiation with radiation on the part on its whole surface.Heating-up temperature is generally 150 ℃ to 250 ℃, is preferably 180 ℃ to 240 ℃.Be generally 5 minutes to 120 minutes heat time heating time, be preferably 15 minutes to 90 minutes.By heating, the sclerosis pattern is to form the hardening resin pattern.
When using radiation-sensitive resin composition of the present invention to form the hardening resin pattern, the wavelength that can be formed on 400nm has the pattern that improves transmittance.
The hardening resin pattern that forms adapts to ground as constituting following hardening resin pattern thus: the dielectric film of TFT substrate, organic EL, camera apparatus, and as the diaphragm of CCD, the display device of LCD.
Embodiment
Embodiment
With embodiment is that the present invention is described on the basis in more detail, but scope much less of the present invention is not subjected to the restriction of these embodiment.
Synthetic embodiment 1
In the 500mL four bottleneck beakers that are equipped with stirrer, cooling tube and thermometer, monomer below adding, the ethyl lactate of 343g and the azoisobutyronitrile of 3.4g, flow down at nitrogen, kept internal temperature to make these reactions in 3 hours simultaneously by stirring, with the solution (solid concentration: 30 weight %) that obtains Resin A 1 at 85 to 95 ℃.Based on the polystyrene calibration standard, the weight-average molecular weight of the A1 of the resin that obtains is 7,800.
Methacrylic acid 22g
N-cyclohexyl maleimide 56g
3-ethyl-3-methacryloxy methyl oxetanes 70g
Based on the polystyrene calibration standard, the condition of described weight-average molecular weight is described below above measuring:
Instrument: HLC-8120GPC (by Tosoh Corp. preparation)
Post: TSK-GELG2000HXL, TSK-GELG4000HXL series connection
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0ml/ minute
Injection volume: 50 μ l
Detector: RI
Measuring samples concentration: 0.6 weight % (solvent: tetrahydrofuran)
The standard substance of calibration usefulness: TSK STANDARD POLYSTYRENE F-40, V-4, F-1, A-2500, A-500 (Tosoh Corp. preparation)
Synthetic embodiment 2
Sealing resin A1 solution in container under the pressure of 60 to 70 ℃ temperature and 0.5 to 1kPa, reduces pressure, concentrates to distill solvent, to obtain Resin A 2 solution (solid concentration: 40 weight %).Based on the polystyrene calibration standard, the weight-average molecular weight of the Resin A 2 that obtains and the molecular weight of A1 do not change.
Synthetic embodiment 3
Except the ethyl lactate/3-ethoxyl ethyl propionate that uses 36g/146g replaces the ethyl lactate of 343g, react in the mode identical, to obtain Resin A 3 solution (solid concentration: 30 weight %) with synthetic embodiment 1.Based on the polystyrene calibration standard, the weight-average molecular weight of the Resin A 3 that obtains is 7,900.
Embodiment 1
23 ℃ of components below mixed, under pressure, be the teflon core strainer filtration of 1.0 μ m then, to obtain radiation-sensitive resin composition 1 as filter liquor by the aperture.The solid concentration of radiation-sensitive resin composition 1 is 30%.
Resin A 1 333 weight portions
(solid constituent: 100 weight portions)
The compound of formula (2)
24 weight portions
Adeka Optomer SP-172 (light cationic polymerization catalyst :) by Asahi Denka Kogyo K.K. preparation
2 weight portions
Sun Aid SI-100L (hot cationic polymerization catalyst :) by Sanshin Kagaku Kogyo K.K. preparation
2 weight portions
KBM-403 (silane coupling agent: γ-glycidoxy propyl group-trimethoxy monosilane: by Shin-EtsuChemical Co., the Ltd. preparation)
2 weight portions
Isoamyl acetate (compound of formula (1))
60 weight portions
(wherein, Q
4The substituting group of expression (2-1))
On transparent substrate (#1737 :) by the Corning preparation, the radiation-sensitive resin composition that spin coating obtains above, use electric hot plate 2 minutes (baking and banking up with earth in advance) of 100 ℃ of heating, to form radiation-sensitive resin composition layer 1, use DUV lamp (UXM-501MD :) on its whole surface, to use irradiation with radiation by Ushio Inc. preparation.After the exposure, layer 1 is immersed in the aqueous solution (tetramethylammonium hydroxide that in 100 weight portions, contains 0.4 weight portion) of 23 ℃ tetramethylammonium hydroxide 70 seconds, to develop, then, with the ultrapure water washing, and dry.In addition, (intensity under the 313nm wavelength is 300mJ/cm with radiant rays to use DUV lamp recited above
2) shine whole surface, in the cleaning stove in 220 ℃ of heating 30 minutes, to obtain the radiation-sensitive resin composition layer 1 that hardens.Use film thickness instrument (DEKTAK3: by ULVAC K.K. preparation) to measure its thickness, recording its thickness is 3.6 μ m.Use microspectrophotometer (OSP-200: by Olympus Optical Co., Ltd. preparation) the transmittance of measurement sclerosis photosensitive resin solid layer 1, so, under the wavelength of 400nm, film thickness for per 3 μ m, the transmittance of the sclerosis photosensitive resin solid layer 1 that obtains is 94.3%, shows high transmittance.
Embodiment 2
Except the KBM-303 (β-(3, the 4-epoxycyclohexyl) ethyl-trimethoxy monosilane: by Shin-Etsu Chemical Co., Ltd. prepares) that uses 5 weight portions replaces outside the KBM-403, to obtain radiation-sensitive resin composition 2 with the embodiment same way as.The radiation-sensitive resin composition 2 that use obtains is to test with embodiment 1 same way as, to obtain the sclerosis radiation-sensitive resin composition layer 2 that film thickness is 3.4 μ m.Under the wavelength of 400nm, for the film thickness of per 3 μ m, the transmittance of the sclerosis photosensitive resin composition layer 2 that obtains is 95.4%, shows high transmittance.
Comparative example 1
Except not using the KBM-403, obtain radiation-sensitive resin composition 3 in the mode identical, to obtain the sclerosis radiation-sensitive resin composition layer 3 that film thickness is 3.5 μ m with embodiment 1.Under the wavelength of 400nm, for the film thickness of per 3 μ m, the transmittance of the sclerosis photosensitive resin composition layer 3 that obtains is 93.8%.
Claims (13)
1. radiation-sensitive resin composition, it comprises alkali soluble resins that (A) have hardening capacity, (B) quinone di-azido compound, (C) solvent and (D) silane coupling agent.
2. according to the composition of claim 1, wherein silane coupling agent (D) has epoxy radicals in its structure.
3. according to the composition of claim 1 or 2, wherein the content of silane coupling agent (D) is 0.01 to 10 weight % based on radiation-sensitive resin composition.
4. according to the composition of claim 1 or 2, wherein solvent (C) comprises the compound that selects free style (1) and at least a solvent in the ethyl lactate:
R
1-COO-R
2 (1)
Wherein, R
1Expression contains the alkyl of 1 to 4 carbon atom, R
2Expression contains the alkyl of 3 to 10 carbon atoms.
5. according to the composition of claim 4, R wherein
1Expression contains the straight chained alkyl of 1 or 2 carbon atom, and R
2Expression contains the straight chained alkyl of 4 to 8 carbon atoms or contains the branched alkyl of 4 to 8 carbon atoms.
6. according to the composition of claim 1 or 2, wherein the content of solvent (C) is 50 to 80 weight % based on radiation-sensitive resin composition.
7. according to the composition of claim 4, the content of the compound of its Chinese style (1) based on the solvent total amount by weight mark count 10 to 90 weight %.
8. according to the composition of claim 4, wherein the content of ethyl lactate is 5 to 50 weight % based on the solvent total amount.
9. according to the composition of claim 1 or 2, the alkali soluble resins (A) that wherein has hardening capacity be comprise derived from unsaturated carboxylic acid component units (a1) and derived from being different from the harden multipolymer of component units (a2) of unsaturated compound of group of containing of unsaturated carboxylic acid.
10. according to the composition of claim 9, wherein hardening in the component units (a2) of unsaturated compound of group derived from being different from containing of unsaturated carboxylic acid, the sclerosis group is an oxetanyl.
11. according to the composition of claim 9, the alkali soluble resins (A) that wherein has hardening capacity is also to comprise at least a multipolymer that is selected from the component units (a3) in following: the component units (a34) that the unsaturated link of the component units of derived from carboxylic acid ester (a31), the maleimide compound that replaces derived from the component units (a33) of the component units (a32) of aromatic vinyl compound, derived from ethylene base cyanogen compound with by fracture N-is derived.
12. one kind by the hardening resin pattern that forms according to any one composition of claim 1 to 11.
13. display that comprises according to the hardening resin pattern of claim 12.
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|---|---|---|---|
| JP2004193264 | 2004-06-30 | ||
| JP2004-193264 | 2004-06-30 | ||
| JP2004193264 | 2004-06-30 |
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| CN1716094B true CN1716094B (en) | 2010-12-15 |
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| JP4849251B2 (en) * | 2007-01-18 | 2012-01-11 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof |
| JP5915532B2 (en) * | 2010-09-16 | 2016-05-11 | 日立化成株式会社 | Positive photosensitive resin composition, method for producing resist pattern, and electronic component |
| TWI570509B (en) * | 2010-10-05 | 2017-02-11 | Sumitomo Chemical Co | Coloring the photosensitive resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288529A (en) * | 1998-11-09 | 2001-03-21 | 克拉瑞特国际有限公司 | Radiation-sensitive resin composition |
| US6391513B1 (en) * | 1999-01-27 | 2002-05-21 | Clariant Finance (Bvi) Limited | Positively photosensitive resin composition |
| CN1479173A (en) * | 2002-04-15 | 2004-03-03 | 夏普株式会社 | Radiation sensitive resin composite, method for forming insulating film having pattern, active matrix plate and panel display equipped with the film and method for producing panel display device |
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2005
- 2005-06-28 KR KR1020050056329A patent/KR20060048626A/en not_active Application Discontinuation
- 2005-06-28 CN CN2005100791719A patent/CN1716094B/en not_active Expired - Fee Related
- 2005-06-28 TW TW094121804A patent/TW200617590A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288529A (en) * | 1998-11-09 | 2001-03-21 | 克拉瑞特国际有限公司 | Radiation-sensitive resin composition |
| US6391513B1 (en) * | 1999-01-27 | 2002-05-21 | Clariant Finance (Bvi) Limited | Positively photosensitive resin composition |
| CN1479173A (en) * | 2002-04-15 | 2004-03-03 | 夏普株式会社 | Radiation sensitive resin composite, method for forming insulating film having pattern, active matrix plate and panel display equipped with the film and method for producing panel display device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200617590A (en) | 2006-06-01 |
| CN1716094A (en) | 2006-01-04 |
| KR20060048626A (en) | 2006-05-18 |
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