JP2002341521A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition capable of forming a transparent film having a high transmissivity to visible light and satisfactory solvent resistance. SOLUTION: The radiation sensitive resin composition contains a high molecular compound (A) having carboxyl groups and no epoxy group, a quinonediazide- containing compound (B), a polyhydric phenol compound (C) having no quinonediazide group and a crosslinker (D). The contents of the high molecular compound (A), the quinonediazo compound (B), the polyhydric phenol compound (C) and the crosslinker (D) are usually 5-90 mass%, 2-30 mass%, 0.1-10 mass% and 1-30 mass%, respectively, based on the solid content of the radiation sensitive resin composition. A layer (1) comprising the radiation sensitive resin composition is formed on a substrate (2), exposed and developed to form a pattern and a transparent film (5) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition.

[0002]

2. Description of the Related Art A radiation-sensitive resin composition is useful as a material for forming a transparent film such as a TFT insulating film used for a thin film transistor (TFT) type liquid crystal display device. is there. Here, in order to obtain a brighter display image, a high transmittance with respect to visible light is required for an insulating film or the like of a TFT. In addition, high solvent resistance is also required in terms of TFT productivity. Further, a radiation-sensitive resin composition is required to have high sensitivity to radiation used for forming an insulating film from the viewpoint of TFT productivity.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies to develop a radiation-sensitive resin composition that has a high visible light transmittance, can form a transparent film with sufficient solvent resistance, and has high radiation sensitivity, it has a carboxyl group-containing epoxy group. The radiation-sensitive resin composition containing a combination of a polymer compound (A) without a quinonediazide compound (B), a polyhydric phenol compound without a quinonediazide group (C) and a crosslinking agent (D) has a sensitivity to radiation. And a transparent film having higher transparency with respect to visible light was formed. Further, it was found that this transparent film was excellent in solvent resistance, and the present invention was reached.

[0004]

That is, the present invention relates to a polymer compound (A) having a carboxyl group and no epoxy group, a quinonediazide compound (B), a polyhydric phenol compound (C) having no quinonediazide group, and a crosslinking agent. It is intended to provide a radiation-sensitive resin composition containing (D).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound (A) contained in the radiation-sensitive resin composition of the present invention is a polymer compound having a carboxyl group and no epoxy group. Such a polymer compound is a polymer compound which is generally called a binder resin, and has a property of dissolving in an alkaline aqueous solution by itself. Examples of such a high molecular compound include a copolymer of a carboxyl group-containing monomer unit and another monomer unit.

Here, examples of the carboxyl group-containing monomer include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. Specific examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Such a carboxyl group-containing monomer is a monomer having no epoxy group.

Examples of the other monomer include a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and methyl acrylate Unsaturated carboxylic acid esters such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate, and unsaturated carboxylic acids such as aminoethyl acrylate Carboxylic acid vinyl esters such as aminoalkyl esters, vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloronitrile Things. Such other monomers are used alone or in combination of two or more.

[0008] The polymer compound (A) contains the carboxyl group-containing monomer and another monomer as monomer units, and the content of the carboxyl group-containing monomer unit in the polymer compound is expressed by mass fraction. Usually 1
It is at least 0%, preferably at least 15%, usually at most 50%, preferably at most 40%.

Examples of the polymer compound (A) include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methacrylic acid / methyl methacrylate copolymer, and methacrylic acid / methyl methacrylate. / Styrene copolymer. Such a polymer compound (A) has a weight average molecular weight (Mw) in terms of polystyrene of 5,000 to 40.
In the range of 10,000, or even between 10,000 and 300,0.
It is preferably in the range of 00. The content of the copolymer (A) in the radiation-sensitive resin composition of the present invention is usually 5% by mass fraction based on the solid content after volatilizing volatile components from the radiation-sensitive resin composition. Above, preferably 30
%, Usually 90% or less, preferably 80% or less.

The quinonediazide compound (B) is a compound having a quinonediazide group, and generates an acid when the quinonediazide group absorbs radiation. Examples of such quinonediazide compounds include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide, and 1,2-naphthoquinonediazidesulfonic acid amide. Can be

Specifically, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5
-Sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-naphthoquinonediazidosulfonic acid esters of trihydroxybenzophenones such as

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide −
5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,3′-
Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4
4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3
4,4'-tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 2,
3,4,2'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
2,3,4,2'-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-
1,2-naphthoquinonediazide sulfones of tetrahydroxybenzophenones such as 4-sulfonic acid ester and 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Acid esters,

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4
1,2-naphthoquinonediazidesulfonic acid esters of pentahydroxybenzophenones such as -sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,4,6,3 ′, 4 ′, 5′-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′,
4 ', 5'-hexahydroxybenzophenone-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone 1,2-naphthoquinonediazidosulfonic acid esters of hexahydroxybenzophenones such as -1,2-naphthoquinonediazide-5-sulfonic acid ester,

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester , Bis (p-hydroxyphenyl) methane-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,
1-tri (p-hydroxyphenyl) ethane-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 1,
1,1-tri (p-hydroxyphenyl) ethane-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
Bis (2,3,4-trihydroxyphenyl) methane-
1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2′-bis (2,3 , 4-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-
4-sulfonic acid ester, 2,2′-bis (2,3,4
-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3
-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxy Phenyl) -3-
Phenylpropane-1,2-naphthoquinonediazide-5
-Sulfonic acid ester, 4,4 '-[1- [4- [1-
[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5
-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, bis (2,5-dimethyl-4-
(Hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-
Spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-
1,1′-spirobiindene-5,6,7,5 ′,
6 ', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
1,2-naphthoquinonediazidesulfonic acid of (polyhydroxyphenyl) alkanes such as 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester Esters and the like.

These quinonediazide compounds are used alone or in combination of two or more. The content of such a quinonediazide compound in the radiation-sensitive resin composition of the present invention is usually 2% or more, preferably 5% or more, and usually 30% by mass fraction based on the solid content of the radiation-sensitive resin composition. Or less, preferably 20% or less.

The polyhydric phenol compound (C) having no quinonediazide group is a compound having two or more phenolic hydroxyl groups in the molecule and having no quinonediazide group in the molecule. The same polyhydric phenols as trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, (polyhydroxyphenyl) alkanes and the like can be mentioned. Novolak resins obtained by condensation polymerization of one or more compounds selected from phenols, cresols and catechols with one or more compounds selected from aldehydes and ketones are also included. Further, polyhydroxystyrene compounds and the like are also included.

The content of the polyhydric phenol compound in the radiation-sensitive resin composition of the present invention is usually 0.1% or more, preferably 1% or more by mass fraction based on the solid content of the radiation-sensitive resin composition. It is usually 10% or less, preferably 5% or less, in that the obtained transparent film shows higher transmittance to visible light.

Examples of the crosslinking agent (D) include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins, and epoxy compounds.

Here, the alkoxymethylated melamine resin includes methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, and the like. Methylated urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, butoxymethylated urea resins, and the like.

The epoxy compound includes an aromatic epoxy compound, an alicyclic epoxy compound and an aliphatic epoxy compound. Aromatic epoxy compounds, for example, a monofunctional epoxy compound such as phenylglycidyl ether,
Polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, specifically a bisphenol compound such as bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S or a bisphenol compound Glycidyl ethers, phenol-novolak-type epoxy resins, cresol-novolak-type epoxy resins, brominated phenol-novolak-type epoxies produced by reacting an alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct with epichlorohydrin Novolak type epoxy resins such as resin, trisphenol methane triglycidyl ether, and the like.

As the alicyclic epoxy compound, for example, 4
-Vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,
4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-
Epoxycyclohexylmethyl) adipate, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2- (3,4-epoxycyclohexyl-5,5-
Spiro-3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, B
HPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point: 71 ° C.)) and the like.

Examples of the aliphatic epoxy compound include 1,4-butanediol dicricidyl ether, 1,6
-Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , Neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether,
Trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, hydrogenated bisphenol A type epoxy resin (manufactured by Kyoeisha Chemical; "Epolite 400
0 ").

Such crosslinking agents may be used alone or in combination.
Used in combination of more than one species. The content of the crosslinking agent in the radiation-sensitive resin composition of the present invention is usually 1% or more, preferably 5% or more, and usually 30% or less in terms of mass fraction based on the solid content of the radiation-sensitive resin composition. , Preferably 20
% Or less.

The radiation-sensitive resin composition of the present invention usually comprises
It is mixed with the solvent (E) and used in a diluted state.
As the solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Diethylene glycol dialkyl ethers such as ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Propylene glycol alkyl ether acetates such as acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methyl ethyl ketone, ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ethanol, propanol, butanol, hexanol, cyclo Alcohols such as hexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate,
Esters such as methyl methoxypropionate and cyclic esters such as γ-butyrolactone are exemplified.
Such solvents are used alone or in combination of two or more, and the amount of the solvent used is such that the proportion of the solvent in the radiation-sensitive resin composition is usually 50% or more, preferably 60% or more by mass fraction. 90% or less, preferably 8%
It is used so as to be 5% or less.

The radiation-sensitive resin composition of the present invention may contain a polymerizable monomer. By containing a polymerizable monomer, an insulating film or the like having higher hardness can be formed. As the polymerizable monomer, for example, a polymerizable monomer capable of undergoing radical polymerization by heating, a polymerizable monomer capable of undergoing cationic polymerization, and the like are used.

Examples of the polymerizable monomer capable of undergoing radical polymerization include a compound having a polymerizable carbon-carbon unsaturated bond, and may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer or a trifunctional polymerizable monomer. It may be a polyfunctional polymerizable monomer such as a functional or higher functional polymerizable monomer. Examples of the monofunctional polymerizable monomer include, for example, nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-ethylhexyl carbitol acrylate, -Ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone and the like. Examples of the bifunctional polymerizable monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, Examples thereof include triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, and 3-methylpentanediol dimethacrylate. Also, 3
Examples of the polymerizable monomer having a functionality of not less than trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, and pentaerythritol penta Examples include methacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. Among such polymerizable monomers,
Bifunctional or trifunctional or higher polymerizable monomers are preferably used. Further, a bifunctional or trifunctional or higher polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.

Examples of the polymerizable monomer capable of undergoing cationic polymerization include polymerizable monomers having a cationic polymerizable functional group such as a vinyl ether group and a propenyl ether group. Specifically, for example, triethylene glycol divinyl ether, ISP Investment Co., Ltd. under the compound name of 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one (propenyl ether propion carbonate) Product name "RAPI-C
It is commercially available as "URE PEPC". ).

When such a polymerizable monomer is used, each of the polymerizable monomers may be used alone or in combination of two or more. The content of the polymerizable monomer in the radiation-sensitive resin composition of the present invention is determined by the content of the radiation-sensitive resin composition. The mass fraction is usually 0.1% or more, preferably 1% or more, and usually 50% or less, preferably 30% or less, based on the solid content of the product.

The radiation-sensitive resin composition of the present invention may contain additives such as an antioxidant, an ultraviolet absorber, and an adhesion promoter. As the antioxidant, for example, 2,2′-
Thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like. As the ultraviolet absorber, for example, 2- (3-tert-butyl-2-hydroxy-5-
Methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

The radiation-sensitive resin composition of the present invention may be prepared, for example, by dissolving a copolymer (A) in a solvent, dissolving a quinonediazide compound (B) in a solvent, or dissolving a polyhydric phenol compound (C) in a solvent. Dissolved solution and crosslinking agent (D)
Can be produced by a method of mixing a solution in which is dissolved in a solvent. When a polymerizable monomer, an additive, or the like is used, a polymerizable monomer, an additive, or the like may be further added. After mixing, a solvent may be further added. After mixing, it is preferable to remove solids by filtration. For example, it is preferable to filter using a filter having a pore size of 3 μm or less, preferably about 1 μm or more and 2 μm or less.

In order to form a transparent film using the radiation-sensitive resin composition of the present invention, for example, a layer (1) made of the radiation-sensitive resin composition of the present invention is formed on a substrate (2) ( FIG.
(a)), the layer (1) is irradiated with radiation (4) through a positive mask (3) and exposed (FIG. 1 (b)), and then developed (FIG. 1 (c)).

Examples of the substrate (2) include a transparent glass plate. On such a substrate, a TFT circuit,
A color filter or the like may be formed.

Layer composed of radiation-sensitive resin composition (1)
Can be formed by a usual method, for example, a method of applying the radiation-sensitive resin composition of the present invention onto the substrate (2). The application is performed by, for example, spin coating. After application, the radiation-sensitive resin composition layer (1) is formed by heating and drying (pre-baking) to evaporate the solvent, and thus the radiation-sensitive resin composition layer (1) after evaporating the solvent. ) Is composed of the solid content of the radiation-sensitive resin composition and contains almost no volatile components. The thickness of the radiation-sensitive resin composition layer is, for example, about 4 μm to 5 μm.

Next, the radiation-sensitive resin composition layer (1)
Is irradiated with radiation (4) through a positive mask (3). The pattern of the positive mask (3) is appropriately selected according to the intended pattern of the transparent film. As radiation,
For example, light rays such as g-line and i-line are used. Radiation is
Irradiation is preferably performed using, for example, a mask aligner (not shown) so that irradiation can be performed in parallel over the entire surface of the radiation-sensitive resin composition layer. Thus, by being able to be irradiated with radiation, the positioning between the positive mask and the radiation-sensitive resin composition layer can be accurately performed.

After the exposure, development is performed. Development is
The radiation-sensitive resin composition layer (1) after exposure can be contacted with, for example, a developer. As a developer, an alkaline aqueous solution is used as in the usual case. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used as usual, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, and silicic acid. Examples include sodium, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia. Examples of the organic alkaline compound include, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Ethanolamine and the like can be mentioned. Such alkaline compounds are used alone or in combination of two or more. The developer generally contains at least 0.1 part by weight, preferably 0.1 part by weight, of an alkaline compound per 100 parts by weight of the developer.
It is contained in an amount of 2 parts by weight or more, usually 10 parts by weight or less, preferably 5 parts by weight or less.

[0038] The developer may contain a surfactant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and the like. Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether; oxyethylene / oxypropylene block copolymer; sorbitan fatty acid ester; Examples thereof include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine. Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, kill sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecylnaphthalene sulfone. Certain aryl aryl sulfonates, such as sodium acid salts. These surfactants are used alone or in combination of two or more.

The developer may contain an organic solvent. Such organic solvents include, for example, methanol,
Examples include water-soluble organic solvents such as ethanol.

To contact the radiation-sensitive resin composition layer (1) with a developer, for example, the radiation-sensitive resin composition layer (1)
What is necessary is just to immerse the board | substrate (2) in which it formed in the developing solution.

By the development, the radiation-irradiated area (12) of the radiation-sensitive resin composition layer (1), which has been irradiated with the radiation in the previous exposure, is dissolved in the developing solution, and the radiation-irradiated area which has not been irradiated with the radiation is exposed. The irradiation area (11) remains without being dissolved in the developer to form a pattern (5).

Since the radiation-sensitive composition of the present invention contains the quinonediazide compound (B), even if the time for contacting the radiation-sensitive resin composition layer (1) with the developer is short, the radiation-sensitive area (11) Is easily dissolved and removed. In addition, since it contains the quinonediazide compound (B) and the polyhydric phenol compound (C), even if the time for which the radiation-sensitive resin composition layer (1) is brought into contact with the developer becomes longer, the radiation-irradiated region (12) Does not dissolve in the developer and disappear.

After development, it is usually washed with water and dried. After drying, it is preferable to irradiate the entire surface of the obtained pattern (5) with radiation since a more transparent film can be formed. Here, the irradiation amount of the radiation to be irradiated per unit area is usually larger than the irradiation amount in the previous exposure.

The pattern (5) thus formed is preferably further subjected to a heat treatment (post-baking) in that the heat resistance and the solvent resistance of the transparent film are improved. The heating is performed by a method of heating the substrate after irradiation of the entire surface with a heating device such as a hot plate or a clean oven. The heating temperature is usually 150 ° C to 25
0 ° C., preferably about 180 ° C. to 240 ° C., and the heating time is usually about 5 minutes to 90 minutes, preferably about 15 minutes to 90 minutes. By heating in this manner, the pattern hardens and a transparent film is formed.

The thus formed transparent film is obtained by curing the radiation-sensitive resin composition of the present invention, and is useful, for example, as a transparent film constituting a TFT.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 Benzyl methacrylate / methacrylic acid copolymer [weight ratio of benzyl methacrylate unit to methacrylic acid unit is 79.2: 20.8, weight average molecular weight (Mw) in terms of polystyrene is 25,000] ( 18.5 parts by weight), Formula (1) (Wherein Q ¹ , Q ² and Q ³ are each independently a hydrogen atom or a formula (1-1) And a substituent represented by A mixture of quinonediazide compounds represented by the formula (1) [The ratio of the hydrogen atom in the substituents represented by Q ¹ , Q ² and Q ³ in the formula (1) to the substituent represented by the formula (1-1) is a substance ratio. (Molar ratio) 1: 2]
(1.1 parts by weight), Equation (2) A polyhydric phenol compound (2.2 parts by weight), hexamethylol melamine hexamethyl ether (4.3
Parts by weight), propylene glycol monomethyl ether acetate (70.1 parts by weight) and 3-glycidoxypropyltrimethoxysilane (3.7 parts by weight) at about 23 ° C.
Then, the mixture was filtered under pressure with a cartridge filter having a pore size of 1.5 μm to obtain a radiation-sensitive resin composition (filtrate).

A transparent glass substrate having an area of 5.08 cm × 5.08 cm [Corning's “# 7059”] (2)
After washing with a neutral detergent, washing with water, washing with alcohol, and drying, the radiation-sensitive resin composition obtained above was spin-coated on the surface thereof, and dried in a clean oven.
Heating (prebaking) at 20 ° C. for 3 minutes formed a radiation-sensitive resin composition layer (1) (FIG. 1 (a)). Thereafter, the radiation-sensitive resin composition layer (1) is irradiated with radiation (4) through a positive mask (3) using a mask aligner (“M-2Li type” manufactured by Mikasa Corporation) to expose the radiation-sensitive resin composition layer. (Fig. 1 (b)). For the positive mask (3), a line width of 10 μm
A positive mask for forming a linear transparent film of m at an interval of 10 μm was used. Radiation (4) was applied so that the intensity at a wavelength of 365 nm was 250 mJ / cm ² .
After exposure, a developing solution (containing 0.4 parts by weight of tetramethylammonium hydroxide in 100 parts by weight, 23 ° C.)
Immersed in water for 60 seconds, washed with ultrapure water and dried.
After drying, radiation was applied over the entire surface using an ultra-high pressure mercury lamp (the intensity based on a wavelength of 365 nm was 800 mJ / cm ² ).
And heated at 230 ° C. for 30 minutes in a clean oven to form a transparent film (5) (FIG. 1 (c)). The obtained transparent film (5) is a linear pattern (width 10 μm) arranged in parallel at an interval of 10 μm, and the thickness (T ₁ ) is measured using a film thickness gauge [“DEKTAK3” manufactured by Nihon Vacuum Corporation]. As a result, it was 4 μm.

The wavelength of the obtained transparent film was 450 nm and 550.
The light transmittance (T _t ) at 650 nm and 650 nm was measured using a microspectrophotometer (“OSP-200”, manufactured by Olympus Corporation). Further, the substrate on which the transparent film was formed was treated with γ-butyllactone or N-methylpyrrolidone (2
(3 ° C.) for 30 minutes to conduct a solvent resistance test. The evaluation was performed by visually observing the appearance of the transparent film before and after immersion, and based on the following criteria. ○: no change was observed before and after immersion ×: the transparent film was peeled off after immersion

The thickness (T ₂ ) of the transparent film after immersion was measured in the same manner as described above, and from the thickness (T ₁ ) of the transparent film measured above, the formula (10) R _T = (T ₁ − T ₂₎ / T was calculated thickness change rate (R _T) by _one (10).

Further, after the exposure, a transparent film is formed over the entire surface of the substrate by the same operation as described above except that the operation of immersion in the developing solution is omitted, and the thickness (T ₀ ) is the same as above. The remaining film ratio (R) was determined by the equation (11) R = T ₁ / T ₀ (11). Table 1 shows the results.

Example 2 The same benzyl methacrylate / methacrylic acid copolymer (16.2 parts by weight) as used in Example 1, formula (3) (Wherein Q ⁴ represents a substituent represented by the formula (1-1)) (3.8 parts by weight), a hydroxystyrene / t-butyl methacrylate copolymer [hydroxystyrene unit and t The mass ratio to -butyl methacrylate unit is 62:38] (2.9 parts by weight), hexamethylolmelamine hexamethyl ether (3.8 parts by weight),
Propylene glycol monomethyl ether acetate (70.0 parts by weight) and 3-glycidoxypropyltrimethoxysilane (3.7 parts by weight) were mixed at about 23 ° C. A resin composition was obtained.

Except that the radiation-sensitive resin composition obtained above was used instead of the radiation-sensitive resin composition obtained in Example 1,
By operating in the same manner as in Example 1, a transparent film was formed on the substrate. The thickness (T ₁ ) of the obtained transparent film was measured in the same manner as in Example 1 in a linear pattern (width 10 μm) arranged in parallel at an interval of 10 μm and found to be 4 μm. By operating in the same manner as in Example 1, the light transmittance (T _t ) was measured.
A solvent resistance test was performed to determine a film thickness change rate ( _RT ) and a residual film rate (R). Table 1 shows the results.

Example 3 The same benzyl methacrylate / methacrylic acid copolymer (18.4 parts by weight) as used in Example 1, a quinonediazide compound of the formula (3) (2.7 parts by weight), a compound of the formula (2) ), (0.9 parts by weight), hexamethylolmelamine hexamethyl ether (4.3 parts by weight), propylene glycol monomethyl ether acetate (70.0 parts by weight) and 3-glycidoxypropyl tri Methoxysilane (3.7 parts by weight) was mixed at about 23 ° C. and operated in the same manner as in Example 1 to obtain a radiation-sensitive resin composition.

Except that the radiation-sensitive resin composition obtained above was used instead of the radiation-sensitive resin composition obtained in Example 1,
By operating in the same manner as in Example 1, a transparent film was formed on the substrate. The thickness (T ₁ ) of the obtained transparent film was measured in the same manner as in Example 1 in a linear pattern (width 10 μm) arranged in parallel at an interval of 10 μm and found to be 4 μm. By operating in the same manner as in Example 1, the light transmittance (T _t ) was measured.
A solvent resistance test was performed to determine a film thickness change rate ( _RT ) and a residual film rate (R). Table 1 shows the results.

Example 4 Benzyl methacrylate / methacrylic acid copolymer [weight ratio of benzyl methacrylate unit to methacrylic acid unit is 84.78: 15.3, weight average molecular weight (Mw) in terms of polystyrene is 20,000] ( 18.5 parts by weight),
The quinonediazide compound represented by the formula (3) (2.8 parts by weight) and the polyhydric phenol compound represented by the formula (2) (1.
1 part by weight), hydrogenated bisphenol A type epoxy resin [“Epolite 4000”, manufactured by Kyoeisha Chemical] (2.2 parts by weight), hexamethylolmelamine hexamethyl ether (4.8 parts by weight), propylene glycol methyl ether acetate (57.1 parts by weight) and 3-glycidoxypropyltrimethoxysilane (4.1 parts by weight) were mixed at about 23 ° C. and operated in the same manner as in Example 1 to obtain a radiation-sensitive resin composition. Was.

The radiation-sensitive resin composition obtained in Example 1 was used instead of the radiation-sensitive resin composition obtained in Example 1, except that
By operating in the same manner as in Example 1, a transparent film was formed on the substrate. The thickness (T ₁ ) of the obtained transparent film was measured in the same manner as in Example 1 in a linear pattern (width 10 μm) arranged in parallel at an interval of 10 μm and found to be 4 μm. By operating in the same manner as in Example 1, the light transmittance (T _t ) was measured.
A solvent resistance test was performed to determine a film thickness change rate ( _RT ) and a residual film rate (R). Table 1 shows the results.

As described above, the transparent films obtained in Examples 1 to 4 each have a thickness of 4 μm and a light transmittance of 80 μm.
% Or more.

Comparative Example 1 The same benzyl methacrylate copolymer (18.5 parts by weight) as used in Example 1, the same mixture of quinonediazide compounds (3.3 parts by weight) as used in Example 1, hexamethylolmelamine hexamethyl Ether (4.3 parts by weight), propylene glycol monomethyl ether acetate (70.1 parts by weight) and 3-glycidoxypropyltrimethoxysilane (3.7 parts by weight) were mixed at about 23 ° C. The same operation was performed to obtain a radiation-sensitive resin composition.

Except that the radiation-sensitive resin composition obtained above was used instead of the radiation-sensitive resin composition obtained in Example 1,
A transparent film was formed on the substrate in the same manner as in Example 1, but the obtained transparent film was easily peeled off from the substrate.

Comparative Example 2 The same quinonediazide compound as used in Example 1 (3.7
Parts by weight), Equation (4) (Where n is 18 to 24), a polyhydric phenol compound (18.8 parts by weight), hexamethylolmelamine hexamethyl ether (3.7 parts by weight), and propylene glycol monomethyl ether acetate (70.
1 part by weight) and 3-glycidoxypropyltrimethoxysilane (3.7 parts by weight) were mixed at about 23 ° C., and the same operation as in Example 1 was performed to obtain a radiation-sensitive resin composition.

The radiation-sensitive resin composition obtained in Example 1 was used in place of the radiation-sensitive resin composition obtained in Example 1, except that
By operating in the same manner as in Example 1, a transparent film was formed on the substrate. The thickness (T ₁ ) of the obtained transparent film was measured in the same manner as in Example 1 in a linear pattern (width 10 μm) arranged in parallel at an interval of 10 μm and found to be 4 μm. When the light transmittance (T _t ) was measured in the same manner as in Example 1, the light transmittance (T _t ) was 56.4% at a wavelength of 450 nm, and the wavelength was 550 n.
m was 68.2%, and wavelength 650 nm was 70.5%, and the residual film ratio (R) was determined to be 90%. Table 1 shows the results.

[0063]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a schematic view showing a step of forming a transparent film using the radiation-sensitive resin composition of the present invention.

[Explanation of symbols]

1: Radiation-sensitive resin composition layer 11: Non-irradiated area 12: Irradiated area 2: Substrate 3: Positive mask 4: Radiation 5: Transparent film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/022 G03F 7/022 7/40 501 7/40 501 H01L 21/027 H01L 21/30 502R (72 Inventor Jiro Hozumi 3-1-98 Kasuganaka, Konohana-ku, Osaka-shi F-term (reference) 2H025 AA01 AA06 AB16 AB17 AC01 AD03 BE01 CB13 CB43 CC17 CC20 FA17 FA29 FA30 2H096 AA25 AA28 BA10 EA02 GA08 HA01 HA03 4J002 BC041 BC081 BC091 BF011 BF021 BG011 BG041 BG051 BG061 BG071 BG101 BH021 CC042 CC052 CC163 CC183 CD013 CD023 CD043 CD063 EJ017 EJ027 EL028 EQ036 EV246 EV286 FD143 FD

Claims (5)

[Claims] 1. A radiation-sensitive composition containing a polymer compound (A) having a carboxyl group and no epoxy group, a quinonediazide compound (B), a polyhydric phenol compound having no quinonediazide group (C) and a crosslinking agent (D). Resin composition. 2. The content of the polymer compound (A) is from 5% to 90% by mass based on the solid content of the radiation-sensitive resin composition.
Or less, the content of the quinonediazide compound is from 2% to 30% by mass relative to the solid content, and the content of the polyhydric phenol compound (C) is 0.1% by mass to the solid content. The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition is 1% or more and 10% or less, and the content of the crosslinking agent (D) is 1% or more and 30% or less based on the solid content. 3. A pattern comprising the steps of: forming a layer comprising the radiation-sensitive resin composition according to claim 1 on a substrate, exposing the layer to light, and developing the pattern to form a pattern. A method for forming a transparent film. 4. The method according to claim 3, wherein after the development, radiation is applied to the entire surface of the formed pattern. 5. The method according to claim 4, wherein the entire surface is irradiated with radiation and then heated.