TWI443463B - A positive-type photosensitive resin composition and a method for forming a pattern of the composition - Google Patents

Description

Positive photosensitive resin composition and method for forming pattern of the composition

The present invention relates to a positive photosensitive resin composition and a method of forming a pattern using the composition. In particular, a positive photosensitive resin composition excellent in crack resistance and a method of forming a pattern using the composition in the production of a liquid crystal display element of a semiconductor integrated circuit element and a thin film transistor (hereinafter referred to as TFT) are provided.

An insulating film or a conductive metal film having a fine circuit pattern such as a liquid crystal display element circuit or a semiconductor integrated circuit is formed on the substrate, and the photoresist composition is uniformly applied and exposed and developed under a mask of a predetermined shape. The desired shape pattern is produced. Next, after the patterned photoresist film is removed as a mask, the metal film or the insulating film is removed, and then the remaining photoresist film is removed to form a fine circuit on the substrate. The photoresist composition can be classified into two types, a positive photoresist and a negative photoresist, depending on whether the photoresist composition is soluble or insoluble in the exposed portion or the photoresist film portion.

Japanese Patent Publication No. Hei 2-51499 discloses a positive photosensitive resin composition comprising a novolak resin obtained by condensing a mixture of m-cresol, p-cresol and xylenol with an aldehyde. The quinone diazide compound has advantages such as high sensitivity and high residual film ratio in application. However, in recent years, the pattern formed by the product has poor heat resistance and has failed to meet the standard.

Therefore, compared with the above-mentioned photosensitive resin composition, the patent document of Japanese Patent Laid-Open No. 2007-304592 discloses the use of the phenol represented by the following structural formula. As the photosensitive resin composition, the aldehyde varnish resin can form a pattern having excellent heat resistance on the substrate. However, the pattern formed thereon has a problem of poor crack resistance.

(wherein R represents H, -OH or -CH ₃ , and n is an integer from 3 to 20.)

A main object of the present invention is to provide a positive photosensitive resin composition, and more particularly to provide a positive photosensitive resin which is excellent in crack resistance in the manufacture of a liquid crystal display element of a semiconductor integrated circuit element and a thin film transistor (hereinafter referred to as TFT). Composition.

Another object of the present invention is to provide a method of forming a pattern using the above-described positive photosensitive resin composition.

In order to satisfy the above object, the present invention is a positive photosensitive resin composition comprising a novolak resin (A), an oxetanyl-containing epoxy resin (B), an o-naphthoquinone diazide sulfonate. An acid ester (C) and a solvent (D), wherein the novolak resin (A) comprises a hydroxy novolac resin (A-1), and the hydroxy novolac resin (A-1) is hydroxybenzaldehyde The hydroxy type novolac resin (A-1) is used in an amount of 30 to 100 parts by weight based on 100 parts by weight of the novolac resin (A).

a positive photosensitive resin composition as described above, wherein the hydroxybenzene The formaldehyde compound is selected from the group consisting of a hydroxybenzaldehyde compound, a dihydroxybenzaldehyde compound, a trihydroxybenzaldehyde compound, and a hydroxyalkylbenzaldehyde compound.

The positive photosensitive resin composition as described above, wherein the hydroxybenzaldehyde compound is selected from the group consisting of o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde.

The positive photosensitive resin composition as described above, wherein the dihydroxybenzaldehyde compound is selected from the group consisting of 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, and 2,5-dihydroxybenzene. A group consisting of formaldehyde, 3,4-dihydroxybenzaldehyde and 3,5-dihydroxybenzaldehyde.

The positive photosensitive resin composition as described above, wherein the trihydroxybenzaldehyde compound is selected from the group consisting of 2,3,4-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,4 a group consisting of 6-trihydroxybenzaldehyde and 3,4,5-trihydroxybenzaldehyde.

a positive photosensitive resin composition as described above, wherein the hydroxyalkylbenzaldehyde compound is selected from the group consisting of o-hydroxymethylbenzaldehyde, m-hydroxymethylbenzaldehyde, and p-hydroxymethylbenzaldehyde. The group consisting of.

The positive photosensitive resin composition as described above, wherein the oxetane group-containing epoxy resin (B) is used in an amount of 5 to 40 parts by weight based on 100 parts by weight of the novolac resin (A). The ester of the o-naphthoquinonediazidesulfonic acid ester (C) is used in an amount of 1 to 100 parts by weight, and the solvent (D) is used in an amount of 500 to 2000 parts by weight.

A pattern forming method of the present invention is to apply a positive photosensitive resin composition as described above to a substrate, and then sequentially apply a pre-bake, an exposure, A development and a post-baking process are performed to form a pattern on the substrate.

A thin film transistor array substrate of the present invention comprises a pattern as described above.

A liquid crystal display device of the present invention comprises the thin film transistor array substrate.

In the present invention, (meth)acrylic acid means acrylic acid and/or methacrylic acid, and similarly, (meth) acrylate means acrylate and/or methacrylate; (meth) propylene fluorenyl means propylene. An anthracenyl group and/or a methacryloxy group; a (meth) propylene oxime group represents an acryloxy group and/or a methacryloxy group.

The components of the present invention will be described in detail below.

<Positive Photosensitive Resin Composition> [Novolak resin (A)]

The novolac resin (A) of the positive photosensitive resin composition of the present invention contains a hydroxy novolak resin (A-1), and optionally further contains another novolak resin (A-2).

The hydroxy novolak resin (A-1) is obtained by a condensation reaction of a hydroxybenzaldehyde compound and an aromatic hydroxy compound in the presence of an acidic catalyst.

Specific examples of the hydroxybenzaldehyde compound are: hydroxybenzaldehyde compounds such as o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, etc.; 2,3-dihydroxybenzaldehyde, 2,4-di Dihydroxybenzaldehyde compound of hydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, etc.; 2,3,4-trihydroxybenzaldehyde, 2 ,4,5-trihydroxybenzene a trihydroxybenzaldehyde compound such as formaldehyde, 2,4,6-trihydroxybenzaldehyde or 3,4,5-trihydroxybenzaldehyde; o-hydroxymethylbenzaldehyde, m-hydroxymethylbenzaldehyde, p-hydroxyl A hydroxyalkylbenzaldehyde compound such as methyl benzaldehyde. The hydroxybenzaldehyde compound may be used alone or in combination of plural kinds. Among them, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2, 3,4-trihydroxybenzaldehyde is preferred.

Specific examples of the aromatic hydroxy compound which is condensed and reacted with the hydroxybenzaldehyde compound of the present invention are: phenol, m-cresol, p-cresol, o-cresol Cresols such as (o-cresol); xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol (xylenol); m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-third Phenolic, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 6-third Alkyl phenols such as benzyl-3-methylphenol; p-methoxy phenol, m-methoxy phenol, p-ethoxy phenol, m-ethoxy phenol, p-propoxy Alkoxy phenols such as phenol and m-propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl Isopropenyl phenol such as 4-isopropenylphenol; aryl pheno of phenyl phenol l); 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, etc. Polyhydroxyphenols and the like. The above aromatic hydroxy compounds may be used singly or in combination of plural kinds. Among them, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol and the like are preferred.

Specific examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and the like.

The amount of the hydroxy novolak resin (A-1) to be used is usually 30 to 100 parts by weight, preferably 40 to 100 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the novolak resin (A). When the amount of the hydroxy novolak resin (A-1) used is less than 30 parts by weight, the pattern formed of the photosensitive resin composition is liable to cause cracks and a low residual film ratio.

The other novolac resin (A-2) is generally obtained by a condensation reaction of the above-mentioned aromatic hydroxy compound and aldehyde of a non-hydroxybenzaldehyde in the presence of the above-mentioned acidic catalyst.

Specific examples of the aldehydes of non-hydroxybenzaldehydes are: formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein (acrolein) ), crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, alpha-benzene Propionaldehyde, β-phenylpropanal, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, Cinnamaldehyde and the like. The above aldehydes may be used singly or in combination of plural kinds. Among them, formaldehyde is preferred.

A single type of novolac resin may be used for the above-mentioned hydroxy novolak resin (A-1) and other novolak resins (A-2), or two or more kinds of different types of novolak resins may be mixed.

[Oxecyclobutane-containing epoxy resin (B)]

The oxetane group-containing epoxy resin (B) of the positive photosensitive resin of the present invention is composed of an unsaturated carboxylic acid monomer (b1), an oxetane group-containing compound (b2) and other unsaturated monomers. The body (b3) is obtained by copolymerization. Wherein: specific examples of the unsaturated carboxylic acid monomer (b1) are: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, Malay An unsaturated dicarboxylic acid (anhydride) such as an acid anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride; an unsaturated polyvalent carboxylic acid (anhydride) having a trivalent or higher value and the like. Among them, acrylic acid and methacrylic acid are preferred. The unsaturated carboxylic acid monomer (b1) may be used singly or in combination of plural kinds.

Specific examples of the oxetane-containing compound (b2) are: 3-(meth)acryloyloxy-methyl]oxetane, 3-(A) Acryl oxime oxymethyl-3-ethyloxetane, 3-(methyl) propylene oxime oxymethyl-2-methyl oxetane, 3-(methyl) propylene oxime Benzyl-2-trifluoromethyloxetane, 3-(methyl)propenyloxymethyl-2-pentafluoroethyloxetane, 3-(methyl)propene oximeoxymethyl- 2-phenyloxetane, 3-(methyl)propenyloxymethyl-2,2-difluorooxetane, 3-(meth)acrylomethoxymethyl-2,2, 4-trifluorooxetane, 3-(meth)acryloyloxymethyl-2,2,4,4-tetrafluorooxetane, 3-(methyl)propene oxiranyloxy Heterocyclobutane, 3-(methyl)propene oxiranyl-3-ethyloxy Heterocyclobutane, 2-ethyl-3-(methyl)propene oxiranyloxyoxetane, 3-(methyl)propenyloxyethyl-2-trifluoromethyloxetane , 3-(methyl) propylene oxiranyl ethyl-2-pentafluoroethyl oxetane, 3-(methyl) propylene oxirane ethyl-2-phenyl oxetane, 2, 2 -difluoro-3-(methyl)propene oxiranyl oxetane, 3-(methyl) propylene oxyethyl-2,2,4-trifluorooxetane, 3-( Methyl) propylene oxiranyl ethyl-2,2,4,4-tetrafluoro oxetane, 2-(methyl) propylene oxiranoxymethyl oxetane, 2-methyl-2-( Methyl) propylene oxime methyl oxetane, 3-methyl-2-(methyl) propylene oxiranoxymethyl oxetane, 4-methyl-2-(methyl) propylene oxime Methyl oxetane, 2-(methyl) propylene oxime methyl 2-trifluoromethyl oxetane, 2-(methyl) propylene oxymethyl-3-fluoromethyl Oxetane, 2-(methyl)propenyloxymethyl-4-trifluoromethyloxetane, 2-(methyl)propenyloxymethyl-2-pentafluoroethyloxalate Cyclobutane, 2-(meth)acryloyloxymethyl-3-pentafluoroethyloxetane, 2-(methyl)propenyloxymethyl-4-pentafluoroethyloxetane alkyl 2-(Methyl)acryloyloxymethyl-2-phenyloxetane, 2-(methyl)propenyloxymethyl-3-phenyloxetane, 2-(methyl) Propylene oxime methyl 4-phenyl oxetane, 2,3-difluoro-2-(methyl) propylene oxiranoxymethyl oxetane, 2,4-difluoro-2-( Methyl) propylene oxime methyl oxetane, 3,3-difluoro-2-(methyl) propylene oxiranyl oxetane, 2,4-difluoro-2-(methyl ) propylene oxime methyl oxetane, 3,4-difluoro-2-(methyl) propylene oxiranoxymethyl oxetane, 4,4-difluoro-2-(methyl) propylene Oxyxymethyloxetane, 2-(meth)acryloyloxymethyl-3,3,4-trifluorooxetane, 2-(meth)acrylomethoxymethyl-3, 4,4-trifluorooxetane, 2-(methyl)propene oxime methyl-3,3,4,4-tetrafluorooxetane, 2-(methyl) propylene oxime Oxyethyl oxetane, 2-(methyl) propylene oxirane ethyl 2-methyl oxetane, 2-(methyl) propylene oxirane ethyl 4-methyl oxacyclohexane Butane, 2-(methyl) propylene oxiranyl-2-trifluoromethyl oxetane, 2-(methyl) propylene oxiranyl ethyl-3-trifluoromethyl oxetane 2-(Methyl)acryloyloxyethyl-4-trifluoromethyloxetane, 2-(methyl)propenyloxyethyl-2-pentafluoroethyloxetane, 2 -(Meth)acryloyloxyethyl-3-pentafluoroethyloxetane, 2-(methyl)propenyloxyethyl-4-pentafluoroethyloxetane, 2-( Methyl)propenyloxyethyl-2-phenyloxetane, 2-(meth)acryloyloxyethyl-3-phenyloxetane, 2-(methyl)propene oxime Ethyl-4-phenyloxetane, 2,3-difluoro-2-(methyl)propene oxiranyl oxetane, 2,4-difluoro-2-(methyl) Propylene oxiranyl oxetane, 3,3-difluoro-2-(methyl) propylene oxiranyl oxetane, 3,4-difluoro-2-(methyl) propylene oxime Oxyethyl oxetane, 4,4-difluoro-2-(methyl) propylene oxiranyl oxetane, 2-(methyl) propylene oxyethyl-3, 3, 4 -trifluoroox Cyclobutane, 2-(meth)acryloyloxyethyl-3,4,4-trifluorooxetane, 2-(methyl)propene oxiranylethyl-3,3,4,4- Tetrafluorooxetane, cyclobutyl (meth)acrylate, and the like. The oxetane group-containing compound (b2) can be used singly or in combination of plural kinds.

Specific examples of the other unsaturated monomer (b3) are: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, (A) Base) butyl acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, Dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, diethyl diethylate (diethyl Maleate), diethyl fumarate, diethyl itaconate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzene Ethylene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like. Among them, styrene, butyl methacrylate, dicyclopentanyl methacrylate, dicyclopentyloxyethyl acrylate, and p-methoxy styrene are preferred. The other unsaturated monomers (b3) may be used singly or in combination of plural kinds.

The oxetane group-containing epoxy resin (B) of the present invention is generally used as a solvent for the synthesis, and is generally used as ethylene glycol monopropyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxyethyl acetate, ethoxyethyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl ketone and acetone. Among them, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate are preferred. The foregoing solvents may be used singly or in combination of plural kinds.

The oxetane group-containing epoxy resin (B) of the present invention is used as a starter for the synthesis, and is generally a radical-type polymerization initiator, which is specifically, for example, 2,2'-azobis. 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' An azo compound such as azobis(4-methoxy-2,4-dimethylvaleronitrile); a peroxy compound such as benzoylperoxide.

The epoxy group containing an oxetane group (B) is usually used in an amount of 5 to 40 parts by weight, preferably 7 to 35 parts by weight, more preferably 10%, based on 100 parts by weight of the novolak resin (A). 30 parts by weight. Since the oxetane group-containing epoxy resin (B) can form a relatively compact structure with the hydroxy novolak resin (A-1) after baking, it is less likely to cause cracks or wrinkles. When the epoxy group (B) containing oxetane group is used in an amount of 5 to 40 parts by weight, a pattern having excellent crack resistance can be formed on the substrate.

[Esterified product of o-naphthoquinonediazidesulfonic acid (C)]

The photosensitive material of the positive photosensitive resin composition of the present invention is an ester (C) of o-naphthoquinonediazidesulfonic acid, and the esterified product (C) is not particularly limited, and may be used by a regular user. The preferred one is an esterified product of o-naphthoquinonediazidesulfonic acid and a hydroxy compound, more preferably an esterified product of o-naphthoquinonediazidesulfonic acid and a polyvalent hydroxy compound, and the esterified product can be completely esterified or partially esterified. Specific examples of the o-naphthoquinonediazidesulfonic acid are: o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid, o-naphthoquinonediazide-6-sulfonate Acid, etc. The types of the aforementioned hydroxy compounds are listed below:

(1) Hydroxybenzophenone compounds, specific examples thereof are: 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-three Hydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6 - pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5'-pentahydroxybenzophenone, 2,3' , 4,5,5'-pentahydroxybenzophenone, 2,3,3',4,4',5'-hexahydroxybenzophenone and the like.

(2) a hydroxyaryl compound represented by the general formula (I)

In the formula, R ¹ to R ³ are a hydrogen atom or a lower alkyl group, and R ⁴ to R ⁹ are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower aliphatic alkenyl group (alkenyl). Or a cycloalkyl group, R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom or a lower alkyl group, and x, y and z are integers of 1 to 3, and n is 0 or 1. Specific examples of the hydroxyaryl compound represented by the general formula (I) are: tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane , bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, double (4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis (4 -hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis ( 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-dihydroxyphenyl Methane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane , bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl- 4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylaryl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyl) -6-methyl 3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methyl Phenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)- 4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyl Phenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3 , 4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1 -(3-Methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene.

(3) (hydroxyphenyl) hydrocarbon compounds represented by general formula (II)

In the formula, R ¹² and R ¹³ are a hydrogen atom or a lower alkyl group, and x' and y' are an integer of 1 to 3. Specific examples of the (hydroxyphenyl) hydrocarbon represented by the general formula (II) are: 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxybenzene Propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyl Phenyl)propane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like.

(4) Other aromatic hydroxy compounds, specific examples are: phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, Pyroallol monomethyl ether, pyrogallol-1,3-dimethyl ether, 3,4, 5-galhydroxybenzoic acid, partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid, and the like.

The above hydroxy compound is preferably 2,3,4-trihydroxybenzophenone or 2,3,4,4'-tetrahydroxyoxybenzophenone. The above hydroxy compounds may be used singly or in combination of several kinds.

The ester material of the ortho-naphthoquinonediazide sulfonic acid (C), which is a photosensitive material in the resin composition of the present invention, may be a compound containing a quinonediazide group, for example, o-naphthoquinonediazide-4 (or 5). The sulfonic acid halide salt is obtained by completely or partially esterifying a hydroxy compound represented by the above (1) to (4) by a condensation reaction, and the condensation reaction is usually carried out in dioxane or N-pyrrolidone. It is carried out in an organic solvent such as (N-pyrrolidone) or acetamide, and the condensation reaction is advantageously carried out in the presence of an alkaline condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.

In this case, based on the total amount of hydroxyl groups in the hydroxy compound of 100 mol%, preferably 50 mol% or more, more preferably 60 mol% or more and o-naphthoquinonediazide-4 (or 5)-sulfonic acid halide Salt condensation to form an esterified product, that is, the degree of esterification is 50% The above is preferred, and it is preferably 60% or more.

The ortho-naphthoquinone diazide sulfonic acid ester ester (C) of the present invention is used in an amount of usually 1 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the novolak resin (A). When the amount of the ester of the o-naphthoquinonediazidesulfonic acid ester (C) is from 1 to 100 parts by weight, the sensitivity of the resin composition can be increased from 20 to 40 parts by weight.

[solvent (D)]

The solvent (D) used in the present invention requires an organic solvent which is relatively easy to dissolve with other organic components.

Specific examples of the solvent (D) used in the present invention are: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and Ethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol single B (poly)alkylene glycol monoalkyl ethers such as alkyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Other ethers such as ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Ketones; alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate , 3-methoxypropionic acid methyl ester, 3 -ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, Isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate, etc. Other esters; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amines such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Among them, propylene glycol monomethyl ether acetate and ethyl lactate are preferred. The foregoing solvents may be used singly or in combination of plural kinds.

The solvent (D) of the photosensitive resin composition of the present invention is usually used in an amount of 500 to 2,000 parts by weight, preferably 600 to 1,800 parts by weight, more preferably 700 to 1,500 parts by weight based on 100 parts by weight of the novolak resin (A). Share.

[Additive (E)]

In the positive photosensitive resin composition of the present invention, an aromatic hydroxy compound can be further added to adjust the sensitivity or viscosity of the composition. Specific examples of aromatic hydroxy compounds suitable for the present invention are, for example, TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200-26X, TPPA-1300 Commercial products such as -235T, TPPA-1600-3M6C, and TPPA-MF (manufactured by Nippon Chemical Co., Ltd.), wherein TPPA-600-3M6C and TPPA-MF are preferred, and the aromatic hydroxy compound may be used alone or Mix multiple uses. The aromatic hydroxy compound is used in an amount of usually 0 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1.0 to 15 parts by weight, based on 100 parts by weight of the novolak resin (A).

In the positive photosensitive resin composition of the present invention, an adhesion aid, a surface leveling agent, a diluent, and a dye having good compatibility may be further added as needed.

The adhesion aid of the present invention contains a melamine compound or a silane compound, and functions to increase the adhesion between the positive photosensitive resin composition and the attached substrate. Among them, specific examples of melamine are: Cymel-300, Cymel-303 (manufactured by Mitsui Chemicals), MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706 (Sanhe Chemical), etc. Commercial products. Specific examples of the decane-based compound are, for example, vinyltrimethoxydecane, vinyltriethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, vinyltris(2-methoxyB) Oxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiol Propyltrimethoxydecane, bis-1,2-(trimethoxyindolyl)ethane, and the like. The amount of the adhesion aid of the melamine compound is usually from 0 to 20 parts by weight, preferably from 0.5 to 18 parts by weight, more preferably from 1.0 to 15 parts by weight, based on 100 parts by weight of the novolak resin (A); the decane compound The amount of the adhesion aid is usually 0 to 2 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.8 part by weight.

The surface flat agent of the present invention contains a fluorine-based surfactant and a lanthanoid surfactant. Specific examples of the fluorine-based surfactant are Flourate FC-430, FC-431 (made by 3M), F-top EF122A, 122B, 122C, 126, Commercial products such as BL20 (made by Tochem product). Specific examples of the lanthanoid surfactants include commercially available products such as SF8427 and SH29PA (manufactured by Toray Dow Corning Silicon). The surfactant is usually used in an amount of from 0 to 1.2 parts by weight, preferably from 0.025 to 1.0 part by weight, more preferably from 0.050 to 0.8 part by weight, based on 100 parts by weight of the novolak resin (A).

Commercially available products such as RE801 and RE802 (manufactured by Imperial Ink) are suitable for the diluent of the present invention.

Specific examples of the dyes suitable for the compatibility of the present invention include curcumin, coumarin, azo dyes, and the like. Further, other additives may be added to the present invention as needed. For example: plasticizers, stabilizers, etc.

<Method of Forming Pattern by Positive Photosensitive Resin Composition>

In the method of forming a pattern by using the positive photosensitive resin composition of the present invention, the photosensitive resin composition is applied onto a substrate by a coating method such as spin coating, cast coating or roll coating. After the coating, the solvent is removed in a prebake manner to form a prebaked coating film. Among them, the pre-baking conditions vary depending on the type and blending ratio of each component, and are usually carried out at a temperature of 70 to 110 ° C for 1 to 15 minutes.

After pre-baking, the coating film is exposed to a designated mask, and then immersed in a developing solution at a temperature of 23±2° C. for 15 seconds to 5 minutes, thereby removing unnecessary portions to form a specific one. pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp and a metal halide lamp.

Specific examples of the developer used in the present invention are: sodium hydroxide, hydrogen hydroxide Potassium, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide A basic compound such as ammonium, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene.

Preferably, the concentration of the developer is between 0.001% and 10% by weight, more preferably between 5% and 5% by weight, and even more preferably between 0.01% and 1% by weight. %between.

When the developer composed of the above basic compound is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen. Next, the coating film is post-baked using a heating device such as a hot plate or an oven. The post-baking temperature is usually 100 to 250 ° C, wherein the heating time using the hot plate is 1 minute to 60 minutes, and the heating time using the oven is 5 minutes to 90 minutes. After the above processing steps, a pattern can be formed on the substrate.

<Thin Film Array Substrate>

The method for producing a thin film transistor array substrate (abbreviated as a TFT array substrate) of the present invention is constituted by the above-described method of forming a pattern. In other words, the positive photosensitive resin composition of the present invention is applied to a coating containing aluminum, chromium, tantalum nitride or amorphous ruthenium by spin coating, cast coating or roll coating. Forming a positive photoresist layer on the glass substrate or the plastic substrate of the film, and then performing pre-baking, exposure, development, and post-baking to form a photosensitive resin pattern, performing etching and photoresist stripping; repeating the above steps can be performed A thin film transistor array substrate containing a plurality of thin film transistors or electrodes is obtained.

Here, a pair of TFT array substrates for LCD will be described with reference to the drawings.

Fig. 1 is a schematic cross-sectional view showing a TFT array substrate for LCD. (1) first First, a gate electrode 102a and a storage capacitor Cs electrode 102b are provided on an aluminum film or the like on the glass substrate 101; (2) Next, a yttrium oxide film (SiOx) 103 or a tantalum nitride film (SiNx) 104 is coated on the gate electrode 102a. And forming an insulating film on the insulating film; (3) forming an amorphous germanium layer (a-Si) 105 as a semiconductor active layer; (4) then, in order to reduce the junction resistance, a nitrogen-doped impurity is provided. The amorphous germanium layer 106; (5) then, using a metal such as aluminum to form a collector 107a and a source 107b, the collector 107a is connected to a data signal line (not shown), and the source 107b is connected to the drawing (6) Finally, in order to protect the amorphous ruthenium layer (a-Si) 105, the collector 107a or the source 107b as a semiconductor active layer, a tantalum nitride film or the like is provided. As the protective film 108.

<Liquid crystal display element>

The liquid crystal display device of the present invention comprises the TFT array substrate of the present invention as described above, and the TFT array substrate is constructed by the pattern forming method of the present invention. In addition, other parts may be included as needed.

Specifically, the basic configuration of the liquid crystal display device is, for example, (1) a TFT array substrate (drive substrate) of the present invention formed by arranging a driving element such as a TFT and a pixel electrode (conductive layer), and color filtering by the color filter. A color filter substrate composed of a sheet and a counter electrode (conductive layer) is interposed between the color filter substrates and disposed opposite to each other, and finally a liquid crystal material is sealed in the gap portion. Alternatively, (2) a color filter-integrated TFT array substrate in which a color filter is directly formed on the TFT array substrate of the present invention, and a spacer interposed between the opposite substrate on which the counter electrode (conductive layer) is disposed, and In the arrangement, the liquid crystal material is sealed in the gap portion to form and the like.

Specific examples of the conductive layer include an ITO film; a metal film of aluminum, zinc, copper, iron, nickel, chromium, molybdenum or the like; a metal oxide film of cerium oxide or the like. Among them, a film having transparency is preferred, and an ITO film is preferred.

Specific examples of the substrate used for the TFT array substrate, the color filter substrate, and the counter substrate of the present invention include, for example, a known glass such as soda lime glass, low expansion glass, alkali-free glass, or quartz glass. A substrate composed of a plastic film or the like can also be used.

The invention is further described in the following examples and comparative examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

[Synthesis Example 1]

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, 64.89 g (0.6 mol) of m-cresol and 43.26 g of p-cresol were added. Mole), 3,4-dihydroxybenzaldehyde 55.25 g (0.4 mol) and oxalic acid 1.80 g (0.02 mol). The reaction solution was warmed to 100 ° C with gentle stirring, and polymerized at this temperature for 5 hours. Then, the reaction solution was heated to 180 ° C, dried under reduced pressure at a pressure of 10 mmHg, and the solvent was devolatilized to obtain a hydroxy novolak resin (A-1-1).

[Synthesis Example 2]

The hydroxy novolac resin (A-1-2) was prepared in the same manner as in the above Synthesis Example 1, except that 3,4-dihydroxybenzaldehyde was replaced with o-hydroxybenzaldehyde 48.85 g (0.4 mol).

[Synthesis Example 3]

The hydroxy novolac resin (A-1-3) was prepared in the same manner as in the above Synthesis Example 1, except that 3,4-di was replaced by 2,3,4-trihydroxybenzaldehyde 61.65 g (0.4 mol). Hydroxybenzaldehyde.

[Synthesis Example 4]

The novolac resin (A-2-1) was prepared in the same manner as in the aforementioned Synthesis Example 1, except that 3,4-dihydroxybenzaldehyde was replaced with 37.3% by weight of formaldehyde (0.4 mol).

[Synthesis Example 5]

The novolak resin (A-2-2) was prepared in the same manner as in the above Synthesis Example 1, except that 3,4-dihydroxybenzaldehyde was replaced with benzaldehyde 42.45 g.

[Synthesis Example 6]

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, propylene glycol monomethyl ether acetate 200 g, 3-(meth)acrylomethoxymethyl group was added. 30 g of -2-phenyloxetane, 25 g of methacrylic acid, 35 g of dicyclopentanyl methacrylate, and 10 g of styrene. Slowly stir the reaction solution to 80 ° C, then 2 g of 2,2 '-azobisisobutyronitrile was dissolved in propylene glycol monomethyl ether acetate 20 g, and added in four equal intervals at five hour intervals in five equal portions. In the cone bottle. The reaction temperature of the polymerization process was maintained at 80 ° C and the polymerization time was 4 hours. After completion of the polymerization, the solvent is devolatilized to obtain an oxetane group-containing epoxy resin (B-1).

[Synthesis Example 7]

Preparation of an oxetane group in the same manner as in the aforementioned Synthesis Example 6 Epoxy resin (B-2), the difference is in changing the feed composition, replacing 3-(methyl) propylene oxide with 30 g of 3-(methyl) propylene oxymethyl-3-ethyl oxetane Methyl-2-phenyloxetane.

[Synthesis Example 8]

An oxetane group-containing epoxy resin (B-3) was prepared in the same manner as in the aforementioned Synthesis Example 6, except that the feed composition was changed to 2-(meth)acryloyloxymethyl-4- 30 g of trifluoromethyloxetane was substituted for 3-(meth)acryloyloxymethyl-2-phenyloxetane.

[Synthesis Example 9]

A nitrogen inlet, stirrer, heater, condenser and thermometer were placed on a four-necked flask of 1000 ml volume. After introducing nitrogen, 200 g of diethylene glycol dimethyl ether, 30 g of methacrylic acid, and methacrylic acid epoxy were added. 25 g of glycidyl methacrylate, 20 g of styrene and 25 g of butyl methacrylate. Slowly stir the reaction solution to 85 ° C, then 2 g of 2,2 '-azobisisobutyronitrile was dissolved in diethylene glycol dimethyl ether and added in four equal intervals at five hour intervals in five equal portions. In the cone bottle. The reaction temperature of the polymerization process was maintained at 85 ° C and the polymerization time was 6 hours. After the completion of the polymerization, the solvent is devolatilized to obtain an epoxy resin (B'-1).

[Synthesis Example 10]

The epoxy resin (B'-2) was prepared in the same manner as in the aforementioned Synthesis Example 9, except that the feed composition was changed, and glycidyl methacrylate was replaced with 25 g of o-vinylbenzyl glycidyl ether.

<Examples and Comparative Examples of Photosensitive Resin Composition> [Example 1]

100 parts by weight of a hydroxy novolac resin (A-1-1), 15 parts by weight of an oxetane group-containing epoxy resin (B-1), and 25 parts by weight of 2,3,4-three a mixture of hydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid ester (C-1) (average degree of esterification 85%), adding 750 parts by weight of propylene glycol monomethyl In the solvent (D-1) of the ether acetate, the mixture was dissolved in a solvent by stirring with a stirring stirrer, and polymerization was carried out for 3 hours to obtain a positive photosensitive resin composition of the present invention. Each test item described below was tested, and the results obtained are shown in Table 1.

[Examples 2 to 8]

The operation method of the same manner as in the first embodiment is different in that the type of the raw material and the amount thereof are changed, and the formulation and test results are shown in Table 1.

[Comparative Examples 1 to 6]

The operation method of the same manner as in the first embodiment is different in that the type of the raw material and the amount thereof are changed, and the formulation and test results are shown in Table 1.

【Test items】 <Fracture resistance>

The positive photosensitive resin composition was spin-coated on a 6-inch wafer, and then pre-baked at 110 ° C for 160 seconds to form a 1.2 μm prebaked film. Next, under a designated mask, irradiated with a light amount of 6 mJ/cm ² by ultraviolet light (exposure model: AG500-4N; manufactured by M&R Nano Technology), and then the coating film was immersed in a developing solution at 23 ° C (2.38% of four). Methylammonium hydroxide was removed for 60 seconds, and the coating film of the exposed portion was removed, and then washed with pure water, and baked at a temperature of 160 ° C for 5 minutes to form a pattern of the positive photosensitive resin composition.

After immersing a part of the pattern in N-methylpyrrolidone (NMP) for 30 minutes, the state of the surface of the pattern was observed by an optical microscope.

○: The pattern has not changed

×: The pattern has cracks

<residual film rate>

A film thickness (δ) was measured on a pre-baked coating film obtained in the test item <Fracture resistance>. Next, the coating film was immersed in a developing solution (2.38% tetramethylammonium hydroxide) at 23 ° C for 1 minute, and another film thickness (δ _d ) was measured at the same measurement point. Finally, the residual film rate can be obtained by the following formula.

Residual film rate (%) = [(δ _d ) / (δ)] × 100

○: residual film rate ≧90%

△: 90%> residual film rate ≧ 80%

×: residual film rate <80%

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All should remain within the scope of the invention patent.

101‧‧‧ glass substrate

102a‧‧‧ gate

102b‧‧‧Cs electrode

103‧‧‧Oxide film (SiOx)

104‧‧‧ nitride film (SiNx)

105‧‧‧Amorphous enamel layer (a-Si)

106‧‧‧Amorphous ruthenium layer doped with nitrogen impurities

107a‧‧‧集极

107b‧‧‧ source

108‧‧‧Protective film

109‧‧‧ pixel electrodes

Fig. 1 is a schematic cross-sectional view showing a TFT array substrate for LCD.

Claims (11)

A positive photosensitive resin composition comprising: a novolac resin (A); an oxetane group-containing epoxy resin (B); an o-naphthoquinonediazidesulfonic acid ester ester (C); and a solvent (D); wherein the novolak resin (A) comprises a hydroxy novolak resin (A-1) which is condensed with an aromatic hydroxy compound by a hydroxybenzaldehyde compound In addition, the hydroxyl type novolak resin (A-1) is used in an amount of 30 to 100 parts by weight based on 100 parts by weight of the novolak resin (A). The positive photosensitive resin composition according to claim 1, wherein the hydroxybenzaldehyde compound is selected from the group consisting of a hydroxybenzaldehyde compound, a dihydroxybenzaldehyde compound, a trihydroxybenzaldehyde compound, and a hydroxyalkyl group. A group consisting of benzaldehyde compounds. The positive photosensitive resin composition according to claim 2, wherein the hydroxybenzaldehyde compound is selected from the group consisting of o-hydroxybenzaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde. group. The positive photosensitive resin composition according to claim 2, wherein the dihydroxybenzaldehyde compound is selected from the group consisting of 2,3-dihydroxybenzaldehyde and 2,4-dihydroxybenzaldehyde, 2. A group consisting of 5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, and 3,5-dihydroxybenzaldehyde. The positive photosensitive resin composition according to claim 2, wherein the trihydroxybenzaldehyde compound is selected from the group consisting of 2,3,4-trihydroxybenzene. A group consisting of formaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, and 3,4,5-trihydroxybenzaldehyde. The positive photosensitive resin composition according to claim 2, wherein the hydroxyalkylbenzaldehyde compound is selected from the group consisting of o-hydroxymethylbenzaldehyde, m-hydroxymethylbenzaldehyde, and p-hydroxyl A group consisting of methyl benzaldehyde. The positive photosensitive resin composition according to the first aspect of the invention, wherein the oxetane group-containing epoxy resin (B) is used in an amount of 5 parts by weight based on 100 parts by weight of the novolak resin (A). The amount of the ester of the o-naphthoquinonediazidesulfonic acid ester (C) is from 1 to 100 parts by weight, and the solvent (D) is used in an amount of from 500 to 2000 parts by weight. The positive photosensitive resin composition according to claim 1, wherein the oxetane group-containing epoxy resin (B) is composed of an unsaturated carboxylic acid monomer (b1) and an oxetane. The alkyl compound (b2) and other unsaturated monomers (b3) are obtained by copolymerization, and wherein the other unsaturated monomer (b3) comprises methyl (meth)acrylate, ethyl (meth)acrylate, (a) Base) n-butyl acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid -2-methylcyclohexyl ester, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, diethyl maleate, Fumar Diethyl acid, diethyl itaconate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, α-methylstyrene, m-methyl Styrene, p-methylstyrene or p-methoxystyrene. A pattern forming method is applicable to any of the first to eighth patent applications The positive photosensitive resin composition described in the above is applied to a substrate, and then a pre-bake, an exposure, a development, and a post-baking treatment are sequentially applied to form a pattern on the substrate. A thin film transistor array substrate comprising a pattern formed by the pattern forming method according to claim 9 of the patent application. A liquid crystal display element comprising the thin film transistor array substrate according to claim 10 of the patent application.