KR102183741B1 - Positive-type photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom, (1) (1-1) a structural unit derived from a carboxyl group-containing unsaturated monomer, (1-2) unsaturated containing a phenolic hydroxyl group Constituent units derived from monomers, (1-3) constituent units derived from unsaturated monomers containing lactone groups, and (1-4) derived from unsaturated monomers different from the constituent units (1-1) to (1-3) A copolymer comprising a structural unit to be formed; And (2) a photosensitive agent, the positive photosensitive resin composition of the present invention has excellent sensitivity and a high residual film rate after post-curing, and provides high pattern formation, so it can be usefully used in the manufacture of an insulating film for a liquid crystal display. have.

Description

Positive photosensitive resin composition and cured film prepared therefrom {POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION AND CURED FILM PREPARED THEREFROM}

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom, and more particularly, useful as an interlayer insulating film material of a thin film transistor (TFT) array of a liquid crystal display (LCD). It relates to a positive type photosensitive resin composition that can be used and a cured film prepared therefrom.

A TFT substrate used in a liquid crystal display device has an interlayer insulating film for protecting a TFT array element between a transparent conductive film forming a TFT element and a pixel electrode, and the insulating film is formed by a drain electrode of a TFT array and a transparent conductive film. A contact hole for connecting the wiring to be formed is formed, and for this purpose, the insulating film is required to have high light transmittance, chemical stability, and excellent interlayer adhesion.

As a material of such an interlayer insulating film, a positive type and a negative type photosensitive resin composition are used.

The conventional positive photosensitive composition containing an alkali-soluble resin and a 1,2-quinonediazide compound is thermally decomposed to cause coloration or impurities when exposed to light, hard bake after development, and absorbed in short wavelengths such as ultraviolet rays. There was a problem in which an afterimage was caused in the liquid crystal display device.

Accordingly, various studies on a positive photosensitive resin composition having improved physical properties have been conducted (Korean Patent Publication No. 10-2004-0078554, Korean Patent No. 10-0758867, and Japanese Patent Publication No. 2004. -286968). However, although this photosensitive resin composition achieved relatively high transparency, it was not satisfactory in terms of sensitivity.

Korean Patent Publication No. 10-2004-0078554 Korean Patent No. 10-0758867 Japanese Patent Publication No. 2004-286968

Accordingly, an object of the present invention is to provide a positive photosensitive resin composition capable of providing a high pattern formability as well as having excellent sensitivity and a high residual film rate after post-curing, and a cured film prepared therefrom.

In order to achieve the above object, the present invention

(1) (1-1) a structural unit derived from an unsaturated monomer containing a carboxyl group, (1-2) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1-3) an unsaturated monomer containing a lactone group A copolymer comprising a derived structural unit, and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3); And

(2) photoactive compound

It provides a photosensitive resin composition containing.

The positive photosensitive resin composition of the present invention not only has excellent sensitivity and a high residual film rate after post-curing, but also can provide high pattern formation, and thus can be usefully used in the manufacture of a cured film that can be used as an insulating film for a liquid crystal display.

The positive photosensitive resin composition according to the present invention comprises (1) (1-1) a structural unit derived from an unsaturated monomer containing a carboxyl group, (1-2) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1 -3) a copolymer comprising a structural unit derived from an unsaturated monomer containing a lactone group, and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3); And (2) a photoactive compound, and if necessary, (3) an epoxy compound; (4) phenolic compounds; (5) solvent; And (6) as other components, (6-1) a surfactant and/or (6-2) a silane coupling agent may be further included.

Hereinafter, the components of the present invention will be described in detail.

(1) copolymer

The copolymer is (1-1) a structural unit derived from an unsaturated monomer containing a carboxyl group, (1-2) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1-3) an unsaturated monomer containing a lactone group Constituent units derived from, and (1-4) constituent units derived from unsaturated monomers different from the constituent units (1-1) to (1-3), and, if necessary, (1-5) an epoxy group of 1 Constituent units derived from unsaturated monomers containing at least two may be further included.

(1-1) Constituent units derived from unsaturated monomers containing carboxyl groups

The carboxyl group-containing unsaturated monomer may be an unsaturated carboxylic acid such as an unsaturated polyhydric carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated tricarboxylic acid. Examples of the unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among them, (meth)acrylic acid is preferable from the viewpoint of developability, and methacrylic acid is more preferable from the viewpoint of polymerization.

The content of the constituent units derived from the (1-1) carboxyl group-containing unsaturated monomer may be 5 to 50% by weight, preferably 16 to 35% by weight, based on the total weight of the copolymer. In this range, exposure sensitivity is improved and good developability can be maintained.

(1-2) Constituent units derived from unsaturated monomers containing phenolic hydroxyl groups

The structural unit derived from the unsaturated monomer containing the phenolic hydroxyl group may be represented by the following formula (1):

In the above formula,

R ¹ is hydrogen, C ₁ -C ₆ alkyl, halogen or cyano;

R ² is C ₁ -C ₆ alkyl, a is an integer of 0 to 4, and when a is an integer of 2 or more, a plurality of R ² may be the same or different from each other;

b is an integer from 1 to 5, and the sum of a and b is an integer from 1 to 5;

Y is a single bond or C ₁ -C ₆ alkylene;

The alkyl and alkylene may be substituted with one or more halogen, nitro, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl.

Specific examples of unsaturated monomers containing a phenolic hydroxyl group include p-hydroxyphenyl (meth)acrylate, m-hydroxyphenyl (meth)acrylate, p-hydroxyphenylmethyl (meth)acrylate, p-hydroxy Phenylmethyl-α-chloroacrylate, m-hydroxyphenylmethyl (meth)acrylate, 2-(p-hydroxyphenyl)ethyl (meth)acrylate, 2-(p-hydroxyphenyl)ethyl-α- Trifluoromethylacrylate, 2-(p-hydroxyphenyl)ethyl-α-chloroacrylate, 2-(p-hydroxyphenyl)ethyl-α-bromoacrylate, 2-(p-hydroxyphenyl )Ethyl-α-cyanoacrylate, 2-(m-hydroxyphenyl)ethyl(meth)acrylate, 2-(3,5-dihydroxyphenyl)ethyl(meth)acrylate, 2-(3, 5-Dimethyl-4-hydroxyphenyl)ethyl (meth)acrylate, 1-(p-hydroxyphenyl)-1-methylethyl (meth)acrylate, 1-(m-hydroxyphenyl)-1-methyl Ethyl (meth)acrylate, 1-(3,5-dihydroxyphenyl)-1-methylethyl (meth)acrylate, and mixtures thereof.

The content of the constituent unit derived from the (1-2) unsaturated monomer containing a phenolic hydroxyl group may be 5 to 40% by weight, preferably 5 to 30% by weight, based on the total weight of the copolymer. In this range, high pattern formation can be implemented.

(1-3) Constituent units derived from unsaturated monomers containing lactone groups

The structural unit derived from the unsaturated monomer containing the lactone group may be represented by the following formula (2):

In the above formula,

R ³ is hydrogen, C ₁ -C ₆ alkyl, halogen or cyano;

R ⁴ is C ₁ -C ₆ alkyl, m is an integer of 0 to 11, and when m is an integer of 2 or more, a plurality of R ⁴ may be the same or different from each other;

n is an integer from 0 to 4, and m≦2n+3;

X is a single bond or C ₁ -C ₆ alkylene;

The alkyl and alkylene may be substituted with one or more halogen, nitro, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl.

Specific examples of unsaturated monomers containing a lactone group include α-(meth)acryloyloxy-γ-butyrolactone, α-(2-trifluoromethyl)acryloyloxy-γ-butyrolactone, α-( 2-Chloro)acryloyloxy-γ-butyrolactone, α-(2-bromo)acryloyloxy-γ-butyrolactone, α-(2-cyano)acryloyloxy-γ-buty Lolactone, α-(meth)acryloyloxy-α-methyl-γ-butyrolactone, α-(meth)acryloyloxy-α-ethyl-γ-butyrolactone, α-(meth)acrylo Iloxy-β,β-dimethyl-γ-butyrolactone, α-(2-chloro)acryloyloxy-β,β-dimethyl-γ-butyrolactone, β-(meth)acryloyloxy-γ -Butyrolactone, β-(meth)acryloyloxy-β-methyl-γ-butyrolactone, α-(1-(meth)acryloyloxy-1-methyl)ethyl-γ-butyrolactone, β-(meth)acryloyloxy-δ-valerolactone, β-(meth)acryloyloxy-β-methyl-δ-valerolactone, and mixtures thereof.

The content of the constituent units derived from the (1-3) unsaturated monomer containing a lactone group may be 1 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the copolymer. Within the above range, developability and exposure sensitivity for a developer may be improved.

(1-4) A structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3)

Specific examples of the unsaturated monomer different from the structural units (1-1) to (1-3) include an aromatic ring-containing ethylenically unsaturated monomer, an N-substituted maleimide monomer, and other ethylenically unsaturated monomers.

Specific examples of the aromatic ring-containing ethylenically unsaturated monomer include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonyl Phenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; Styrene; Styrene having an alkyl substituent such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; Styrene having halogens such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; Styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, and propoxystyrene; At least one or more selected from the group consisting of acetylstyrene, vinyltoluene, divinylbenzene, (o,m,p)-vinylbenzylmethyl ether, and (o,m,p)-vinylbenzyl glycidyl ether. In particular, styrene is preferably used from the viewpoint of polymerization, and benzyl (meth)acrylate or phenyl (meth)acrylate is preferably used from the viewpoint of the residual film rate.

Examples of the N-substituted maleimide monomer include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt- Butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-methoxyphenylmaleimide Mid, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-naphthylmaleimide, or mixtures thereof, preferably N-phenylmaleimide, N-cyclohexylmaleimide in terms of improving the residual film rate. Or a mixture thereof is mentioned, More preferably, N-phenylmaleimide is used.

Specific examples of the other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) Acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxy Methyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) Acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol)methyl ether (meth)acrylate, tetrafluoro Lopropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylic Rate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylic Unsaturated carboxylic acid esters including rates; N-vinyl tertiary amines including N-vinyl such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; And unsaturated ethers including vinyl methyl ether and vinyl ethyl ether.

The content of the constituent unit (1-4) derived from an unsaturated monomer different from the above (1-1) to (1-3) is 15 to 70% by weight, preferably 20 to 50% by weight, based on the total weight of the copolymer. I can. In the above range, pattern formation is excellent.

(1-5) Constituent units derived from unsaturated monomers containing at least one epoxy group

In the present invention, the structural unit (1-5) is derived from an unsaturated monomer containing at least one epoxy group, and specific examples of the unsaturated monomer containing at least one epoxy group include glycidyl (meth)acrylate, 4-hydroxy Butyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (Meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylic Rate, α-n-butylglycidylacrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-2,3-epoxypropoxy )-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methyl allyl glycidyl ether, and mixtures thereof, preferably glycidyl in terms of room temperature storage stability and solubility. (Meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and mixtures thereof are mentioned.

The content of the structural unit derived from the unsaturated monomer containing at least one (1-5) epoxy group is 0 to 50% by weight, preferably 1 to 40% by weight, and more preferably 10 to 50% by weight based on the total weight of the copolymer. It may be 35% by weight. If it is within the above range, the storage stability of the composition is maintained, and it is advantageous in improving the residual film rate after post-curing.

In the present invention, (meth)acrylic refers to acrylic and/or methacrylic, and (meth)acrylate refers to acrylate and/or methacrylate.

In addition, the copolymer used in the present invention may have a weight average molecular weight of 500 to 50,000, preferably 1,000 to 50,000, more preferably 3,000 to 30,000. When it has a weight average molecular weight in the above range, adhesion to the substrate is improved, and excellent physical properties and chemical resistance are obtained. The weight average molecular weight refers to a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as an elution solvent).

The copolymer used in the present invention can be synthesized by a known method.

The content of the copolymer may be 50 to 95% by weight, preferably 60 to 85% by weight, based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. Within the above range, pattern development after development is good, and properties such as a film residual rate and chemical resistance are improved.

(2) photosensitizer

The photosensitive resin composition of the present invention may include a quinone diazide photosensitive agent sensitive to g, h, i-rays as the photosensitive agent, and the quinone diazide photosensitive agent generates a carboxylic acid by irradiation with radiation. It is a 1,2-quinone diazide compound, and a condensation product of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinone diazide sulfonic acid halide can be used.

As the parent nucleus, for example, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone or (polyhydroxyphenyl)alkane may be used.

Specific examples of these include, for example, trihydroxybenzophenone, such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone; As tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc.; As pentahydroxybenzophenone, 2,3,4,2',6'- pentahydroxybenzophenone, etc.; As hexahydroxybenzophenone 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; As (polyhydroxyphenyl)alkane, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tri(p-hydroxyphenyl)methane, 1,1,1-tri( p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris( 2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene] Bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'spirobiindene-5,6,7 ,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxypropane, etc.; As other parent nuclei, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychromen, 2-[bis{(5-isopropyl- 4-hydroxy-2-methyl)phenyl}methyl]benzene, 1-[1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)- 1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl)benzene, 4, 6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene.

In addition, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the parent nucleus exemplified above is changed to an amide bond, such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid amide and the like are also preferably used.

In addition, as the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, it is preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

The amount of the parent nucleus and 1,2-naphthoquinone diazide sulfonic acid halide used in the condensation reaction may be 1.0 to 6.0 moles, preferably 1.0 to 5.0 moles of 1,2-naphthoquinone diazide sulfonic acid halide per 1 mole of the parent nucleus. have. The condensation reaction can be carried out by a known method.

The quinone diazide-based photosensitive agent may be a compound represented by the following Formula 3 in terms of excellent sensitivity and high film residual rate:

In the above formula,

Each R is independently hydrogen or a compound of the following formula 3a or 3b, of which at least one is a compound of formula 3a or 3b.

[Formula 3a]

[Formula 3b]

The photosensitizer may be used in an amount of 0.5 to 40 parts by weight, preferably 10 to 30 parts by weight based on 100 parts by weight of the copolymer (based on solid content). In the above range, excellent sensitivity and excellent developability can be exhibited.

(3) Epoxy compound

The epoxy-based compound used in the present invention is a compound containing a repeating unit represented by the following formula (4):

In the above formula,

R ⁵ is hydrogen or C ₁ -C ₄ Alkyl;

R ⁶ is C ₁ -C ₁₀ alkylene, phenylene, C ₃ -C ₁₀ cycloalkylene, C ₃ -C ₁₀ heterocycloalkylene or C ₂ -C ₁₀ heteroalkylene, wherein R ⁶ is at least one hydroxy group Can be substituted with

The term "heteroalkylene" used in the present invention means an alkylene containing one or more heteroatoms selected from O, S, and N in the chain unless otherwise stated.

Specific examples of R ⁵ in Formula 4 may include hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, and tert-butyl, and preferably hydrogen or methyl.

Specific examples of R ⁶ include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, -C ₂ H ₄ -OC ₂ H ₄ -, -C ₄ H ₈ -OC ₄ H ₈ -, -C ₄ H ₈ -O-CH ₃ -, -C ₄ H ₈ -OC ₂ H ₄ -, -C ₂ H ₄ -O-CH ₃ -, -C ₂ H ₄ -COO -C ₂ H ₄ -, -C ₄ H ₈ -COO-C ₄ H ₈ -, -C ₄ H ₈ -COO-CH ₃ -, -C ₄ H ₈ -COO-C ₂ H ₄ -, -C ₂ H ₄ -COO-CH ₃ -, -C ₂ H ₄ -OCONH-C ₂ H ₄ -, and -C ₂ H ₄ -CH(OH)-C ₂ H ₄ -, and the like, preferably methylene Or -C ₄ H ₈ -O-CH ₃ -.

The weight average molecular weight of the epoxy-based compound including the repeating unit of Formula 4 used in the present invention may be 1,000 to 9,000, preferably 1,000 to 7,000, more preferably 2,000 to 5,000. When it has a weight average molecular weight in the above range, adhesion is improved and has excellent chemical resistance. The weight average molecular weight refers to a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as an elution solvent).

The epoxy-based compound can be synthesized by a known method.

The epoxy compound may be used in an amount of 0.5 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the copolymer (based on solid content). If it is within the above range, excellent residual film rate and chemical resistance may be implemented.

(4) phenolic compounds

The phenolic compound used in the present invention is a compound having the structure of the following formula 5 or 6, or both:

In the above formula,

R ⁷ , R ⁸ and R ⁹ are each independently C ₁ -C ₆ alkylene or C ₆ -C ₁₂ arylene, and the alkylene and arylene are at least one halogen, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl.

Specific examples of the phenolic compound include compounds of the following formulas (7) and (8).

The phenolic compound may be used in an amount of 0.2 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the copolymer (based on the solid content). Within the above range, high sensitivity and excellent developability can be exhibited.

(5) solvent

The photosensitive resin composition of the present invention may be prepared by a conventional method, and preferably may be prepared as a liquid composition obtained by mixing the above-described components with a solvent. In the photosensitive resin composition according to the present invention, the content of the solvent is not particularly limited, but from the viewpoint of coating properties and stability of the obtained photosensitive resin composition, the solid content is 5 to 70% by weight, preferably based on the total weight of the composition. May include a solvent such that 10 to 50% by weight.

In the above, the solid content means removing the solvent from the composition of the present invention.

Specific examples of such a solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; Cellosolves such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolactone; And mixtures thereof. Among these, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are more preferable from the viewpoint of good coating properties and high stability.

(6) Other ingredients

The present invention may further include other components to improve the properties of the photosensitive resin composition. Examples of the other components include (6-1) surfactant and/or (6-2) silane coupling agent.

(6-1) surfactant

If necessary, the positive photosensitive resin composition of the present invention may further include a surfactant for improving coating properties and preventing defects. The type of the surfactant is not particularly limited, but preferably, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and other surfactants are mentioned. Examples of the surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F -482, F-489 (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Florade FC-135, Florade FC-170C, Florade FC-430, Florade FC-431 (Sumitomo 3M Co., Ltd.) Manufacture), Supron S-112, Supron S-113, Supron S-131, Supron S-141, Supron S-145, Supron S-382, Supron SC-101, Supron SC-102 , Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF301, Ftop 303, Ftop 352 (Shin Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicon Co., Ltd.), DC 3PA, DC7PA, SH11PA, SH21PA, SH8400, GE, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF Fluorine-based and silicone-based surfactants such as -4446, TSF-4460, TSF-4452 (manufactured by Toshiba Silicon Corporation), and BYK-333 (manufactured by BYK Corporation); Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , And nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; And organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Yuji Kagaku High School Co., Ltd.), and the like. These can be used alone or in combination of two or more.

The surfactant may be used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the copolymer (based on solid content). In the above range, the coating of the composition becomes smooth.

(6-2) Silane coupling agent

The photosensitive resin composition according to the present invention may further include a silane coupling agent as an adhesive agent in order to improve adhesion between the coating film and the substrate. Such a silane coupling agent may have a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, an imidazole group, a thiol group, or an amine group. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and And mixtures of these.

The silane coupling agent may be used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the copolymer (based on solid content). In the above range, the adhesion to the substrate becomes good.

In addition, the photosensitive resin composition of the present invention may contain other additives such as a dissolution accelerator, a sensitizer, an antioxidant, and a light stabilizer (ultraviolet absorber) within a range that does not harm physical properties.

In addition, the present invention provides a cured film prepared by using the positive photosensitive resin composition.

The cured film may be prepared by a method known in the art, for example, applying the positive photosensitive resin composition on a substrate and then curing it. More specifically, in the curing, the composition applied on the substrate is pre-bake at 60 to 130° C. for 60 to 130 seconds to remove the solvent, and then exposed using a photomask having a desired pattern, and a developer ( Example: A pattern can be formed on the coating layer by developing with a tetramethylammonium hydroxide solution (TMAH). Thereafter, if necessary, the patterned coating layer may be post-bake at 150 to 300° C. for 10 minutes to 5 hours to prepare a desired cured film. The exposure may be performed at an exposure amount of 20 to 100 mJ/cm 2 in a wavelength range of 200 to 450 nm.

As described above, when a cured film is formed using the positive photosensitive resin composition according to the present invention, a cured film having high pattern formation, excellent film residual rate, and chemical stability can be achieved with excellent sensitivity.

The cured film prepared according to the present invention can be usefully used as an interlayer insulating film of a liquid crystal display due to its excellent physical properties. Accordingly, the present invention provides an electronic component including an insulating film made of the cured film.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

The weight average molecular weight described in the following Preparation Examples is a polystyrene conversion value measured by gel permeation chromatography (GPC).

Preparation Example 1: Preparation of Copolymer A-1

In a flask equipped with a cooling tube and a stirrer, 200 parts by weight of propylene glycol monomethyl ether acetate as a solvent was added, and the temperature of the solvent was raised to 70° C. while slowly stirring, and 21.5 parts by weight of methacrylic acid, p-hydroxyphenylmethyl 13 parts by weight of methacrylate, 22.5 parts by weight of glycidyl methacrylate, 38 parts by weight of styrene, and 5 parts by weight of gamma butyrolactone methacrylate were added, followed by 2,2'-azobis (2, 3 parts by weight of 4-dimethylvaleronitrile) was added dropwise over 5 hours to carry out polymerization. The weight average molecular weight of the obtained copolymer A-1 (solid content concentration = 30% by weight) was 12,100.

Preparation Examples 2 to 14: Preparation of copolymers A-2 to A-14

Copolymers A-2 to A-14 were prepared in the same manner as in Preparation Example 1, except that the type and/or content of each component was changed as shown in Table 1 below.

Manufacturing example
Copolymer MAA HPMA CHDMMA 4HBA GMA Sty GBLMA Mw A-1 21.5 13 0 0 22.5 38 5 12100 A-2 21.5 10 0 0 22.5 41 5 12350 A-3 21.5 15 0 0 22.5 36 5 12220 A-4 21.5 13 0 0 22.5 41 2 12100 A-5 21.5 13 0 0 22.5 33 10 11900 A-6 19.5 10 0 0 22.5 43 5 12050 A-7 19.5 13 0 0 22.5 40 5 12400 A-8 19.5 16 0 0 22.5 37 5 11800 A-9 19.5 13 0 0 22.5 38 7 12350 A-10 19.5 13 0 0 22.5 35 10 11700 A-11 19.5 0 13 0 22.5 40 5 12500 A-12 21.5 0 0 15 22.5 36 5 11900 A-13 21.5 13 0 0 22.5 43 0 11700 A-14 21.5 13 0 5 22.5 38 0 11800

MAA: methacrylic acid

HPMA: hydroxyphenylmethyl methacrylate

CHDMMA: Cyclohexanedimethanol monoacrylate

4HBA: 4-hydroxybutylacrylate

GMA: glycidyl methacrylate

Sty: styrene

GBLMA: Gamma Butyrolactone Methacrylate

Preparation Example 15: Preparation of epoxy-based compound C-1

In a flask equipped with a cooling tube and a stirrer, 100 parts by weight of glycidyl methacrylate and 195 parts by weight of methyl 3-methoxypropionate as a solvent were added, and nitrogen was added thereto, and the temperature of the solvent was raised to 60° C. while stirring slowly. After adding 3 parts by weight of azobisisobutyronitrile as a photoinitiator, the polymerization reaction is carried out over 2 hours while maintaining the temperature, so that the weight average molecular weight is 3,500 and the solid content is 34.5% by weight. I got 1.

Example 1

Copolymer A-1 prepared in Preparation Example 1 100 parts by weight (solid content), (2) quinone diazide photosensitive agent (MIPHOTO TPA523, manufactured by Miwon Corporation) 22 parts by weight (solid content), (3) in Preparation Example 15 Prepared epoxy-based compound C-1 6 parts by weight (solid content), (4) phenolic compound D-1 5.8 parts by weight (solid content), (5) surfactant (FZ-2122, manufactured by Dow Corning Toray Silicone Co., Ltd.) 0.15 parts by weight (solid content), and (6) 0.22 parts by weight (solid content) of a silane coupling agent (KBE-9007, manufactured by Shin-Etsu Silicone Co., Ltd.) with 340 parts by weight of methyl 3-methoxypropionate (MMP) as a solvent for 2 hours By mixing, a liquid photosensitive resin composition was prepared.

Examples 2 to 20

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the type and content (parts by weight) of each component were changed as shown in Table 2 below.

Comparative Examples 1 to 12

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the type and content (parts by weight) of each component were changed as shown in Table 2 below.

Copolymer Photosensitizer Epoxy compound Phenolic compounds Surfactants Silane coupling agent Example 1 A-1 100 22 6 D-1 5.8 0.15 0.22 Example 2 A-1 100 22 6 D-2 17.5 0.15 0.22 Example 3 A-2 100 20.5 6 D-1 5.8 0.15 0.22 Example 4 A-2 100 20.5 6 D-2 17.5 0.15 0.22 Example 5 A-3 100 23 6 D-1 5.8 0.15 0.22 Example 6 A-3 100 23 6 D-2 17.5 0.15 0.22 Example 7 A-4 100 22 6 D-1 5.8 0.15 0.22 Example 8 A-4 100 22 6 D-2 17.5 0.15 0.22 Example 9 A-5 100 22 6 D-1 5.8 0.15 0.22 Example 10 A-5 100 22 6 D-2 17.5 0.15 0.22 Example 11 A-6 100 20.5 6 D-1 5.8 0.15 0.22 Example 12 A-6 100 20.5 6 D-2 17.5 0.15 0.22 Example 13 A-7 100 22 6 D-1 5.8 0.15 0.22 Example 14 A-7 100 22 6 D-2 17.5 0.15 0.22 Example 15 A-8 100 20.5 6 D-1 5.8 0.15 0.22 Example 16 A-8 100 20.5 6 D-2 17.5 0.15 0.22 Example 17 A-9 100 22 6 D-1 5.8 0.15 0.22 Example 18 A-9 100 22 6 D-2 17.5 0.15 0.22 Example 19 A-10 100 22 6 D-1 5.8 0.15 0.22 Example 20 A-10 100 22 6 D-2 17.5 0.15 0.22 Comparative Example 1 A-11 100 22 - - - 0.15 0.22 Comparative Example 2 A-12 100 22 - - - 0.15 0.22 Comparative Example 3 A-13 100 22 - - - 0.15 0.22 Comparative Example 4 A-14 100 22 - - - 0.15 0.22 Comparative Example 5 A-11 100 22 6 D-1 5.8 0.15 0.22 Comparative Example 6 A-11 100 22 6 D-2 17.5 0.15 0.22 Comparative Example 7 A-12 100 22 6 D-1 5.8 0.15 0.22 Comparative Example 8 A-12 100 22 6 D-2 17.5 0.15 0.22 Comparative Example 9 A-13 100 22 6 D-1 5.8 0.15 0.22 Comparative Example 10 A-13 100 22 6 D-2 17.5 0.15 0.22 Comparative Example 11 A-14 100 22 6 D-1 5.8 0.15 0.22 Comparative Example 12 A-14 100 22 6 D-2 17.5 0.15 0.22

(D-1: compound of formula 7, manufacturer: Miwon Corporation)

(D-2: compound of formula 8, manufacturer: Othsuka Chemical Co., Ltd.)

A film was prepared from the photosensitive resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 12, and the sensitivity, pattern formation, and post-curing residual film rate were measured when the cured film was prepared, and the results are shown in Table 3 below. Done.

1. Sensitivity measurement

[Preparation of specimen]

The photosensitive resin composition was spin-coated on a silicon substrate and then pre-cured for 90 seconds on a high-temperature plate maintained at 100° C. to form a dry film having a thickness of 4.0 μm. After applying a mask having a square hole pattern with a difference of 1 μm in size from 1 to 15 μm on the top of the film, an aligner (model name MA6) emitting a wavelength of 200 to 450 nm was used, and the mask and The spacing between the substrates is 25 µm, and 15 mW/cm ² based on 365 nm is exposed for a certain period of time to be 0 to 200 mJ/cm 2, and 2.38 wt% tetramethylammonium hydroxide aqueous developer at 23° C. Each specimen was prepared by developing through a spray nozzle.

[Sensitivity measurement]

By the above process, exposure energy for implementing a CD (critical dimension: line width, unit: µm) of 10 µm of a patterned hole pattern for a mask size of 10 µm was obtained.

2. Pattern formation evaluation (exposure amount: 70 mJ/㎠, mask size: 10 μm)

In the manufacturing process of the specimen for measuring the sensitivity, an exposure amount of 70 mJ/cm 2 was applied and the patterned hole pattern was measured for a mask size of 10 µm, and a pattern formability (%) value was obtained from the following equation. It can be said that the smaller the pattern formability value, the better.

Pattern formation (%)=[(mask size-CD of hole pattern)/(mask size)]X100

3. Evaluation of residual film rate after post-curing

In the preparation of the specimen, the cured film obtained through precuring without applying a mask was heated in a convection oven at 230° C. for 30 minutes to obtain a cured film after post-curing. The film thickness after pre-curing and the film thickness after post-curing were measured with a film thickness evaluation device (trade name Nanospec.), and the value of the residual film ratio (%) after post-curing was obtained from the following equation. It can be said that the higher the value of the residual film rate after post-curing, the better.

Percentage of residual film after post-curing (%) = (film thickness after post-curing / film thickness after pre-curing) X100

Sensitivity [mJ/cm ² ] Pattern formation [%] Film residual rate after post-curing [%] Example 1 75 3 77 Example 2 75 2 77 Example 3 90 14 79 Example 4 90 11 78 Example 5 65 -4 76.5 Example 6 65 -4 76 Example 7 80 3 79 Example 8 80 2.5 79 Example 9 70 0 76 Example 10 70 0 76 Example 11 110 8 81 Example 12 110 7.5 81 Example 13 100 6 80.5 Example 14 100 6 80 Example 15 90 4.5 76 Example 16 90 4 76.5 Example 17 95 5.5 77.5 Example 18 95 5.5 77 Example 19 70 0 76.5 Example 20 70 0 76 Comparative Example 1 160 30 73 Comparative Example 2 >200 100 74 Comparative Example 3 160 35 73 Comparative Example 4 160 35 73 Comparative Example 5 120 20 77 Comparative Example 6 120 20 76 Comparative Example 7 >200 100 77 Comparative Example 8 >200 100 77 Comparative Example 9 120 25 76 Comparative Example 10 120 20 77 Comparative Example 11 140 25 78 Comparative Example 12 140 25 77.5

From the experimental results in Table 3, it was found that when a cured film was prepared using the photosensitive resin composition of Examples 1 to 20 according to the present invention, it not only had excellent sensitivity and pattern formation, but also had a high post-curing residual film rate I can.

On the other hand, the photosensitive resin compositions of Comparative Examples 1, 2, 5, 6, 7 and 8 have low sensitivity and poor pattern formation due to the absence of a hydroxyphenyl group in the copolymer (alkali-soluble binder), and Comparative Example 3, It can be seen that the photosensitive resin compositions of 4, 9, 10, 11 and 12 are poor in sensitivity and pattern formation due to the absence of lactone groups in the copolymer (alkali-soluble binder).

Claims (8)

(1) (1-1) a structural unit derived from an unsaturated monomer containing a carboxyl group, (1-2) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1-3) an unsaturated monomer containing a lactone group A copolymer comprising a derived structural unit, and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3);
(2) photosensitizer
(3) epoxy compounds; And
(4) a phenolic compound; including,
The copolymer contains the structural unit (1-1) in an amount of 16 to 35% by weight based on the total weight of the copolymer, and the structural unit (1-3) is included in an amount of 1 to 15% by weight,
The epoxy-based compound is a compound containing a repeating unit of the following formula (4),
The photosensitive resin composition, characterized in that the phenolic compound is a compound having a structure represented by the following Formula 5 or 6, or both:
[Formula 4]

In the above formula,
R ⁵ is hydrogen or C ₁ -C ₄ alkyl;
R ⁶ is C ₁ -C ₁₀ alkylene, phenylene, C ₃ -C ₁₀ cycloalkylene, C ₃ -C ₁₀ heterocycloalkylene or C ₂ -C ₁₀ heteroalkylene, wherein R ⁶ is at least one hydroxy group Can be substituted with
[Formula 5]

[Formula 6]

In the above formula,
R ⁷ , R ⁸ and R ⁹ are each independently C ₁ -C ₆ alkylene or C ₆ -C ₁₂ arylene, and the alkylene and arylene are at least one halogen, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl. The method of claim 1,
A photosensitive resin composition, characterized in that the structural unit derived from the unsaturated monomer containing the (1-2) phenolic hydroxyl group is represented by the following formula (1):
[Formula 1]

In the above formula,
R ¹ is hydrogen, C ₁ -C ₆ alkyl, halogen or cyano;
R ² is C ₁ -C ₆ alkyl, a is an integer of 0 to 4, and when a is an integer of 2 or more, a plurality of R ² may be the same or different from each other;
b is an integer from 1 to 5, and the sum of a and b is an integer from 1 to 5;
Y is a single bond or C ₁ -C ₆ alkylene;
The alkyl and alkylene may be substituted with one or more halogen, nitro, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl. The method of claim 1,
A photosensitive resin composition, characterized in that the structural unit derived from the unsaturated monomer containing the (1-3) lactone group is represented by the following formula (2):
[Formula 2]

In the above formula,
R ³ is hydrogen, C ₁ -C ₆ alkyl, halogen or cyano;
R ⁴ is C ₁ -C ₆ alkyl, m is an integer of 0 to 11, and when m is an integer of 2 or more, a plurality of R ⁴ may be the same or different from each other;
n is an integer from 0 to 4, and m≦2n+3;
X is a single bond or C ₁ -C ₆ alkylene;
The alkyl and alkylene may be substituted with one or more halogen, nitro, C ₁ -C ₆ alkoxy or C ₆ -C ₁₂ aryl. The method of claim 1,
The copolymer contains the structural units (1-2) and (1-4) in an amount of 5 to 40% by weight and 15 to 70% by weight based on the total weight of the copolymer, and further (1-5) an epoxy group A photosensitive resin composition comprising a constituent unit derived from an unsaturated monomer containing one or more in an amount of 0 to 50% by weight. The method of claim 1,
The photosensitive resin composition, characterized in that the photosensitive agent is a quinone diazide photosensitive agent having the structure of the following formula (3):
[Formula 3]

In the above formula,
Each R is independently hydrogen or a compound of the following formula 3a or 3b, of which at least one is a compound of formula 3a or 3b.
[Formula 3a]

[Formula 3b]

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