KR20140092068A - Positive-type photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

The present invention relates to a positive type photosensitive resin composition which comprises: copolymers (1) including an organization unit (1-1) induced from an unsaturated monomer containing a carboxyl group, an organization unit (1-2) induced from an unsaturated monomer containing a phenolic hydroxyl group, an organization unit (1-3) induced from an unsaturated monomer containing a lactone group and an organization unit (1-4) induced from an unsaturated monomer different from the organization unit (1-1) through the organization unit (1-3); and a photoresist (2), and to a cured film manufactured thereby. The positive type photosensitive resin composition of the present invention has excellent sensitivity and high normalized thickness after post cure and provides high pattern formability, thereby being usefully applied in manufacture of an insulation film for a liquid crystal display.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a positive-working photosensitive resin composition and a cured film prepared therefrom. BACKGROUND OF THE INVENTION < RTI ID =

The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom, and more particularly, to a positive photosensitive resin composition useful as an interlayer insulating film material of a thin film transistor (TFT) array of a liquid crystal display And a cured film prepared from the positive photosensitive resin composition.

A TFT substrate used for a liquid crystal display device has an interlayer insulating film for protecting TFT array elements between a TFT element and a transparent conductive film forming a pixel electrode and 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. For this purpose, the insulating film is required to have high light transmittance, chemical stability, and excellent interlayer adhesion.

Positive type and negative type photosensitive resin compositions are used as the material of the interlayer insulating film.

When a conventional positive photosensitive composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound is subjected to hard bake after exposure, development, and short wavelength absorption such as ultraviolet rays, it is thermally decomposed to cause a coloring phenomenon, There is a problem that a residual image is generated in the liquid crystal display device.

Accordingly, various studies have been made on a positive photosensitive resin composition having improved physical properties (Korean Patent Laid-Open Nos. 10-2004-0078554, Korean Patent 10-0758867, and Japanese Laid-Open Patent Application No. 2004 -286968). However, such a photosensitive resin composition achieves relatively high transparency, but is not satisfactory in terms of sensitivity.

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

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

In order to achieve the above object,

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

(2) Photosensitive compound

The present invention provides a photosensitive resin composition.

The positive photosensitive resin composition of the present invention can provide a high pattern forming property as well as an excellent sensitivity and a high residual film ratio after curing and can be usefully used in the production of a cured film which can be used as an insulating film for liquid crystal display devices.

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

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

(1) Copolymer

(1) a constituent unit derived from a carboxyl group-containing unsaturated monomer, (1-2) a constituent unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1-3) an unsaturated monomer containing a lactone group (1-4) a structural unit derived from an unsaturated monomer different from the above-mentioned structural units (1-1) to (1-3), and optionally (1-5) Or more of the constituent units derived from the unsaturated monomer.

(1-1) a structural unit derived from a carboxyl group-containing unsaturated monomer

The carboxyl group-containing unsaturated monomer may be an unsaturated carboxylic acid such as an unsaturated polycarboxylic acid having at least one carboxyl group in the 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,? -Chloroacrylic acid, cinnamic acid and the like. Of these, (meth) acrylic acid is preferable in terms of developability, and methacrylic acid is more preferable in terms of polymerization.

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

(1-2) a structural unit derived from an unsaturated monomer containing a phenolic hydroxyl group

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

In this 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 s} may be the same or different;

b is an integer from 1 to 5, 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 the unsaturated monomer containing a phenolic hydroxyl group include p-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenylmethyl (meth) (Meth) acrylate, 2- (p-hydroxyphenyl) ethyl- (meth) acrylate, 2- 2- (p-hydroxyphenyl) ethyl- alpha -chloroacrylate, 2- (p-hydroxyphenyl) ethyl- alpha -bromoacrylate, 2- 2- (3-hydroxyphenyl) ethyl (meth) acrylate, 2- (3,5-dihydroxyphenyl) ethyl (meth) acrylate, 2- (Meth) acrylate, 1- (m-hydroxyphenyl) ethyl (meth) acrylate, 1- 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. Within this range, a high pattern forming property can be realized.

(1-3) a structural unit derived from an unsaturated monomer containing a lactone group

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

In this 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 m is an integer of 2 or more, the plurality of R ⁴ may be the same or different from each other;

n is an integer from 0 to 4, 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 the unsaturated monomer containing a lactone group include? - (meth) acryloyloxy-? -Butyrolactone,? - (2-trifluoromethyl) acryloyloxy-? -Butyrolactone, (2-chloro) acryloyloxy- gamma -butyrolactone, alpha - (2-bromo) acryloyloxy- gamma -butyrolactone, alpha - (2-cyano) acryloyloxy- (Meth) acryloyloxy-? -Methyl-? -Butyrolactone,? - (meth) acryloyloxy-? -Ethyl-? -Butyrolactone,? - (2-chloro) acryloyloxy- beta, beta -dimethyl- gamma -butyrolactone, beta - (meth) acryloyloxy-gamma -butyrolactone, -Butyrolactone,? - (meth) acryloyloxy-? -Methyl-? -Butyrolactone,? - (1- (meth) acryloyloxy- ? - (meth) acryloyloxy-? -valerolactone,? - (meth) acryloyloxy-? -methyl-? - valerolactone, and mixtures thereof.

The content of the constituent unit 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 this range, the developing performance and exposure sensitivity for a developing solution can be improved.

(1-4) Structural units derived from unsaturated monomers different from the above-mentioned constituent units (1-1) to (1-3)

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

Specific examples of the aromatic ring-containing ethylenic unsaturated monomer include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; Styrene; Styrene having alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; Styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, propoxystyrene; At least one selected from the group consisting of acetyl styrene, vinyl toluene, divinyl benzene, (o, m, p) -vinylbenzyl methyl ether and (o, m, p) -vinyl benzyl glycidyl ether In particular, styrene is preferable from the viewpoint of polymerizability, and benzyl (meth) acrylate or phenyl (meth) acrylate is preferable in view of the residual film ratio.

Examples of the N-substituted maleimide monomer include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Butyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, Carboxyphenylmaleimide, N-nitrophenylmaleimide, N-naphthylmaleimide, or a mixture thereof, and it is preferable to use N-phenylmaleimide, N-cyclohexylmaleimide, Or a mixture thereof, and more preferably N-phenylmaleimide.

Specific examples of the other ethylenic unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) Hydroxypropyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydroperfuryl (Meth) acrylate, glycerol (meth) acrylate, methyl? -Hydroxy (meth) acrylate, 2-hydroxy-3-chloropropyl (Meth) acrylates such as methyl acrylate, ethyl? -Hydroxymethyl acrylate, propyl? -Hydroxymethylacrylate, butyl? -Hydroxymethylacrylate, 2-methoxyethyl (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (Meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Unsaturated carboxylic acid esters including acrylate; 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 the 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 . Within this range, the pattern forming property is excellent.

(1-5) Structural unit derived from an unsaturated monomer containing at least one epoxy group

In the present invention, the constituent 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, (Meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, -ethylglycidyl acrylate, (4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, N- (4-2,3-epoxypropoxy ) -3,5-dimethylphenylpropyl) acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, and mixtures thereof. It said, and preferably there may be mentioned glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether and mixtures thereof in terms of the room temperature storage stability and solubility.

The content of the constituent unit derived from the unsaturated monomer containing at least one of (1-5) epoxy groups is 0 to 50% by weight, preferably 1 to 40% by weight, more preferably 10 to 30% by weight, 35% by weight. Within this range, the storage stability of the composition is maintained and it is advantageous to improve the residual film ratio after the post-curing.

In the present invention, (meth) acryl is acrylic and / or methacrylic, and (meth) acrylate is 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 the weight average molecular weight is in the above range, adhesion to a substrate is improved, and excellent physical properties and chemical resistance are obtained. The weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, 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 favorable, and characteristics such as residual film ratio and chemical resistance are improved.

(2) Photosensitizer

The photosensitive resin composition of the present invention may contain a quinonediazide-based photosensitizer sensitive to g, h, i-ray as the photosensitizer, and the quinonediazide-based photosensitizer may be a compound which generates a carboxylic acid A condensation product of a 1,2-quinonediazide compound and a phenolic compound or an alcoholic compound (hereinafter referred to as " parent compound ") and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

Examples of the above-mentioned mother nucleus may be trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, or (polyhydroxyphenyl) alkane.

Specific examples thereof include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like as trihydroxybenzophenone; Examples of the tetrahydroxybenzophenone include 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 and the like; As the pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like; 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like as hexahydroxybenzophenone; (P-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) methane, (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] pyrimidin- Bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1' spirobindene- , 5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxypropane and the like; (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychromene, 2- [bis { Methyl] benzene, 1- [1- (3- {1- (4-hydroxyphenyl) -1- methylethyl} -4,6-dihydroxyphenyl) - 1-methylethyl) benzene, 4, 6-dihydroxyphenyl) -1- Bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

In addition, 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the above-mentioned mother nucleus is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid amide and the like are also preferably used.

As the 1,2-naphthoquinonediazide sulfonic acid halide, 1,2-naphthoquinonediazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2- 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among them, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

The amount of 1,2-naphthoquinonediazide sulfonic acid halide used in the condensation reaction and the amount of 1,2-naphthoquinonediazide sulfonic acid halide used may be 1.0 to 6.0 moles, preferably 1.0 to 5.0 moles, of 1,2-naphthoquinonediazide sulfonic acid halide per mole of the mother 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 residual film ratio:

In this formula,

Each R is independently hydrogen or a compound of formula 3a or 3b wherein at least one is a compound of formula 3a or 3b.

[Chemical Formula 3]

(3b)

The photosensitive agent 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 (based on the solid content) of the copolymer. Excellent sensitivity and excellent developability can be exhibited in the above range.

(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 this 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 . ≪ / RTI >

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

Specific examples of R ⁵ in the above formula (4) include hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl and tert-butyl, 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 compound containing the repeating unit represented by the 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 the weight average molecular weight is in the above range, the adhesion is improved and excellent chemical resistance is obtained. The weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, tetrahydrofuran as an elution solvent).

The epoxy 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 (based on the solid content) of the copolymer. Within this range, excellent residual film ratios and chemical resistance can be realized.

(4) Phenolic compound

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

In this formula,

R ⁷ , R ⁸ and R ⁹ are each independently C ₁ -C ₆ alkylene or C ₆ -C ₁₂ arylene, wherein said alkylene and arylene are optionally substituted by one or more of halogen, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or which may be substituted with C ₆ -C ₁₂ aryl.

Specific examples of the phenolic compound include compounds represented by 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 (based on the solid content) of the copolymer. Within this 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, a liquid composition in which the above-mentioned components are mixed 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 coatability and stability of the resulting photosensitive resin composition, the solid content is preferably 5 to 70% by weight based on the total weight of the composition, May be from 10 to 50% by weight.

In the above, the solid content means that the solvent is removed 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; Cellosolve 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; 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -butyrolactone; And mixtures thereof. Of these, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are more preferable in view of good film stability and high stability.

(6) Other ingredients

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

(6-1) Surfactant

The positive-working photosensitive resin composition of the present invention may further contain a surfactant, if necessary, for the purpose of improving coatability and preventing defect formation. The kind of the surfactant is not particularly limited, but a fluorine surfactant, a silicone surfactant, a nonionic surfactant and other surfactants are preferable. Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Megafac F172, Megafac F173, Megafac F183, F- 470, F- 471, F- F-482 and F-489 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC-135, Florad FC-170C, Florad FC-430 and Florad FC- Surflon S-112, Surflon SC-101, Surflon SC-101, Surflon S-145, Surflon S-382, , Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (manufactured by Asahi Glass Co., Ltd.), Efstop EF301, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), DC 3PA, DC7PA, SH11PA, SH- FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF -4446, TSF-4460, TSF-4452 (manufactured by Toshiba Silicone Co., Ltd.), and BYK-333 (Manufactured by BYK Co., Ltd.), and the like; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, 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 an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow No. 1. 57, and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These may 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 (based on the solids content) of the copolymer. In this range, the coating of the composition is smooth.

(6-2) Silane coupling agent

The photosensitive resin composition according to the present invention may further include a silane coupling agent as an adhesion aid in order to improve the 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,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane,? - (glycidoxypropyltriethoxysilane),? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl- And mixtures thereof.

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 (based on the solid content) of the copolymer. The adhesion with the substrate is improved in the above range.

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 impair physical properties.

The present invention also provides a cured film produced using the positive photosensitive resin composition.

The cured film may be manufactured by a method known in the art, for example, a method of applying the positive photosensitive resin composition onto a substrate and then curing. More specifically, the curing is performed by pre-bake the composition coated on the substrate, for example, at 60 to 130 ° C for 60 to 130 seconds to remove the solvent, expose using a photomask having a desired pattern, For example, tetramethylammonium hydroxide (TMAH) solution, to form a pattern on the coating layer. Thereafter, the patterned coating layer may be post-baked at 150 to 300 ° C for 10 minutes to 5 hours, for example, if necessary, to produce a desired cured film. The exposure can be performed at an exposure amount of 20 to 100 mJ / cm < 2 > at a wavelength range of 200 to 450 nm.

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

The cured film produced according to the present invention can be usefully used as an interlayer insulating film of a liquid crystal display device 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 with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

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

Production 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 gradually elevated to 70 ° C with stirring. Then, 21.5 parts by weight of methacrylic acid, 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, and then 2,2'-azobis (2, 4-dimethylvaleronitrile) were added dropwise over 5 hours to carry out the polymerization reaction. The weight average molecular weight of the obtained copolymer A-1 (solid concentration = 30% by weight) was 12,100.

Production 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 kind 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-hydroxybutyl acrylate

GMA: glycidyl methacrylate

Sty: Styrene

GBLMA: gamma butyrolactone methacrylate

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

Cooling tube and stirrer, glycidyl methacrylate (100 parts by weight) and methyl 3-methoxypropionate (195 parts by weight) as a solvent were added to the flask. Nitrogen was added thereto, and the temperature of the solvent was raised to 60 ° C with gentle stirring. 3 parts by weight of azobisisobutyronitrile as a photopolymerization initiator was added and polymerization reaction was carried out for 2 hours while maintaining the temperature to obtain a compound C-9 having a weight average molecular weight of 3,500 and a solid content of 34.5% by weight, 1.

Example 1

(Solid content) of the copolymer A-1 prepared in Preparation Example 1, (2) 22 parts by weight (solid content) of a quinonediazide photosensitive agent (MIPHOTO TPA523, Phenol compound D-1 5.8 parts by weight (solid content), (5) surfactant (FZ-2122, manufactured by Dow Corning Toray Silicone Co., Ltd.) And 340 parts by weight of methyl 3-methoxypropionate (MMP), which was a solvent, and 0.25 parts by weight (solids content) of a silane coupling agent (KBE-9007, To prepare a photosensitive resin composition in the form of a liquid.

Examples 2 to 20

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the kinds and contents (parts by weight) of the respective components 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 kinds and contents (parts by weight) of the respective components were changed as shown in Table 2 below.

Copolymer Photosensitive agent Epoxy compound Phenolic compound 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: Mi Won Sang Company)

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

The films were prepared from the photosensitive resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 12, and the sensitivity, pattern forming property and post-curing residual film ratio in the production of the cured films were measured. The results are shown in Table 3 below .

1. Sensitivity measurement

[Preparation of specimen]

The photosensitive resin composition was spin-coated on a silicon substrate and pre-baked for 90 seconds on a high-temperature plate maintained at 100 캜 to form a dried film having a thickness of 4.0 탆. A mask having a square hole pattern with a size difference of 1 mu m from 1 to 15 mu m is applied to the upper portion of this film, and then an aligner (model name MA6) having a wavelength of 200 to 450 nm is used, the spacing between the substrate to 25 ㎛ with and, 365 nm reference to the 15 mW / cm ² a predetermined time exposure such that the ultraviolet 0 to 200 mJ / ㎠, and 2.38% by weight tetramethyl ammonium hydroxide aqueous developer solution in 23 ℃ Each specimen was prepared by spraying through a spray nozzle.

[Sensitivity measurement]

By the above procedure, the exposure energy for realizing a CD (critical dimension: line width, unit: 탆) of 10 탆 of a patterned hole pattern was determined for a mask size of 10 탆.

2. Pattern Formability Evaluation (exposure dose: 70 mJ / cm 2, mask size: 10 탆)

A patterning property (%) value was obtained from the following equation by measuring a patterned hole pattern with a mask size of 10 μm by applying an exposure dose of 70 mJ / cm 2 in the process of manufacturing the sample for the sensitivity measurement. The smaller the value of the pattern formability, the better.

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

3. Evaluation of residual film ratio after post-curing

In the preparation of the specimen, the cured film obtained through the preliminary curing without applying a mask was heated in a convection oven at 230 ° C for 30 minutes to obtain a post-cured cured film. The film thickness after the pre-curing and the film thickness after the post-curing were measured with a film thickness evaluating equipment (trade name Nanospec.), And the residual film percentage (%) after post-curing was calculated from the following formula. The larger the residual film ratio value after the post-curing, the better.

(%) = (Film thickness after post-curing / film thickness after pre-curing) X100

Sensitivity [mJ / cm ² ] Pattern Formability [%] Residual film ratio 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 shown in Table 3, it was found that when the cured film was prepared using the photosensitive resin compositions of Examples 1 to 20 according to the present invention, not only the excellent sensitivity and pattern forming property but also the residual film ratio after high post- .

On the other hand, the photosensitive resin compositions of Comparative Examples 1, 2, 5, 6, 7, and 8 had low sensitivity due to the absence of hydroxyphenyl groups in the copolymer (alkali soluble binder) 4, 9, 10, 11 and 12 show poor sensitivity and pattern-forming properties due to the absence of a lactone group in the copolymer (alkali-soluble binder).

Claims (8)

(1) (1) a copolymer comprising a constituent unit derived from a carboxyl group-containing unsaturated monomer, (1-2) a constituent unit derived from an unsaturated monomer containing a phenolic hydroxyl group, (1-3) (1-4) a copolymer comprising a constituent unit derived from an unsaturated monomer different from the constituent units (1-1) to (1-3); And
(2) Photosensitizer
. The method according to claim 1,
The photosensitive resin composition according to the above (1-2), wherein the constitutional unit derived from the unsaturated monomer containing a phenolic hydroxyl group is represented by the following formula (1)
[Chemical Formula 1]

In this 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 s} may be the same or different;
b is an integer from 1 to 5, 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 according to claim 1,
Wherein the constituent unit derived from the unsaturated monomer containing the (1-3) lactone group is represented by the following formula (2): < EMI ID =
(2)

In this 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 m is an integer of 2 or more, the plurality of R ⁴ may be the same or different from each other;
n is an integer from 0 to 4, 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 according to claim 1,
(1), (1-2), (1-3) and (1-4) in an amount of 5 to 50% by weight, 5 to 40% by weight, 1 to 20% by weight and 15 to 70% by weight, and further comprising 0 to 50% by weight of a constituent unit derived from an unsaturated monomer containing at least one (1-5) epoxy group Wherein the photosensitive resin composition is a photosensitive resin composition. The method according to claim 1,
Wherein the photosensitive agent is a quinonediazide photosensitive agent having a structure represented by the following formula (3): < EMI ID =
(3)

In this formula,
Each R is independently hydrogen or a compound of formula 3a or 3b wherein at least one is a compound of formula 3a or 3b.
[Chemical Formula 3]

(3b)

The method according to claim 1,
Wherein the photosensitive resin composition further comprises an epoxy compound, a phenolic compound, or both of them. The method according to claim 6,
Wherein the epoxy compound is a compound containing a repeating unit represented by the following formula (4): < EMI ID =
[Chemical Formula 4]

In this 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 . ≪ / RTI > The method according to claim 6,
Wherein the phenolic compound is a compound having a structure represented by the following formula (5) or (6), or both:
[Chemical Formula 5]

[Chemical Formula 6]

In this formula,
R ⁷ , R ⁸ and R ⁹ are each independently C ₁ -C ₆ alkylene or C ₆ -C ₁₂ arylene, wherein said alkylene and arylene are optionally substituted by one or more of halogen, nitro, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or which may be substituted with C ₆ -C ₁₂ aryl.