KR20140035180A - Positive-type photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

The present invention relates to a positive type photosensitive resin composition and a cured film manufactured thereby. The positive type photosensitive resin composition of the present invention comprises: copolymers (1) which are produced by making a compound represented by a chemical formula 1 with an alkali soluble copolymer 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 at least one epoxy group, an organization unit (1-3) induced from an unsaturated monomer containing a phenolic hydroxyl group and an organization unit (1-4) containing an unsaturated monomer different from the unsaturated monomer of (1-1) to (1-3); quinonediazide-based photoactive compounds (2); photoacid generators (3); and solvents (4). The positive type photosensitive resin composition of the present invention exhibits excellent sensitivity, high residual film rate after phenomenon and postcuring and provides high pattern formation, thereby being able to be usefully used in the manufacture of an insulation layer for a liquid crystal display.

Description

Positive type photosensitive resin composition and cured film manufactured 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, 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.

A conventional positive photosensitive composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound is thermally decomposed upon hard bake after exposure and development and upon absorption of a short wavelength such as ultraviolet light, There is a problem that a residual image is generated in the liquid crystal display device.

Accordingly, various studies have been conducted on positive photosensitive resin compositions having improved physical properties (Korean Patent Laid-Open No. 10-2004-0078554). 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

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, a high residual film ratio after development and post-curing, and a cured film prepared therefrom.

The present invention to achieve the above object

(1) A structural unit derived from (1-1) a carboxyl group-containing unsaturated monomer, (1-2) A structural unit derived from an unsaturated monomer containing at least one epoxy group, (1-3) containing a phenolic hydroxyl group An alkali-soluble copolymer comprising a structural unit derived from an unsaturated monomer and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3) and represented by the following general formula (1) Copolymers obtained by reacting a compound;

(2) a quinonediazide photoactive compound;

(3) photoacid generators; And

(4) Solvent

It provides a positive photosensitive resin composition comprising:

In Formula 1, R ₁ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, the alkylene group may have an ether bond in the main chain, R ₂ is It is a coupling group or a C1-C3 alkylene group.

The positive photosensitive resin composition of the present invention can provide a high pattern forming property as well as an excellent sensitivity, a high residual film ratio after development and after curing, and can be used as an insulating film for a liquid crystal display device .

The positive photosensitive resin composition according to the present invention comprises (1) a structural unit derived from (1-1) a carboxyl group-containing unsaturated monomer, (1-2) a structural unit derived from an unsaturated monomer containing at least one epoxy group, ( 1-3) Alkali including structural units derived from unsaturated monomers containing phenolic hydroxyl groups and (1-4) structural units derived from unsaturated monomers different from the structural units (1-1) to (1-3). Copolymers obtained by reacting a soluble copolymer with a compound represented by the following formula (1); (2) a quinonediazide photoactive compound; (3) photoacid generators; And (4) a solvent, and may further include (5-1) surfactants and / or (5-2) silane coupling agents as necessary, as (5) other components.

[Formula 1]

In Formula 1, R ₁ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, the alkylene group may have an ether bond in the main chain, R ₂ is It is a coupling group or a C1-C3 alkylene group.

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

(1) copolymer

The copolymer includes (1-1) a structural unit derived from a carboxyl group-containing unsaturated monomer, (1-2) a structural unit derived from an unsaturated monomer containing at least one epoxy group, and (1-3) a phenolic hydroxyl group. An alkali-soluble copolymer comprising a structural unit derived from an unsaturated monomer and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3), and the following general formula (1) It is a copolymer obtained by making the compound represented by these react.

[Formula 1]

In Formula 1, R ₁ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, the alkylene group may have an ether bond in the main chain, R ₂ is It is a coupling group or a C1-C3 alkylene group.

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

The said carboxyl group-containing unsaturated monomer can illustrate unsaturated carboxylic acid, such as unsaturated polycarboxylic acid which has 1 or more carboxyl groups in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-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 structural unit derived from the (1-1) carboxyl group-containing unsaturated monomer may be 5 to 50% by weight, preferably 10 to 45% by weight based on the total weight of the alkali-soluble copolymer. Within this range, the exposure sensitivity is improved and good developability can be maintained.

(1-2) Structural units derived from unsaturated monomers containing one or more epoxy groups

In the present invention, the constituent unit (1-2) 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 or mixtures thereof , And preferably there may be mentioned glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether or a mixture thereof from the viewpoint of room temperature storage stability and solubility.

The content of the structural unit derived from the unsaturated monomer containing one or more epoxy groups (1-2) may be 1 to 40% by weight, preferably 3 to 30% by weight based on the total weight of the alkali-soluble copolymer. The storage stability of a composition is maintained in it being the said range, and a residual film rate after postcure is advantageous for improvement.

(1-3) Structural units derived from unsaturated monomers containing phenolic hydroxyl groups

In the present invention, the structural unit (1-3) is derived from an unsaturated monomer containing a phenolic hydroxyl group, and specific examples of the unsaturated monomer containing a phenolic hydroxyl group include (o, m, p) -hydroxystyrene, (o, m, p) -isopropenylphenol, p-hydroxy-α-methylstyrene (o, m, p) -hydroxyphenyl (meth) acrylate, N-hydroxyphenylmaleimide or mixtures thereof Preferably, (o, m, p) -hydroxyphenyl (meth) acrylate is mentioned in terms of the ease of polymerization and high pattern formation. More preferably, p-hydroxyphenyl methacrylate is mentioned.

In the present invention, (o, m, p)-refers to each compound having the prefix of ortho, meta, para.

The content of the structural unit derived from the unsaturated monomer containing the (1-3) phenolic hydroxyl group may be 3 to 50% by weight, preferably 5 to 45% by weight based on the total weight of the alkali-soluble copolymer. Within this range, high pattern forming properties can be realized.

(1-4) Structural units derived from unsaturated monomers different from (1-1) to (1-3)

In the present invention, the structural unit (1-4) is derived from an unsaturated monomer different from the structural units (1-1) to (1-3), and specific examples of the unsaturated monomer 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, benzyl (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, Maleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-methoxyphenylmaleimide , N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-naphthylmaleimide or a mixture thereof, and preferably N-phenylmaleimide, N-cyclohexylmaleimide or N- And mixtures thereof. More preferred examples thereof include 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) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, hydroxyethyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, gamma -butyrolactone (meth) acrylate, glycerol Methyl acrylate, methyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, propyl? -Hydroxymethylacrylate, butyl? -Hydroxymethylacrylate, 2-methoxy (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethyleneglycol (meth) acrylate, (Ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobonyl ) Acrylates, unsaturated carboxylic acid esters including dicyclopentenyloxyethyl (meth) 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.

On the other hand, the content of the structural unit (1-4) derived from unsaturated monomers different from the structural units (1-1) to (1-3) is 10 to 65% by weight, preferably based on the total weight of the alkali-soluble copolymer. 10 to 60% by weight. Within this range, the pattern forming property is excellent.

In the present invention, (meth) acryl and (meth) acrylate refer to acrylic and / or methacryl, acrylate and / or methacrylate.

In addition, the alkali-soluble 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 a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as an eluting solvent).

Alkali-soluble copolymers used in the present invention can be synthesized by known methods.

The copolymer obtained by reacting the alkali-soluble copolymer with the compound represented by the following formula (1) includes an acetal skeleton in the molecule. Therefore, when the positive photosensitive resin composition comprising the copolymer of the present invention is coated on a substrate, dried, and then exposed, the acetal group is broken by the photosensitive acid generator to reduce the weight average molecular weight (Mw) of the copolymer. As a result, the exposed portion has high pattern formability and excellent sensitivity, and the non-exposed portion secures a residual film and improves chemical resistance.

[Formula 1]

In Formula 1, R ₁ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, the alkylene group may have an ether bond in the main chain, R ₂ is It is a coupling group or a C1-C3 alkylene group. Preferably, in view of high patternability, R ₁ may be cyclohexylene, and R ₂ may be a methylene group.

The reaction between the alkali-soluble copolymer and the compound represented by Chemical Formula 1 may be carried out by a known method, and the content of the compound represented by Chemical Formula 1 may be derived from an unsaturated monomer containing (1-3) phenolic hydroxyl group. It is preferably 1 to 15 parts by weight, preferably 1 to 10 parts by weight based on 100 parts by weight (based on the solid content) of the structural unit. It is possible to implement excellent sensitivity and high residual ratio in the above range.

The weight average molecular weight (Mw) in terms of polystyrene of the copolymer may be 6,000 to 100,000, preferably 10,000 to 80,000. In the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

The content of the binder resin may be 0.5 to 60% by weight, preferably 5 to 50% by weight based on the total weight of the photosensitive resin composition excluding the residual 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) Quinone diazide photosensitizer

The photosensitive resin composition of this invention contains the quinonediazide type photosensitizer which responds to g, h, and i-line, The said quinonediazide type photosensitizer 1,2-quinone which generate | occur | produces a carboxylic acid by irradiation of radiation. It is a diazide compound and can use the condensate of a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), and 1,2-naphthoquinone diazide sulfonic-acid halide.

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; 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 and the like; As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .; 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like as hexahydroxybenzophenone; 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 and the like; As another parent nucleus, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycycloman, 2- [bis {(5-isopropyl- 4-hydroxy-2-methyl) phenyl} methyl], 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-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-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1, 2-naphthoquinonediazido-5-sulfonic acid chloride. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

The amount of the mother nucleus and 1,2-naphthoquinone diazide sulfonic acid halide used for the condensation reaction may be 1.0 to 6.0 mol, preferably 1.0 to 5.0 mol, with respect to 1 mol of the mother nucleus. have.

Condensation reaction can be performed by a well-known method.

The quinonediazide-based photosensitive agent may be a compound represented by the following Chemical Formula 2 in terms of excellent sensitivity and high residual film ratio.

In Formula 2, R is independently hydrogen, a compound of Formula 3 or Formula 4, wherein at least one is a compound of Formula 3 or Formula 4.

The quinone diazide type photosensitive agent may be used in an amount of 0.5 to 40 parts by weight, preferably 5 to 25 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) photosensitive acid generator

The photosensitive resin composition of the present invention includes a photosensitive acid generator capable of generating an acid by light irradiation in response to g, h, and i-ray, and the photosensitive acid generator is a visible ray, ultraviolet ray, , Electron beams, and X-rays.

Examples of such photosensitive acid generators include trichloromethyl-s-triazine compounds, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and the like described in Japanese Laid-Open Patent Publication No. 2011-209679 Oxime sulfonate compounds, and acid generators disclosed in Korean Patent Publication No. 2004-0002498.

Among them, preferably sulfonic acid esters of N-hydroxyimide compounds represented by the following general formula (5).

In Formula 5, R ₃ is a substituted or unsubstituted arylene group, an alkylene group or an alkenylene group, and R ₄ is a substituted or unsubstituted alkyl group or an aryl group.

In the above R ₃ and R ₄ , the arylene group may be monocyclic, or bicyclic or more, preferably a phenylene group or a naphthylene group. Examples of the arylene group include a halogen atom, a nitro group, an acetylamine group, and the like. Can be mentioned. The alkylene group may be a straight or branched chain having 1 to 6 carbon atoms, preferably an ethylene or propylene group, and the substituent may be those mentioned in the arylene group. The alkenylene group includes those having 2 to 4 carbon atoms, preferably a vinylidene group, and the substituent includes a phenyl group and the like.

Examples of the alkyl group include linear, branched or cyclic C1-12. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, an octyl group or a nonyl group and examples of the substituent include a halogen atom, a lower alkoxy group or a monocyclic aryl group . The aryl group may be monocyclic or bicyclic, and preferably a phenyl group.

As a specific compound represented by the said Formula (5), the thing of Unexamined-Japanese-Patent No. 07-295220 and Korea Patent Publication No. 2004-0002498 is mentioned. In the sulfonic acid ester of such an N-hydroxyimide compound, preferably, the compound represented by the following Chemical Formula 6 in terms of sensitivity and room temperature storage stability.

When the photosensitive acid generator other than the sulfonic acid ester of the N-hydroxyimide compound is included, the content ratio of the sulfonic acid ester of the N-hydroxyimide compound to the other photosensitive acid generator is in the range of 100: 0 to 10:90 Which is preferable in terms of sensitivity.

The photosensitive acid generator may be used in an amount of 0.2 to 12 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the copolymer (based on the solid content). Within this range, high sensitivity and excellent developability can be exhibited.

(4) solvent

The photosensitive resin composition which concerns on this invention is manufactured by mixing and dissolving the above-mentioned component in an organic 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 an organic solvent such that the concentration of the organic solvent is 10 to 55% by weight.

Solid content in the above means that the solvent is removed from the composition of the present invention.

Specific examples of the organic 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.

(5) Other ingredients

The present invention may additionally include other components to improve the properties of the photosensitive resin composition. As said other components, a (5-1) surfactant or a (5-2) silane coupling agent etc. are mentioned, for example.

(5-1) 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- 482, F-489 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC-135, Florad FC-170C, Florad FC-430 and Florad FC-431 (manufactured by Sumitomo 3M Ltd.) Surflon S-112, Surflon SC-101, Surflon SC-102, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S- Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (manufactured by Asahi Glass Co., Ltd.), Efstop EF301, Efoptop 303, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), DC 3PA, DC 7PA, SH 11PA, SH 21PA 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 Corporation), and the like; Polyoxyethylene aryl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxy ethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl 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 copolymer polyflow No. 57, and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These can be used individually or in combination of 2 or more types.

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.

(5-2) Silane coupling agent (adhesion aid)

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, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ- Glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxy silane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, and mixtures thereof are mentioned.

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 type photosensitive resin composition which concerns on this invention, the cured film which has a high pattern formation property, the outstanding residual film rate, and chemical stability of a pattern can be achieved with the outstanding 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).

Preparation Example 1 Preparation of Alkali Soluble Copolymer a

200 parts by weight of methyl 3-methoxypropionate as a solvent was added to a flask equipped with a cooling tube and a stirrer, and the temperature of the solvent was raised to 70 ° C. while stirring slowly, followed by 34.63 parts by weight of benzyl methacrylate and γ-butyrolactone. 5.98 parts by weight of methacrylate, 17.53 parts by weight of 4-hydroxyphenylmethacrylate, 16.92 parts by weight of methacrylic acid and 24.94 parts by weight of glycidyl methacrylate were added, followed by 2,2'-azobis as a radical polymerization initiator. 10 parts by weight of (dimethylvaleronitrile) was added dropwise over 5 hours to conduct a polymerization reaction. The weight average molecular weight of the alkali-soluble copolymer a (solid content concentration = 30 weight%) in the obtained solution was 5,500.

Preparation Example 2 Preparation of Copolymer a-1

2.7 parts by weight of 1,4-cyclohexanedimethanoldivinylether (CHDVE) was added to 100 parts by weight (based on solids content) of the alkali-soluble copolymer obtained in Preparation Example 1, and reacted at 50 to 70 ° C for 5 hours. The weight average molecular weight of the obtained copolymer a-1 was 15,000.

Example 1

(1) 100 parts by weight of the copolymer a-1 prepared through Preparation Examples 1 and 2 (solid content), (2) 23.7 parts by weight (solid content) of a quinonediazide-based photosensitive agent (MIPHOTO TPA523, manufactured by Miwon Corporation), ( 3) photosensitive acid generator (NIT-PAG, ENF Technology Co., Ltd.) 3.3 parts by weight (solid content), (4) surfactant (FZ2110, Dow Corning Toray Silicone Co., Ltd.) 0.1 parts by weight (solid content) and (5) Photosensitive resin in liquid form by mixing 0.2 part by weight (solid content) of γ-glycidoxypropyltriethoxysilane with 359 parts by weight of methyl 3-methoxypropionate (MMP) as a silane coupling agent for 2 hours. The composition was prepared.

Examples 2 and 3 and Comparative Examples 1 to 3

It was prepared in the same manner as in Example 1 except for changing the type and content of each component as shown in Table 1.

Copolymer a-1
(Parts by weight) Quinone diazide system
Photosensitizer
(Parts by weight) Photosensitive
Acid generator
(Parts by weight) Surfactants
(Parts by weight) Silane coupling agent
(Parts by weight) menstruum
(Parts by weight) Example 1 100.0 20.8 3.3 0.1 0.2 359.0 Example 2 100.0 22.1 3.3 0.1 0.2 359.0 Example 3 100.0 23.4 3.3 0.1 0.2 359.0 Comparative Example 1 100.0 20.8 0.0 0.1 0.2 359.0 Comparative Example 2 100.0 0.0 3.3 0.1 0.2 359.0 Comparative Example 3 100.0 0.0 0.0 0.1 0.2 359.0

A film was prepared from the photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 to measure the sensitivity, pattern formability, post-development residual film ratio, and post-curing residual film ratio when the cured film was prepared. Is shown in Table 2 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. After applying a mask having a square hole pattern with a size difference of 1 μm from 1 to 15 μm on the top of the film, using an aligner (model name MA6) having a wavelength of 200 to 450 nm, The interval between the substrates is 25 μm, and UV light at 15 mW / cm 2 is exposed for a predetermined time to be 0 to 200 mJ / cm 2 based on 365 nm, and sprayed at 23 ° C. with a 2.38% by weight tetramethylammonium hydroxide solution. Each specimen was prepared by developing through a nozzle.

[Sensitivity measurement]

By the above procedure, the exposure energy for obtaining 10 μm of CD (critical dimension: line width, unit: μm) of the patterned hole pattern with respect to the mask size of 10 μm was determined.

2. Pattern Formability  evaluation ( Exposure dose : 50 mJ / Cm 2, mask size: 10 μm)

A patterning property (%) value was obtained from the following equation by measuring a patterned hole pattern with a mask size of 10 μm by performing an exposure dose of 50 mJ / cm 2 in the process of manufacturing the sample for sensitivity measurement. The smaller the pattern formability value, the better.

Pattern Formability (%) = [(CD of Mask Size-Hole Pattern) / (Mask Size)] × 100

3. Evaluation of residual film ratio after development

The photosensitive resin composition was spin-coated on a silicon substrate and pre-cured for 90 seconds on a high-temperature plate maintained at 100 캜 to form a dried film having a thickness of 4.0 탆. And developed with a 2.38 wt% tetramethylammonium hydroxide aqueous developer at 23 캜 through a spray nozzle. The thickness of the obtained film was measured with a film thickness evaluating equipment (trade name: Nanospec.), And the value of the residual film ratio (%) after development was obtained from the following formula. The larger the residual film ratio value after development, the better.

Residual film rate (%) = (film thickness after development / film thickness after precure) × 100

4. After curing Residual film ratio  evaluation

The film obtained in the evaluation of the residual film ratio after the development was heated in a convection oven at 230 캜 for 30 minutes to obtain a cured film. The thickness of the obtained film was measured by a film thickness evaluating equipment (trade name Nanospec.), And the value of the remaining film ratio (%) after post-curing was obtained from the following equation. The larger the residual film ratio value after the post-curing, the better.

Residual film rate (%) after postcure = (film thickness after postcure / film thickness after precure) × 100

Sensitivity [mJ / cm ² ] Pattern Formability (%) Post-development percentage Retention rate after post curing (%) Example 1 35.0 -15 77.2 66.6 Example 2 56.0 7 82.1 71.0 Example 3 67.0 19 88.0 75.3 Comparative Example 1 45.0 -2 70.9 60.7 Comparative Example 2 200.0 65 61.0 53.4 Comparative Example 3 Not rated 100 59.5 52.1

From the experimental results of Table 2, when the cured film is prepared using the photosensitive resin compositions of Examples 1 to 3 according to the present invention, not only has excellent sensitivity and pattern formability, but also high post-developmental and post-curing residual film rate It can be seen that it has.

Claims (7)

(1) A structural unit derived from (1-1) a carboxyl group-containing unsaturated monomer, (1-2) A structural unit derived from an unsaturated monomer containing at least one epoxy group, (1-3) containing a phenolic hydroxyl group An alkali-soluble copolymer comprising a structural unit derived from an unsaturated monomer and (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3) and represented by the following general formula (1) Copolymers obtained by reacting a compound;
(2) a quinonediazide photoactive compound;
(3) photoacid generators; And
(4) solvent
Photosensitive resin composition comprising:
[Chemical Formula 1]

In Formula 1, R ₁ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, the alkylene group may have an ether bond in the main chain, R ₂ is It is a coupling group or a C1-C3 alkylene group.
The method of claim 1,
In Chemical Formula 1, R ₁ is cyclohexylene, and R ₂ is a methylene group.
The method of claim 1,
The unsaturated monomer containing the said phenolic hydroxyl group is (o, m, p) -hydroxyphenyl (meth) acrylate, The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
The photosensitive resin composition includes the compound represented by Formula 1 in an amount of 1 to 15 parts by weight based on 100 parts by weight (based on solids content) of the structural unit derived from an unsaturated monomer containing the (1-3) phenolic hydroxyl group. The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
The quinone diazide-based photosensitive agent has a photosensitive resin composition, characterized in that:
(2)

In Formula 2, R is independently hydrogen, a compound of Formula 3 or Formula 4, wherein at least one is a compound of Formula 3 or Formula 4.
(3)

[Chemical Formula 4]

The method of claim 1,
The photosensitive acid composition has a structure of the following formula (5):
[Chemical Formula 5]

In Formula 5, R ₃ is a substituted or unsubstituted arylene group, an alkylene group or an alkenylene group, and R ₄ is a substituted or unsubstituted alkyl group or an aryl group.
The method of claim 1,
The photosensitive acid generator has a structure of the following formula (6).
[Chemical Formula 6]