KR102069746B1 - 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, comprising: (1) a structural unit derived from a (1-1) carboxyl group-containing unsaturated monomer, and (1-2) one or more epoxy groups. A copolymer comprising a structural unit derived from an unsaturated monomer and a structural unit derived from a divinyl monomer containing (1-3) an acetal skeleton; (2) quinonediazide-based photoactive compounds; And (3) a photosensitive acid generator, the positive photosensitive resin composition of the present invention not only has excellent sensitivity, high residual film ratio after development and post curing, but also provides high pattern formation property, thereby providing liquid crystal display. It can be usefully used for the manufacture of an insulating film for a device.

Description

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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition and a cured film prepared therefrom, and more particularly, as an interlayer insulating film material of a thin film transistor (TFT) array of a liquid crystal display (LCD). It relates to a positive photosensitive resin composition and a cured film prepared therefrom that can be used.

The TFT substrate used for the liquid crystal display device has an interlayer insulating film for protecting the TFT array element between the TFT element and the transparent conductive film forming the pixel electrode, and the insulating film is formed by the drain electrode and the transparent conductive film of the TFT array. Contact holes are formed for connecting the wirings, which are required for the insulating film to have high light transmittance, chemical stability and excellent interlayer adhesion.

Positive and negative photosensitive resin compositions are used as materials for such interlayer insulating films.

Conventional positive photosensitive compositions comprising alkali-soluble resins and 1,2-quinonediazide compounds are thermally decomposed at the time of hard bake after exposure and development, and upon absorption of short wavelengths such as ultraviolet rays, resulting in coloration or impurities. There was a problem that the afterimage caused in the liquid crystal display device.

Accordingly, various studies have been conducted on the positive photosensitive resin composition having more improved physical properties (Korean Patent Publication No. 10-2004-0078554). However, such a photosensitive resin composition achieved relatively high transparency, but was not satisfactory in terms of sensitivity.

Korean Patent Publication No. 10-2004-0078554

Accordingly, it is an object of the present invention to provide a positive photosensitive resin composition and a cured film prepared therefrom that can not only have excellent sensitivity, high residual film ratio after development and post curing, but also can provide high pattern formability.

In order to achieve the above object, the present invention provides a structural unit derived from (1) (1-1) a carboxyl group-containing unsaturated monomer, (1-2) a structural unit derived from an unsaturated monomer containing one or more epoxy groups, and ( 1-3) a copolymer comprising a structural unit derived from a divinyl monomer containing an acetal skeleton; (2) quinonediazide-based photoactive compounds; And (3) provides a photosensitive resin composition comprising a photoacid generator (photoacid generator).

The positive type photosensitive resin composition of the present invention not only has excellent sensitivity, high residual film ratio after development and post curing, but also can provide high pattern formability, so that the positive photosensitive resin composition can be usefully used for the production of a cured film that can be used as an insulating film for liquid crystal display devices. Can be.

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, and (1-3) a copolymer comprising a structural unit derived from a divinyl monomer containing an acetal skeleton; (2) quinonediazide-based photoactive compounds; And (3) a photoacid generator, and optionally, (4) a solvent, (5) other components as (5-1) surfactants and / or (5-2) silane coupling agents. It may further comprise.

Hereinafter, the structural component of this invention is demonstrated concretely.

(1) copolymer

The copolymer includes 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, and (1-3) an acetal skeleton It may include a structural unit derived from a divinyl monomer, and may further include a structural unit derived from (1-4) unsaturated monomers different from the structural units (1-1) to (1-3), if necessary. have.

(1-1) Structural units derived from carboxyl group-containing unsaturated monomers

The said carboxyl group-containing unsaturated monomer can illustrate unsaturated carboxylic acids, such as unsaturated polyhydric carboxylic acid which has 1 or more carboxyl groups in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and 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 view of developability, and methacrylic acid is more preferable in view of polymerization.

The content of the structural unit derived from the (1-1) carboxyl group-containing unsaturated monomer is 5 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 45% by weight based on the total weight of the copolymer. Can be. If it is the said range, exposure sensitivity will improve and it can maintain favorable developability.

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

In the present invention, the structural unit (1-2) is derived from an unsaturated monomer containing one or more epoxy groups, and specific examples of the unsaturated monomer containing one or more epoxy groups include glycidyl (meth) acrylate and 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-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) is 1 to 50% by weight, preferably 1 to 40% by weight, more preferably 3 to 1% by weight of the copolymer. 35 weight percent. The storage stability of a composition is maintained in it being the said range, and it is advantageous for the improvement of the residual film ratio after postcure.

(1-3) Structural unit derived from divinyl monomer containing acetal skeleton

In the present invention, the structural unit (1-3) is derived from a divinyl monomer including an acetal skeleton, and the divinyl monomer including the acetal skeleton may be represented by the following Chemical Formula 1.

In Formula 1, R ₁ is each independently a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, or an arylene group, alkylarylene group or arylalkylene group having 6 to 12 carbon atoms, The alkylene group may have a carbonyl group, an ether bond or both in the main chain, and R ₂ and R ₃ are each independently hydrogen or a linear alkyl group having 1 to 4 carbon atoms.

As said substituent, a nitro group, an acetylamine group, a C1-C6 alkoxy group, or a monocyclic aryl group etc. are mentioned.

As a preferable example of the divinyl monomer containing the said acetal frame | skeleton, the monomer represented by following formula (2) or formula (3) is mentioned.

The content of the structural unit derived from the divinyl monomer containing the (1-3) acetal skeleton is 0.1 to 50% by weight, preferably 0.1 to 25% by weight, more preferably 1 to 15, based on the total weight of the copolymer. Weight percent. Within this range, high pattern formability can be realized.

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

The copolymer of the present invention may further include structural units derived from unsaturated monomers different from the structural units (1-1) to (1-3) as the structural unit (1-4).

Specific examples of the unsaturated monomers different 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 ethylenically unsaturated monomer include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and p-nonyl Phenoxy polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; Styrene; Styrene with alkyl substituents such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; Styrenes having halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodine styrene; Styrenes having alkoxy substituents such as methoxy styrene, ethoxy styrene, propoxy styrene; And at least one or more selected from the group consisting of acetyl styrene, vinyl toluene, divinyl benzene, (o, m, p) -vinylbenzylmethyl ether, and (o, m, p) -vinylbenzyl glycidyl ether. In particular, in view of the residual film ratio, benzyl (meth) acrylate is preferable.

Examples of the N-substituted maleimide monomers include N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide and Nt-butyl Maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-bromophenyl maleimide, N-methoxyphenyl maleimide , N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-naphthylmaleimide or mixtures thereof, and preferably N-phenylmaleimide, N-cyclohexylmaleimide or the like in terms of improving the residual film ratio. The mixture is mentioned, More preferably, N-phenylmaleimide is mentioned.

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, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylic Rate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, glycerol ( Meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxy (Meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tripropylene 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, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth Unsaturated carboxylic acid esters including) acrylate and dicyclopentenyloxyethyl (meth) acrylate; N-vinyl tertiary amines including N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine; And unsaturated ethers containing 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 above (1-1) to (1-3) is 0 to 70% by weight, preferably 15 to 70% by weight based on the total weight of the copolymer %, More preferably 20 to 65% by weight. It is excellent in pattern formation property in it being the said range.

In the present invention, (meth) acryl refers to acryl and / or methacryl, 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. In the case having the weight average molecular weight in the above range, the adhesion to the substrate is improved, and has excellent physical properties and 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 eluting solvent).

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

Since the copolymer of the present invention includes an acetal skeleton in the molecule, when the positive photosensitive resin composition comprising the copolymer is coated on a substrate, and dried and then exposed to light, the acetal group is broken by the photosensitive acid generator and the weight of the copolymer is reduced. The average molecular weight (Mw) is reduced, which causes the exposed portion to have high pattern formation and excellent sensitivity, and the non-exposed portion secures a residual film and improves chemical resistance.

The content of the copolymer 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. The pattern development after image development is favorable in it being the said range, and characteristics, such as a residual film rate and chemical resistance, improve.

(2) quinonediazide photosensitive agent

The photosensitive resin composition of this invention contains the quinonediazide type photosensitizer which responds to g, h, i-rays, The said quinonediazide type photosensitizer 1,2-quinone which generate | occur | produces a carboxylic acid by irradiation of a 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.

As said mother nucleus, it may be trihydroxy benzophenone, tetrahydroxy benzophenone, pentahydroxy benzophenone, hexahydroxy benzophenone, or (polyhydroxyphenyl) alkanes, etc., for example.

As specific examples of these, for example, 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 etc. as hexahydroxy benzophenone; 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-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.

Moreover, the 1, 2- naphthoquinone diazide sulfonic acid amides which changed the ester bond of the above-mentioned mother-nucleus into an amide bond, for example, 2,3, 4- trihydroxy benzophenone- 1, 2- naphthoquinone Diazido-4-sulfonic acid amide and the like are also preferably used.

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 diazido-4-sulfonic acid chloride and 1, 2-naphthoquinone diazido-5-sulfonic acid chloride is mentioned. Among them, it is preferable to use 1,2-naphthoquinone diazido-5-sulfonic acid chloride.

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. The condensation reaction can be carried out by a known method.

The quinonediazide-based photosensitive agent may be a compound represented by the following Chemical Formula 4 in terms of excellent sensitivity and high residual film ratio:

In Formula 4, R is independently hydrogen, a compound of Formula 5 or Formula 6, at least one of which is a compound of Formula 5 or Formula 6.

The quinonediazide-based 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. It is possible to exhibit excellent sensitivity and excellent developability 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-rays, and the photosensitive acid generator includes visible light, ultraviolet light, and ultraviolet rays. It is a compound which can generate an acid by irradiation of electron beam, X-ray, etc.

Such photosensitive acid generators include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and the like described in JP 2011-209679 A, and An oxime sulfonate compound and the acid generator of Unexamined-Japanese-Patent No. 2004-0002498 are mentioned.

Among them, preferably sulfonic acid esters of N-hydroxyimide compounds represented by the following general formula (7):

In Formula 7, R ₄ is a substituted or unsubstituted arylene group, an alkylene group or an alkenylene group, and R ₅ is a substituted or unsubstituted alkyl or aryl group.

In R ₄ and R ₅ , 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. Examples of the alkylene group include linear or branched carbon atoms of 1 to 6 carbon atoms, preferably ethylene and propylene groups, and examples of the substituent include those mentioned in the arylene group. Examples of the alkenylene group include those having 2 to 4 carbon atoms, preferably vinylidene group, and examples of the substituent include a phenyl group and the like.

Examples of the alkyl group include linear, branched or cyclic C1-12. Specifically, 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 etc. are mentioned, As a substituent, a halogen atom, a lower alkoxy group, or a monocyclic aryl group etc. are mentioned. . Examples of the aryl group include monocyclic or bicyclic ones, and preferably a phenyl group.

As a specific compound represented by the said General formula (7), 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 8 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 and the other photosensitive acid generator is in the range of 100: 0 to 10:90. It 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, based on 100 parts by weight of the copolymer (based on the solid content). If it is the said range, it can exhibit high developability and excellent sensitivity.

(4) solvent

The photosensitive resin composition of the present invention may be prepared by a conventional method, and preferably may be prepared in a liquid composition obtained by mixing the above components with a solvent. In the photosensitive resin composition according to the present invention, the content of the solvent is not particularly limited, but the solid content is 5 to 70% by weight based on the total weight of the composition, preferably from the viewpoint of coating property, stability and the like of the obtained photosensitive resin composition. May include an organic solvent to be 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; 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 them, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are more preferable from the viewpoint of having good coating properties and high stability.

(5) other ingredients

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

(5-1) surfactant

Positive type photosensitive resin composition of this invention can further contain surfactant for the effect of a coating improvement and the prevention of defect formation, as needed. Although the kind of said surfactant is not specifically limited, Preferably, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, and other surfactant are mentioned. Examples of the surfactant 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 Dainippon Ink & Chemicals Co., Ltd.), Florade FC-135, Florade FC-170C, Florade FC-430, Florade FC-431 (Sumitomo ThreeM Co., Ltd.) ), Supron S-112, Supron S-113, Supron S-131, Supron S-141, Supron S-145, Supron S-382, Supron SC-101, Supron SC-102, Supron SC-103, Supron SC-104, Supron SC-105, Supron SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, F-Top 303, F-Top 352 (Shin Akita Kasei ( Note) manufactured), 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, 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- Fluorine-based and silicone-based surfactants such as 333 (manufactured by BYK Corporation); 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, 95 (manufactured by Kyoeisha Oil Co., Ltd.) and the like. 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 of the copolymer (based on the solid content). The coating of the composition is smooth in the above range.

(5-2) Silane Coupling Agent

The photosensitive resin composition according to the present invention may further include a silane coupling agent as an adhesive aid to improve adhesion between the coating film and the substrate. Such silane coupling agents may have reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, imidazole groups, thiol groups, amine groups and the like. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and 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 of the copolymer (based on the solid content). Adhesive force with a board | substrate becomes favorable in the said range.

In addition, the photosensitive resin composition of this invention can contain other additives, such as a dissolution accelerator, a sensitizer, antioxidant, a light stabilizer (ultraviolet absorber), within the range which does not impair physical properties.

Moreover, this invention provides the cured film manufactured using the said 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 the same. More specifically, the curing is performed by pre-bake the composition applied on the substrate at 60 to 130 ℃ for 60 to 130 seconds to remove the solvent, and then exposed using a photomask in which a desired pattern is formed and developing solution ( Example: A pattern can be formed on the coating layer by developing with tetramethylammonium hydrooxide solution (TMAH). Thereafter, the patterned coating layer may be post-baked at 150 to 300 ° C. for 10 minutes to 5 hours, if necessary, 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 band of 200 to 450 nm.

Thus, when a cured film is formed using the positive photosensitive resin composition which concerns on this invention, the cured film which has a high pattern formability of a pattern, the outstanding residual ratio, and chemical stability can be achieved with the outstanding sensitivity.

The cured film prepared 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 only for illustrating the present invention, and the scope of the present invention is not limited thereto.

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

Preparation Example 1 Preparation of Copolymer A

200 parts by weight of methyl 3-methoxypropionate as a solvent was added to the 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 14.55 parts by weight of methacrylic acid and glycidyl methacrylate. 24.02 parts by weight, 29.91 parts by weight of styrene, 14.63 parts by weight of N-phenylmaleimide, 2-methyl-5-((1- (2-((2-methylallyl) oxy) ethoxy) ethyl) peroxy) pentene 5.89 By weight and 11.00 parts by weight of methyl methacrylate were added, and then 10 parts by weight of 2,2'-azobis (dimethylvaleronitrile) as a radical polymerization initiator was added dropwise over 5 hours to carry out the polymerization reaction. The weight average molecular weight of copolymer A (solid content concentration = 30 weight%) in the obtained solution was 12,800.

Preparation Examples 2 and 3: Preparation of Copolymers B and C

Copolymers B and C 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.

Example  One

(1) 100 parts by weight of the copolymer prepared in Preparation Example 1 (solid content), (2) 19.7 parts by weight (solid content) of the 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 (FZ-2122, Dow Corning Toray Silicone Co., Ltd.) 0.1 parts by weight (solid content) and (5) silane 0.2 parts by weight (solid content) of the coupling agent (KBE-9007, manufactured by Shin-Etsu Silicone Co., Ltd.) was mixed with 359 parts by weight of methyl 3-methoxypropionate (MMP) as a solvent for 2 hours to prepare a photosensitive resin composition in a liquid form.

Examples 2-5

Except for changing the type and content of each component as shown in Table 2 below, a photosensitive resin composition was prepared in the same manner as in Example 1.

Comparative Examples 1 to 3

Except for changing the type and content of each component as shown in Table 2 below, a photosensitive resin composition was prepared in the same manner as in Example 1.

A film was prepared from the photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 to measure the sensitivity, pattern formability, post-development residual film rate, and post-cured residual film rate when the cured film was prepared. The results are shown in Table 3 below.

1. Sensitivity Measurement

Preparation of Specimen

After spin-coating the photosensitive resin composition on a silicon substrate, the film was pre-baked 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 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 on a 365 nm basis is exposed for a predetermined time to be 0 to 200 mJ / cm ² , and at 23 ° C. with a 2.38% by weight tetramethylammonium hydroxide solution. Each specimen was prepared by developing through a spray nozzle.

[Sensitivity measurement]

By the above procedure, the exposure energy for achieving 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 obtained.

2. Pattern formation evaluation (exposure amount: 50 mJ / cm 2, mask size: 10 μm)

In the manufacturing process of the specimen for measuring the sensitivity was carried out at an exposure dose of 50 mJ / ㎠, the patterned hole pattern was measured for a mask size of 10 ㎛, to obtain a pattern formability (%) value from the following equation. The smaller the pattern formability value, the better.

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

3. Evaluation of residual film rate after development

After spin-coating the photosensitive resin composition on a silicon substrate, it was precured for 90 seconds on a high temperature plate maintained at 100 ° C. to form a dry film having a thickness of 4.0 μm. It was developed through a spray nozzle at 23 ° C. with a 2.38 wt% tetramethylammonium hydrooxide aqueous developer. The film thickness obtained at this time was measured by a film thickness evaluation equipment (trade name Nanospec.), And the residual film percentage (%) value after development was obtained from the following equation. The higher the residual film ratio after development, the better.

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

4. Evaluation of Residual Rate after Post-cure

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

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

From the experimental results of Table 3, when the cured film is prepared using the photosensitive resin compositions of Examples 1 to 5 according to the present invention, not only has excellent sensitivity and pattern formability, but also high post-development and post-curing residual film rate It can be seen that it has.

On the other hand, the photosensitive resin composition of Comparative Example 1 does not contain a photosensitive acid generator, but the sensitivity is good, but the residual film ratio is relatively lower than that of the photosensitive resin compositions of Examples 1 to 5, and the pattern formability (resolution) is not good. Able to know. In addition, since the photosensitive resin composition of Comparative Example 2 does not contain a quinonediazide-based photosensitive agent, the residual film ratio of the pattern is very low, and thus the physical characteristics of storage stability and pattern formation were not good. On the other hand, Comparative Example 3 does not include a structural unit derived from a divinyl monomer containing an acetal skeleton in the copolymer, it was found that the development speed is slow during development, so the sensitivity and pattern formation of the photosensitive resin composition is not good. .

Claims (7)

(1) (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) represented by the following formula (2) Copolymers comprising structural units derived from monomers;
(2) quinonediazide-based photoactive compounds; And
(3) photoacid generator
Photosensitive resin composition comprising a.
[Formula 2]

delete delete The method of claim 1,
The copolymer (1) is 5 to 60% by weight, 1 to 50% by weight, and 0.1 to 1 of the structural units (1-1), (1-2) and (1-3), respectively, based on the total weight of the copolymer. In an amount of 0 to 70% by weight, and in addition to (1-4) a structural unit derived from an unsaturated monomer different from the structural units (1-1) to (1-3). The photosensitive resin composition characterized by the above-mentioned.
The method of claim 1,
The quinone diazide-based photosensitive agent has a structure of the formula (4):
[Formula 4]

In Formula 4, R is independently hydrogen, a compound of Formula 5 or Formula 6, at least one of which is a compound of Formula 5 or Formula 6.
[Formula 5]

[Formula 6]

The method of claim 1,
A photosensitive resin composition, wherein the photosensitive acid generator has a structure of Formula 7 below:
[Formula 7]

In Formula 7, R ₄ is a substituted or unsubstituted arylene group, an alkylene group or an alkenylene group, and R ₅ is a substituted or unsubstituted alkyl or aryl group.
The method of claim 1,
The photosensitive acid generator has a structure of the following formula (8).
[Formula 8]