KR20140003087A - Photosensitive resin composition and insulating film using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an insulating film using the same. The photosensitive resin composition of the present invention comprises: a compound (1) which includes a repeating unit represented by chemical formula 1; a random copolymer (2) which includes a building unit (2-1) induced from ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, and a mixture thereof, and a building unit (2-2) induced from an ethylenically unsaturated compound containing an aromatic ring; a polymerizable unsaturated compound (3); and a photopolymerization initiator (4) and is able to be usefully used in the manufacture of an insulation film for a liquid crystal display since the photosensitive resin composition is able to provide a hardened film having the high remaining rate of a membrane while having properties such as excellent chemical resistance, adhesiveness and the likes.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND INSULATING FILM USING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and an insulating film using the same, and more particularly, to a photosensitive film for forming an insulating film used in an initial process of a thin film transistor (TFT) for a liquid crystal display (LCD). It relates to a resin composition and an insulating film produced using the same.

The TFT substrate used in 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 to have high chemical stability and good interlayer adhesion.

Positive and negative photosensitive 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 during post-bake after exposure and development, and when absorbing short wavelengths such as ultraviolet rays, resulting in coloration or impurities. There was a problem that the afterimage is caused in the liquid crystal display device.

Therefore, in order to solve this problem, a negative photosensitive composition having high light transmittance and sensitivity after thermal curing can be used.

However, recent trends in technology development require better residual film rate properties (properties on the thickness of films formed after the post-curing process), chemical resistance and interlayer adhesion.

For example, Korean Patent Publication No. 2001-0029142 includes (A) a copolymerization matrix resin containing a carboxylic acid, (B) a multifunctional monomer containing two or more ethylenically unsaturated groups, and (C) a photopolymerization initiator, wherein (D) ) A photosensitive resin composition further comprising a multifunctional epoxy monomer containing two or more epoxy groups is disclosed. Korean Patent Publication No. 2009-0059227 discloses (A) a copolymer of a polymer obtained by addition polymerization of a monomer having a carboxyl group with (a-2) a polymer obtained by addition polymerization of a styrene monomer, (B) (b- 1) a resin composition comprising a curing agent comprising a monomer having an epoxy functional group or a monomer having a (b-2) oxetane functional group, (C) a shrinkage inhibitor comprising a hydrogenated bisphenol A epoxy oligomer, and (D) a solvent. It is starting. However, the above patents do not disclose the compounds of the present invention, and do not disclose or imply any improvement in the interlayer adhesion and chemical resistance required for an interlayer insulating film such as a liquid crystal display device.

Korean Patent Publication No. 2001-0029142 Korean Patent Publication No. 2009-0059227

Accordingly, it is an object of the present invention to provide a negative photosensitive resin composition having a high residual film ratio and excellent interlayer adhesion and chemical resistance, and an insulating film prepared therefrom.

The present invention to achieve the above object

(1) a compound comprising a repeating unit represented by the following formula (1);

(2) a structural unit derived from (2-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (2-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound Random copolymers;

(3) a polymerizable unsaturated compound; And

(4) It provides the photosensitive resin composition containing a photoinitiator:

[Formula 1]

Where

R ₁ , R ₃ and R ₄ are each independently hydrogen or C ₁ -C ₄ alkyl;

R ₂ 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 ₂ is one Or more of the hydroxyl groups;

R ₅ is C ₁ -C ₁₀ alkyl, phenyl, benzyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ heterocycloalkyl or C ₂ -C ₁₀ heteroalkyl;

n is a molar ratio of 0.9 to 0.3, m is a molar ratio of 0.1 to 0.7, and n + m = 1.

The photosensitive resin composition of the present invention can provide a cured film having a high residual film ratio while having properties such as excellent chemical resistance and adhesiveness, and thus can be usefully used in the manufacture of an insulating film for a liquid crystal display device.

The photosensitive resin composition according to the present invention is (1) a compound comprising a repeating unit of the following formula (1); (2) a structural unit derived from (2-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (2-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound Random copolymers; (3) a polymerizable unsaturated compound; And (4) a photopolymerization initiator:

 [Formula 1]

Where

R ₁ , R ₃ and R ₄ are each independently hydrogen or C ₁ -C ₄ alkyl;

R ₂ 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 ₂ is one Or more of the hydroxyl groups;

R ₅ is C ₁ -C ₁₀ alkyl, phenyl, benzyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ heterocycloalkyl or C ₂ -C ₁₀ heteroalkyl;

n is a molar ratio of 0.9 to 0.3, m is a molar ratio of 0.1 to 0.7, and n + m = 1.

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

(1) a compound containing a repeating unit represented by the formula (1)

As used herein, the terms "heteroalkylene", "heterocycloalkylene", "heteroalkyl" and "heterocycloalkyl", unless otherwise indicated, refer to a heteroatom Alkylene, cycloalkylene, alkyl and cycloalkyl containing alkylene, cycloalkylene, alkyl and cycloalkyl.

Specific examples of R ₁ , R ₃ and R ₄ in Formula 1 include hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl and tert-butyl, preferably hydrogen or methyl.

Specific examples of R ₂ 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 -.

Specific examples of R ₅ include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, phenyl, benzyl and the like, preferably n-butyl, isobutyl, .

n is a molar ratio of 0.9 to 0.3, m is a molar ratio of 0.1 to 0.7, and n + m = 1.

The compound containing the repeating unit represented by formula (1) used in the present invention may be an oligomer having a weight average molecular weight of 1,000 to 9,000, preferably 1,000 to 7,000, more preferably 2,000 to 5,000. In the case of having the weight average molecular weight in the above range, adhesion is improved and has excellent chemical resistance. The weight average molecular weight refers to a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as an eluting solvent).

The compound containing the repeating unit of the formula (1) used in the present invention can be synthesized by a known method.

(2) Random copolymer

The photosensitive resin composition of the present invention comprises (2-1) a constituent unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (2-2) a constituent unit derived from an aromatic ring-containing ethylenically unsaturated compound Random copolymer comprising units < RTI ID = 0.0 > . The random copolymer may be an alkali-soluble resin that realizes developability in the development step, and may serve as a base for realizing a base role and a final pattern for forming a coating film after coating.

(2-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof

In the present invention, the constituent unit (2-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and the ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, (Meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, and anhydrides thereof; Unsaturated polycarboxylic acids of trivalent or more and their anhydrides; And mono [(meth) acryloyloxyalkyl] of divalent or higher polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate It may be at least one selected from esters, but is not limited thereto. Among them, (meth) acrylic acid can be preferably used from the viewpoint of developability.

The content of the constituent unit derived from (2-1) the ethylenically unsaturated carboxylic acid, the ethylenically unsaturated carboxylic acid anhydride, or the mixture thereof may be from 5 to 98 mol% based on the total number of moles of the constituent units constituting the random copolymer , And preferably 15 to 50 mol% in order to maintain good developability.

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

(2-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound

In the present invention, the structural unit (2-2) is derived from an aromatic ring-containing ethylenically unsaturated compound, and the aromatic ring-containing ethylenically unsaturated compound is 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; p-hydroxy-α-methylstyrene, acetylstyrene; Vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and It may be at least one or more selected from the group consisting of p-vinylbenzyl glycidyl ether, and may be preferably a styrene-based compound in particular in terms of polymerizability.

The content of the constituent unit derived from the aromatic ring-containing ethylenically unsaturated compound (2-2) may be from 2 to 95 mol% based on the total number of moles of the constituent units constituting the random copolymer, 10 to 60 mol%.

The random copolymer of the present invention may further comprise a constituent unit derived from an ethylenically unsaturated compound which is different from (2-1) and (2-2) as the constituent unit (2-3).

(2-3) a structural unit derived from an ethylenically unsaturated compound which is different from (2-1) and (2-2)

In the present invention, the constituent unit (2-3) is derived from an ethylenically unsaturated compound different from the above (2-1) and (2-2), and the ethylenic unsaturation different from the (2-1) (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, methyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, propyl? -Hydroxy (meth) acrylate, Butylmethyl acrylate, butyl? -Hydroxymethyl Acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene Glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3, 3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, isobornyl (meth Acrylic Ray , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylic Latex, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, Unsaturated carboxylic acid esters including 2,3-epoxycyclopentyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; N-vinyl tertiary amines including N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; Unsaturated ethers including vinyl methyl ether and vinyl ethyl ether; Unsaturated ethers containing epoxy groups such as allyl glycidyl ether and 2-methylallyl glycidyl ether; At least one selected from the group consisting of unsaturated imides including N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide The above may be an ethylenically unsaturated compound including an epoxy group in view of copolymerization and strength improvement of the insulating film, and preferably glycidyl (meth) acrylate.

The content of the structural unit derived from ethylenically unsaturated compounds different from the above (2-3), (2-1) and (2-2) is 0 to 50 moles based on the total moles of the structural units constituting the random copolymer. %, Preferably 10 to 45 mol%. The storage stability of the composition is maintained in the above range, and the residual film ratio is improved.

Examples of the random copolymer (2) include (meth) acrylic acid / styrene copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (Meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl methacrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl methacrylate / (Meth) acrylic acid / styrene / n-butyl (meth) acrylate / glycidyl methacrylate / glycidyl methacrylate / N-cyclohexylmaleimide copolymer, Dile methacrylate / N-phenylmaleimide copolymer, or a mixture thereof.

The content of the random copolymer (2) is 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 this range, pattern development after development is favorable, and properties such as chemical resistance are improved. The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC; tetrahydrofuran as the eluting solvent) of the random copolymer (2) is 3,000 to 50,000, preferably 5,000 to 40,000. In the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

The photosensitive resin composition of the present invention contains the compound (1) containing the repeating unit represented by the formula (1) and the random copolymer (2) in a weight ratio of 1:99 to 50:50, preferably 5:95 to 20:80 can do. Within the above range, a desirable film residual ratio can be obtained.

(3) polymerizable unsaturated compounds

The polymerizable unsaturated compound is a compound which can be polymerized by the action of a photopolymerization initiator and is a monomer, an oligomer or a polymer generally used in a photosensitive resin composition, and is an acrylic acid or methacrylic acid having at least one ethylenic unsaturated double bond Functional or multifunctional ester compound, but from the viewpoint of chemical resistance, it may preferably be a multifunctional compound having two or more functional groups.

Wherein the polymerizable unsaturated compound is at least one selected from the group consisting of ethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (Meth) acrylate, monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified di (Reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol But are not limited to, at least one selected from the group consisting of lithol octa (meth) acrylate, bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate.

In addition, a compound having two or more isocyanate groups and having a straight chain alkylene group and an alicyclic structure, and a compound having at least one hydroxyl group in the molecule and having 3, 4 or 5 acryloyloxy groups and / or methacryloyloxy And a polyfunctional urethane acrylate compound obtained by reacting a compound having a period of 1 to 30 minutes.

As said polymerizable unsaturated compound which can be purchased commercially, it is a commercial item of monofunctional (meth) acrylate, and it is Aronix M-101, copper M-111, copper M-114 (made by Toagosei Co., Ltd.), AKAYARAD TC- 110S, copper TC-120S (made by Nippon Kayaku Co., Ltd.), V-158, and V-2311 (made by Osaka Yuka Kagaku Kogyo Co., Ltd.), etc., are commercially available products of a bifunctional (meth) acrylate. Knicks M-210, M-240, M-6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335 HP (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), and the like, are commercially available products of trifunctional or higher (meth) acrylates such as Aronix M-309, M-400, M-403, M-405, M -450, East M-7100, East M-8030, East M-8060, TO-1382 (Toagosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPH1-40H, East DPC1-20, East-30, Copper-60, copper-120 (product of Nippon Kayaku Co., Ltd.), V-295, copper-300, copper-360, copper-GPT, copper-3PA, copper-400 (Osaka-yu The cultivating can be a bridge Co., Ltd.) and the like. When the polymerizable unsaturated compound is used as an oligomer or polymer, it may have a weight average molecular weight of 6000 to 10,000.

The compound (3) may be used alone or in combination of two or more. The compound (1) and the random copolymer (2) containing the repeating unit represented by the formula (1) may be used in an amount of 100 parts by weight May be used in an amount of 1 to 150 parts by weight, preferably 50 to 120 parts by weight. Pattern formation is easy in it being the said range, and the shape of a contact hole is excellent.

(4) Photopolymerization initiator

The photosensitive resin composition which concerns on this invention contains (4) photoinitiator. The photopolymerization initiator serves to initiate a polymerization reaction of monomers that can be cured by visible light, ultraviolet light, deep-ultraviolet radiation, and the like. The photopolymerization initiator may be a radical initiator, and the type thereof is not particularly limited, but may be acetophenone-based, benzophenone-based, benzoin-based and benzoyl-based, xanthone-based, triazine-based, halomethyloxadiazole-based and ropindimer-based photopolymerized initiators. One or more selected from the group consisting of can be used.

Specific examples include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl Peroxide, t-butylperoxy pivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2- (dimethylamino) -1- [4- ( 4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethyl thioxanthone, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacrylic Dine, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- (O-benzoyloxime ), o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphoro-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and mixtures thereof It may include, but is not limited to. See also KR 2004-0007700, KR 2005-0084149, KR 2008-0083650, KR 2008-0080208, KR 2007-0044062, KR 2007-0091110, KR 2007-0044753, KR 2009-0009991, KR 2009-0093933, KR 2010-0097658 And oxime compounds described in KR 2011-0059525, WO 10102502, WO 10133077.

The photopolymerization initiator is used in an amount of 0.1 to 20 parts by weight, preferably 3 to 17 parts by weight, based on 100 parts by weight (based on the solids content) of the total amount of the compound (1) and the random copolymer (2) More preferably 5 to 15 parts by weight. The residual film ratio can be improved in the above content range.

(5) Other ingredients

The present invention may further include other components for improving the properties of the photosensitive resin composition. Examples of the other components include (5-1) surfactants, (5-2) silane coupling agents and / or (5-3) solvents.

(5-1) Surfactant

The photosensitive resin composition of the present invention may further contain a surfactant, if necessary, for improving coating properties 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. Among them, BYK 333 of BYK may be preferably used in terms of dispersibility.

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-170 C, Florade FC-430, Florade FC-431 (Sumitomo 3M Co., Ltd.) Manufacture), Supron S-112, Supron S-113, Supron S-131, Supron S-141, Supron S-145, Supron S-382, Supron SC-101, Supron SC-102 , 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-Aki Kasei) Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicon Co., Ltd.), DC3PA, DC7PA, SH11PA, SH21PA , SH8400, FZ-2100, FZ-2110, 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 GE Toshiba Silicone Co., Ltd.), and BY Fluorine-based and silicone-based surfactants such as K-333 (manufactured by BYK Co., Ltd.); 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, 95 (manufactured by Kyoeisha Oil Chemical Industries, Ltd.), and the like. These can be used individually or in combination of 2 or more types.

The surfactant is used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 1 part by weight based on 100 parts by weight (based on the solids content) of the total amount of the compound (1) and the random copolymer (2) Can be used. Within this range, coating of the composition is smooth.

(5-2) Silane coupling agent

The photosensitive resin composition of the present invention is at least one or more reactive substituents selected from the group consisting of carboxyl group, (meth) acryloyl group, isocyanate group, amino group, mercapto group, vinyl group and epoxy group in order to improve adhesion to the substrate. It may further comprise a silane coupling agent having.

The kind of the silane coupling agent is not particularly limited, but trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-isocyanatopropyltrie At least 1 selected from the group consisting of oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane More than one species may be used, and preferably γ-glycidoxypropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane having an epoxy group having good adhesion to the substrate while improving the residual film ratio may be used. . To improve the chemical resistance,? -Isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) having an isocyanate group may also be used.

The silane coupling agent is used in an amount of 0.001 to 5 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight (based on the solid content) of the total amount of the compound (1) and the random copolymer (2) It can be used in quantities. If it is the said range, adhesive force with a board | substrate becomes favorable.

In addition, the photosensitive resin composition of the present invention may include other additives such as antioxidants, stabilizers, etc. within a range that does not impair physical properties.

(5-3) solvent

The photosensitive resin composition of the present invention may preferably be prepared from a liquid composition in which the above-mentioned components are mixed with a solvent.

The solvent is compatible with the above-described photosensitive resin composition components and does not react with the above photosensitive resin composition components, and any known solvent used in the photosensitive resin composition can be used.

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. These solvents may be used alone or in combination of two or more.

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, from the viewpoints of coating properties, stability, and the like of the obtained photosensitive resin composition. Preferably from 10 to 55% by weight may include an organic solvent.

Here, the solid content means that the solvent is removed from the composition of the present invention.

The photosensitive resin composition according to the present invention may be coated on a substrate and then cured to form an insulating film. The insulating film may be used as an electronic component.

In addition, the insulating film cured from the photosensitive resin composition of the present invention can be used in a liquid crystal display device.

The insulating film may be prepared by a method known in the art, and for example, the photosensitive resin composition is coated on a silicon substrate by a spin coating method and pre-bake at 60 to 130 ° C. for 60 to 130 seconds. After removing the solvent, a pattern may be formed on the coating layer by exposing using a photomask having a desired pattern and developing with a developer (eg, tetramethylammonium hydroxide solution (TMAH)). Thereafter, the patterned coating layer may be thermally cured (post-bake) at 150 to 300 ° C. for 10 minutes to 5 hours to obtain a desired insulating film.

The exposure may be performed by irradiating with an exposure amount of 20 to 100 mJ / cm ² in a wavelength band of 200 to 450 nm.

The cured film obtained by the photosensitive resin composition of this invention shows a high residual film rate after image development, is excellent in chemical resistance and adhesiveness to a board | substrate, and is suitable for the material for LCD.

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.

Preparation Example 1 Preparation of Oligomer (A)

100 parts by weight of glycidyl methacrylate, 81 parts by weight of phenylmaleimide, and 430 parts by weight of methyl 3-methoxypropionate as a solvent were placed in a flask equipped with a stirrer, a cooling tube and a stirrer. Gt; 60 C. < / RTI > After adding 3 parts by weight of azobisisobutyronitrile as a polymerization initiator, the polymerization was carried out over 2 hours while maintaining the temperature, where n and m were the molar ratios of 0.6 and 0.4, the weight average molecular weight was 4,000, and the solid content was An oligomer (A) of Formula 2 was obtained, which is 30% by weight.

(2)

Preparation Example 2 Preparation of Oligomer (B)

Into a flask equipped with a cooling tube and a stirrer, 100 parts by weight of 4-hydroxybutyl acrylate glycidyl ether, 58 parts by weight of phenylmaleimide, and 370 parts by weight of methyl 3-methoxypropionate as a solvent were added, followed by nitrogen. The temperature of the solvent was raised to 60 ° C. while stirring. After adding 3 parts by weight of azobisisobutyronitrile as a polymerization initiator, the polymerization was carried out over 2 hours while maintaining the temperature, where n and m were the molar ratios of 0.6 and 0.4, the weight average molecular weight was 4,000, and the solid content was An oligomer (B) of formula (3) was obtained, which is 30% by weight.

(3)

Preparation Example 3 Preparation of Oligomer (C)

100 parts by weight of glycidyl methacrylate, 72 parts by weight of tert-butyl maleimide and 402 parts by weight of methyl 3-methoxypropionate as a solvent were placed in a flask equipped with a stirrer, a cooling tube and a stirrer. Lt; RTI ID = 0.0 > 60 C. < / RTI > After adding 3 parts by weight of azobisisobutyronitrile as a polymerization initiator, the polymerization was carried out over 2 hours while maintaining the temperature, where n and m were the molar ratios of 0.6 and 0.4, the weight average molecular weight was 4,000, and the solid content was An oligomer (C) of the following formula (4) was obtained that is 30% by weight.

[Chemical Formula 4]

Preparation Example 4 Preparation of Random Copolymer (D)

In a flask equipped with a cooling tube and a stirrer, 100 parts by weight of a monomer mixture composed of 55 mol% of styrene, 20 mol% of methyl methacrylate, 20 mol% of methacrylic acid, and 5 mol% of glycidyl methacrylate was added, After adding 4 parts by weight of azobisisobutyronitrile as an initiator, 240 parts by weight of methyl 3-methoxypropionate as a solvent was added. The polymerization was carried out at 65 ° C. for 5 hours to obtain a random copolymer (D) having a weight average molecular weight of 13,000 and a solid content of 30% by weight.

Example 1

10 parts by weight (solid content) of the oligomer (A) synthesized in Preparation Example 1, 90 parts by weight (solid content) of the random copolymer (D) synthesized in Preparation Example 4, dipentaerythritol hexaacrylate as a polymerizable unsaturated compound. (Trade name DPHA, Nippon Kayaku) 80 parts by weight (solid content), photopolymerization initiator 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (brand name Irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd. 10 parts by weight (solid content), 0.6 parts by weight of γ-glycidoxypropyltriethoxysilane (solid content), a silane coupling agent, surfactant FZ-2110 (trade name, Dow Corning Toray Corporation Silicone parts) 0.2 parts by weight (solid content), and 100 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed for 2 hours using a shaker to prepare a photosensitive resin composition in liquid form.

Examples 2 to 6

Except for changing the content of the components used as shown in Table 1 below, the same process as in Example 1 was carried out to prepare a photosensitive resin composition.

Comparative Examples 1 and 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the oligomer was not used and the contents of the components used were changed as shown in Table 1 below.

Photosensitive
Resin composition Example Comparative Example One 2 3 4 5 6 One 2 Oligomer (A) 10 5 - - - - - - Oligomer (B) - - 10 5 - - - - Oligomer (C) - - - - 10 5 - - Random copolymer (D) 90 95 90 95 90 95 100 100 Polymerizable unsaturated
Compound A 80 80 80 80 80 80 80 80 Photopolymerization Initiator A 10 10 10 10 10 10 10 17 Silane Coupling Agent A 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Surfactant A 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Solvent A 100 100 100 100 100 100 100 100

* Polymerizable unsaturated compound A = dipentaerythritol hexaacrylate (trade name DPHA, Nippon Kayaku)

* Photoinitiator A = 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)

* Silane coupling agent A = γ-glycidoxypropyltriethoxysilane

* Surfactant A = FZ-2110 (manufactured by Dow Corning Toray Industries, Ltd.)

Solvent A = Propylene Glycol Methyl Ether Acetate

A film was prepared from the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2, and the residual film ratio, adhesion and chemical resistance (chemical resistance) of the cured film were measured, and the results are shown in Table 2 below.

[Production of Cured Film]

The photosensitive resin composition was applied on a silicon substrate by a spin coating method, and then pre-baked for 90 seconds on a hot plate maintained at a temperature of 105 ° C. to form a coating film having a thickness of 4 μm. This film was irradiated with an exposure dose of 60 mJ / cm ² at a wavelength of 365 nm using a MA6 exposure machine (manufactured by SUSS Microtec), and developed through a spray nozzle at 23 ° C. with a developer composed of an aqueous 2.38 wt% tetramethylammonium hydroxide solution. It was. The obtained exposure film was post-baked at 230 ° C. for 30 minutes in a convection oven to obtain a cured film.

1. Evaluation of residual film rate (after thermosetting)

The remaining film ratio (%) of the prepared cured film was obtained by the following equation.

[Equation 1]

Residual film rate (%) = (film thickness after post cure / film thickness after precure) X 100

The thickness of the membrane was measured using a non-contact thickness measuring instrument (product name: Nanospec 6500).

2. Chemical resistance evaluation

The prepared cured film was immersed in each of the following solutions at 60 ° C. for 10 minutes, and the change in thickness before and after was measured by a contact thickness measuring instrument (Tencor Alphastep IQ), and the change rate was measured by Equation 2 below.

&Quot; (2) "

Thickness change rate (%) = (film thickness after dipping / film thickness before dipping) X 100

3. Evaluation of adhesion

The photosensitive resin composition was applied on a silicon substrate by a spin coating method, and then pre-baked for 90 seconds on a hot plate maintained at a temperature of 105 ° C. to form a coating film having a thickness of 4 μm. The film was irradiated with an exposure dose of 10 mJ / cm ² at a wavelength of 365 nm using a photomask having a 1: 1 line pattern and a MA6 exposure machine (manufactured by SSUS Microtec) having a size difference of 1 μm from 1 μm to 10 μm. It was developed through a spray nozzle at 23 ° C. with a developer consisting of an aqueous 2.38 wt% tetramethylammonium hydrooxide solution. The remaining line size of the line pattern formed on the substrate after development was measured to evaluate that adhesion was better when a smaller size line pattern remained.

Example Comparative Example One 2 3 4 5 6 One 2 Retention rate after post curing (%) 91.5 88.6 91.2 87.8 90.9 87.1 76.8 85.7 Chemical resistance
(% Change in thickness) Methyl-2-pyrrolidone 1.5 2.1 1.6 2.2 1.8 2.4 16.3 10.2 Propylene Glycol Methyl Ether Acetate 0.4 0.8 0.5 0.8 0.5 0.9 4.5 3.6 3-methoxypropionic acid
methyl 0.6 0.8 0.6 0.8 0.8 1.0 5.1 4.2 Mixed Solution A 0.9 1.0 1.1 1.5 1.1 1.6 1.3 0.7 Adhesiveness (residual line pattern size, μm) One 2 One 3 One 3 10 9

* Mixed solution A = 78% by weight of dimethyl sulfoxide + 2% by weight of tetramethylammonium hydroxide + 20% by weight of tertiary distilled water

As can be seen through the contents of Table 1 and Table 2, the cured film prepared using the composition of Examples 1 to 6 using the oligomer (A), (B) or (C) is compared without using the oligomer It can be seen that the residual film ratio, chemical resistance and adhesion are clearly excellent as compared with the case of the example. Therefore, it can be seen that the cured film obtained from the composition of the present invention can be usefully used as an interlayer insulating film of a liquid crystal display device.

Claims (5)

(1) a compound comprising a repeating unit represented by the following formula (1);
(2) a structural unit derived from (2-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (2-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound Random copolymers;
(3) a polymerizable unsaturated compound; And
(4) Photosensitive resin composition containing a photoinitiator:
[Chemical Formula 1]

In this formula,
R ₁ , R ₃ and R ₄ are each independently hydrogen or C ₁ -C ₄ alkyl;
R ₂ 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 ₂ is one Or more of the hydroxyl groups;
R ₅ is C ₁ -C ₁₀ alkyl, phenyl, benzyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ heterocycloalkyl or C ₂ -C ₁₀ heteroalkyl;
n is a molar ratio of 0.9 to 0.3, m is a molar ratio of 0.1 to 0.7, and n + m = 1. The method of claim 1,
Said component (1) is an oligomer which has a weight average molecular weight of 1,000-9,000, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The random copolymer of the component (2) has 5 to 5 structural units derived from (2-1) ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic anhydride, or a mixture thereof with respect to the total moles of structural units constituting the copolymer. 98 mol%, (2-2) 2 to 95 mol% of a structural unit derived from an aromatic ring containing ethylenically unsaturated compound, and (2-3) said (2-1) and (2-2) A photosensitive resin composition comprising 0 to 50 mol% of structural units derived from ethylenically unsaturated compounds different from). The method of claim 3, wherein
The structural unit (2-3) comprises the structural unit (2-3) in an amount of 10 to 45 mol% based on the total moles of structural units of the component (2) random copolymer. The photosensitive resin composition containing the structural unit guide | induced from the ethylenically unsaturated compound containing this epoxy group. The method of claim 1,
Wherein the photosensitive resin composition contains the component (1) and the component (2) in a weight ratio of 1:99 to 50:50 and the total amount of the component (1) and the component (2) Wherein the photosensitive resin composition contains the component (3) and the component (4) in an amount of 1 to 150 parts by weight and 0.1 to 20 parts by weight, respectively.