KR20160133724A - Negative-type photosensitive resin composition and insulating film using same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, and to an insulation film using the same. The photosensitive resin composition comprises: (A) a copolymer; (B) a photopolymerizable monomer having at least seven functional groups; (C) a photopolymerization initiator; and (D) a phenylamino-based silane compound. The photosensitive resin composition has excellent characteristics such as heat resistance, chemical resistance, and the like, and can provide a cured product exhibiting high halftone adhesive strength and remaining rate, thereby being useful to prepare an insulation film for a liquid crystal display device.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative photosensitive resin composition and an insulating film using the negative photosensitive resin composition.

The present invention relates to a negative photosensitive resin composition and an insulating film using the negative photosensitive resin composition. More particularly, the present invention relates to a negative photosensitive resin composition and a method of manufacturing the same, ; LCD), and an insulating film made using the photosensitive resin composition.

Positive and negative photosensitive compositions are used for the production of insulating films for various display devices such as liquid crystal display devices and organic light emitting devices.

Conventional positive photosensitive compositions containing an alkali-soluble resin and a 1,2-quinonediazide compound are thermally decomposed upon post-bake after exposure and development and upon short wavelength absorption such as ultraviolet rays, There is a problem that a residual image is generated in the liquid crystal display device.

Therefore, in order to solve such a problem, research on a negative photosensitive composition capable of providing high light transmittance and sensitivity after heat curing has been continued. At this time, in a display device such as a thin film transistor (TFT) type liquid crystal display device, in order to protect the TFT circuit and ensure heat resistance, light resistance, etc., a photosensitive resin containing a photopolymerizable monomer containing a functional group and an adhesion- Compositions have been proposed for use in organic insulating films.

In this regard, Korean Patent Laid-Open Publication No. 2009-0114494 discloses a photosensitive resin composition containing an oxime-based initiator and an epoxy-based silane as an adhesion-increasing agent, but does not mention the halftone adhesive strength of the organic insulating film formed .

On the other hand, Korean Patent Publication No. 0911076 discloses a photosensitive resin composition comprising a photopolymerizable monomer containing a lower functional group and a phenylamino silane compound as an adhesion promoter, but the cured film obtained from such a photosensitive resin composition has a low degree of curing It is vulnerable to the membrane ratio.

Korean Laid-Open Publication No. 2009-0114494 Korean Patent Publication No. 0911076

Accordingly, an object of the present invention is to provide a resin composition which has excellent properties such as heat resistance and chemical resistance by using a photopolymerizable monomer having 7 or more functional groups together with a phenylamino silane compound as an adhesion promoter, and exhibits a high halftone adhesive strength and a residual film ratio A negative photosensitive resin composition and an insulating film produced therefrom.

In order to achieve the above object,

(A) a copolymer;

(B) a photopolymerizable monomer having 7 or more functional groups;

(C) a photopolymerization initiator; And

(D) a phenylamino-based silane compound

The present invention provides a photosensitive resin composition comprising

The photosensitive resin composition of the present invention can provide a cured film having improved half-tone adhesive strength, excellent room temperature stability, heat resistance, and chemical resistance and exhibiting a high residual film ratio and is useful for the production of insulating films for liquid crystal displays .

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

(A) Copolymer (alkali-soluble resin)

The photosensitive resin composition of the present invention may include a copolymer, and the copolymer may be a random copolymer.

The copolymer includes a structural unit derived from (A-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (A-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound (A-3) a structural unit derived from an ethylenically unsaturated compound different from (A-1) and (A-2) above. The copolymer may be an alkali-soluble resin that realizes developability in the development step, and may serve as a base for performing a base role of forming a coating film after coating and a final pattern.

(A-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 (A-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; Mono [(meth) acryloyloxyalkyl] acrylate of a dicarboxylic or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] And esters. However, the present invention is not limited thereto. Among them, (meth) acrylic acid can be preferably used from the viewpoint of developability.

The content of the constituent units derived from the (A-1) 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 molar amount 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 methacrylic, and (meth) acrylate refers to acrylate and / or methacrylate.

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

In the present invention, the structural unit (A-2) is derived from an aromatic ring-containing ethylenically unsaturated compound, and the aromatic ring-containing ethylenically unsaturated compound is derived from phenyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) Rate; 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-a-methyl styrene, acetyl styrene; And vinyl toluene, divinylbenzene, vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, And p-vinylbenzyl glycidyl ether. In view of polymerizability, it may preferably be a styrene compound.

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

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

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

In the present invention, the structural unit (A-3) is derived from an ethylenically unsaturated compound different from the above (A-1) and (A-2), and the ethylenic unsaturation (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 (Meth) acrylate, methoxytriethyleneglycol (meth) acrylate, methoxytripropylene (meth) acrylate, 2-methoxyethyl (Meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl , Dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) Pentyl (meth) acrylate, 5,6 (Meth) acrylate, 3-epoxycyclopentyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) Unsaturated carboxylic acid esters; 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 including an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether and 2-methylallyl glycidyl ether; And unsaturated imides comprising N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide. And may be an ethylenically unsaturated compound containing an epoxy group in view of improvement of copolymerization and strength of the insulating film, and is preferably an ethylenically unsaturated compound containing glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl Ether and 3,4-epoxycyclohexyl (meth) acrylate. From the viewpoint of the chemical resistance and the retentivity, it is more preferable to use 3,4-epoxycyclohexyl (meth) acrylate.

The content of the constituent unit derived from the ethylenically unsaturated compound different from the above (A-3), that is, the (A-1) and (A-2) is preferably 0 to 75 Mol%, preferably 10 to 65 mol%. Within this range, the storage stability of the composition is maintained and the retention rate is improved.

The copolymer (A) may be, for example, (meth) acrylic acid / styrene copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (Meth) acrylate / styrene / methyl (meth) acrylate / glycidyl methacrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / 3,4-epoxycyclohexyl (Meth) acrylic acid / styrene / methyl (meth) acrylate / glycidyl methacrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate / 4-hydroxybutyl acrylate glycidyl ether copolymer, (Meth) acrylate / styrene / methyl (meth) acrylate / 4-hydroxybutyl acrylate glycidyl ether / 3,4-epoxycyclohexyl (Meth) acrylate copolymer, (meth) acrylic acid / (Meth) acrylate / styrene / methyl (meth) acrylate / glycidyl methacrylate / N-cyclohexyl methacrylate / N-phenylmaleimide copolymer, (Meth) acrylic acid / styrene / n-butyl (meth) acrylate / glycidyl methacrylate / N-phenylmaleimide copolymer, or a mixture thereof. The copolymer may be contained in the photosensitive resin composition at least in one kind or more.

The content of the copolymer (A) is 0.5 to 75% by weight, preferably 5 to 65% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. Within this range, pattern development after development is favorable, and properties such as residual film ratio and chemical resistance are improved. The weight average molecular weight (Mw) of the random copolymer (A) measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) in terms of polystyrene is 500 to 50,000, preferably 3,000 to 30,000. When it is in the above range, it has good adhesion with the substrate, has good physical and chemical properties, and has a suitable viscosity.

(B) a photopolymerizable monomer having 7 or more functional groups

The photosensitive resin composition of the present invention may contain a photopolymerizable monomer having 7 or more functional groups.

The photopolymerizable monomer is a compound which can be polymerized by the action of a photopolymerization initiator and may be a polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenic unsaturated group. Functional compound.

The photopolymerizable monomer having 7 or more functional groups has a structure represented by the following Formula 1:

Wherein each X is independently hydrogen or a methyl group;

Y is an OH group, an acryloxy group or a methacryloxy group,

n is an integer of 1 to 4;

Examples of the photopolymerizable monomer having 7 or more functional groups include tripentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol decane (meth) Acrylate, pentapentaerythritol undeca (meth) acrylate, and pentapentaerythritol dodeca (meth) acrylate. Commercially available products include V-802: tripentaerythritol Heptaacrylate, tripentaerythritol octaacrylate and the like (manufactured by Osaka Yukigai Kogyo Co., Ltd.).

The photopolymerizable monomer (B) having 7 or more functional groups may be used in an amount of 1 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. Within this content range, high sensitivity and excellent pattern formation and coating film characteristics can be obtained.

The photosensitive resin composition of the present invention may further comprise other photopolymerizable monomer in addition to the photopolymerizable monomer having 7 or more functional groups.

The other photopolymerizable monomer is a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenic unsaturated group and may be a photopolymerizable monomer having less than 7 functional groups. In addition, as other photopolymerizable monomer, a compound having two or more isocyanate groups and having a straight chain alkylene group and an alicyclic structure, a compound having at least one hydroxyl group in the molecule and three, four or five acryloyloxy groups and And / or a compound having a methacryloyloxy group, and the like.

Examples of the other photopolymerizable monomer include ethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Acrylate, monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Acrylate, pentaerythritol triacrylate, hexamethylene diisocyanate (a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate. More than one species may be used, but is not limited thereto.

The other photopolymerizable monomer may be used in an amount of 1 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the photopolymerizable monomer (B) having 7 or more functional groups of the formula (1) have. Within the above content range, excellent contact hole shapes can be obtained.

(C) a photopolymerization initiator

The photosensitive resin composition according to the present invention includes a photopolymerization initiator. The photopolymerization initiator serves to initiate polymerization of monomers that can be cured by visible light, ultraviolet light, deep ultraviolet radiation, or the like. The photopolymerization initiator may be a radical initiator, and the kind thereof is not particularly limited, and examples thereof include acetophenone, benzophenone, benzoin and benzoyl, xanthone, oxime, triazine, halomethyloxadiazole, And a photopolymerization initiator may be used.

Specific examples of the photopolymerization initiator include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) Butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2- (dimethylamino) -1 Phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, benzoin propyl ether, di (2-hydroxy-2- (Trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenyl-2- 2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane- 1,2-dione- 2- (o-benzoyloxime), o-benzoyl-4 '- (benzmercaptan ) Benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'- Benzothiazolyl disulfide, and mixtures thereof, but are not limited thereto.

The oxime-based compound is not particularly limited as long as it is a radical initiator containing an oxime structure. For example, it may be an oxime ester-based compound.

The oxime-based compounds are disclosed in Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753 , 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467 and 2011-0015683, and International Patent Publication WO 2010 / 102502 and WO 2010/133077, from the viewpoint of high sensitivity. Examples of these trade names include OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 (ADEKA).

The photopolymerization initiator (C) may be used in an amount of 1 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. Within the above content range, high sensitivity and better pattern developability and coating film characteristics can be obtained.

(D) a phenylamino-based silane compound

The photosensitive resin composition according to the present invention may contain a phenylamino silane compound.

The phenylamino-based silane compound has a structure represented by the following formula (2)

Wherein R ₁ and R ₂ are each independently hydrogen or a straight, branched or cyclic C _1-6 alkyl group,

R ₃ , R ₄ , and R ₅ are each independently a C _1-6 alkoxy group or a C _1-6 hydrocarbon group, and at least one of R ₃ , R ₄ , and R ₅ is an alkoxy group;

m is an integer from 1 to 6;

a is an integer of 1 to 5;

Preferably, in the above formula (2), R ₁ and R ₂ are hydrogen, a is 5, R ₃ , R ₄ , and R ₅ are each methoxy and m is 3. That is, the compound of Formula 2 is preferably N-phenylaminopropyltrimethoxysilane.

The content of the phenylamino silane compound of Formula 2 may be 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent . Within the above content range, it is possible to prevent the loss of the pattern, achieve high adhesion with the substrate, easily maintain the halftone margin and high resolution, and improve the processability.

In addition to the phenylamino-based silane compound, the photosensitive resin composition of the present invention may further include other silane coupling agents. The kind of the silane coupling agent is not particularly limited, but includes, for example, at least one reactive group selected from the group consisting of a carboxyl group, a (meth) acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group and an epoxy group May be used.

Specific examples of other silane coupling agents include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane, ? -glycidoxypropyltrimethoxysilane,? -glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or a mixture thereof, and preferably Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane and the like, which have good adhesion with the substrate while improving the residual film ratio. In order to improve the chemical resistance,? -Isocyanatopropyltriethoxysilane having an isocyanate group (e.g., KBE-9007 from Shin-Etsu) may be used.

The other silane coupling agent may be used in an amount of 1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the phenylamino silane compound (D) based on the solid content excluding the solvent. Within the above content range, an excellent pattern shape can be obtained.

(E) Other ingredients

The present invention may further include other components for improving the properties of the photosensitive resin composition. For example, the other components include (E-1) a surfactant or (E-2) a solvent.

(E-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.

Examples of the surfactant include BM-1000 and BM-1100 from BM CHEMIE, Megapac F-142D, F-172, F-173, F-183, F- F-475, F-482 and F-489 of Sumitomo 3M, Florad FC-135, FC-170C, FC-430 and FC-431 of Sumitomo 3M, Surflon S-112, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC- SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 of Dow Corning Toray Silicone Co., DC3PA, DC7PA, SH11PA, SH21PA, SH8400, TSF-4400, TSF-4400, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicone Co., Ltd., FZ-2100, FZ-2110, FZ-2122, FZ- Fluorine-based and silicone-based surfactants such as BYK-333; 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 Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

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

Of these, BYK-333 manufactured by BYK Corporation, FZ-2100, FZ-2110, FZ-2122 and FZ-2222 manufactured by Dow Corning Toray Silicone Co., Ltd. can be preferably used from the viewpoint of dispersibility.

The surfactant (E-1) may be used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the copolymer (A) based on the solid content excluding the solvent. Within this range, coating of the composition may be more smooth.

In addition, the photosensitive resin composition of the present invention may further contain other additives such as an antioxidant, a stabilizer, and a radical scavenger within the range not deteriorating the physical properties thereof.

(E-2) 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-mentioned photosensitive resin composition components, 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 alcohols such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl myristate, isopropyl propionate, n-butyl propionate, Carboxylic acid esters; 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 of the present invention, the content of the solvent (E-2) is not particularly limited, but from the viewpoint of coatability, stability, and the like of the resulting photosensitive resin composition, a solid content of 5 to 70 wt% %, Preferably 10 to 55 wt%, based on the total weight of the composition. Here, the solid content means the remaining components in the composition except for the solvent.

The photosensitive resin composition according to the present invention can be used as a negative type photosensitive resin composition.

In particular, the photosensitive resin composition may be coated on a substrate and cured to form an organic insulating film.

The organic insulating layer can be formed by a method known in the art. For example, the photosensitive resin composition is coated on a silicon substrate by a spin coating method and pre-cured at 60 to 130 ° C for 60 to 130 seconds -bake) to remove the solvent, exposure is performed using a photomask in which a desired pattern is formed, and development is performed with a developer (for example, tetramethylammonium hydroxide (TMAH) solution) to form a pattern on the coating layer. The above exposure can be performed by irradiating light at an exposure amount of 10 to 100 mJ / cm 2 at a wavelength range of 200 nm to 450 nm. Thereafter, the patterned coating layer is post-baked at 150 ° C to 300 ° C for 10 minutes to 5 hours to obtain a desired organic insulating film.

The photosensitive resin composition of the present invention has high flatness at the time of forming a coating film, and is excellent in heat resistance, chemical resistance, aging stability, resolution, and residual film ratio.

Therefore, the photosensitive resin composition of the present invention is suitable as a material for an organic insulating film or the like used in a liquid crystal display device, particularly, for simultaneously realizing an organic insulating film and a white pixel, or as a material for electronic parts in various other fields.

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 Copolymer

100 parts by weight of a monomer mixture composed of 38 mol% of styrene, 8 mol% of methyl methacrylate, 24 mol% of methacrylic acid, and 30 mol% of glycidyl methacrylate was added to a flask equipped with a cooling tube and a stirrer, After adding 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent was added. After the addition of nitrogen, the temperature of the solution was raised to 70 DEG C while being slowly stirred, and the polymerization reaction was carried out while maintaining the temperature for 5 hours to obtain a solution of a copolymer having a weight average molecular weight of 7,500.

Example 1

, 100 parts by weight of the copolymer (A) synthesized in Production Example 1, 63 parts by weight of a photopolymerizable monomer V-802 having seven or more functional groups (manufactured by Osaka Yuzugaku Kogyo Co., Ltd.) as a solid content and Irgacure OXE-01 (BASF Corp.), 1.2 parts by weight of Irgarcure OXE-02 (BASF Corp.) as another photopolymerization initiator, 0.5 parts by weight of N-phenylaminopropyltrimethoxysilane (XS1075, JNC Corp.) And 0.3 parts by weight of FZ-2122 (manufactured by Dow Corning Toray Silicone Co., Ltd.) as a surfactant. Propylene glycol methyl ether acetate (PGMEA) was added thereto so that the total solid content of the components was 25% For a period of time to prepare a liquid photosensitive resin composition.

Examples 2 to 6 and Comparative Examples 1 to 3

The photosensitive resin composition was prepared in the same manner as in Example 1 except that the kind and content of the components used were changed as shown in Table 1 below.

Composition of photosensitive resin composition (parts by weight, based on solids) division Copolymer Photopolymerizable monomer Photopolymerization initiator Silane compound Surfactants Example 1 A 100 B-1 63 C-1 6 C-2 1.2 D-1 0.5 E-1 0.3 Example 2 A 100 B-1 63 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Example 3 A 100 B-1 37.8 B-2 25.2 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Example 4 A 100 B-1 25.2 B-2 37.8 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Example 5 A 100 B-1 37.8 B-3 25.2 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Example 6 A 100 B-1 25.2 B-3 37.8 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Comparative Example 1 A 100 B-1 63 C-1 6 C-2 1.2 D-2 0.2 E-1 0.2 Comparative Example 2 A 100 B-2 63 C-1 6 C-2 1.2 D-1 0.2 E-1 0.2 Comparative Example 3 A 100 B-2 63 C-1 6 C-2 1.2 D-2 0.2 E-1 0.2

(B-1): tripentaerythritol heptamethacrylate (V-802, manufactured by Osaka Yuzen Chemical Industry Co., Ltd.)

(B-2): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(B-3): trimethylpropane triacrylate (TMPTA, manufactured by Nippon Kayaku Co., Ltd.)

(C-1): Irgarcure OXE-01 (BASF)

(C-2): Irgarcure OXE-02 (BASF)

(D-1): N-phenylaminopropyltrimethoxysilane (XS1075, JNC)

(D-2):? -Isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu Co.)

(E-1): FZ-2122 (manufactured by Dow Corning Toray Silicone Co., Ltd.)

Films were prepared from the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and the residual film ratios, halftone adhesive strength characteristics, stability at room temperature stability, heat resistance and chemical resistance were measured after thermal curing of the cured films, The results are shown in Table 2 below.

[Preparation of cured film]

The photosensitive resin composition was spin-coated on a silicon substrate and pre-baked on a hot plate maintained at a temperature of 100 캜 for 90 seconds to form a dry film having a thickness of 3 탆. This film was subjected to exposure for a predetermined time so as to be 30 mJ / cm 2 on the basis of 365 nm without using a mask as an exposure standard using an aligner (model name MA6) having a wavelength of 200 nm to 450 nm, and 2.38 wt% tetramethyl Aqueous solution of ammonium hydroxide at 23 DEG C for 100 seconds through a spray nozzle. The resultant exposed film was heated in a convection oven at 230 DEG C for 30 minutes (post-bake) to obtain a cured film.

1. Evaluation of residual film ratio (after heat curing)

Each of the film thicknesses after the pre-curing and the post-curing processes in the production of the cured film was measured with a film thickness evaluating equipment (trade name: Nanospec 6500) and calculated according to the following equation (1). The higher the residual film ratio (%), the better the residual film ratio.

[Equation 1]

(%) = (Film thickness after post-curing / film thickness after pre-curing) X 100

2. Evaluation of Halftone Adhesion

A cured film was prepared in the same manner as above except that various tone masks capable of being 10 to 100% transmissive were used in the production of the cured film and exposure was performed at 10 mJ / cm 2 instead of 30 mJ / cm 2, The thickness of the pattern below 40% transmittance area was measured using a thickness gauge (trade name SNU). The halftone adhesive strength can be said to be excellent when a pattern having a transmittance of 40% or less is formed.

3. Stability evaluation at room temperature

10 g of the photosensitive resin composition having a solid content of 25% was placed in a 20 ml glass vial bottle and stored in an oven for 24 hours at 40 ° C. The degree of increase in viscosity was measured using a TV-22 rotary viscometer (TOKI SANGYO ). In the viscosity measurement method, 1 ml sample was taken and stabilized at 25 ° C in a viscosity measuring instrument, and the pressure applied to the spindle of the viscosity measuring instrument was used. The measured viscosity was calculated according to the following equation (2). When the viscosity increase rate (%) is 5% or less, it is excellent and when it is 3% or less, it is excellent.

&Quot; (2) "

Viscosity Rate of increase (%) = [(40 DEG C / 24 hr Oven  Viscosity after storage - initial viscosity) / (initial viscosity)] X100

4. Evaluation of heat resistance

A cured film was prepared in the same manner, except that a glass substrate was used instead of the silicon substrate and the substrate was developed for 70 seconds instead of 100 seconds in the production of the cured film. The cured film was scratched with a knife to raise the 5 mg film to a temperature of 230 ° C at a rate of 10 ° C per minute from a room temperature to a 230 ° C using a thermogravimetric analyzer, and the weight was measured while maintaining the temperature at 250 ° C for 60 minutes. Heat resistance (weight reduction rate) was calculated. The lower the weight reduction rate (%), the better the heat resistance.

&Quot; (3) "

Weight reduction rate (%) = [(Weight at initial 25 ° C - Weight after remaining at 250 ° C for 60 minutes) / Weight at initial 25 ° C] X 100

5. Chemical resistance evaluation

A cured film was prepared in the same manner, except that the cured film was developed for 70 seconds instead of 100 seconds, and the thickness was measured using a contact type alpha step. N-methyl pyrrolidinone (NMP) was placed in a thermostat in a beaker at 70 ° C, and the cured film was immersed in the beaker for 10 minutes. From this, the chemical resistance value was calculated according to the following equation (4). The lower the chemical resistance (%) value, the better.

&Quot; (4) "

Chemical resistance (%) = [( NMP  Thickness after dipping - NMP  Thickness before soaking) / NMP  Thickness before immersion] X 100

The physical property results (%) obtained above are evaluated according to the categories shown in Table 2 below and summarized in Table 3 below.

category Remaining film ratio (%) Halftone adhesion properties Stability at room temperature (%) Heat resistance (%) Chemical Resistance (%) ◎  80% to 100% Pattern formation in 10 to 40% transmission area 0% to 3% 0% to 5% 0% to 10% ○ 75% to 80% Pattern formation in 20-40% transmission area 3% to 5% 5% to 15% 10% to 20% Δ 60% to 75% Pattern formation in 40% transmission area 5% to 10% 15% to 25% 20% to 30% X Less than 60% Pattern exfoliation Greater than 10% Greater than 25% More than 30%

division Remaining film ratio (%) Halftone adhesion properties Stability at room temperature (%) Heat resistance (%) Chemical Resistance (%) Example 1 ○ ◎ ◎ ◎ ◎ Example 2 ○ ○ ○ ◎ ◎ Example 3 ○ ○ ○ ◎ ◎ Example 4 ○ ○ ○ ◎ ○ Example 5 ○ ○ ○ ◎ ○ Example 6 ○ ○ ○ ○ ○ Comparative Example 1 ○ △ △ ○ ○ Comparative Example 2 △ X ○ △ △ Comparative Example 3 △ X △ △ △

As shown in Table 3, the compositions of the Examples belonging to the scope of the present invention are excellent in terms of residual film ratios, halftone adhesive strength characteristics, stability at room temperature, heat resistance and chemical resistance, while those of Comparative Examples The compositions were poor in at least one of these results. Therefore, it can be seen that the cured film obtained from the composition of the present invention can be usefully used as an insulating film of a liquid crystal display device.

Claims (8)

(A) a copolymer;
(B) a photopolymerizable monomer having 7 or more functional groups;
(C) a photopolymerization initiator; And
(D) a phenylamino-based silane compound
.
The method according to claim 1,
Wherein the photopolymerizable monomer having 7 or more functional groups is a compound represented by the following formula (1)
Wherein the phenylamino silane compound is a compound represented by the following formula (2).
[Chemical Formula 1]

Wherein each X is independently hydrogen or a methyl group;
Y is an OH group, an acryloxy group or a methacryloxy group,
n is an integer of 1 to 4;
(2)

Wherein R ₁ and R ₂ are each independently hydrogen or a straight, branched or cyclic C _1-6 alkyl group,
R ₃ , R ₄ , and R ₅ are each independently a C _1-6 alkoxy group or a C _1-6 hydrocarbon group, and at least one of R ₃ , R ₄ , and R ₅ is an alkoxy group;
m is an integer from 1 to 6;
a is an integer of 1 to 5;
3. The method of claim 2,
Wherein the photopolymerizable monomer having 7 or more functional groups of Formula 1 is tripentaerythritol hepta methacrylate.
3. The method of claim 2,
Wherein the compound of Formula 2 is N-phenylaminopropyltrimethoxysilane.
3. The method according to claim 1 or 2,
Wherein the copolymer (A) comprises a structural unit derived from (A-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (A-2) a constituent unit derived from an aromatic ring-containing ethylenically unsaturated compound Wherein the photopolymerizable compound is a copolymer comprising a unit represented by the following formula (1).
6. The method of claim 5,
Wherein the copolymer (A) contains a constituent unit derived from an ethylenically unsaturated carboxylic acid (A-1), an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, relative to the total moles of the constituent units constituting the copolymer, (A-2) an aromatic ring-containing ethylenically unsaturated compound in an amount of 2 to 95 mol%, and further (A-3) And 0 to 75 mol% of constitutional units derived from different ethylenically unsaturated compounds.
3. The method according to claim 1 or 2,
Wherein the photopolymerization initiator (C) is a oxime-based compound.
3. The method according to claim 1 or 2,
Wherein the photosensitive resin composition contains the copolymer (A) in an amount of 0.5 to 75% by weight based on the total weight of the photosensitive resin composition (based on the solid content)
1 to 100 parts by weight of the photopolymerizable monomer (B) having 7 or more functional groups, 1 to 20 parts by weight of the photopolymerization initiator (C), and 1 to 20 parts by weight of the phenylamino (meth) acrylate based on 100 parts by weight (based on the solid content) , And 0.001 to 5 parts by weight of a silane compound (D).