KR20150066816A - Negative-type photosensitive resin composition - Google Patents

Abstract

The present invention relates to a negative-type photosensitive resin composition comprising: (A) a copolymer including (a1) a group unit induced from an ethylene unsaturated carboxylic acid, an ethylene unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a group unit induced from an unsaturated monomer containing a substituted epoxy group, and (a3) a group unit induced from an ethylene unsaturated compound different from the group unit (a1) and (a2); (B) a polymerizable unsaturated compound; (C) a photopolymerization initiator; and (D) a silane coupling agent of chemical formula 1. The photosensitive resin composition of the present invention can provide a cured film which has excellent remain film ratio properties after heat curing, has excellent binding force with a substrate even when manufactured in a half-tone pattern, and shows improved half-tone margin and resolution, thereby being used for manufacturing an OLED and an insulation film for a liquid crystal display device.

Description

NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a negative photosensitive resin composition, and more particularly to a negative photosensitive resin composition for forming an interlayer insulating film of an organic light emitting diode (OLED) and a thin film transistor (TFT) .

A positive type and a negative type photosensitive resin composition are used for the production of insulating films for various display devices such as a liquid crystal display device and an organic light emitting device.

Conventional positive photosensitive resin compositions containing an alkali-soluble resin (copolymer) 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 phenomenon is generated or an impurity is generated to cause a residual image in the liquid crystal display device.

Therefore, in order to solve such a problem, research on a negative photosensitive resin composition capable of providing high light transmittance and sensitivity after thermal curing has been continued. At this time, in a display device such as a thin film transistor (TFT) type liquid crystal display device, a constitutional unit derived from glycidyl (meth) acrylate and / or a constitutional unit derived from an alicyclic epoxy- A photosensitive resin composition contained in an alkali-soluble resin has been proposed for use as an organic insulating film (see Korean Patent Laid-Open Publication Nos. 2010-0099048 and 2012-0029319).

However, the cured film obtained from these conventional photosensitive resin compositions is excellent in transmittance, but when it is manufactured in a half-tone pattern, the adhesive force to the substrate is insufficient and margin of the halftone cured film and maintenance of the resolution are not easy There were disadvantages.

Korean Patent Publication No. 2010-0099048 Korea Patent Publication No. 2012-0029319

Accordingly, an object of the present invention is to provide a negative photosensitive resin composition for an insulating film which can maintain an excellent halftone margin and resolution by having an excellent adhesive property to a substrate even when it is produced in a halftone pattern, .

In order to achieve the above object,

(A1) a constitutional unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a constitutional unit derived from an unsaturated monomer containing an alicyclic epoxy group, and (a3) A copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the units (a1) and (a2);

(B) a polymerizable unsaturated compound;

(C) a photopolymerization initiator; And

(D) a silane coupling agent represented by the following formula

A photosensitive resin composition comprising:

Wherein each R ₁ is independently hydrogen or a straight, branched or cyclic C _1-6 alkyl group or C _1-6 alkoxy group;

X, Y and Z are each independently a linear, branched or cyclic C _1-6 alkyl group;

n and a are each independently an integer of 1 to 5;

The photosensitive resin composition of the present invention not only has a good residual ratio characteristic after thermal curing, but also can provide a cured film having excellent halftone margin and resolution because of its excellent adhesion with a substrate even when it is produced in a halftone pattern. And can be usefully used in the production of insulating films for display devices.

The photosensitive resin composition according to the present invention comprises (A) a constitutional unit derived from (a1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a constituent unit derived from an unsaturated monomer containing an alicyclic epoxy group And (a3) a copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the constituent units (a1) and (a2); (B) a polymerizable unsaturated compound; (C) a photopolymerization initiator; And (D) a silane coupling agent of formula (1), optionally further comprising (E) a surfactant and / or (F) a solvent.

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

(A) Copolymer

The copolymer used in the present invention is a copolymer comprising (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group, and (a3) a structural unit derived from an ethylenically unsaturated compound which is different from the structural units (a1) and (a2).

(a1) 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 (a1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, wherein the ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, As the polymerizable unsaturated monomer having a group, 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 unit (a1) may be 5 to 50 mol%, and preferably 10 to 40 mol% based on the total molar amount of the constituent units constituting the copolymer. It is possible to achieve pattern formation of the coating film with good developability in the above range.

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

(a2) a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group

In the present invention, the constituent unit (a2) is derived from an unsaturated monomer containing an alicyclic epoxy group, and the monomer may be represented by the following formula (2)

In this formula,

R ₁ is hydrogen or C ₁ -C ₄ alkyl;

R ₂ is C ₁ -C ₄ alkylene.

Preferably, in Formula 2, R ₁ is hydrogen or methyl, and the unsaturated monomer containing the alicyclic epoxy group may be 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate have.

The content of the structural unit (a2) may be 10 to 50 mol%, and preferably 15 to 45 mol%, based on the total number of moles of the constituent units constituting the copolymer. Within this range, the storage stability of the composition is maintained and the retention rate is improved.

(a3) a structural unit derived from an ethylenically unsaturated compound which is different from the structural units (a1) and (a2)

In the present invention, the structural unit (a3) is derived from an ethylenically unsaturated compound different from the structural units (a1) and (a2), and the ethylenically unsaturated compound different from the structural units (a1) and (a2) (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypoly (meth) acrylate, (Meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptyl Styrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy-? -Methylstyrene, acetyl Aromatic ring-containing ethylenically unsaturated compounds including styrene, vinyl toluene, divinyl benzene, vinyl phenol, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether and p-vinyl benzyl methyl ether; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, Hydroxypropyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, methyl (meth) acrylate, ethyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, propyl? -Hydroxymethyl (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-methoxyethyl Met) (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3- (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl Unsaturated carboxylic acid esters, including unsaturated carboxylic acid esters, including 4,5-epopentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, and 6,7-epoxyheptyl (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; And unsaturated imides comprising N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide. It can be more than a species.

The content of the structural unit (a3) may be from 5 to 70 mol%, and preferably from 15 to 65 mol%, based on the total number of moles of the constituent units constituting the copolymer. In the above range, the reactivity of the alkali-soluble resin can be controlled and the solubility in an alkali aqueous solution can be increased, thereby remarkably improving the applicability of the photosensitive resin composition.

The copolymer according to the present invention is prepared by adding nitrogen into a molecular weight regulator, a polymerization initiator, a solvent, and a compound which provides each of the constituent units (a1), (a2) and (a3) and then polymerizing the mixture while gradually stirring . The weight average molecular weight (Mw) of the prepared copolymer in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) may be 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.

The molecular weight modifier is not particularly limited, but may be a mercaptan compound such as butyl mercaptan, octylmercaptan, lauryl mercaptan, or? -Methylstyrene dimer.

The polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate or 1,1-bis (t-butylperoxy) cyclohexane . These polymerization initiators may be used alone or in combination of two or more.

The solvent may be any solvent used in the production of the copolymer, preferably methyl 3-methoxypropionate or propylene glycol monomethyl ether acetate (PGMEA).

The content of the copolymer may be 1 to 90% by weight, preferably 15 to 75% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. Within the above range, pattern development after development is favorable, and the characteristics such as heat resistance are improved.

(B) a polymerizable unsaturated compound

The polymerizable unsaturated compound used in the present invention is a compound which can be polymerized by the action of a polymerization initiator and may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenic unsaturated group, From the viewpoint of chemical properties, it may preferably be a polyfunctional compound having two or more functional groups.

Examples of the polymerizable unsaturated compound 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), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate , At least one selected from the group consisting of epoxy acrylate, bisphenol A epoxy acrylate, bisphenol A diacrylate, 2,2-bis-4-acryloxy polyethoxyphenyl propane and ethylene glycol monomethyl ether acrylate But are not limited thereto.

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.

Examples of commercially available polymerizable unsaturated compounds include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), AKAYARAD TC- (Commercially available from Nippon Kayaku Co., Ltd.), V-158 and V-2311 (manufactured by Osaka Kikogaku Kogyo Co., Ltd.), and commercially available products of bifunctional (meth) KAYARAD HDDA, copper HX-220, copper R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335 (manufactured by Toagosei Co., Ltd.) HP (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) and Aronix M-309, M-400, M-403, M-405 and M- 40, D-PTA-40, D-PTA-40, D-PTA-40, D-MTA- -60, -120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, -300, -360, -GPT, -3PA, -400, Yukki cultivate a car can be a bridge Co., Ltd.) and the like.

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

The content of the polymerizable unsaturated compound may be 1 to 80% by weight, preferably 5 to 50% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. The pattern is easily formed in the above range, and the sensitivity and the residual film ratio are improved.

(C) a photopolymerization initiator

The photopolymerization initiator used in the present invention 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. The photopolymerization initiator may be a radical initiator. The type of the photopolymerization initiator is not particularly limited, and examples thereof include acetophenone, benzophenone, benzoin and benzoyl, xanthone, triazine, halomethyloxadiazole, May be used.

Specific examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy- Butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl- - (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy- , Benzoin propyl ether, diethyl thioxanthone, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-stilbene-4,6-bis- trichloromethyl 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino- ((s- Phenyl) -1, 2-propanediol-2- (o-ethoxy) Carbonyl) oxime, 1- [4- (phenylthio) phenyl -Octane-l, 2-dione-2- (O-benzoyloxime), 1- [ 1-onoxime-O-acetate, o-benzoyl-4 '- (benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl- -Trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, and mixtures thereof, but are not limited thereto. 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 , KR 2011-0059525, KR 2011-0091742, KR 2011-0026467, KR 2011-0015683, WO 10102502, and WO 10133077 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 content of the photopolymerization initiator may be 0.1 to 20% by weight, preferably 0.5 to 15% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. In the above range, curing by exposure is sufficiently carried out, and pattern formation and residual film ratio can be easily improved, and the hardness of the formed insulating film is improved.

(D) a silane coupling agent represented by the general formula (1)

The silane coupling agent used in the present invention has the following structure:

[Chemical Formula 1]

Wherein each R ₁ is independently hydrogen or a straight, branched or cyclic C _1-6 alkyl group or C _1-6 alkoxy group;

X, Y and Z are each independently a linear, branched or cyclic C _1-6 alkyl group;

n and a are each independently an integer of 1 to 5;

Preferably, in the formula 1 R ₁ is hydrogen, a is 1, and, X, Y and Z is methyl, n is 3, respectively. That is, the compound of Formula 1 is preferably N-phenylaminopropyltrimethoxysilane.

The content of the silane coupling agent of Formula 1 may be 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight based on the total weight of the photosensitive resin composition excluding the residual amount of the solvent. It is possible to prevent the loss of the pattern in the above range, to achieve high adhesion with the substrate, to easily maintain the halftone margin and high resolution, and to improve the processability.

Other components may be further included to improve the properties of the photosensitive resin composition. For example, the other components include (E) a surfactant and / or (F) a solvent.

(E) 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. Of these, BYK 333 from BYK is preferably used from the viewpoint of dispersibility.

Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Megafac F172, Megafac F173, Megafac F183, F- 470, F- 471, F- F-482 and F-489 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC-135, Florad FC-170C, Florad FC-430 and Florad FC- Surflon S-112, Surflon SC-101, Surflon SC-101, Surflon S-145, Surflon S-382, , Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (manufactured by Asahi Glass Co., Ltd.), Efstop EF301, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), DC3PA, DC7PA, SH11PA, SH21PA , TSF-4440, TSF-4300, TSF-4445, TSF-4446 and FZ-2233 (manufactured by Dow Corning Toray Silicone Co., Ltd.), SH8400, FZ-2100, FZ-2110, FZ- 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 Corporation); Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , And nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; And an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow No. 1. 57, and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The surfactant may be 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. In this range, the coating of the composition is smooth.

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

(F) 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 it is preferably 5 to 70% by weight based on the total weight of the composition from the viewpoint of coatability and stability of the resulting photosensitive resin composition The organic solvent may be 10 to 55% by weight.

Here, the solid content means that the solvent is excluded 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 for OLED and liquid crystal display devices.

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

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 to 450 nm.

The cured film obtained by the photosensitive resin composition of the present invention not only exhibits the residual film-ratio characteristics after excellent thermal curing, but also exhibits an improved halftone margin and resolution, and is suitable as a material for an OLED and a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

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

Production Example 1: Preparation of copolymer (A-1)

In a three-necked flask equipped with a cooling tube and a stirrer, 2.5 parts by weight of octylmercaptan as a molecular weight regulator, 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, 2 parts by weight of propylene glycol monomethyl ether And 100 parts by weight of a monomer mixture composed of 50 mol% of styrene, 20 mol% of 3,4-epoxycyclohexylmethyl methacrylate, 5 mol% of methyl methacrylate and 25 mol% of methacrylic acid were added. After the addition of nitrogen, the temperature of the solution was raised to 60 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 the copolymer (A-1) having a weight average molecular weight of 6,050.

Production Examples 2 to 4: Preparation of Copolymers (A-2) to (A-4)

Polymerization was carried out in the same manner as in Preparation Example 1, except that the contents of the components constituting the monomer mixture were changed as shown in Table 1 below to obtain copolymers (A-2) to (A-4) ≪ / RTI >

Preparation Example (Copolymer) St METHB GMA MMA MAA Molecular Weight (A-1) 50 20 0 5 25 6,050 (A-2) 50 23 0 2 25 6,100 (A-3) 50 25 0 0 25 6,000 (A-4) 50 0 25 0 25 6,300

St: Styrene

METHB: 3,4-epoxycyclohexylmethyl methacrylate

GMA: glycidyl methacrylate

MMA: methyl methacrylate

MAA: methacrylic acid

Example 1

2,294 parts by weight (based on solid content) of the copolymer (A-1) synthesized in Production Example 1, 1,160 parts by weight (based on the solid content) of dipentaerythritol hexaacrylate (B-1) as a polymerizable unsaturated compound, 0.300 parts by weight (based on the solids content) of OXE-02 (trade name, BASF Corp.), 0.010 part by weight (based on the solids content) of FZ-2122 (trade name, manufactured by Dow Corning Toray Silicone Co.) as a surfactant, Propylene glycol monomethyl ether acetate (PGMEA) was added as a solvent so that 0.005 part by weight (based on the solid content) of the aminopropyltrimethoxysilane (D-1) and 20% by weight of the solid content of the composition were added, For 2 hours to prepare a liquid photosensitive resin composition.

Examples 2 to 6 and Comparative Examples 1 to 3

A photosensitive resin composition was prepared by following the same procedure as in Example 1, except that the kinds of the components used were changed as shown in Table 2 below.

Copolymer The polymerizable unsaturated compound Silane coupling agent Example 1 (A-1) (B-1) (D-1) Example 2 (A-1) (B-2) (D-1) Example 3 (A-1) (B-3) (D-1) Example 4 (A-1) (B-4) (D-1) Example 5 (A-2) (B-1) (D-1) Example 6 (A-3) (B-1) (D-1) Comparative Example 1 (A-1) (B-1) (D-2) Comparative Example 2 (A-1) (B-1) (D-3) Comparative Example 3 (A-4) (B-1) (D-1)

(B-1): dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(B-2): Epoxy acrylate (R-551, manufactured by Nippon Kayaku Co., Ltd.)

(B-3): Bisphenol A diacrylate (A-BPE-4, manufactured by Shin Nakamura)

(B-4): 2,2-bis-4-acryloxypolyethoxyphenylpropane (A-BPE-20, manufactured by Shin Nakamura)

(D-1): N-phenylaminopropyltrimethoxysilane

(D-2): 3-glycidoxypropyltrimethoxysilane

(D-3): 3-isocyanatopropyltrimethoxysilane

The films were prepared from the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and the residual film ratio, transmittance, halftone residual film thickness, and line resolution were measured after thermosetting of the cured films. Respectively.

[Preparation of cured film]

The photosensitive resin composition was spin-coated on a glass substrate and then pre-baked on a hot plate maintained at a temperature of 105 DEG C for 90 seconds to form a coating film having a thickness of 4.0 mu m. This film was irradiated with an aligner (model name MA6) having a wavelength of 200 nm to 450 nm at a dose of 20 mJ / cm 2 on the basis of 365 nm without using a mask as an exposure reference. Subsequently, the resist film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution (developer) at 23 DEG C for 60 seconds, and then washed with pure water for 1 minute. By this operation, unnecessary portions can be removed and only holes and line patterns can be left. The formed coating film pattern was heated in a convection oven at 230 캜 for 30 minutes to cure (post-bake) to finally obtain a cured film pattern.

(1) Residual film ratio after heat curing (%)

The thickness of the obtained cured film was measured with a non-contact type thickness measuring instrument (trade name: Nanospec. 6500) and the residual film ratio (%) was calculated according to the following formula. The higher the residual film ratio after the thermal curing, the better.

(%) = (Film thickness after post-curing / initial coating film thickness (4 탆)) X 100

(2) Transmittance (%)

The cured film obtained was measured for transmittance at a wavelength of 400 nm using an ultraviolet / visible light absorber.

(3) Halftone film thickness (Å) and line resolution (㎛)

For the halftone measurement on the cured film pattern, a cured film was prepared in the same manner as in the above [Preparation of cured film] using a mask capable of adjusting the transmittance of light at each region during exposure. The minimum line size of the obtained halftone pattern was observed using a micro-optical microscope to measure the halftone line resolution. The thickness of the halftone retroreflective film was measured using a non-contact type thickness measuring instrument (trade name: Nanospec 6500).

It can be said that the halftone film thickness is smaller with respect to the film thickness of the Fulton film (3.5 (± 0.2) μm), and the halftone line resolution is higher, and the halftone process margin is better.

Permeability
(%) Residual film ratio after thermal curing
(%) Halftone thickness
(A) Halftone Line Resolution
(탆) Example 1 92.4 78.6 7132 5 Example 2 92.4 78.7 10334 8 Example 3 92.8 77.9 10312 8 Example 4 93.1 78.8 10113 10 Example 5 92.8 78.5 7032 5 Example 6 92.4 78.4 7158 5 Comparative Example 1 92.5 78.3 23415 20 Comparative Example 2 92.4 77.9 25782 20 Comparative Example 3 92.1 78.1 28338 20

As can be seen from the results of Table 3, the cured films prepared from the compositions of Examples 1 to 6 using specific silane coupling agents together with the specific copolymer not only have excellent residual film rate characteristics after excellent thermal curing, It can be seen that the halftone margin and the resolution are significantly improved as compared with the comparative examples 1 to 3. 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 an OLED and a liquid crystal display device.

Claims (5)

(A1) a constitutional unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a constitutional unit derived from an unsaturated monomer containing an alicyclic epoxy group, and (a3) A copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the units (a1) and (a2);
(B) a polymerizable unsaturated compound;
(C) a photopolymerization initiator; And
(D) a silane coupling agent represented by the following formula
: ≪ EMI ID =
[Chemical Formula 1]

Wherein each R ₁ is independently hydrogen or a straight, branched or cyclic C _1-6 alkyl group or C _1-6 alkoxy group;
X, Y and Z are each independently a linear, branched or cyclic C _1-6 alkyl group;
n and a are each independently an integer of 1 to 5; The method according to claim 1,
The photosensitive resin composition according to claim 1, wherein the silane coupling agent of Formula 1 is N-phenylaminopropyltrimethoxysilane. The method according to claim 1,
Wherein the unsaturated monomer containing an alicyclic epoxy group that provides the structural unit (a2) is represented by the following formula (2): < EMI ID =
(2)

In this formula,
R ₁ is hydrogen or C ₁ -C ₄ alkyl;
R ₂ is C ₁ -C ₄ alkylene. The method of claim 3,
Wherein the monomer represented by the general formula (2) is 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. The method according to claim 1,
The copolymer (A) contains 5 to 50 mol%, 10 to 50 mol% and 5 to 70 mol% of the constituent units (a1), (a2) and (a3), respectively, based on the total molar amount of the constituent units constituting the copolymer Mol% based on the total amount of the photosensitive resin composition.