KR20200122272A - Negative-type photosensitive resin composition and insulating film using same - Google Patents

Abstract

The present invention relates to a negative type photosensitive resin composition and an insulating film using the same. According to the present invention, the photosensitive resin composition comprises an alkali-soluble resin, which includes the sum of the constituent units derived from the unsaturated monomer containing an alicyclic epoxy group and the constituent units derived from the unsaturated monomer containing a non-alicyclic epoxy group in an amount of 10 to 50 mol% based on the total number of moles of the constituent units. The photosensitive resin composition of the present invention provides a cured film exhibiting excellent pattern developability, stability over room temperature, thermal shock stability, heat resistance and chemical resistance, and thus can be useful in the preparation of an insulating film for a liquid crystal display device.

Description

Negative photosensitive resin composition and insulating film using the same {NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION AND INSULATING FILM USING SAME}

The present invention relates to a negative photosensitive resin composition and an insulating film using the same, and more particularly, it is possible to form a cured film having excellent stability over room temperature, high thermal shock stability and heat resistance, and excellent chemical resistance as well as high-resolution pattern developability. The present invention relates to a photosensitive resin composition usefully used in forming an insulating film of a display device such as a liquid crystal display (LCD), and an insulating film manufactured using the same.

Positive and negative photosensitive compositions are used to manufacture insulating films of various display devices such as liquid crystal displays and organic light emitting devices.

Conventional positive photosensitive compositions containing an alkali-soluble resin and a 1,2-quinonediazide compound are thermally decomposed during post-bake after exposure and development, and upon absorption of short wavelengths such as ultraviolet rays, causing coloration or impurities. There is a problem that afterimage is caused in the liquid crystal display device by generating

Therefore, in order to solve this problem, research on a negative photosensitive composition that can provide high light transmittance and sensitivity after heat curing has been continued. At this time, in display devices such as thin film transistor (TFT) type liquid crystal displays, alkali-soluble constituent units derived from glycidyl (meth)acrylate to protect the TFT circuit and secure heat resistance and light resistance. A photosensitive resin composition contained in a resin has been proposed for use in an organic insulating film.

However, the constituent units derived from the existing glycidyl (meth)acrylate tend to deteriorate the stability over room temperature of the photosensitive resin composition, so the content of the constituent units derived from the glycidyl (meth)acrylate when forming the organic insulating film There was a problem that the existing organic insulating film was not enough heat resistance due to this limitation.

In this regard, Korean Laid-Open Patent Publication No. 2010-0109370 discloses a constituent unit derived from an alicyclic epoxy group-containing unsaturated compound in addition to a constituent unit derived from glycidyl (meth)acrylate used in the past. A photosensitive resin composition for an insulating film comprising an alkali-soluble resin contained in an amount of not less than% by weight has been disclosed. However, the insulating film obtained from the photosensitive resin composition has a disadvantage in that the stability over room temperature is poor and the pattern is not properly implemented due to the problem of actual developability.

Republic of Korea Patent Publication No. 2010-0109370

Accordingly, an object of the present invention is to provide a negative photosensitive resin composition capable of providing not only high-resolution pattern developability, but also excellent room temperature aging stability, thermal shock stability, heat resistance and chemical resistance, and an insulating film prepared therefrom.

In order to achieve the above object, the present invention

(A) (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof, (a2) a structural unit derived from a monomer represented by the following formula (1), (a3) by the following formula (2) Constituent units derived from the displayed monomer, and (a4) constituent units derived from ethylenically unsaturated compounds different from the constituent units (a1), (a2) and (a3), wherein the constituent unit (a2) and an alkali-soluble resin comprising the sum of (a3) in an amount of 10 to 50 mol% based on the total number of moles of the structural unit;

(B) photopolymerizable monomer; And

(C) photopolymerization initiator

It provides a photosensitive resin composition comprising:

[Formula 1] [Formula 2]

In the above formula,

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

R ₂ and R ₄ are each independently C ₁ -C ₄ alkylene.

The photosensitive resin composition of the present invention can provide a cured film exhibiting excellent pattern developability, stability over room temperature, heat resistance and chemical resistance, and thus can be usefully used in the manufacture of an insulating film for a liquid crystal display.

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

(A) alkali-soluble resin

The alkali-soluble resin used in the present invention is (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof, (a2) an unsaturated monomer containing an alicyclic epoxy group represented by the following formula (1). A structural unit derived from, (a3) a structural unit derived from an unsaturated monomer containing a non-alicyclic epoxy group represented by the following formula (2), and (a4) ethylene different from the structural units (a1), (a2) and (a3). Constituent units derived from a sexually unsaturated compound are included, wherein the sum of the constituent units (a2) and (a3) is included in an amount of 10 to 50 mol% based on the total number of moles of the constituent units.

(a1) structural units derived from ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic anhydrides, or mixtures thereof

In the present invention, the structural unit (a1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof, and the ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof is As a grouped polymerizable unsaturated monomer, 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; Trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof; 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 or more selected from esters, but is not limited thereto. Among these, it may be preferably (meth)acrylic acid, particularly in terms of developability.

The content of the constituent units derived from the (a1) ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic anhydride, or a mixture thereof may be 5 to 50 mol% with respect to the total molar ratio of the constituent units constituting the alkali-soluble resin, preferably It may be 10 to 40 mol%. In the above range, it is possible to achieve a pattern formation of a coating film while having good developability.

In the present invention, (meth)acrylic 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 represented by Formula 1

In the present invention, the structural unit (a2) is derived from an unsaturated monomer containing an alicyclic epoxy group, and the monomer is represented by the following formula (1):

[Formula 1]

Wherein R ₁ is hydrogen or C ₁ -C ₄ alkyl; R ₂ is C ₁ -C ₄ alkylene.

Preferably, R ₁ in Formula 1 is hydrogen or methyl, and the unsaturated monomer containing an alicyclic epoxy group may be 3,4-epoxycyclohexylmethylacrylate or 3,4-epoxycyclohexylmethylmethacrylate. have.

(a3) a structural unit derived from an unsaturated monomer containing a non-alicyclic epoxy group represented by Formula 2

In the present invention, the structural unit (a3) is derived from an unsaturated monomer containing a non-aliphatic epoxy group, and the monomer is represented by the following formula (2):

[Formula 2]

Wherein R ₃ is hydrogen or C ₁ -C ₄ alkyl; R ₄ is C ₁ -C ₄ alkylene.

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

The sum of the constituent units (a2) and (a3) 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 alkali-soluble resin. In the above range, the storage stability of the composition is maintained and the residual film rate is improved.

In addition, the molar ratio of the structural unit (a2) to (a3) is 50 to 99 to 50 to 1, and preferably 50 to 80 to 50 to 20. In the above range, excellent stability over room temperature, heat resistance and chemical resistance can be obtained, and pattern implementation is improved.

(a4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a1), (a2) and (a3)

In the present invention, the structural unit (a4) is derived from an ethylenically unsaturated compound different from the structural units (a1) to (a3), and the ethylenically unsaturated compound different from the structural units (a1) to (a3) is phenyl (meth) Acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxypoly Propylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl Styrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene , Vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether, and aromatic ring-containing ethylenically unsaturated compounds containing p-vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl ( Meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3- Chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethyl Acrylate, butyl α-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)methylether (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3 -Hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Unsaturated carboxylic acid esters including dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (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 at least 1 selected from the group consisting of unsaturated imides including N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. It can be more than a species.

The content of the constituent unit (a4) may be 5 to 70 mol%, preferably 10 to 65 mol%, based on the total molar ratio of the constituent units constituting the alkali-soluble resin. In the above range, the reactivity of the alkali-soluble resin can be adjusted and the solubility in an aqueous alkali solution can be increased, thereby remarkably improving the applicability of the photosensitive resin composition.

In addition, the alkali-soluble resin used in the present invention may have a weight average molecular weight of 500 to 50,000, preferably 3,000 to 30,000. When it has a weight average molecular weight in the above range, adhesion to the substrate is excellent, physical and chemical properties are good, and viscosity is appropriate. 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 elution solvent).

The alkali-soluble resin used in the present invention can be synthesized by copolymerization by a known method.

The content of the alkali-soluble resin may be 1 to 80% by weight, preferably 5 to 60% 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 good, and properties such as a film residual rate and chemical resistance are improved.

(B) photopolymerizable monomer

The photopolymerizable monomer used in the present invention is a compound that can be polymerized by the action of a photopolymerization initiator, and may include a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenic unsaturated group, but chemical resistance In terms of, preferably, it may be a bifunctional or more multifunctional compound.

As the photopolymerizable monomer, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol Di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate )Acrylate, monoester product of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylic Rate, monoester product of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (pentaerythritol triacrylate And hexamethylenediisocyanate), tripentaerythritolhepta (meth)acrylate, tripentaerythritol octa (meth)acrylate, bisphenol A epoxy acrylate, and selected from the group consisting of ethylene glycol monomethyl ether acrylate One or more of which may be used may be used, but the present invention is not limited thereto.

In addition, a compound having a straight-chain alkylene group and an alicyclic structure and having two or more isocyanate groups, and three, four or five acryloyloxy groups and/or methacryloyl oxy groups having one or more hydroxyl groups in the molecule A polyfunctional urethane acrylate compound obtained by reacting a compound having a time period, but is not limited thereto.

As the commercially available photopolymerizable monomer, as a commercial product of monofunctional (meth)acrylate, Aaronics M-101, Copper M-111, Copper M-114 (manufactured by Doagosei Co., Ltd.), AKAYARAD TC-110S , TC-120S (manufactured by Nippon Kayaku Co., Ltd.), V-158, V-2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), etc., and as a commercial product of bifunctional (meth)acrylate, Aaronics M-210, Bldg M-240, Bldg M-6200 (manufactured by Doa Kosei Co., Ltd.), KAYARAD HDDA, Dong HX-220, Bldg. R-604 (product of Nippon Kayaku Corporation), V260, V312, V335 HP (Osaka Yuki Chemical Industry Co., Ltd.), etc., and as commercial products of trifunctional or higher (meth)acrylates, Aaronics M-309, Copper M-400, Copper M-403, Copper M-405, and M- 450, East M-7100, East M-8030, East M-8060, TO-1382 (manufactured by Doagosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPH1-40H, East DPC1-20, East-30, East -60, Dong-120 (made by Nippon Kayaku Co., Ltd.), V-295, Dong-300, Dong-360, Dong-GPT, Dong-3PA, Dong-400 (made by Osaka Yuki Chemical High School) And the like.

The photopolymerizable monomer may be used alone or in combination of two or more, and 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 alkali-soluble resin (based on solid content). . In the above range, it is possible to obtain high sensitivity and excellent pattern developability and coating properties.

(C) photopolymerization initiator

The photopolymerization initiator used in the present invention serves to initiate a polymerization reaction 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 its kind is not particularly limited, but an acetophenone-based, benzophenone-based, benzoin-based and benzoyl-based, xanthone-based, triazine-based, halomethyloxadiazole-based, and lopindimeric photopolymerization initiator One or more selected from the group consisting of may be used.

Specific examples include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl Peroxide, t-butylperoxypivalate, 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-propan-1-one, benzyldimethylketal, benzophenone, benzoinpropyl ether, diethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacry Din, 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-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazoryl 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, WO 10102502, and the oxime compounds described in WO 10133077.

The photopolymerization initiator 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 alkali-soluble resin (based on solid content). In the above range, it is possible to obtain high sensitivity and excellent pattern developability and coating properties.

(D) other ingredients

The present invention may further include other components to improve the properties of the photosensitive resin composition. For example, the other components include (1) surfactant, (2) silane coupling agent and/or (3) solvent.

(1) surfactant

If necessary, the photosensitive resin composition of the present invention may further include a surfactant to improve coating properties and prevent defects.

The type of the surfactant is not particularly limited, but preferably, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and other surfactants are mentioned. Among these, in terms of dispersibility, BYK 333 of BYK may be preferably used.

Examples of the surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F- 482, F-489 (manufactured by Dai Nippon Ink Chemical Industry 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 , Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF301, Ftop 303, Ftop 352 (Shin Akita 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 Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, Fluorine-based and silicone-based surfactants such as TSF-4460, TSF-4452 (manufactured by GE Toshiba Silicon Corporation), and BYK-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 organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based copolymer polyflow No. 57, 95 (Kyoeisha Yuji Chemical Co., Ltd. product), etc. are mentioned. These can be used alone or in combination of two or more.

The surfactant 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 alkali-soluble resin (based on solid content). In the above range, the coating of the composition becomes smooth.

(2) Silane coupling agent

The photosensitive resin composition of the present invention has at least one reactive substituent 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 in order to improve adhesion to the substrate. It may further include a silane coupling agent having.

The kind of the silane coupling agent is not particularly limited, but trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 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, preferably γ-glycidoxypropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane having an epoxy group having good adhesion to the substrate while improving the residual film rate may be used. . In addition, γ-isocyanatopropyltriethoxysilane having an isocyanate group (KBE-9007 from Shin-Etsu) may be used to improve chemical resistance.

The silane coupling agent 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 alkali-soluble resin (based on solid content). In the above range, the adhesion to the substrate becomes good.

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

(3) solvent

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

The solvent is compatible with the above-described photosensitive resin composition components, but does not react with them, and any known solvent used in the photosensitive resin composition may 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; Cellosolves such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolactone; And mixtures thereof, but are not limited thereto. 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 from the viewpoint of coating properties and stability of the photosensitive resin composition obtained, the solid content is 5 to 70% by weight, preferably based on the total weight of the composition. It may contain an organic solvent so that it is 10 to 55% by weight.

Here, the solid content means removing the solvent 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 prepare an insulating film, and the insulating film may be used as an electronic component.

Further, 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 can be prepared 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. After removing the solvent, a pattern can be formed on the coating layer by exposure to light using a photomask having a desired pattern and developing with a developer (eg, tetramethylammonium hydroxide solution (TMAH)). Thereafter, the patterned coating layer is 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 10 to 100 mJ/cm ² in a wavelength range of 200 to 450 nm.

The cured film obtained by the photosensitive resin composition of the present invention exhibits excellent pattern developability, stability over room temperature, heat resistance and chemical resistance, and is suitable for a material for LCD.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

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

Preparation Example 1: Preparation of alkali-soluble resin (A-1)

2,2'-azobis (2,4-dimethylvaleronitnyl) 3 parts by weight, propylene glycol monomethyl ether as polymerization initiator in a cooling tube with a drying tube, a stirrer with a stirrer and a thermostat and a three-necked flask 100 parts by weight of acetate, and 10 mol% of glycidyl methacrylate, 20 mol% of 3,4-epoxycyclohexylmethyl methacrylate, 23 mol% of methacrylic acid, 12 mol% of methyl methacrylate, 35 mol% of styrene 100 parts by weight of the monomer mixture consisting of was added. After nitrogen was added thereto, the temperature of the solution was gradually increased to 70° C. while stirring, and polymerization was performed while maintaining this temperature for 5 hours to obtain a solution of the copolymer (A-1) having a weight average molecular weight of 10,200.

Preparation Examples 2 to 13: Preparation of alkali-soluble resins (A-2) to (A-13)

Polymers (A-2) to (A) by performing a polymerization reaction in the same manner as in Preparation Example 1, except that the types and contents of the components constituting the monomer mixture were variously changed as shown in Table 1 below. -13) Each solution was obtained.

Manufacturing example GMA METHB MAA Styrene MMA CHMI DCPMA Molecular Weight (A-1) 10 20 23 35 12 0 0 10,200 (A-2) 10 20 23 0 16 0 31 10,100 (A-3) 5 25 21 35 14 0 0 9,700 (A-4) 15 15 22 35 13 0 0 10,000 (A-5) 15 15 24 36 0 10 0 9,900 (A-6) 10 30 24 36 0 0 0 10,300 (A-7) 10 15 21 37 17 0 0 9,800 (A-8) 10 10 20 34 21 5 0 9,900 (A-9) 20 0 22 38 20 0 0 9,800 (A-10) 40 0 21 35 4 0 0 10,500 (A-11) 0 30 22 35 13 0 0 10,100 (A-12) 60 20 20 0 0 0 0 9,900 (A-13) 72 10 18 0 0 0 0 10,200

GMA: Glycidyl methacrylate METHB: 3,4-epoxycyclohexylmethyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

CHMI: Cyclohexyl methacrylate

DCPMA: Dicyclopentenyl methacrylate

Example 1

Alkali-soluble resin synthesized in Preparation Example 1 (A-1) 100 parts by weight (solid content), (B-1) dipentaerythritol hexaacrylate 65 parts by weight as a photopolymerization monomer, (C-1) OXE as a photopolymerization initiator -01 (brand name, BASF) 4 parts by weight and (C-2) OXE-02 (brand name, BASF) 1 parts by weight, as a surfactant (D-1) FZ-2110 (brand name, Dow Corning Toray Corporation silicone company make ) 0.3 parts by weight (solid content), 0.5 parts by weight (solid content) of the silane coupling agent (E-1) γ-glycidoxypropyltriethoxysilane, and the solid content of the sum of the above components is 25% by weight Propylene glycol monomethyl ether acetate as a solvent was added in an amount and mixed for 2 hours using a shaker to prepare a photosensitive resin composition in a liquid form.

Examples 2 to 8 and Comparative Examples 1 to 5

A photosensitive resin composition was prepared by performing the same process as in Example 1, except for changing the content (parts by weight) of the constituent components used as shown in Table 2 below.

A film was prepared from the photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 5, and the pattern resolution, stability over room temperature, thermal shock stability, heat resistance and chemical resistance of the cured film were measured, and the results are shown in Table 2 below. Done.

[Manufacture of cured film]

The photosensitive resin composition was spin-coated on a glass substrate and then pre-cured for 90 seconds on a high-temperature plate maintained at a temperature of 100° C. to form a dry film having a thickness of 3 μm. Using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm on this film, exposure was performed for a certain period of time to be 30 mJ/cm 2 based on 365 nm without using a mask as an exposure standard, and 2.38 wt% tetramethyl It was developed for 70 seconds through a spray nozzle at 23° C. with an ammonium hydroxide aqueous developer. The obtained exposed film was heated (post-cured, post-bake) at 230° C. for 30 minutes in a convection oven to obtain a cured film.

1. Pattern resolution (%)

In the preparation of the cured film, a mask having a square hole pattern having a difference of 1 µm in size from 1 to 15 µm is applied on a dry film having a thickness of 3 µm, and the gap between the mask and the substrate is set to 10 µm as an exposure standard. The CD (critical dimension: line width, unit: µm) of the patterned hole pattern for 10 µm was measured using a three-dimensional surface measuring machine, and a pattern resolution (%) value was obtained from the following equation. It can be said that the smaller the pattern resolution (%) value, the better the resolution.

Pattern resolution (%)=[(mask size-CD of hole pattern)/(mask size)]×100

2. Stability over room temperature (%)

10 g of the photosensitive resin composition having a solid content of 25% by weight was put into a 20 ml glass vial bottle and stored in an oven at 40° C. for 48 hours, and the degree of increase in viscosity (%) was measured. The viscosity was measured using a TV-22 rotary viscometer manufactured by TOKI SANGYO. At this time, a 1 ml sample was collected and put in a viscometer, the temperature stabilized at 25°C, and the viscosity was measured using a pressure applied to the spindle of the viscometer. If the degree of viscosity increase (%) is 5% or less, it can be said to be excellent, and if it is 3% or less, it can be said to be very excellent.

Viscosity increase rate (%) = [(Viscosity after storage at 40℃/48 hours oven-initial viscosity)/(initial viscosity)]×100

3. Thermal shock stability (%)

In the production of the cured film, a 6-inch wafer substrate was used instead of the glass substrate. Further, after measuring the thickness of the obtained cured film, the exposed film was further heated in a convection oven at 250° C. for 60 minutes, and then the thickness was measured. The thickness of the obtained film was measured with a film thickness evaluation equipment (trade name Nanospec.), and the thickness reduction rate due to thermal shock was calculated from the following equation. It can be said that the lower the rate of thickness reduction due to thermal shock, the better the thermal shock stability.

Thickness reduction rate due to thermal shock (%) = [(film thickness after 1st curing-thickness after 2nd curing) / (film thickness after 1st curing)]×100

4. Heat resistance (TGA, %)

The cured film was scraped off with a knife, and the weight of 5 mg was increased from room temperature to 230° C. by 10° C. per minute using a thermogravimetric analyzer, and then the weight was measured while maintaining at 250° C. for 60 minutes. Heat resistance (weight reduction rate) was calculated from the following equation. It can be said that the lower the weight reduction rate (%), the better the heat resistance.

Weight reduction rate (%) = [(Initial weight at 25℃-remaining weight after maintaining 250℃ for 60 minutes) / (Initial weight at 25℃)]×100

5. Chemical resistance (%)

In the production of the cured film, a 6-inch wafer substrate was used instead of the glass substrate. Furthermore, the thickness of the obtained cured film specimen was measured using a contact-type film thickness meter (Alpha step). After NMP (N-methyl-2-pyrrolidone) was put in a beaker to reach 70° C. in a thermostat, the above cured film specimen was immersed for 10 minutes, and the thickness was measured in the same manner. The chemical resistance (%) value was calculated from the following formula. The lower the chemical resistance (%) value, the better it can be said.

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

division alkali
Soluble resin Light polymerization
Monomer Photopolymerization initiator resolution
(%) Room temperature
stability
(%) Thermal shock
stability
(%) Heat resistance
(TGA)
(%) Chemical resistance
(%) Example 1 A-1 100 B-1 65 C-1 4 C-2 One 23% 3.3 4.1 15.2 10.3 Example 2 A-2 100 B-1 65 C-1 4 C-2 One 29% 3.0 3.6 14.5 10.1 Example 3 A-3 100 B-1 65 C-1 4 C-2 One 26% 2.7 2.8 16.6 13.1 Example 4 A-4 100 B-1 65 C-1 4 C-2 One 24% 3.9 4.3 12.8 8.6 Example 5 A-5 100 B-1 65 C-1 4 C-2 One 32% 4.2 4.6 12.1 9.2 Example 6 A-6 100 B-1 65 C-1 4 C-2 One 35% 3.7 1.8 11.9 9.7 Example 7 A-7 100 B-1 65 C-1 4 C-2 One 21% 2.4 4.1 15.9 11.3 Example 8 A-8 100 B-1 65 C-1 4 C-2 One 16% 2.2 4.8 17.1 11.6 Comparative Example 1 A-9 100 B-1 65 C-1 4 C-2 One 33% 9.4 8.4 16.8 12.3 Comparative Example 2 A-10 100 B-1 65 C-1 4 C-2 One 54% 15.4 5.0 12.8 9.6 Comparative Example 3 A-11 100 B-1 66 C-1 5 C-2 One 28% 3.8 2.5 20.3 16.8 Comparative Example 4 A-12 100 B-1 65 C-1 4 C-2 One 100% 24.5 2.1 9.6 9.4 Comparative Example 5 A-13 100 B-1 65 C-1 4 C-2 One 100% 29.8 1.5 8.5 8.1

As can be seen from the results of Table 2, the cured film prepared from the compositions of Examples 1 to 8 using an alkali-soluble resin containing a specific structural unit in a specific content does not contain a specific structural unit or deviates from a specific content. Compared to the case of Comparative Examples 1 to 5 using the alkali-soluble resin contained in an amount, it can be seen that overall pattern resolution, stability with time at room temperature, thermal shock stability, heat resistance and chemical resistance are shown. Accordingly, 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 (4)

(A) (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof, (a2) a structural unit derived from a monomer represented by the following formula (1), (a3) by the following formula (2) Constituent units derived from the displayed monomer, and (a4) constituent units derived from ethylenically unsaturated compounds different from the constituent units (a1), (a2) and (a3), wherein the constituent unit (a2) and an alkali-soluble resin containing the sum of (a3) in an amount of 10 to 50 mol% based on the total number of moles of the structural unit;
(B) photopolymerizable monomer; And
(C) photopolymerization initiator
Photosensitive resin composition comprising:
[Formula 1] [Formula 2]

In the above formula,
R ₁ and R ₃ are each independently hydrogen or C ₁ -C ₄ alkyl;
R ₂ and R ₄ are each independently C ₁ -C ₄ alkylene. The method of claim 1,
The photosensitive resin composition, wherein the monomer represented by Formula 1 is 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethylmethacrylate. The method of claim 1,
The photosensitive resin composition, wherein the monomer represented by Formula 2 is glycidyl acrylate or glycidyl methacrylate. The method of claim 1,
The photosensitive resin composition, characterized in that the molar ratio of the structural unit (a2) to (a3) is 50 to 99 to 50 to 1.