KR102360238B1 - Negative-type photosensitive resin composition and insulating film using same - Google Patents

Abstract

The present invention relates to a negative photosensitive resin composition and an insulating film using the same. The photosensitive resin composition of the present invention, comprising an alkali-soluble resin in an amount of 10 to 50 mol%, can provide a cured film exhibiting excellent pattern developability, stability over time at room temperature, thermal shock stability, heat resistance and chemical resistance, It can be usefully used in the manufacture of an insulating film for a liquid crystal display device.

Description

Negative photosensitive resin composition and insulating film using the same

The present invention relates to a negative photosensitive resin composition and an insulating film using the same, and more particularly, it can form a cured film that not only exhibits high-resolution pattern developability, but also has excellent stability over room temperature, high thermal shock stability and heat resistance and excellent chemical resistance. It relates to a photosensitive resin composition useful for forming an insulating film of a display device such as a liquid crystal display (LCD), and an insulating film manufactured using the same.

Positive-type and negative-type photosensitive compositions are used in the manufacture of insulating films of various display devices, such as liquid crystal displays and organic light emitting devices.

A conventional positive-type photosensitive composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound is thermally decomposed during post-bake after exposure and development and absorption of a short wavelength such as ultraviolet light to cause coloring or impurities There was a problem in that an afterimage was induced in the liquid crystal display device.

Therefore, in order to solve this 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, a constituent unit derived from glycidyl (meth)acrylate is alkali-soluble 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 as an organic insulating film.

However, the structural unit derived from the existing glycidyl (meth) acrylate tends to decrease the stability over room temperature of the photosensitive resin composition. There was a problem in that the existing organic insulating film had insufficient heat resistance.

In this regard, Korean Patent Application Laid-Open No. 2010-0109370 discloses that, in addition to the previously used structural units derived from glycidyl (meth) acrylate, structural units derived from alicyclic epoxy group-containing unsaturated compounds as a sum of 71 A photosensitive resin composition for an insulating film comprising an alkali-soluble resin contained in an amount of at least % by weight has been disclosed. However, the insulating film obtained from the photosensitive resin composition has disadvantages 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 not only exhibiting high-resolution pattern developability, but also providing excellent stability over room temperature, 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 acid anhydride, or a mixture thereof, (a2) a structural unit derived from a monomer represented by the following formula (1), (a3) a structural unit derived from the following formula (2) a structural unit derived from the represented monomer, and (a4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a1), (a2) and (a3), wherein the structural unit (a2) and alkali-soluble resin comprising the sum of (a3) in an amount of 10 to 50 mol% with respect to the total number of moles of structural units;

(B) a photopolymerizable monomer; and

(C) photoinitiator

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 device.

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

(A) alkali-soluble resin

The alkali-soluble resin used in the present invention is an unsaturated monomer containing (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) 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) A structural unit derived from a sexually unsaturated compound is included, and in this case, the sum of the structural units (a2) and (a3) is included in an amount of 10 to 50 mol% based on the total number of moles of the structural units.

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

In the present invention, the structural 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, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof contains one or more carboxyl groups in the molecule 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 and anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof; and mono[(meth)acryloyloxyalkyl] of polycarboxylic acids having at least divalence such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate It may be at least one selected from among esters, but is not limited thereto. Among them, it may be preferably (meth)acrylic acid in terms of developability.

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

In the present invention, (meth)acryl refers to acrylic and/or methacryl, 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 the 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, in Formula 1, R ₁ is hydrogen or methyl, and the unsaturated monomer containing an alicyclic epoxy group may be 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. have.

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

In the present invention, the structural unit (a3) is derived from an unsaturated monomer containing a non-alicyclic 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, in Formula 2, R ₃ is hydrogen or methyl, and the unsaturated monomer containing the non-alicyclic epoxy group may be glycidyl acrylate or glycidyl methacrylate.

The combined content of the structural units (a2) and (a3) may be 10 to 50 mol%, preferably 15 to 45 mol%, based on the total number of moles of the structural units constituting the alkali-soluble resin. In the above range, the storage stability of the composition is maintained and the remaining film rate is improved.

Further, the molar ratio of the structural unit (a2) to (a3) is 50 to 99 to 50 to 1, 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-nonylphenoxypolyethylene 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, iodine styrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene , an aromatic ring-containing ethylenically unsaturated compound including vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether, and 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, tetrahydropurpril (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) methyl ether (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 one selected from the group consisting of unsaturated imides including N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. may be more than one species.

The content of the structural unit (a4) may be 5 to 70 mol%, preferably 10 to 65 mol%, based on the total molar ratio of the structural units constituting the alkali-soluble resin. In the above range, it is possible to control the reactivity of the alkali-soluble resin and increase the solubility in aqueous alkali solution, 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. In the case of having a weight average molecular weight in the above range, the adhesion to the substrate is excellent, physical and chemical properties are good, and the viscosity is appropriate. The weight average molecular weight refers to the 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 wt%, preferably 5 to 60 wt%, based on the total weight of the photosensitive resin composition excluding the remainder of the solvent. If it is the above range, the pattern development after development is favorable, and characteristics, such as a residual film rate and chemical resistance, improve.

(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 ethylenically unsaturated group, but chemical resistance In terms of preferably, it may be a bifunctional or more polyfunctional compound.

Examples of the photopolymerizable monomer include 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, 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 hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate. One or more of these 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 methacryloyloxy groups having one or more hydroxyl groups in the molecule and polyfunctional urethane acrylate compounds obtained by reacting a compound having a group, but is not limited thereto.

Commercially available photopolymerizable monomers include monofunctional (meth)acrylate, Aronix M-101, Copper M-111, Copper M-114 (manufactured by Toagosei Co., Ltd.), AKAYARAD TC-110S , copper TC-120S (manufactured by Nippon Chemical Co., Ltd.), V-158, V-2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), etc., as a commercial product of bifunctional (meth)acrylate, Aronix M-210, Dong M-240, Dong M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, Dong HX-220, Dong R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335 HP (Osaka Yuki Chemical Co., Ltd. product), etc., and commercially available products of trifunctional or higher (meth)acrylates include Aronix M-309, Copper M-400, Copper M-403, Copper M-405, Copper M- 450, Dong M-7100, Dong M-8030, Dong M-8060, TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, Dong DPHA, Dong DPH1-40H, Dong DPC1-20, Dong-30, Bronze -60, Dong-120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, Dong-300, Dong-360, Dong-GPT, Dong-3PA, Dong-400 (product of 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 the solid content). . In the above range, it is possible to obtain high sensitivity and excellent pattern developability and coating film properties.

(C) photoinitiator

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, and the like. The photopolymerization initiator may be a radical initiator, and the type thereof is not particularly limited, but may include acetophenone-based, benzophenone-based, benzoin-based and benzoyl-based, xanthone-based, triazine-based, halomethyloxadiazole-based and lopin dimer-based photopolymerization initiators. 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, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacrylate 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-diphenylphosphonyloxide, hexafluorophosphoro-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, WO 10102502, WO 10133077, and the oxime-based compounds described.

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 the solid content). In the above range, it is possible to obtain high sensitivity and excellent pattern developability and coating film 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 may include (1) a surfactant, (2) a silane coupling agent and/or (3) a solvent.

(1) Surfactant

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

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 them, BYK 333 manufactured by BYK may be preferably used in terms of dispersibility.

Examples of the surfactant include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F- 482, F-489 (manufactured by Dainippon Ink Chemicals Co., Ltd.), Florad FC-135, Florad FC-170C, Florad FC-430, Florad FC-431 (Sumitomo 3M Co., Ltd.) Manufactured), Surflon S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145, Surfron S-382, Surfron SC-101, Surfron SC-102 , SURFRON SC-103, SUFRON SC-104, SURFRON SC-105, SURFRON SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, F-Top 303, F-Top 352 (Shin-Akita Gassei) (manufactured by Toray Silicone Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone 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 Silicone Co., Ltd.), 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 and 95 (manufactured by Kyoeisha Yuji Chemical Co., Ltd.) and the like. These can be used individually or in combination of 2 or more types.

The surfactant may be used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the alkali-soluble resin (based on the 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 to improve adhesion with a substrate It may further include a silane coupling agent having.

The type of the silane coupling agent is not particularly limited, but trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltrie At least one selected from the group consisting of oxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane More than one species may be used, and preferably γ-glycidoxypropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane having an epoxy group with good adhesion to the substrate while improving the remaining film rate may be used. . In addition, γ-isocyanatopropyltriethoxysilane having an isocyanate group (KBE-9007 manufactured by 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 parts by weight, based on 100 parts by weight of the alkali-soluble resin (based on the solid content). In the above range, the adhesion to the substrate becomes good.

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

(3) solvent

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

As the solvent, any known solvent used in the photosensitive resin composition may be used as long as it has compatibility with the above-described photosensitive resin composition components but does not react with them.

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 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 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. The solvent 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 applicability and stability of the obtained photosensitive resin composition, the solid content is 5 to 70% by weight, preferably based on the total weight of the composition. Preferably, the organic solvent may be included in an amount of 10 to 55% by weight.

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

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

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

The insulating film may be prepared by a method known in the art, for example, the photosensitive resin composition is applied on a silicon substrate by a spin coating method, and pre-bake at 60 to 130° C. for 60 to 130 seconds. After removing the solvent, the pattern can be formed on the coating layer by exposure using a photomask having a desired pattern formed thereon, 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 way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

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

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

3 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as polymerization initiator, propylene glycol monomethyl ether in a cooling tube with drying tube, stirrer and three-necked flask equipped with stirrer and automatic temperature controller 100 parts by weight of acetate, 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 a monomer mixture consisting of After nitrogen was added, the temperature of the solution was raised to 70° C. while stirring slowly, and polymerization was performed while maintaining this temperature for 5 hours to obtain a solution of 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)

A polymerization reaction was performed 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 to perform copolymers (A-2) to (A-2) -13) each solution was obtained.

production 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

100 parts by weight of the alkali-soluble resin (A-1) synthesized in Preparation Example 1 (solid content), (B-1) as a photopolymerization monomer 65 parts by weight of dipentaerythritol hexaacrylate, (C-1) OXE as a photoinitiator -01 (trade name, BASF Corporation) 4 parts by weight and (C-2) OXE-02 (trade name, BASF Corporation) 1 part by weight, as a surfactant (D-1) FZ-2110 (trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.) ) 0.3 parts by weight (solid content), 0.5 parts by weight (solid content) of (E-1) γ-glycidoxypropyltriethoxysilane, which is a silane coupling agent, and the solid content of the sum of the 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 liquid photosensitive resin composition.

Examples 2 to 8 and Comparative Examples 1 to 5

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the content (parts by weight) of the components used was changed 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, room temperature stability, thermal shock stability, heat resistance and chemical resistance of the cured film were measured, and the results are shown in Table 2 below. it was

[Production of cured film]

After spin-coating the photosensitive resin composition on a glass substrate, it was pre-bake 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) that emits a wavelength of 200 nm to 450 nm on this film, without using a mask as an exposure standard, and exposure for a certain period of time so as to be 30 mJ/cm 2 based on 365 nm, 2.38 wt% tetramethyl It was developed for 70 seconds through a spray nozzle at 23 ℃ with an aqueous developer of ammonium hydroxide. The resulting exposed film was heated (post-bake) at 230°C in a convection oven for 30 minutes to obtain a cured film.

1. Pattern resolution (%)

In the production of the cured film, a mask having a square hole pattern with a size difference of 1 µm to 1 µm is applied on a dry film having a thickness of 3 µm, and the interval between the mask and the substrate is 10 µm as an exposure standard. The CD (critical dimension: line width, unit: μm) of the patterned hole pattern with respect to 10 μm was measured using a three-dimensional surface measuring device, and the pattern resolution (%) value was obtained from the following formula. 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 placed in a 20 ml glass vial and stored in an oven at 40° C. for 48 hours, and then the degree of viscosity increase (%) was measured. The viscosity was measured using a TV-22 rotary viscometer manufactured by TOKI SANGYO. At this time, a 1 ㎖ sample was taken, put in a viscosity meter, and after the temperature was stabilized at 25° C., the viscosity was measured using the pressure applied to the spindle of the viscosity meter. 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°C/48 hours-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. Furthermore, after measuring the thickness of the obtained cured film, the exposure 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 device (trade name: Nanospec.), and the thickness reduction rate due to thermal shock was calculated from the following formula. It can be said that the lower the thickness reduction rate due to thermal shock, the better the thermal shock stability.

Thickness reduction rate by thermal shock (%) = [(film thickness after primary curing - film thickness after secondary curing) / (film thickness after primary curing)]×100

4. Heat resistance (TGA, %)

The cured film was scraped off with a knife, and a weight of 5 mg was increased from room temperature to 230° C. at a rate of 10° C. per minute using a thermogravimetric analyzer, and the weight was measured while maintaining at 250° C. for 60 minutes. Heat resistance (weight reduction rate) was calculated from the following formula. 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 holding at 250℃ for 60 minutes) / (Weight at initial 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 putting NMP (N-methyl-2-pyrrolidone) in a beaker to 70° C. in a constant temperature bath, the cured film specimen was immersed for 10 minutes, and then the thickness was measured in the same manner. The chemical resistance (%) value was calculated from the following formula. It can be said that the lower the chemical resistance (%) value, the better.

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

division alkali
soluble resin light curing
monomer photopolymerization initiator resolution
(%) lapse of 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 in Table 2, the cured films prepared from the compositions of Examples 1 to 8 using the alkali-soluble resin containing the specific structural unit in a specific content do not include the specific structural unit or are deviating from the specific content. It can be seen that the overall pattern resolution, stability over room temperature, thermal shock stability, heat resistance and chemical resistance are clearly superior to those of Comparative Examples 1 to 5 using the alkali-soluble resin included in an amount. 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 (4)

(A) (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 a monomer represented by the following formula (1), (a3) to the following formula (2) a structural unit derived from the represented monomer, and (a4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a1), (a2) and (a3), wherein the structural unit (a2) and an alkali-soluble resin comprising the sum of (a3) in an amount of 25 to 30 mol% with respect to the total number of moles of the structural units, wherein the molar ratio of the structural units (a2) to (a3) is 15:10 to 25:5;
(B) a photopolymerizable monomer; and
(C) photoinitiator
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 method of claim 1,
The photosensitive resin composition, characterized in that the monomer represented by Formula 1 is 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. The method of claim 1,
The photosensitive resin composition, characterized in that the monomer represented by Formula 2 is glycidyl acrylate or glycidyl methacrylate. delete