TW201610581A - Photosensitive resin composition, and insulating film and electric device using same - Google Patents

Abstract

Disclosed herein are a photosensitive resin composition, and insulating film and electric device using same. The photosensitive resin composition can exhibit good pattern formation when prepared as a cured film, and also show excellent surface formation when a metal film is applied onto the cured film, by controlling the amounts of the polymerizable compound and residual monomers of the copolymer that have not been consumed in the copolymerization, and thus can be effectively used as an interlayer insulating film in a TFT-LCD.

Description

Photosensitive resin composition and insulating film and electronic device using the same

The present invention relates to a photosensitive resin composition, more specifically, to a negative photosensitive resin composition for forming an interlayer insulating film in a thin film transistor type liquid crystal display (TFT-LCD).

The positive photosensitive resin composition and the negative photosensitive resin composition are used for producing an insulating film for use in various display devices including a liquid crystal display (LCD), an organic light emitting diode (OLED), and the like.

However, during the exposure treatment, post-development baking, and absorption of short-wavelength light such as UV rays, the positive-type photosensitive resin composition particularly contains conventional alkali-soluble resins and 1,2-quinonediazide compounds. Problems such as discoloration due to thermal cracking, or undesired image sticking of the LCD due to the formation of impurities.

Attempts have been made to remedy such problems by providing a negative photosensitive resin composition which produces a cured film having excellent light transmittance and sensitivity after a heat curing treatment process.

In particular, as a display device such as a TFT-LCD The curable resin composition of the organic insulating film has been proposed as a negative photosensitive resin composition because of its high insulating properties and other good properties required for the process, including chemical resistance and heat resistance, smoothness, post-process stability, and the like. (Refer to Korean Patent Publication No. 2006-0128715).

But using a conventional negative photosensitive resin composition to form a pattern As an example of a cured film, a patterned electrode (metal film) is formed on the cured film, and then an additional treatment is performed on the electrode, causing a problem that the surface of the metal film becomes uneven and wrinkles.

Accordingly, it is an object of the present invention to provide a photosensitive resin composition which exhibits good pattern formation when prepared as an insulating film, and which is applied to the insulating film even after a patterned metal film is applied thereto Excellent surface formation is also exhibited after harsh additional treatment such as high temperature treatment.

According to one aspect of the present invention, there is provided a photosensitive resin composition comprising a copolymer, a polymerizable compound, a photopolymerization initiator, and a solvent, wherein 100 parts by weight of the copolymer is used as a solid content in the composition, The amount of the polymerizable compound is from 1 to 50 parts by weight, and the amount of the residual monomer of the copolymer which is not consumed in the copolymerization reaction is not more than 2 parts by weight.

According to the photosensitive resin composition of the present invention, by adjusting the amount of the polymerizable compound and the residual monomer amount of the copolymer (adhesive) which is not consumed in the copolymerization reaction, when the cured film is prepared Showing good pattern formation and also showing when a metal film is applied to the cured film Excellent surface formation. Therefore, the photosensitive resin composition can be effectively used as an interlayer insulating film in a TFT-LCD.

The photosensitive resin composition of the present invention comprises (A) a copolymer, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, and if necessary, further comprises (E) a surfactant , (F) adhesion promoter, and the like.

The technical features of the present invention will be described in detail later.

(A) copolymer

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

(a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof

The structural unit (a1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a mixture thereof. The ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic anhydride or a mixture thereof is a polymerizable unsaturated compound having at least one carboxyl group in the molecule. Examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids and An anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methyl fumaric acid, etc.; trivalent or More valence of unsaturated polycarboxylic acids and their anhydrides; and one of the divalent or higher polycarboxylic acids [(meth) propylene decyloxyalkyl] esters such as, succinic acid [2-( Methyl)propenyloxyethyl ester], mono[2-(methyl)propenyloxyethyl phthalate], etc., but not limited thereto. In these examples, (meth)acrylic acid is preferred in terms of developing ability.

The amount of the structural unit (a1) may be 5 to 50 mol%, preferably 10 to 40 mol%, based on the total number of moles of the structural units constituting the copolymer (A). Within this amount range, the resin composition will easily form a patterned film having good developability.

In the present invention, "(meth)acryloyl" means "acryloyl" and/or "methacryl", and "(meth)acrylate" means "acrylate" and/or "Methacrylate".

(a2) a structural unit derived from an unsaturated compound having an alicyclic epoxy group

The structural unit (a2) is derived from an unsaturated compound having an alicyclic epoxy group.

In one embodiment, the alicyclic epoxy group-containing unsaturated compound is represented by formula (I):

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

Preferably, in the formula (I), R ₁ is hydrogen or methyl.

In a preferred embodiment, the alicyclic epoxy group-containing unsaturated compound may be 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate. ester.

The amount of the structural unit (a2) may be 10 to 50 mol%, preferably 15 to 45 mol%, based on the total number of moles of the structural units constituting the copolymer (A). Within this range, the composition will have good storage stability and improved film properties such as high pattern resolution.

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

The structural unit (a3) is derived from an ethylenically unsaturated compound which is different from the structural unit (a1) and the structural unit (a2). Examples thereof may include an aromatic ring-containing ethylenically unsaturated compound such as phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, (meth) acrylate. Phenoxy Diethylene glycol ester, p-nonylphenoxy polyethylene glycol (meth)acrylate, p-nonylphenoxy polypropylene glycol (meth)acrylate, tribromophenyl (meth)acrylate , styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl benzene Ethylene, heptyl styrene, octyl styrene, fluorostyrene, chlorostyrene, bromostyrene, iodine styrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy- Α-methylstyrene, ethyl styrene styrene, vinyl toluene, divinyl benzene, vinyl phenol, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, and p-ethylene Alkylbenzyl ether; an unsaturated carboxylic acid ester such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate , isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydroanthracene (meth)acrylate Ester, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (A) Glyceryl acrylate, α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, α-hydroxypropyl methacrylate, α-hydroxy methacrylate butyl, (meth) acrylate 2-methyl Oxyethyl ester, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, (methyl) Methoxytripropylene glycol acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-(meth)acrylate Hexafluoroisopropyl ester, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (methyl) ) C Dicyclopentenyl enoate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, glycidyl (meth)acrylate, (methyl) 3,4-epoxybutyl acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, and (meth)acrylic acid 6, 7-epoxyheptyl ester; tertiary amine having N-vinyl group such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ether such as vinyl methyl Ether and vinyl ethyl ether; and unsaturated quinone imine such as N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4- Hydroxyphenyl) maleimide, and N-cyclohexylmethyleneimine.

The total molar of the structural units constituting the copolymer (A) The amount of the structural unit (a3) may be from 5 to 70 mol%, preferably from 15 to 65 mol%, based on the number. Within this range, the coatability of the photosensitive resin composition is greatly increased because the reactivity of the alkali-soluble resin is easily regulated, and the solubility of the resin in an aqueous alkaline solution is increased.

The copolymer (A) of the present invention can be prepared via a feed molecule a quantity adjusting agent, a polymerization initiator, a solvent, and an individual compound providing structural units (a1), (a2), and (a3) in a reactor, introducing nitrogen into the reactor, and allowing the mixture to be stirred slowly Perform polymerization.

The molecular weight regulator may be a mercaptan such as butyl sulfide Alcohol, octyl mercaptan, lauryl mercaptan, etc. or α-methylstyrene dimer, but not limited thereto.

The polymerization initiator may be an azo compound such as 2, 2'- Azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-even Azaindole (4-methoxy-2,4-dimethylvaleronitrile), etc.; benzamidine peroxide, laurel peroxide, tert-butyl peroxypivalate; or 1,1-anthracene ( Tert-butylperoxy)cyclohexane, but is not limited by this. The polymerization initiators may be used singly or in combination of two or more.

Further, the solvent may be commonly used in the preparation of the copolymer (A). Any conventional solvent is preferably methyl 3-methoxypropionate or propylene glycol monomethyl ether acetate (PGMEA).

More specifically, during the polymerization reaction, when the reaction When carried out under mild reaction conditions for a long period of time, the amount of residual unreacted monomers can be reduced.

The reaction conditions and reaction time are not particularly limited; In one embodiment, however, the reaction can be carried out at a temperature below the temperature of the conventional process, from room temperature up to 60 ° C or up to 65 ° C, over a period of time sufficient to ensure complete reaction.

The copolymer (A) thus prepared contains only a small amount of residual unreacted Should be monomeric.

The unreacted monomer (residual monomer) of the copolymer (A) means A compound which is a structural unit (a-1) to (a-3) of the copolymer (A) but which does not participate in the polymerization (that is, a compound which fails to form a chain with the copolymer) is supplied.

More specifically, the photosensitive resin composition of the present invention The content of the residual monomer of the copolymer which is not consumed in the copolymerization reaction is not more than 2 parts by weight based on 100 parts by weight of the copolymer as a solid content of the composition. It is preferably 1 part by weight.

The solid content represents the resin composition of the present invention The content of the ingredients other than the solvent contained.

When referring to polystyrene by gel permeation chromatography (GPC, The weight average molecular weight (Mw) of the copolymer thus prepared may be in the range of 500 to 50,000, preferably in the range of 3,000 to 30,000, as measured by an eluent: tetrahydrofuran. Within this range, the composition will have the desired adhesion, physical and chemical properties, and viscosity to the substrate.

(B) polymerizable compound

The polymerizable compound of the present invention may be any compound to be polymerized by a polymerization initiator, and may be a monofunctional ester compound or a polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond. It is preferred to use a polyfunctional compound having chemical resistance to have at least two functional groups.

The polymerizable compound may be one or more compounds selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and di(meth)acrylic acid Ethylene glycol ester, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, di(meth)acrylic acid Polypropylene glycol ester, glyceryl tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tris(meth)acrylate and ester of succinic acid , pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and one ester of succinic acid, Ester modification Dipentaerythritol (meth)acrylate, pentaerythritol triacrylate, hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate Ester, tripentaerythritol octa(meth)acrylate, epoxy acrylate, bisphenol A epoxy acrylate, bisphenol A diacrylate, 2,2-贰-4-propenyloxypolyethoxylate Phenylpropane and ethylene glycol monomethyl ether, but not limited by this.

In addition to the foregoing embodiments, the polymerizable monomer may be a compound having a linear alkylene group, an alicyclic structure and at least two isocyanato groups, and having at least one hydroxyl group, 3, 4 or 5 acryloyloxy groups and/or methacryloxycarbonyl groups The polyfunctional urethane amide compound obtained by the reaction of the compound is not limited thereto.

Examples of commercially available polymerizable compounds may include monofunctional (A) Acrylates such as Aronix M-101, M-111 and M-114 (Toagosei Co., Ltd.), AKAYARAD TC-110S and TC-120S (Nippon Kayaku Co., Ltd.), V-158 and V-2311 (Osaka Yuki Kagaku Kogyo Co., Ltd.), etc.; difunctional (methyl Acrylates such as Yaloni M-210, M-240 and M-6200 (East Asia Synthesis Corporation), KAYARAD HDDA, HX-220 and R-604 (Nippon Chemical Co., Ltd.), V260, V312 and V335 HP (Osaka Uchi Chemical Pharmaceutical Co., Ltd.); and three or more functional (meth) acrylates including, Yaloni M-309, M-400, M-403, M-405, M-450, M -7100, M-8030, M-8060 and TO-1382 (East Asia Synthetic Company), Kayala TPTA, DPHA, DPHA-40H, DPCA-20, DPCA-30, DPCA-60 and DPCA-120 (Japanese Chemicals) Company), V-295, V-300, V-360, V-GPT, V-3PA, V-400, and V-802 (Osaka Uki Chemical Industries, Inc.).

The polymerizable compound may be used singly or in combination of two or more.

The polymerizable compound (B) may be used in an amount of 1 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the copolymer (A) as a solid content. Within this range, the resin composition will be free from problems such as wrinkle formation of a metal film deposited thereon.

(C) Photopolymerization initiator

The photopolymerization initiator of the present invention is a compound which, when exposed to radiation such as visible light, ultraviolet light, deep ultraviolet radiation or the like, produces an active species for polymerization of a starting compound (monomer).

The photopolymerization initiator may be a radical initiator, which is not particularly limited and may be selected from the group consisting of an acetophenone compound, a benzophenone compound, a benzoin compound, and benzamidine. Compound, xanthone compound, three Compound, halomethyl Diazole compounds, lophione dimers, and mixtures thereof.

Specific examples of the photopolymerization initiator include, but are not limited to, 2,2'-azobisisobutyronitrile, 2,2'-arsenazo (2,4-dimethylvaleronitrile), 2, 2'-Azoquinone (4-methoxy-2,4-dimethylvaleronitrile), Benzoyl peroxide, Lauryl peroxide, Tert-butyl peroxypivalate, 1,1-贰(t-butylperoxy)cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholine) Phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethylketal, benzophenone, benzoin propyl ether, two Ethyl thioxanthone, 2,4-indole (trichloromethyl)-6-p-methoxyphenyl-symmetric three 2-stilbene-4,6-fluorene-trichloromethyl-symmetric three 2-trichloromethyl-5-styryl-1,3,4- Diazole, 9-phenyl acridine, 3-methyl-5-amino-((symmetric three) -2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propane Diketo-2-(o-ethoxycarbonyl)anthracene, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzylidenehydrazine) , 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-ethane-1-one oxime-O-acetate, o-benzene Mercapto-4'-(benzothiol)benzimidyl-hexyl-ketooxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonium ruthenium oxide, hexafluorophosphoric acid-three Alkylphenyl sulfonium salts, 2-mercaptobenzimidazoles, 2,2'-benzothiazolyl disulfides, and mixtures thereof.

Also, the preferred one for high sensitivity is disclosed in the following One or more bismuth compounds: Korean public patents 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 and KR 2011-0015683, and International Patent Publications WO 2010/102502 and WO 2010/133077. Particularly preferred examples of commercially available photopolymerization initiators include OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (Asahi Chemical) ), NCI-831 (Asahi Kasei) and so on.

100 parts by weight of the copolymer (A) (as a solid content) The photopolymerization initiator (C) may be included in an amount of 0.1 to 20 parts by weight. It is preferably from 1 to 15 parts by weight. Within this range, the resin composition easily forms a pattern film having good developability and high sensitivity.

(D) solvent

The photosensitive resin composition of the present invention can be prepared into a liquid composition by mixing the aforementioned components and a solvent.

Any solvent known to the artisan The composition of the resin composition is compatible but non-reactive can be used for the preparation of the photosensitive resin composition.

Examples of solvents can include, but are not limited to, acetic acid Ethylene glycol monoalkyl ether esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutylene Ether; propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether; propylene glycol monoalkyl ether acetate such as acetic acid Propylene glycol monomethyl ether ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether; cellulosin such as ethyl cellosolve and butyl cellulolytic; carbachol such as butyl carbinol 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, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, 3 - Ethyl ethoxy propionate, methyl pyruvate and C Ethyl ketoates; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; guanamines such as N-dimethylformamide , N-methylacetamide, N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolactone; and mixtures thereof. The solvent may be used singly or in combination of two or more.

The amount of the solvent in the photosensitive resin composition is not particularly Special restrictions. However, considering the coatability and stability of the composition, the amount of the solvent may be such that the solid content of the composition is from 5 wt% to 70 wt%, preferably from 10 wt% to 55 wt%, based on the total mass of the composition. The range of %. The solid content indicates the content of the components excluding the solvent contained in the resin composition of the present invention.

(E) surfactant

If desired, the photosensitive resin composition of the present invention may further comprise a surfactant to enhance its coating ability and prevent the formation of ruthenium.

The surfactant is not particularly limited, but is preferably a fluorosurfactant, a ruthenium-based surfactant, a nonionic surfactant, or other surfactant.

Examples of the surfactant include a fluorine-based surfactant or a ruthenium-based surfactant such as BM-1000, BM-1100 (BM CHEMIE Co., Ltd.), Meg Package (Megapack) F142 D, F-172, F-173, F-183, F-470, F-471, F-475, F-482, F-489 (Dai Nippon Ink Kagaku Kogyo Co., Ltd.)), Florad FC-135, FC-170 C, FC-430, FC-431 (Sumitomo 3M Ltd.), Sufron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC -102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), Eftop EF301, 303, 352 (New Beida Chemical Co., Ltd. ( Shinakida Kasei Co., Ltd.)), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Co., Ltd.) .)), DC3PA, DC7PA, SH11PA, SH21PA, SH8400, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (Dow Corning), TSF-4440, TSF -4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (GE Toshiba Silicon Co., Ltd.), and BYK-333 (BYK Co) ., Ltd.)); nonionic surfactants such as polyoxyethylene ethyl ethers include polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethyl ether Olefinic ethers, etc., polyoxyethylene ethyl aryl ethers, polyoxyethylene ethyl octyl phenyl ether, polyoxyethylene ethyl phenyl ether, and polyoxyethylene ethyl dialkyl esters contain Polyoxyethylene ethyl laurate, polyoxyethylene ethyl distearate, and the like; and an organic siloxane polymer KP341 (Shin-Etsu Kagaku Kogyo Co., Ltd.), (Methyl) acrylate-based copolymer Polyflow No. 57, 95 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). They may be used singly or in combination of two or more.

Considering the dispersibility of the composition, to BYK-333 (BYK Co., Ltd.) is preferred.

100 parts by weight of the copolymer (A) (as a solid content) The amount of the surfactant may be from 0.001 to 5 parts by weight, preferably from 0.01 to 3 parts by weight. Within this amount range, the composition is easy to coat.

(F) adhesion promoter

The photosensitive resin composition of the present invention may further contain an adhesion promoter to improve adhesion to the substrate.

Preferably, the adhesion promoter may be a decane coupling agent.

For example, the decane coupling agent may have at least one A decane coupling agent selected from the group consisting of a reactive substituent in the group consisting of a carboxyl group, a (meth) propylene group, an isocyanate group, an amine group, a decyl group, a vinyl group, and an epoxy group.

The type of the decane coupling agent is not particularly limited, but may be And at least one selected from the group consisting of: trimethoxymercaptobenzoic acid, γ-methylpropenyloxypropyltrimethoxydecane, vinyltriethoxydecane, ethylene Trimethoxy decane, γ-isocyanatopropyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, N-phenyl Aminopropyltrimethoxydecane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. Preferably, an epoxy group-containing γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, which has good retention and adhesion to a substrate, can be used. Or N-phenylaminopropyltrimethoxydecane. Further, γ-isocyanatopropyltriethoxydecane having an isocyanate having good chemical resistance can be used (for example, KBE-9007 is available from Shin-Etsu Corporation).

100 parts by weight of the copolymer (A) (as a solid content) The amount of the adhesion promoter may be 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight. Within the foregoing range, the adhesion of the composition to the substrate can be improved.

Furthermore, other functional additives may also be included, thus The properties of the photosensitive resin composition are good. For example, the photosensitive resin composition may also contain an antioxidant, a stabilizer, a radical scavenger, and a colorant to such an extent that the physical properties of the photosensitive resin composition are not degraded.

The photosensitive resin composition according to the present invention is prepared as Good patterning is exhibited when the film is cured, and good surface formability is also exhibited when the metal film is applied to the cured film, and even after additional high temperature treatment, because the pattern damage of the corners is reduced or affected. The cured film and the metal film have a reduced wrinkle formation of the coefficient of thermal expansion. Therefore, it can be effectively used as an interlayer insulating film in LCDs and OLEDs, particularly TFT-LCDs and the like.

More specifically, the formation of the insulating film can be achieved by applying light. The resin composition is applied to the substrate, followed by a curing step. The insulating film thus prepared can be used as an electronic component.

The insulating film can be obtained by a conventional method well known in the art preparation. For example, the photosensitive resin composition may be applied to the ruthenium substrate by spin coating; pre-baking at a temperature of, for example, 60 ° C to 130 ° C for 60 seconds to 130 seconds to remove the solvent; using a desired pattern The mask is exposed; and development is carried out using a developer such as tetramethylammonium hydroxide solution (TMAH) to form a pattern on the coating film. Then, the patterned coating thus prepared The film is subjected to heat curing (i.e., post-baking) at a temperature of from 150 ° C to 300 ° C for 10 minutes to 5 hours to prepare a desired insulating film.

The exposure can be carried out at a wavelength in the range of 200 nm to 450 nm and an exposure intensity of 10 to 100 mJ/cm 2 .

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

evaluation method Weight average molecular weight (Mw) of the copolymer

The weight average molecular weight of the copolymer was determined by gel permeation chromatography (GPC) using polystyrene standards.

Determination of residual unreacted monomers

The amount of residual unreacted monomer was determined by liquid chromatography (HPLC) by dissolving each sample copolymer in tetrahydrofuran (THF), and then comparing the result with a monomer standard solution.

Evaluation of cured film (insulating film) and pattern generation

A photosensitive resin composition was coated on a glass substrate using a spin coater. The coated substrate was prebaked at 100 ° C for 90 seconds to form a coating film having a thickness of 3.0 μm. After applying a mask having a square hole having a size of 1 micrometer to 15 micrometers, and maintaining a distance of 10 micrometers between the mask and the substrate, the film is exposed to light emitted from a photolithography machine (model: MA6). Tie 200 The wavelength range from m to 450 nm is based on an exposure intensity of 30 mJ/cm 2 at a wavelength of 365 nm. The film was developed through a fluid nozzle at 23 ° C for 70 seconds by an aqueous solution of 2.38 wt% tetramethylammonium hydroxide (as a developer). The thus obtained exposed film was baked in a convection oven at 230 ° C for 30 minutes to produce a cured film (insulating film).

The cured film was observed to have a pore size of 10 μm from the The pattern formation of the holes formed by the mask was evaluated using a 3-dimensional surface profile analyzer.

Evaluation of wrinkle formation

The cured film (insulating film) thus obtained was subjected to dry etching using an etching system (plasma laboratory system 133, Oxford Instruments) (ICF/RF 1500/150 W, 20 mTorr, 20 ° C, SF ₆ 39 sccm, O ₂ 99sccm, 115 seconds).

Subsequently, the metal layer uses a deposition device (Sinnik (Sunicoat)-IS3000, Sunic System) was deposited onto the cured film (DC 3000W, 2 mTorr, room temperature, Ar 100 sccm, 27 seconds). In the method, molybdenum (Mo) is used for the metal layer.

Receiving light by depositing the deposited side of the cured film (insulating film) Resistive (PR) patterning and wet etching, the deposited metal layer is subjected to a patterning process, and then, by using a photoresist (PR) remover to remove the photoresist, curing of the patterned metal layer is obtained thereon Film (insulating film) substrate.

The substrate thus obtained is immersed in N-methylpyrrolidone (NMP) solution for 10 minutes, heat at 260 ° C for 30 minutes, and then in the light The wrinkle formation of the metal film deposited on the cured film was observed under a microscope and a scanning electron microscope (SEM). The wrinkle formation can be classified according to the following criteria: - Severity: Wrinkles and pattern damage can be observed around the hole pattern, and the surface wrinkles and pattern damage of the metal film can be observed, the thickness of the wrinkles is obvious, and the difference in height Large-pleats can be observed under both optical microscopy and SEM; - moderate: wrinkles can be observed around the pattern of the holes, and the surface wrinkles of the metal film can be observed. The wrinkles can be observed in both optical microscopy and SEM. Observed; - Mild: Some wrinkles can be observed on the surface of the metal film - wrinkles can be observed under SEM, but not under an optical microscope; and - None: no wrinkles are observed.

Preparation of copolymer Preparation of copolymer (A-1)

100 parts by weight of the monomer mixture comprises 25 mol% methacrylic acid (MAA), 25 mol% methacrylic acid 3,4-epoxycyclohexylmethyl ester (METHB) and 50 mol% styrene (St 3 parts by weight of 2,2'-arsenazo (2,4-dimethylvaleronitrile) as a polymerization initiator; and 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent to be supplied with condensation And the three-necked bottle of the stirrer. The temperature of the mixture was raised to 70 ° C under a nitrogen atmosphere, and the solution of the copolymer (A-1) was produced by slowly stirring and maintaining for 5 hours to carry out polymerization.

The copolymer (A-1) thus obtained has a weight average molecular weight of 10,300 The amount (Mw), and the residual amount of the unreacted monomer based on 100 parts by weight of the solid content of the copolymer, was 1.5 parts by weight.

Preparation of copolymer (A-2)

100 parts by weight of the monomer mixture comprises 22 mol% methacrylic acid (MAA), 18 mol% methacrylic acid 3,4-epoxycyclohexylmethyl ester (METHB), 50 mol% styrene (St And 10 mol% of glycidyl methacrylate (GMA); 3 parts by weight of 2,2'-arsenazo (2,4-dimethylvaleronitrile) as a polymerization initiator; and 100 parts by weight Propylene glycol monomethyl ether acetate was fed as a solvent into a three-necked flask equipped with a condenser and a stirrer. The temperature of the mixture was raised to 70 ° C under a nitrogen atmosphere, and the solution of the copolymer (A-2) was produced by slowly stirring and maintaining for 5 hours to carry out polymerization.

The copolymer (A-2) thus obtained had a weight average molecular weight (Mw) of 10,100, and the residual amount of the unreacted monomer was 1.5 parts by weight based on 100 parts by weight of the solid content of the copolymer.

Preparation of copolymer (A-3)

100 parts by weight of the monomer mixture comprises 25 mol% methacrylic acid (MAA), 25 mol% methacrylic acid 3,4-epoxycyclohexylmethyl ester (METHB) and 50 mol% styrene (St 3 parts by weight of 2,2'-arsenazo (2,4-dimethylvaleronitrile) as a polymerization initiator; and 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent to be supplied with condensation And the three-necked bottle of the stirrer. The temperature of the mixture was raised to 60 ° C under a nitrogen atmosphere, and the copolymer (A-3) was dissolved by stirring slowly and maintaining for 8 hours to carry out polymerization. liquid.

The copolymer (A-3) thus obtained had a weight average molecular weight (Mw) of 9,900, and the residual amount of the unreacted monomer was 0.8 part by weight based on 100 parts by weight of the solid content of the copolymer.

Preparation of copolymer (A-4)

100 parts by weight of the monomer mixture comprises 22 mol% methacrylic acid (MAA), 18 mol% methacrylic acid 3,4-epoxycyclohexylmethyl ester (METHB), 50 mol% styrene (St And 10 mol% of glycidyl methacrylate (GMA); 3 parts by weight of 2,2'-arsenazo (2,4-dimethylvaleronitrile) as a polymerization initiator; and 100 parts by weight Propylene glycol monomethyl ether acetate was fed as a solvent into a three-necked flask equipped with a condenser and a stirrer. The temperature of the mixture was raised to 60 ° C under a nitrogen atmosphere, and the solution of the copolymer (A-4) was produced by slowly stirring and maintaining for 8 hours to carry out polymerization.

The copolymer (A-4) thus obtained had a weight average molecular weight (Mw) of 10,200, and the residual amount of the unreacted monomer was 0.7 part by weight based on 100 parts by weight of the solid content of the copolymer.

Preparation of copolymer (A-5)

100 parts by weight of the monomer mixture comprises 25 mol% methacrylic acid (MAA), 25 mol% methacrylic acid 3,4-epoxycyclohexylmethyl ester (METHB) and 50 mol% styrene (St 3 parts by weight of 2,2'-arsenazo (2,4-dimethylvaleronitrile) as a polymerization initiator; and 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent to be supplied with condensation And stirrer Inside the neck bottle. The temperature of the mixture was raised to 80 ° C under a nitrogen atmosphere, and the solution of the copolymer (A-5) was produced by slowly stirring and maintaining for 3.5 hours to carry out polymerization.

The copolymer (A-5) thus obtained had a weight average molecular weight (Mw) of 10,200, and the residual amount of the unreacted monomer was 2.3 parts by weight based on 100 parts by weight of the solid content of the copolymer.

Each of the copolymer (A-1) to the copolymer (A-5) Moerby is summarized in Table 1 below.

MAA: Methacrylic acid

METHB: 3,4-epoxycyclohexylmethyl methacrylate

St: Styrene

GMA: glycidyl methacrylate

Other ingredients

Polymerizable Compound (B-1): Dipentaerythritol hexaacrylate (DPHA)

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

Photopolymerization initiator (C-2): Igchu OXE-02 (BASF)

Solvent (D-1): propylene glycol monomethyl ether acetate

Surfactant (E-1): FZ-2110 (Dow Corning Dongli)

Adhesion promoter (F-1): γ-glycidoxypropyl triethoxy decane

Preparation of photosensitive resin composition Comparative example 1

100 parts by weight of the copolymer (A-1) obtained in the previous step, 55 parts by weight of the polymerizable compound (B-1), and 4 parts by weight of photopolymerization from a reactor, based on the solid content Starting agent (C-1), 1.2 parts by weight of a photopolymerization initiator (C-2), 0.3 parts by weight of a surfactant (E-1), 0.5 parts by weight of an adhesion promoter (F-1), and The solvent (D-1) was used in an amount such that the solid content of the mixture was 30% by weight. The mixture was mixed using a shaker for 2 hours to prepare a liquid phase photosensitive resin composition.

Examples 1-1 to 1-3

The photosensitive resin composition was prepared in accordance with the procedure of Comparative Example 1, but the amounts of the polymerizable compound (B-1) are shown in Table 2 below.

Comparative Example 2, and Examples 2-1 to 2-3

The photosensitive resin composition was prepared in accordance with the procedure of Comparative Example 1, except that the amounts of the copolymer (A-2) and the polymerizable compound (B-1) used in the series are shown in Table 2 below.

Comparative Example 3, and Examples 3-1 to 3-3

The photosensitive resin composition was prepared in accordance with the procedure of Comparative Example 1, except that the amounts of the copolymer (A-3) and the polymerizable compound (B-1) used in the series are shown in Table 2 below.

Comparative Example 4, and Examples 4-1 to 4-3

The photosensitive resin composition was prepared in accordance with the procedure of Comparative Example 1, except that the amounts of the copolymer (A-4) and the polymerizable compound (B-1) used in the series are shown in Table 2 below.

Comparative Example 5

The photosensitive resin composition was prepared in accordance with the procedure of Comparative Example 1, except that the amounts of the copolymer (A-5) and the polymerizable compound (B-1) used in the series are shown in Table 2 below.

The foregoing examples and comparative inverted components and their evaluation results The lines are summarized in Table 2 below.

As shown in Table 2 above, the weight of the polymerizable compound is 55 The results of the contents of the parts (i.e., Comparative Examples 1 to 4) resulted in the formation of "severe" wrinkles.

The results of the remaining samples (ie, Examples 1-1 to 4-3) resulted in "Moderate" or lower incidence of wrinkles.

More specifically, based on 100 parts by weight of the copolymer As an example, the amount of the residual unreacted monomer is more than 1 part by weight to 2 parts by weight, and the sample containing the amount of the polymerizable compound in an amount of 45 parts by weight (that is, Examples 1-1 and 2-1) results in "Moderate" wrinkles were formed, and samples containing 40 parts by weight or less of the polymerizable compound (i.e., Examples 1-2, 1-3, 2-2, and 2-3) resulted in "mild Wrinkles are formed.

On the other hand, based on 100 parts by weight of the copolymer As an example, the amount of the residual unreacted monomer is 1 part by weight, and the sample containing the amount of the polymerizable compound in an amount of 45 parts by weight (that is, Examples 3-1 and 4-1) results in "mild" wrinkles. The pleats were formed, and the samples containing the amount of the polymerizable compound of 40 parts by weight or less (i.e., Examples 3-2, 3-3, 4-2, and 4-3) resulted in "no" wrinkle formation.

Further, based on 100 parts by weight of the copolymer, The amount of the residual unreacted monomer is, for example, more than 2 parts by weight, and the sample containing the content of the polymerizable compound in an amount of 35 parts by weight (i.e., Comparative Example 5) results in "severe" wrinkle formation.

Claims (5)

A photosensitive resin composition comprising a copolymer, a polymerizable compound, a photopolymerization initiator, and a solvent, wherein the amount of the polymerizable compound is 100 parts by weight of the copolymer as a solid content in the composition. The amount of residual monomers of the copolymer which is 1 to 50 parts by weight, and which is not consumed in the copolymerization reaction, is not more than 2 parts by weight. The photosensitive resin composition according to claim 1, wherein the polymerizable compound is used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the copolymer. The photosensitive resin composition according to claim 1, wherein the residual monomer of the copolymer is not more than 1 part by weight based on 100 parts by weight of the copolymer. The photosensitive resin composition according to claim 3, wherein the polymerizable compound is used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the copolymer. The photosensitive resin composition according to claim 1, wherein the copolymer comprises (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 an unsaturated compound having an alicyclic epoxy group; and (a3) a structural unit derived from an ethylenically unsaturated compound, which is different from the structural unit (a1) and the structural unit (a2).