KR102360653B1 - Photosensitive resin composition and organic insulating film using same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an organic insulating film using the same, wherein the photosensitive resin composition comprises a structural unit derived from an unsaturated monomer containing an alicyclic epoxy group and a structural unit derived from an unsaturated ether monomer containing an epoxy group By including alkali-soluble resin, it has high flatness when forming a coating film and is excellent in heat resistance, chemical resistance, stability over time, resolution and residual film rate, so materials such as organic insulating films used in liquid crystal display devices, especially organic insulating films and white pixels It is suitable for the purpose of simultaneously implementing

Description

A photosensitive resin composition and an organic insulating film using the same

The present invention relates to a photosensitive resin composition and an organic insulating film using the same, a negative photosensitive resin composition having high flatness and excellent reliability when forming a coating film, and manufactured using the same as a white pixel in a liquid crystal display device It relates to an organic insulating film.

In a display device such as a thin film transistor (TFT) type liquid crystal display device, an organic insulating film is used to protect and insulate a TFT circuit. Recently, there is a trend to gradually reduce the size of pixels in order to satisfy the demand for high-resolution displays. Accordingly, there is a problem in that the aperture ratio decreases. To improve this, in addition to the blue, green, and red pixels, white pixels without color are introduced, but a loss occurs due to a separate process for this.

Accordingly, a method of simultaneously realizing a white pixel using an organic insulating film is attracting attention. That is, after configuring the substrate to have a region in which the colored layer is present and a region in which the colored layer is not present, the composition for a transparent organic insulating film is applied on the substrate having the region in which the colored layer is present and the region in which the colored layer is not present. By coating and curing, the cured film can simultaneously function as a white pixel and an organic insulating film in an area where the colored layer does not exist. However, in the case of this method, the surface of the organic insulating film is formed unevenly due to a step difference between the region in which the colored layer is present and the region in which the colored layer does not exist, so that defects in the manufacturing process of the liquid crystal display device increase.

Conventionally, in the case of a composition that can simultaneously implement the functions of a white pixel and a protective film, a copolymer (binder resin) including a structural unit derived from an epoxy group-containing unsaturated compound is used (see Korean Patent Application Laid-Open No. 2012-0015996) ), these conventional compositions contain a photopolymerizable monomer in an amount more than 2.5 times that of the copolymer to achieve flatness, so there is a risk of deterioration in chemical resistance and residual film properties.

Korean Patent Publication No. 2012-0015996 (2012.02.22.)

Accordingly, an object of the present invention is to provide a photosensitive resin composition having high flatness and excellent chemical resistance and residual film properties, and an organic insulating film prepared therefrom.

In order to achieve the above object, the present invention provides (A) (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a composition derived from a monomer represented by the following formula (1) unit, (a3) a structural unit derived from a monomer represented by the following formula (2), and (a4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a1), (a2) and (a3) , alkali-soluble resin; (B) a photopolymerizable monomer; And (C) provides a photosensitive resin composition comprising a photoinitiator:

[Formula 1]

[Formula 2]

In Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is a C _1-4 alkylene group;

이고, n 은 2 내지 4의 정수이고, m 은 1 또는 2이다.In Formula 2, R ₁ is hydrogen or a methyl group, and R ₅ is

, n is an integer of 2 to 4, and m is 1 or 2.

The photosensitive resin composition of the present invention has high flatness when forming a coating film and is excellent in heat resistance, chemical resistance, stability over time, resolution, and residual film rate. It is suitable for the purpose of simultaneously implementing

1 illustrates a method for measuring the flatness of an organic insulating film prepared from a photosensitive resin composition (10: organic insulating film, 20: lower cured film, 30: substrate).

The photosensitive resin composition according to the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and optionally (D) a surfactant, (E) an adhesion aid, (F) a solvent and the like may be further included.

Hereinafter, the photosensitive resin composition will be described in detail for each component.

As used herein, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate".

(A) alkali-soluble resin

The alkali-soluble resin (A) is, (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 formula (1), (a3) ) a structural unit derived from a monomer represented by Formula 2, and (a4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a1), (a2) and (a3), wherein the structural unit It is included so that the sum of the number of moles of (a2) and (a3) is 10 to 50 mol%.

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

The structural unit (a1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof. The ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having one or more carboxyl groups in the molecule, and specific examples thereof include 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; Mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids having divalence or higher, such as mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate and the like. Among them, in particular, in terms of developability, it may be preferably (meth)acrylic acid.

The content of the structural unit (a1) may be 1 to 50 mol%, preferably 5 to 40 mol%, based on the total number of moles of the structural units of the alkali-soluble resin (A). Within the above preferred content range, a pattern of a coating film may be formed with better developability.

(a2) a structural unit derived from a monomer represented by Formula 1

The structural unit (a2) is derived from an unsaturated monomer containing an alicyclic epoxy group represented by the following formula (1):

[Formula 1]

In Formula 1, R ₁ is hydrogen or a methyl group, and R ₂ is a C _1-4 alkylene group.

More preferably, the structural unit (a2) is R _{1 in Formula 1} is -CH ₃ and R ₂ is -CH ₂ -, that is, it may be derived from a compound of formula 1a:

[Formula 1a]

(a3) a structural unit derived from a monomer represented by Formula 2

The structural unit (a3) is derived from an unsaturated ether-based monomer containing an epoxy group represented by the following formula (2):

[Formula 2]

이고, n 은 2 내지 4의 정수이고, m 은 1 또는 2이다.In Formula 2, R ₁ is hydrogen or a methyl group, and R ₅ is

, n is an integer of 2 to 4, and m is 1 or 2.

이고, n=4 및 m=1인 화합물, 즉 하기 화학식 2a의 화합물로부터 유도된 것일 수 있다:More preferably, in the structural unit (a3), in Formula 2, R ₁ is H, and R ₅ is

, and n=4 and m=1, that is, it may be derived from a compound of the following formula (2a):

[Formula 2a]

The sum of the number of moles of the structural unit (a2) and the structural unit (a3) is 5 to 50 mol%, preferably 10 to 50 mol%, with respect to the total number of moles of the structural units of the alkali-soluble resin (A), more Preferably, it may be 10 to 45 mol%. Within the above content range, the chemical resistance and residual film rate of the coating film prepared from the composition may be further improved.

In addition, the constituent unit (a2) may be included in the same content as the constituent unit (a3) or greater than the constituent unit (a3). Preferably, the molar ratio (a2:a3) of the constituent unit (a2) and the constituent unit (a3) may be 50:50 to 99:1, and more preferably, the molar ratio (a2:a3) is 50: 50 to 85:15. Within the above preferred molar ratio range, the flatness and the remaining film ratio of the coating film prepared from the composition may be further improved.

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

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

Specific examples of the structural unit (a4) include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 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 styrene, heptyl styrene, octyl styrene, fluoro styrene, chloro styrene, bromo styrene, iodo styrene, methoxy styrene, ethoxy styrene, propoxy styrene, p-hydro aromatic ring-containing ethylenically unsaturated compounds such as hydroxy-α-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene, 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 such as dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy ethylenically unsaturated compounds having an epoxy group such as heptyl (meth)acrylate; tertiary amines having N-vinyl such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; Unsaturated imides, such as N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide, etc. are mentioned.

The content of the structural unit (a4) may be 5 to 70 mol%, preferably 10 to 65 mol%, based on the total number of moles of the structural units of the alkali-soluble resin (A). Within the above preferred content range, it is possible to control the reactivity of the alkali-soluble resin and increase the solubility in an aqueous alkali solution, thereby remarkably improving the applicability of the composition.

Such alkali-soluble resin (A) can be synthesized by copolymerization by a known method.

The alkali-soluble resin (A) may have a weight average molecular weight (Mw) of 500 to 30,000, preferably 1,000 to 10,000. In this case, the weight average molecular weight may be a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as an elution solvent). Within the above preferred range, it is advantageous to improve the step by the lower pattern, and the pattern shape after development may be better.

The content of the alkali-soluble resin (A) in the composition may be 5 to 75 wt%, preferably 10 to 65 wt%, based on the solids weight of the composition excluding the solvent. Within the preferred content range, pattern development after development may be good, and properties such as a residual film rate and chemical resistance may be further 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 be a monofunctional or polyfunctional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated group, and in terms of chemical resistance Preferably, it may be a bifunctional or more multifunctional 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 The polyfunctional urethane acrylate compound obtained by making the compound which has a group react, etc. are mentioned.

Commercially available photopolymerizable monomers include: (i) Aronix M-101, M-111 and M-114 manufactured by Toagosei Corporation, as commercially available monofunctional (meth)acrylates, and KAYARAD TC-110S from Nippon Kayaku Corporation. and TC-120S, V-158 and V-2311 of Osaka Yuki Chemical High School; (ii) Aronix M-210, M-240 and M-6200 by Toagosei Corporation, KAYARAD HDDA, HX-220 and R-604 by Nippon Kayaku, as commercially available products of bifunctional (meth)acrylate, Osaka Yuki There are the V-260, V-312, and V-335 HP of Kyoko High School; (iii) Aronix M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, M of Toagosei Corporation as a commercial product of trifunctional or more (meth)acrylate -8060 and TO-1382, KAYARAD TMPTA, DPHA, DPHA-40H, DPCA-20, DPCA-30, DPCA-60 and DPCA-120 from Nippon Kayaku, V-295, V-300 from Osaka Yuki Chemical High School, V-360, V-GPT, V-3PA, V-400 and V-802, and the like.

The said photopolymerizable monomer (B) can be used individually or in combination of 2 or more types.

The photopolymerizable monomer (B) may be used in an amount of 30 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A) based on the solid content excluding the solvent. Within the above preferred content range, sensitivity and flatness may be further improved.

(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 of the photopolymerization initiator 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, di Ethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenyl Midazolyl 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-tri alkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyldisulfide, and mixtures thereof, but are not limited thereto.

As another example, the photopolymerization initiator may include at least one oxime-based compound.

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

The oxime-based compound is disclosed in Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753 , 2009-0009991, 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467 and 2011-0015683, and International Patent Publication WO 2010/ It is preferable from the viewpoint of high sensitivity to use at least one of the oxime-based compounds described in 102502 and WO 2010/133077. As these brand names, OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA), NCI-831 (ADEKA), etc. are mentioned.

The photopolymerization initiator (C) may be used in an amount of 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A) based on the solid content excluding the solvent. Within the above preferred content range, it is possible to obtain high sensitivity and better pattern developability and coating film properties.

(D) 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.

Examples of the surfactant include BM-1000 and BM-1100 manufactured by BM CHEMIE, Megapack F-142 D, F-172, F-173, F-183, F-470, F-471 manufactured by Dainippon Ink Chemical Co., Ltd. F-475, F-482 and F-489, Florad FC-135, FC-170 C, FC-430 and FC-431 from Sumitomo 3M, Sufflon S-112, S-113, S from Asahi Glass Company -131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106, Shin Akita Kasei EF-Top EF301, EF303 and EF352, SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 from Toray Silicon Corporation, DC3PA, DC7PA, SH11PA, SH21PA, SH8400 from Dow Corning Toray Silicon, FZ-2100, FZ-2110, FZ-2122, FZ-2222 and FZ-2233, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 from GE Toshiba Silicon, BYK fluorine-based and silicone-based surfactants such as BYK-333; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid copolymer polyflow No. 57 and 95 (Kyoeisha Yuji Chemical Co., Ltd.), etc. are mentioned.

These can be used individually or in combination of 2 or more types.

Among them, BYK-333 from BYK may be preferably used in terms of dispersibility.

The surfactant (D) 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 (A) based on the solid content excluding the solvent. When it is within the above range, the coating of the composition may be more smooth.

(E) Adhesive Aids

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

The kind of such an adhesive aid is not particularly limited, but for example, at least one reactive group selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, and an epoxy group. The silane coupling agent which has can be used.

As an example of a more specific adhesion aid, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or these , and preferably, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and N-phenylaminopropyltri Methoxysilane etc. are mentioned. In addition, γ-isocyanatopropyltriethoxysilane having an isocyanate group (eg, KBE-9007 manufactured by Shin-Etsu) may be used to improve chemical resistance.

The adhesion aid (E) 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 (A) based on the solid content excluding the solvent. In the above range, adhesion to the substrate may be better.

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

(F) 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, lactate-n-propyl, and isopropyl lactate; Aliphatic, such as ethyl acetate, acetate-n-propyl, isopropyl acetate, acetate-n-butyl, isobutyl acetate, acetate-n-amyl, isoamyl acetate, isopropyl propionate, propionate-n-butyl, and isobutyl propionate carboxylic acid esters; 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 of the present invention, the content of the solvent (F) 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 based on the total weight of the composition, Preferably, the solvent may be included in an amount of 10 to 55% by weight. Here, the solid content means the remaining components excluding the solvent in the composition.

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

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

The organic 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-cured at 60° C. to 130° C. for 60 seconds to 130 seconds. -bake) to remove the solvent, then exposure using a photomask having a desired pattern formed thereon, and developing with a developer (eg, tetramethylammonium hydroxide (TMAH) solution) to form a pattern on the coating layer. The exposure may be performed by irradiating at an exposure dose of 10 to 100 mJ/cm 2 in a wavelength range of 200 nm to 450 nm. Thereafter, the patterned coating layer is post-bake at 150° C. to 300° C. for 10 minutes to 5 hours to obtain a desired organic insulating film.

The photosensitive resin composition of the present invention is excellent in heat resistance, chemical resistance, stability over time, resolution and residual film rate while having high flatness when forming a coating film.

Therefore, the photosensitive resin composition of the present invention is suitable as a material such as an organic insulating film used in a liquid crystal display device, in particular, an organic insulating film and a white pixel at the same time, or is useful as a material for electronic components in various other fields.

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)

이고, n=4, m=1) 15몰%, 메타크릴산 19몰% 및 스티렌 51몰%로 구성하였다. 이후 서서히 교반하면서 용액의 온도를 60℃로 상승시키고 이 온도를 5시간 유지하며 중합시켜, 중량평균분자량 6,500인 공중합체의 용액을 얻었다.
A cooling tube with a drying tube is installed in a three-necked flask and placed on a stirrer equipped with an automatic temperature controller, 2 parts by weight of octylmercaptan, 2,2'-azobis(2,4-dimethylvaleronitrile) 3 Parts by weight, 100 parts by weight of propylene glycol monomethyl ether acetate, and 100 parts by weight of the monomer mixture were added, and nitrogen was added thereto. In this case, the monomer mixture is 15 mol% of the compound of Formula 1 (R ₁ is -CH ₃ and R ₂ is -CH ₂ ), the compound of Formula 2 (R ₁ is H, and R ₅ is

and n=4, m=1) 15 mol%, methacrylic acid 19 mol%, and styrene 51 mol%. Thereafter, the temperature of the solution was raised to 60° C. while stirring slowly, and polymerization was carried out while maintaining this temperature for 5 hours to obtain a solution of a copolymer having a weight average molecular weight of 6,500.

Preparation Examples 2 to 10: Preparation of alkali-soluble resins (A-2) to (A-10)

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 obtain each copolymer solution.

이고, n=4, m=1) 대신, 화학식 2의 화합물(R₁이 H이고, R₅가

이고, n=2, m=1)을 사용하였다.
In this case, in some preparations, the compound of Formula 2 (R ₁ is H, R ₅ is

and n=4, m=1) instead of the compound of Formula 2 (R ₁ is H, R ₅ is

, and n=2, m=1) were used.

production example Monomer mixture composition (mol%)
copolymer
Molecular Weight Formula 1 Formula 2
(n=4) Formula 2
(n=2) MAA styrene DCPMA MMA A-1 15 15 0 19 51 0 0 6,500 A-2 13 17 0 18 52 0 0 7,100 A-3 20 10 0 20 50 0 0 5,900 A-4 20 10 0 21 0 49 0 6,300 A-5 20 0 10 20 50 0 0 6,600 A-6 25 5 0 21 49 0 0 6,500 A-7 10 5 0 18 52 0 15 6,800 A-8 30 0 0 20 50 0 0 7,200 A-9 0 0 30 19 51 0 0 6,900 A-10 0 0 30 19 51 0 0 7,100

The meanings of the abbreviated components in Table 1 above are as follows:

MAA: methacrylic acid

DCPMA: dicyclopentenyl methacrylate

MMA: methyl methacrylate

Compound of Formula 1: In Formula 1, R ₁ is —CH ₃ and R ₂ is —CH ₂ —.

이고, n=4 및 m=1인 화합물A compound of Formula 2 (n=4): In Formula 2, R ₁ is H, and R ₅ is

and n=4 and m=1

이고, n=2 및 m=1인 화합물
A compound of Formula 2 (n=2): In Formula 2, R ₁ is H, and R ₅ is

and n=2 and m=1

The photosensitive resin compositions of the following Examples and Comparative Examples were prepared using the compounds prepared in Preparation Examples.

In the following examples, the following compounds were used as other components:

Photopolymerizable monomer (B-1): trimethylopropane triacrylate, TMPTA

Photoinitiator (C-1): OXE-01, BASF

Photoinitiator (C-2): OXE-02, BASF

Surfactant (D-1): FZ-2110, Dow Corning Toray Silicone

Adhesion aid (E-1): γ-glycidoxypropyltriethoxysilane

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

Example 1: Preparation of photosensitive resin composition

Based on the solid content weight, 100 parts by weight of the alkali-soluble resin (A-1) synthesized in Preparation Example 1, 100 parts by weight of the photopolymerizable monomer (B-1), 4 parts by weight of the photopolymerization initiator (C-1), the photopolymerization initiator (C -2) 1 part by weight, 0.3 parts by weight of surfactant (D-1), and 0.5 parts by weight of adhesion aid (E-1) are mixed, and the solvent (F-1) so that the total solid content of the components is 25% ), and then mixed using a shaker for 2 hours to prepare a liquid photosensitive resin composition.

Examples 2 to 7 and Comparative Examples 1 to 3: Preparation of photosensitive resin composition

As shown in Table 2 below, each photosensitive resin composition was prepared in the same manner as in Example 1, except that the type of alkali-soluble resin was changed.

Composition of the photosensitive resin composition (parts by weight, based on solid content) division alkali
soluble resin photopolymerization
monomer light curing
initiator interface
activator adhesion
supplements Example 1 A-1 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 2 A-2 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 3 A-3 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 4 A-4 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 5 A-5 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 6 A-6 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Example 7 A-7 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Comparative Example 1 A-8 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Comparative Example 2 A-9 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5 Comparative Example 3 A-10 100 B-1 100 C-1 4 C-2 One D-1 0.3 E-1 0.5

Reference example

Based on the solid content weight, 100 parts by weight of the binder resin (benzyl methacrylate / methacrylic acid / methyl methacrylate, 40/30/30 mol%, Mw 20,000), 4 parts by weight of the photopolymerization initiator (C-1), the photopolymerization initiator ( C-2) 1.2 parts by weight, 0.3 parts by weight of surfactant (D-1), and 0.5 parts by weight of adhesion aid (E-1) are blended, and 30 parts by weight of blue pigment dispersion (containing 30% solid content), and here After the solvent (F-1) was added to the mixture so that the total solid content of the components was 25%, the mixture was mixed for 2 hours using a shaker to prepare a liquid photosensitive resin composition.

The photosensitive resin compositions prepared in Examples and Comparative Examples were evaluated as follows.

Test Example 1: Evaluation of flatness

Step (1) Preparation of the lower cured film

After coating the photosensitive resin composition obtained in the reference example on a glass substrate, it was pre-cured for 100 seconds on a high-temperature plate maintained at 100° C. to form a pre-cured film having a thickness of 3 μm. A mask having a line-space pattern in which 100 μm thick lines are arranged at 300 μm intervals on this pre-cured film is set to 200 μm apart from the substrate, and then an aligner that emits wavelengths of 200 nm to 450 nm , model name MA6) was exposed for a certain period of time so as to be 100 mJ/cm 2 based on 365 nm, and then developed with a 0.4% KOH aqueous developer at 23° C. through a spray nozzle for 120 seconds. The developed film was heated in a convection oven at 230° C. for 30 minutes to obtain a lower cured film having a thickness of 2.5 μm.

Step (2) Formation of an organic insulating film

Each of the photosensitive resin compositions obtained in Examples and Comparative Examples was spin-coated on the lower cured film prepared above, and then pre-cured on a high-temperature plate for 90 seconds to form a pre-cured film having a thickness of about 5 μm. After exposure for a certain period of time to 30 mJ/cm 2 based on 365 nm using the same aligner as used before this pre-cured film, a 2.38 wt% tetramethylammonium hydroxide aqueous developer solution at 23 ° C. through a stream nozzle for 100 seconds developed. The developed film was heated in a convection oven at 230° C. for 30 minutes to form a cured film (organic insulating film).

Step (3) Measuring flatness

As a result, referring to FIG. 1 , the lower cured film 20 is formed on the substrate 30 through step 1 above, and the organic insulating film 10 is formed on the lower cured film 20 through step 2 became In addition, due to the line-space pattern formed on the lower cured film 20 , a region in which the lower cured film 20 is present and a region in which the lower cured film 20 does not exist are formed on the surface of the substrate 30 . At this time, compared to the height T1 from the substrate 30 to the surface of the organic insulating film 10 measured at the point where the lower cured film 20 is present, it is measured at the point where the lower cured film 20 does not exist. The height T2 from the substrate 30 to the surface of the organic insulating layer 10 may be lower, and accordingly, the surface of the organic insulating layer may not be flat.

These heights (T1 and T2) were measured using a three-dimensional surface measuring device (trade name: SIS 2000, manufacturer: SNU precision), and the flatness (%) of the organic insulating film was calculated according to the following equation:

Flatness (%) = (T2 / T1) x 100.

Test Example 2: Resolution Evaluation

Each of the compositions obtained in Examples and Comparative Examples was spin-coated on a glass substrate and then pre-cured for 90 seconds on a high-temperature plate maintained at 100° C. to form a pre-cured film having a thickness of 4 μm. After setting the mask having a rectangular pattern of 20 μm in size on this pre-cured film to be 10 μm apart from the substrate, using an aligner (model name MA6) that emits a wavelength of 200 nm to 450 nm, 365 After exposure for a certain period of time so as to be 30 mJ/cm 2 based on nm, it was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous developer at 23° C. through a stream nozzle for 100 seconds. A cured film was obtained by heating the developed film at 230° C. for 30 minutes in a convection oven.

In the above process, the CD (critical dimension, line width, μm) of the hole pattern patterned on the cured film through a mask having a square pattern of 20 μm in size was measured using a three-dimensional surface measuring device (product name: SIS 2000, manufacturer: SNU precision). By measuring, the resolution (%) was calculated according to the following equation:

Resolution (%) = [(20㎛ - CD of hole pattern (㎛)) / 20㎛)] x 100.

Test Example 3: Remaining film rate evaluation

Each of the compositions obtained in Examples and Comparative Examples was spin-coated on a 6-inch wafer and then pre-cured for 90 seconds on a high-temperature plate maintained at 100° C. to form a pre-cured film having a thickness of 4 μm. Without applying a mask to this pre-cured film, using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm, after exposure for a certain period of time so as to be 30 mJ/cm 2 based on 365 nm, 2.38 wt% It was developed for 100 seconds through a stream nozzle at 23° C. with an aqueous developer of tetramethylammonium hydroxide. A cured film was obtained by heating the developed film at 230° C. for 30 minutes in a convection oven.

The thickness of the film obtained in the above process was measured with a non-contact thickness meter (trade name: Nanospec, manufacturer: Nano metrics), and the remaining film rate (%) was calculated according to the following equation:

Remaining film rate (%) = [final cured film thickness / pre-cured film thickness before exposure] x 100.

Test Example 4: Heat resistance evaluation

Each composition obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a 6-inch wafer in the same manner as in Test Example 3. A primary cured film was obtained by heating the developed film at 230° C. for 30 minutes in a convection oven. Thereafter, the secondary cured film was obtained by further heating the primary cured film at 250° C. for 60 minutes in a convection oven.

The thickness of the film obtained in the above process was measured with a non-contact thickness meter (trade name: Nanospec, manufacturer: Nano metrics), and heat resistance (%) was calculated according to the following equation:

Heat resistance (%) = [(1st cured film thickness - 2nd cured film thickness) / 1st cured film thickness] x 100.

Test Example 5: Evaluation of chemical resistance

Each of the compositions obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a glass substrate in the same manner as in Test Example 3. A cured film was obtained by heating the developed film at 230° C. for 30 minutes in a convection oven. Thereafter, the cured film was taken out after immersing it in N-methylpyrrolidone (NMP) at 70° C. for 10 minutes.

The thickness of the film obtained in the above process was measured with a contact-type thickness meter (brand name: Alpha step, manufacturer: Bruker Dektak), and chemical resistance (%) was calculated according to the following equation:

Chemical resistance (%) = [(thickness after NMP treatment - thickness before NMP treatment) / thickness before NMP treatment] x 100.

The result values (%) obtained in the above test examples were evaluated according to the categories in Table 3 below, and summarized in Table 4 below.

category flatness resolution remaining film rate heat resistance chemical resistance ◎ 90-100% 0-25% 80-100% 0-5% 0-10% ○ 70-90% 25-50% 70-80% 5-15% 10-20% △ 60-70% 50-80% 60-70% 15-25% 20-30% × 0-60% 80-100% 0-60% 25% or more 30% or more

division flatness resolution remaining film rate heat resistance chemical resistance Example 1 ◎ ◎ ○ ○ ○ Example 2 ◎ ◎ △ ○ △ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Example 5 ○ △ ○ ○ ○ Example 6 ○ ○ ○ ○ ○ Example 7 △ ◎ ◎ ◎ ◎ Comparative Example 1 × × ◎ ◎ ◎ Comparative Example 2 ◎ ◎ × △ × Comparative Example 3 ◎ ◎ × △ ×

As shown in Table 4, the compositions of Examples falling within the scope of the present invention were equally excellent in terms of flatness, resolution, residual film rate, heat resistance and chemical resistance, whereas the compositions of Comparative Examples not falling within the scope of the present invention were among them. Any one or more results were poor.

Claims (6)

(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) an alkali-soluble resin comprising 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);
(B) a photopolymerizable monomer; and
(C) comprising a photoinitiator,
Based on the total number of moles of the structural units of the alkali-soluble resin (A), the sum of the moles of the structural units (a2) and the structural units (a3) is 15 to 30 mol%, and the number of moles of only the structural units (a2) is 15 to 30 mol% 13 to 25 mol%, wherein the molar ratio (a2:a3) of the structural unit (a2) and the structural unit (a3) is 50:50 to 85:15, the photosensitive resin composition:
[Formula 1]

[Formula 2]

In Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is a C _1-4 alkylene group;
In Formula 2, R ₁ is hydrogen or a methyl group, and R ₅ is

, n is an integer of 2 to 4, and m is 1 or 2.
delete delete The method of claim 1,
In Formula 1, the structural unit (a2) is R ₁ is —CH ₃ , and R ₂ is —CH ₂ — It is derived from a phosphorus compound,
In the above formula (2), the structural unit (a3) is R ₁ is H, and R ₅ is

and n = 4 and m = 1, characterized in that derived from the compound, the photosensitive resin composition.
The method of claim 1,
Said photoinitiator (C) is an oxime type compound, The photosensitive resin composition characterized by the above-mentioned.
The organic insulating film formed using the photosensitive resin composition in any one of Claims 1, 4, and 5.

Images