KR20160058551A - 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. According to the present invention, the photosensitive resin composition exhibits heat resistance, chemical resistance, time-dependent stability, resolution, and the film retention ratio while having high flatness when forming a paint film, since the composition contains an alkali-soluble resin which includes a forming unit derived from an epoxy group-containing unsaturated ether-based monomer and a forming unit derived from an alicyclic epoxy group-containing unsaturated monomer. Thus, the composition of the present invention can be suitable to be used as materials for organic insulating films used in liquid crystal display device, particularly for creating white pixels and organic insulating films.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, and an organic insulating film using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition and an organic insulating film using the same, and more particularly, to a negative photosensitive resin composition having high flatness and high reliability at the time of forming a coating film, and a negative photosensitive resin composition using the same, And an organic insulating film.

BACKGROUND ART In a display device such as a thin film transistor (TFT) type liquid crystal display device, an organic insulating film is used for protecting and insulating a TFT circuit. In recent years, in order to satisfy the display requirement of high resolving power, the pixel size has been gradually reduced, which causes the aperture ratio to decrease. In order to solve this problem, in addition to blue, green and red pixels, a white pixel which is not colored is introduced, but a loss due to a separate process is generated.

Therefore, a method of simultaneously implementing white pixels using an organic insulating film has been attracting attention. That is, the organic EL device is constructed so as to have a region in which a colored layer exists and a region in which a colored layer does not exist on a substrate, and then a composition for a transparent organic insulating film is formed on a substrate having a region where the colored layer exists, By applying and curing, in the region where the colored layer is not present, the cured film can simultaneously function as a white pixel and an organic insulating film. However, in such a method, there is a problem that the surface of the organic insulating film is formed unevenly due to the step between the region where the coloring layer exists and the region where the coloring layer is not present, thereby increasing defects in the manufacturing process of the liquid crystal display device.

In the case of a composition capable of simultaneously realizing functions of a white pixel and a protective film, a copolymer (binder resin) containing a constituent unit derived from an epoxy group-containing unsaturated compound is conventionally used (see Korean Patent Publication No. 2012-0015996 ), These conventional compositions contain a photopolymerizable monomer in an amount of 2.5 times or more the amount of the copolymer in order to achieve the degree of planarization, and there is a risk of degradation of chemical resistance and residual film properties.

Korean Patent Publication No. 2012-0015996 (Feb. 22, 2012)

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

(A1) a constituent unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (a2) a constituent unit derived from a monomer represented by the following formula (1) (A3) a structural unit derived from a monomer represented by the following general formula (2), and (a4) a structural unit derived from an ethylenically unsaturated compound which is different from the structural units (a1), (a2) , An alkali-soluble resin; (B) a photopolymerizable monomer; And (C) a photopolymerization initiator.

 [Chemical Formula 1]

 (2)

Wherein R ₁ is hydrogen or a methyl group and 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 is excellent in heat resistance, chemical resistance, aging stability, resolution and residual film ratio while having a high flatness at the time of forming a coating film, and thus is useful as a material for an organic insulating film used for a liquid crystal display, As shown in FIG.

1 shows a method of measuring planarization degree of an organic insulating film made 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) And the like.

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

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

(A) an alkali-soluble resin

(A2) a structural unit derived from a monomer represented by the general formula (1), (a3) a structural unit derived from a monomer represented by the general formula (1), (a2) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, (A4) a structural unit derived from an ethylenically unsaturated compound which is different from the structural units (a1), (a2) and (a3), wherein the structural unit (a2) and (a3) is 10 to 50 mol%.

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

The constituent 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 the ethylenically unsaturated carboxylic acid anhydride are polymerizable unsaturated monomers having at least one carboxyl group in the molecule. Specific examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid, ; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, and anhydrides thereof; Unsaturated polycarboxylic acids of trivalent or more and their anhydrides; Mono [(meth) acryloyloxyalkyl] ester of a dicarboxylic acid having two or more carboxyl groups such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate And the like. Among them, (meth) acrylic acid can be preferably used from the viewpoint of developability.

The content of the structural unit (a1) may be 1 to 50 mol%, and preferably 5 to 40 mol% based on the total molar amount of the constituent units of the alkali-soluble resin (A). Within the above preferred range of contents, a pattern of the coating film can be formed with better developing property.

(a2) a structural unit derived from a monomer represented by the general formula (1)

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

 [Chemical Formula 1]

In the above 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 (I) And is -CH _3, R ₂ May be derived from a compound that is -CH ₂ -, that is, a compound of the following formula (1a):

[Formula 1a]

(a3) a structural unit derived from a monomer represented by the general formula (2)

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

 (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, the structural unit (a3) is a structural unit represented by the general formula (2) wherein R ₁ is H and R ₅ is

, And n = 4 and m = 1, i.e. compounds of formula (2a): < EMI ID =

(2a)

The sum of the number of moles of the constituent unit (a2) and the constituent unit (a3) is 5 to 50 mol%, preferably 10 to 50 mol% based on the total molar amount of the constituent units of the alkali-soluble resin (A) And preferably 10 to 45 mol%. Within the above content range, the chemical resistance and the residual film ratio of the coating film produced from the composition can be further improved.

The structural unit (a2) may be the same as or more than the structural unit (a3). Preferably, the molar ratio (a2: a3) of the structural unit (a2) and the structural unit (a3) may be 50:50 to 99: 1, more preferably the molar ratio a2: 50 to 85:15. Within the above preferred molar ratio range, the flatness and residual film ratio of the coating film produced from the composition can be further improved.

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

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

Specific examples of the above-mentioned structural unit (a4) include (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, tribromophenyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene , Triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, methoxystyrene, ethoxystyrene, Containing aromatic rings such as hydroxy-α-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzylmethylether, m-vinylbenzylmethylether and p- Til renseong unsaturated compound; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, Hydroxypropyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydroperfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, methyl (meth) acrylate, ethyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, propyl? -Hydroxymethyl (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-methoxyethyl Met) (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3- (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl Unsaturated carboxylic acid esters such as pentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate; (Meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy (meth) acrylate, An ethylenically unsaturated compound 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; And unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide.

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

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

The weight average molecular weight (Mw) of the alkali-soluble resin (A) may be 500 to 30,000, preferably 1,000 to 10,000. Here, the weight average molecular weight may be a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, tetrahydrofuran as an elution solvent). Within the above-mentioned preferable range, it is advantageous to improve the step difference 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% by weight, preferably 10 to 65% by weight, based on the solid content of the composition excluding the solvent. Within the above preferred range, pattern development after development is favorable and properties such as residual film ratio and chemical resistance can be further improved.

(B) a photopolymerizable monomer

The photopolymerizable monomer used in the present invention is a compound which 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 ethylenic unsaturated group, And preferably a bifunctional or higher functional compound.

Examples of the photopolymerizable monomer include ethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, Acrylates such as di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa , Monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate (Reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol triacrylate, hexamethylene diisocyanate Bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate, but the present invention is not limited thereto.

In addition, a compound having two or more isocyanate groups and having a straight chain alkylene group and an alicyclic structure, and a compound having at least one hydroxyl group in the molecule and having 3, 4 or 5 acryloyloxy groups and / or methacryloyloxy And a polyfunctional urethane acrylate compound obtained by reacting a compound having a period of 2 or more.

Commercially available photopolymerizable monomers include Aronix M-101, M-111 and M-114 of Toagosei Co., Ltd. and KAYARAD TC-110S (trade name, available from Nippon Kayaku Co., Ltd.) as commercial products of (i) monofunctional (meth) And TC-120S, and V-158 and V-2311 of Osaka Yuzuga School of Medicine; M-240 and M-6200 of Toagosei Co., KAYARAD HDDA, HX-220 and R-604 of Nippon Kayaku Co., Ltd., and (ii) And V-260, V-312 and V-335 HP of teachers; (iii) Aronix M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, and M of a commercially available product of trifunctional or higher (meth) V-295, V-300, and D-405 of Daihatsu Kogaku Co., Ltd., KAYARAD TMPTA, DPHA, DPHA-40H, DPCA-20, DPCA-30, DPCA- V-360, V-GPT, V-3PA, V-400, and V-802.

The photopolymerizable monomer (B) may be used alone or in combination of two or more.

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 range of content, the sensitivity and flatness can be further improved.

(C) a photopolymerization initiator

The photopolymerization initiator used in the present invention serves to initiate polymerization of monomers that can be cured by visible light, ultraviolet light, deep ultraviolet radiation, or the like. The photopolymerization initiator may be a radical initiator. The photopolymerization initiator may be a radical initiator. The type of the photopolymerization initiator is not particularly limited, and examples thereof include acetophenone, benzophenone, benzoin and benzoyl, xanthone, triazine, halomethyloxadiazole, May be used.

Specific examples of the photopolymerization initiator include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) Butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2- (dimethylamino) -1 Phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, benzoin propyl ether, di (2-hydroxy-2- (Trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenyl-2- 2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane- 1,2-dione- 2- (O-benzoyloxime), o-benzoyl-4 '- (benzmercaptan ) Benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'- Benzothiazolyl disulfide, and mixtures thereof, but are not limited thereto.

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

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

The oxime-based compounds are disclosed in Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753 , 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467 and 2011-0015683, and International Patent Publication WO 2010 / 102502 and WO 2010/133077, from the viewpoint of high sensitivity. Examples of these trade names include OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 (ADEKA).

The 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-mentioned preferable content range, high sensitivity and better pattern developability and coating film characteristics can be obtained.

(D) Surfactant

The photosensitive resin composition of the present invention may further contain a surfactant, if necessary, for improving coating properties and preventing defect formation.

The kind of the surfactant is not particularly limited, but a fluorine surfactant, a silicone surfactant, a nonionic surfactant and other surfactants are preferable.

Examples of the surfactant include BM-1000 and BM-1100 from BM CHEMIE, Megapac F-142D, F-172, F-173, F-183, F- F-475, F-482 and F-489 of Sumitomo 3M, Florad FC-135, FC-170C, FC-430 and FC-431 of Sumitomo 3M, Surflon S-112, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC- SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 of Dow Corning Toray Silicone Co., DC3PA, DC7PA, SH11PA, SH21PA, SH8400, TSF-4400, TSF-4400, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicone Co., Ltd., FZ-2100, FZ-2110, FZ-2122, FZ- 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-based copolymer polyflow No. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

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

Of these, BYK-333 manufactured by BYK is preferably used in view 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. Within this range, coating of the composition may be more smooth.

(E) Adhesion aid

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

The kind of such an adhesion aid is not particularly limited, but may be, for example, at least one reactive group selected from the group consisting of carboxyl group, (meth) acryloyl group, isocyanate group, amino group, mercapto group, vinyl group and epoxy group May be used.

More specific examples of the adhesion promoter include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and N-phenylaminopropyltriethoxysilane, which have good adhesiveness to the substrate while improving the residual film ratio, Methoxysilane and the like. In order to improve the chemical resistance,? -Isocyanatopropyltriethoxysilane having an isocyanate group (e.g., KBE-9007 from Shin-Etsu) may be used.

The adhesive 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 this range, the adhesion with the substrate can be improved.

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

(F) Solvent

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

The solvent is compatible with the above-mentioned photosensitive resin composition components, does not react with the above photosensitive resin composition components, and any known solvent used in the photosensitive resin composition can be used.

Examples of such a solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Cellosolve such as ethyl cellosolve and butyl cellosolve; Carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; Aliphatic alcohols such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl myristate, isopropyl propionate, n-butyl propionate, Carboxylic acid esters; Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -butyrolactone; And mixtures thereof.

These solvents may be used alone or in combination of two or more.

The content of the solvent (F) in the photosensitive resin composition of the present invention is not particularly limited, but from the viewpoint of coatability and stability of the resulting photosensitive resin composition, the content of the solvent (F) is preferably 5 to 70% And preferably from 10 to 55% by weight. Here, the solid content means the remaining components in the composition except for the solvent.

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

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

The organic insulating layer can be formed by a method known in the art. For example, the photosensitive resin composition is coated on a silicon substrate by a spin coating method and pre-cured at 60 to 130 ° C for 60 to 130 seconds -bake) to remove the solvent, exposure is performed using a photomask in which a desired pattern is formed, and development is performed with a developer (for example, tetramethylammonium hydroxide (TMAH) solution) to form a pattern on the coating layer. The above exposure can be performed by irradiating light at an exposure amount of 10 to 100 mJ / cm 2 at a wavelength range of 200 nm to 450 nm. Thereafter, the patterned coating layer is post-baked 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, aging stability, resolution, and residual film ratio while having a high flatness at the time of forming a coating film.

Therefore, the photosensitive resin composition of the present invention is suitable as a material for an organic insulating film or the like used in a liquid crystal display device, particularly, for simultaneously realizing an organic insulating film and a white pixel, or as a material for electronic parts in various other fields.

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

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

Production Example 1: Preparation of 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 three-necked flask equipped with a condenser equipped with a drying tube was placed on a stirrer equipped with a thermostatic regulator, and 2 parts by weight of octylmercaptan, 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) 3 , 100 parts by weight of propylene glycol monomethyl ether acetate, and 100 parts by weight of a monomer mixture, and nitrogen was added thereto. Wherein the monomer mixture comprises 15 mole% 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, R ₅ is

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

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

Polymerization was carried out in the same manner as in Preparation Example 1, except that the kinds and contents of the components constituting the monomer mixture were varied as shown in Table 1 below to obtain respective copolymer solutions.

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

이고, n=2, m=1)을 사용하였다.
At this time, in some production examples, the compound of formula 2 (R ₁ is H and R ₅ is

(Wherein R < ₁ > is H and R < ₅ > is

, N = 2, m = 1).

Manufacturing example Monomer mixture composition (mol%)
Copolymer
Molecular Weight Formula 1 (2)
(n = 4) (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 abbreviations in Table 1 are as follows:

MAA: methacrylic acid

DCPMA: dicyclopentenyl methacrylate

MMA: methyl methacrylate

A compound of the formula (1): wherein R ₁ is -CH ₃ and R ₂ is -CH ₂ - in the formula

이고, n=4 및 m=1인 화합물Compound 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
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 the above Preparation Examples.

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

Photopolymerizable monomer (B-1): Trimethylpropanetriacrylate, TMPTA

Photopolymerization initiator (C-1): OXE-01,

Photopolymerization initiator (C-2): OXE-02,

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

Adhesion Adjuster (E-1): γ-glycidoxypropyltriethoxysilane

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

Example 1: Preparation of Photosensitive Resin Composition

100 parts by weight of the alkali-soluble resin (A-1) synthesized in Production Example 1, 100 parts by weight of the photopolymerizable monomer (B-1), 4 parts by weight of the photopolymerization initiator (C-1) 1), 0.3 parts by weight of a surfactant (D-1) and 0.5 parts by weight of an adhesion promoter (E-1) were mixed in a solvent (F-1 ) Was added thereto, followed by mixing with 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 the following Table 2, the same processes as in Example 1 were carried out except that the kind of the alkali-soluble resin was changed to prepare each photosensitive resin composition.

Composition of photosensitive resin composition (parts by weight, based on solids) 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

100 parts by weight of a binder resin (benzyl methacrylate / methacrylic acid / methyl methacrylate, 40/30/30 mol%, Mw 20,000), 4 parts by weight of a photopolymerization initiator (C-1) 1.2 parts by weight of a surfactant (C-2), 0.3 part by weight of a surfactant (D-1) and 0.5 part by weight of an adhesion promoter (E-1) , The solvent (F-1) was added so that the total solid content of the components was 25%, and the mixture was stirred for 2 hours using a shaker to prepare a liquid photosensitive resin composition.

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

Test Example 1: Evaluation of planarization degree

Step (1) Production of the lower cured film

The photosensitive resin composition obtained in the above-mentioned Reference Example was coated on a glass substrate and pre-cured for 100 seconds on a high-temperature plate maintained at 100 캜 to form a pre-cured film having a thickness of 3 탆. After a mask having a line-space pattern in which lines having a thickness of 100 mu m are arranged at intervals of 300 mu m is set to 200 mu m in interval from the substrate, the aligner , Model name MA6), exposure was performed for a predetermined time so as to be 100 mJ / cm 2 on the basis of 365 nm, and then developed with a 0.4% KOH aqueous developer at 23 ° C for 120 seconds through a spray nozzle. The developed film was heated in a convection oven at 230 캜 for 30 minutes to obtain a lower cured film having a thickness of 2.5 탆.

Step (2) Formation of organic insulating film

Each of the photosensitive resin compositions obtained in the above Examples and Comparative Examples was spin-coated on the above-prepared lower cured film, and preliminarily cured on a hot plate for 90 seconds to form a pre-cured film having a thickness of about 5 占 퐉. The pre-cured film was exposed to a constant time of 30 mJ / cm 2 on the basis of 365 nm using the same aligner as that used previously, and then developed with a 2.38 wt% tetramethylammonium hydroxide aqueous developer through a stream nozzle at 23 ° C for 100 seconds Respectively. The developed film was heated in a convection oven at 230 DEG C for 30 minutes to form a cured film (organic insulating film).

Step (3) Planarization degree measurement

As a result, referring to FIG. 1, a lower cured film 20 is formed on the substrate 30 through the preceding step 1, and an organic insulating film 10 is formed on the lower cured film 20 through step 2 . In addition, due to the line-space pattern formed on the lower cured film 20, the surface of the substrate 30 has a region where the lower cured film 20 exists and a region where the lower cured film 20 does not exist. At this time, as compared with the height T1 from the substrate 30 to the surface of the organic insulating film 10 measured at the position where the lower cured film 20 exists, The height T2 from the substrate 30 to the surface of the organic insulating film 10 may be lower and the surface of the organic insulating film may not be flat.

The planarization degree (%) of the organic insulating film was calculated according to the following equations by measuring the heights (T1 and T2) using a three-dimensional surface meter (trade name: SIS 2000, manufacturer: SNU precision)

Planarization degree (%) = (T2 / T1) x100.

Test Example 2: Resolution Evaluation

Each of the compositions obtained in the above Examples and Comparative Examples was spin-coated on a glass substrate and pre-cured for 90 seconds on a hot plate kept at 100 占 폚 to form a pre-cured film having a thickness of 4 占 퐉. The mask having a square pattern of 20 mu m in size was set to 10 mu m in gap between the substrate and the pre-cured film, and then an aligner (model name MA6) having a wavelength of 200 to 450 nm was used to measure 365 Nm, and developed with a 2.38 wt% tetramethylammonium hydroxide aqueous developer at 23 DEG C through a stream nozzle for 100 seconds. The cured film was obtained by heating the developed film in a convection oven at 230 DEG C for 30 minutes.

In the above procedure, the CD (critical dimension, line width, μm) of the hole pattern patterned on the cured film through a mask having a rectangular pattern of a size of 20 μm was measured using a three-dimensional surface analyzer (trade name: SIS 2000, manufactured by SNU precision) , And the resolution (%) was calculated according to the following equation:

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

Test Example 3: Residual film ratio evaluation

Each of the compositions obtained in the above Examples and Comparative Examples was spin-coated on a 6-inch wafer, and pre-cured for 90 seconds on a hot plate maintained at 100 캜 to form a pre-cured film having a thickness of 4 탆. The pre-cured film was exposed for a predetermined time at 30 mJ / cm 2 on the basis of 365 nm using an aligner (model name MA6) having a wavelength of 200 to 450 nm, And developed with a tetramethylammonium hydroxide aqueous developer at 23 DEG C through a stream nozzle for 100 seconds. The cured film was obtained by heating the developed film in a convection oven at 230 DEG C for 30 minutes.

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

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

Test Example 4: Evaluation of heat resistance

Each of the compositions obtained in the above 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 above. The developed film was heated in a convection oven at 230 DEG C for 30 minutes to obtain a primary cured film. Then, the primary cured film was further heated in a convection oven at 250 DEG C for 60 minutes to obtain a secondary cured film.

The thickness of the obtained film was measured with a non-contact type thickness measuring instrument (trade name: Nanospec, manufactured by Nano metrics) and heat resistance (%) was calculated according to the following equation:

Heat resistance (%) = [(primary cured film thickness - secondary cured film thickness) / primary cured film thickness] x 100.

Test Example 5: Evaluation of chemical resistance

Each of the compositions obtained in the above Examples and Comparative Examples was coated, precured, exposed and developed on a glass substrate in the same manner as in Test Example 3 above. The cured film was obtained by heating the developed film in a convection oven at 230 DEG C for 30 minutes. Then, the cured film was immersed in N-methylpyrrolidone (NMP) at 70 ° C for 10 minutes and then taken out.

The chemical resistance (%) was calculated according to the following equation by measuring the thickness of the film obtained in the above procedure with a contact type thickness meter (trade name: Alpha step, manufactured by Bruker Dektak)

Chemical Resistance (%) = [(Thickness after NMP - Thickness before NMP) / Thickness before NMP] x 100.

The results (%) obtained in the above Test Examples are evaluated according to the categories shown in Table 3 below and summarized in Table 4 below.

category Planarization degree resolution Residual film ratio Heat resistance Chemical resistance ◎ 90 to 100% 0 to 25% 80 to 100% 0 to 5% 0 to 10% ○ 70 to 90% 25 to 50% 70 to 80% 5 to 15% 10 to 20% △ 60 to 70% 50 to 80% 60 to 70% 15 to 25% 20 to 30% × 0 to 60% 80 to 100% 0 to 60% 25% or more More than 30%

division Planarization degree resolution Residual film ratio 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 the Examples belonging to the scope of the present invention are superior in terms of flatness, resolution, residual film ratio, heat resistance and chemical resistance, while compositions of Comparative Examples not belonging to the scope of the present invention include More than one outcome was poor.

Claims (6)

(A2) a structural unit derived from a monomer represented by the following general formula (1), (a3) a structural unit derived from a monomer represented by the following general formula (2): (a1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, (A4) an alkali-soluble resin comprising a constituent unit derived from an ethylenically unsaturated compound different from the above-mentioned constituent units (a1), (a2) and (a3);
(B) a photopolymerizable monomer; And
(C) a photopolymerization initiator.
[Chemical Formula 1]

(2)

Wherein R ₁ is hydrogen or a methyl group and 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.
The method according to claim 1,
Wherein the sum of the number of moles of the structural unit (a2) and the structural unit (a3) relative to the total number of moles of the structural units of the alkali-soluble resin (A) is 10 to 50 mol%.
3. The method of claim 2,
The structural unit (a2) and the structural unit (a3)
Is contained in a molar ratio (a2: a3) of 50:50 to 99: 1.
The method according to claim 1,
Wherein the structural unit (a2) is represented by the general formula (1) wherein R ₁ is -CH ₃ and R ₂ is -CH ₂ - Phosphorus compounds,
When the structural unit (a3) is a structural unit represented by the general formula (2), R ₁ is H and R ₅ is

, And n = 4 and m = 1.
The method according to claim 1,
Wherein the photopolymerization initiator (C) is a oxime-based compound.
An organic insulating film formed using the photosensitive resin composition according to any one of claims 1 to 5.

Images