KR100671142B1 - Photosensitive resin composition for forming spacer of liquid crystal device - Google Patents

Abstract

Provided is a photosensitive resin composition capable of forming a spacer which can maintain uniform cell gap irrespective of size of liquid crystal display device and prevent a change of cell gap owing to moving, vibration, shock of the liquid crystal display panel. The photosensitive resin composition comprises a binder resin, a multifunctional monomer, and a photoinitiator. The binder resin comprises a copolymer represented by the formula(1); and unsaturated carboxylic acid or unsaturated carboxylic anhydride; unsaturated hydrocarbon; and a first copolymer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid derivative, and methacrylic acid derivative. The binder resin is a copolymer having molecular weight of 1,000-20,000 obtained by copolymerizing monomers of the formulas(2), (3), and (4) with a molecular ratio of 1;2-4:8. In the formulas, R is -(CH2)m-(m is an integer of 1-10), or -O(CH2)n-(n is an integer of 1-8), x is halogen atom.

Description

Photosensitive resin composition for liquid crystal display device spacers

The present invention relates to a photosensitive resin composition for a liquid crystal display device spacer. More specifically, the present invention relates to a photosensitive resin composition for a liquid crystal display device spacer excellent in heat stability and strength.

Typically, in order to maintain a constant distance between two substrates, spherical or cylindrical silica beads, plastic beads, etc. having a constant diameter are used for the liquid crystal display device. Since the beads are dispersed and coated on a glass substrate, when the beads are positioned inside the effective pixels, a decrease in aperture ratio or light leakage (a phenomenon in which light is emitted in a direction other than the entire surface) may occur, thereby reducing the contrast ratio of the liquid crystal display. Occurs.

In order to solve this problem, a method of forming a spacer by photolithography has begun to be used. In this method, a photosensitive resin is coated on a glass substrate, ultraviolet rays are irradiated through a mask, and then developed to form spacers in places other than the inside of the effective pixel according to a pattern formed on the mask. However, if the thermal stability and the strength of the spacer formed by the above method are weak, abnormal deformation occurs in the lower layer of the pixel of the color filter of the liquid crystal display device, causing gaps between R, G, and B pixels, or gaps in each pixel. ) Problems such as spots occur, which results in color spots or contrast spots, resulting in deterioration of image quality.

Therefore, as described above, in the case of the photosensitive resin composition for forming a spacer, it is required to have excellent heat stability and strength, and the need for development of the photosensitive resin composition having such a requirement is still required at a high level.

An object of the present invention is to provide a photosensitive resin composition for a liquid crystal display device spacer excellent in heat stability and strength.

An object of the present invention as described above, cardo-based binder resin; At least one first copolymer selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic anhydrides with unsaturated hydrocarbons and acrylic acid, methacrylic acid, acrylic acid derivatives and methacrylic acid derivatives; Polyfunctional monomers having ethylenically unsaturated bonds; Photoinitiators; And it is achieved by the photosensitive resin composition for a liquid crystal display device spacer comprising a solvent.

Other objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description of the invention and the preferred embodiments.

The photosensitive resin composition for a liquid crystal display device spacer according to the present invention includes a cardo-based binder resin; At least one first copolymer selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic anhydrides with unsaturated hydrocarbons and acrylic acid, methacrylic acid, acrylic acid derivatives and methacrylic acid derivatives; Polyfunctional monomers having ethylenically unsaturated bonds; Photoinitiators; And including a solvent, 10 to 40% by weight of the mixture of the cardo-based binder resin and the first copolymer, 1 to 20% by weight of the multifunctional monomer, 0.5 to 10% by weight of the photoinitiator and a solvent do.

Hereinafter, the present invention will be described in more detail.

The composition is a cardo-based binder resin;
Unsaturated carboxylic acid or unsaturated carboxylic anhydride; Unsaturated hydrocarbons; And one first copolymer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid derivatives and methacrylic acid derivatives;
Polyfunctional monomers having ethylenically unsaturated bonds; And
Photoinitiators.

Formula 1 may be used as the cardo-based binder resin used in the present invention.

The copolymer of Chemical Formula 1 is prepared by copolymerization of monomers of Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4.

, 또는 -O(CH₂)n- (단, n은 1 내지 8의 정수)이고, X는 할로겐원자이다.)Wherein R is-(CH ₂ ) m-, where m is an integer from 1 to 10,

Or -O (CH ₂ ) n- (where n is an integer of 1 to 8) and X is a halogen atom.)

, 또는 -O(CH₂)n- (단, n은 1 내지 8의 정수)이고, X는 할로겐원자이다.)Wherein R is-(CH ₂ ) m-, where m is an integer from 1 to 10,

Or -O (CH ₂ ) n- (where n is an integer of 1 to 8) and X is a halogen atom.)

The cardo-based binder resin may preferably be a copolymer having a molecular weight of 1,000 to 20,000, in which the monomers of Chemical Formula 2: Chemical Formula 3: Chemical Formula 4 are copolymerized in a ratio of 1 mol: 2 to 4 mol: 8 mol. In copolymerizing the cardo-based binder resin, it is impossible to prepare a copolymer unless the monomers of Chemical Formula 2: Chemical Formula 3: Chemical Formula 4 are maintained at a ratio of 1 mol: 2 to 4 mol: 8 mol. Further, when the molecular weight of the cardo-based binder resin exceeds 1,000, the pattern shape and heat resistance of the spacer formed are lowered, and when the molecular weight of the cardo-based binder resin is less than 20,000, the sensitivity of the photosensitive resin for the spacer is lowered.

The first copolymer used in the present invention also acts as a binder and, when producing a spacer, is soluble in a developer, particularly preferably an alkaline developer, used in the development step, and is particularly limited. Although not preferred, an alkali-soluble resin having a carboxyl group is preferable, and in particular, a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as a carboxyl group-containing unsaturated monomer) and a copolymerizable unsaturated monomer (hereinafter referred to as a carboxyl group-containing copolymer). Is preferred.

As an example of the said carboxyl group-containing unsaturated monomer, Unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, (alpha)-currol acrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Trivalent or higher carboxylic acids or their anhydrides; (2-acryloyloxyethyl)-zucchiniic acid, (2-methacryloyloxyethyl)-zucchiniic acid, (2-acryloyloxyethyl)-phthalic acid, (2-methacryloyloxyethyl)-phthalic acid, etc. Carboxylic acid ester of the 2nd group subphase, etc. are mentioned. Among these carboxyl group-containing monomers, (2-acryloyloxyethyl) -amber acid and (2-acryloyloxyethyl) -phthalic acid are commercially available under the trade names M-5300 and M-5400 (Toa Synthesis, Japan). Products). The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Moreover, as said copolymerizable unsaturated monomer, styrene, (alpha) -methylstyrene, o-vinyl styrene, m-vinyl toluene, p-vinyl toluene, p-curol styrene, o-methoxy styrene, m-methoxy styrene, for example aromatic vinyl compounds such as p-methoxy styrene, 2-vinyl benzyl methyl ether, 3-vinyl benzyl methyl ether, 4-vinyl benzyl methyl ether, and 2-vinyl benzyl glycidyl ether; Indenes such as indene and 1-methylindene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene acrylate , Methoxydiethylene methacrylate, methoxy triethylene acrylate, methoxy triethylene methacrylate, methoxy propylene acrylate, methoxy propylene methacrylate, methoxy dipropylene acrylate, methoxy dipropylene methacrylate, iso Bonylacrylate, isobonyl methacrylate, tricyclo [5,2,1] -decane-8-yl-acrylate, tricyclo [5,2,1] -decane-8-yl-methacrylate, 2 Unsaturated carboxylic acid esters such as hydroxy-3-phenoxy-propyl acrylate, 2-hydroxy-3-phenoxy-propyl methacrylate, glycerol acrylate and glycerol methacrylate; 2-ethyl acrylate, 2-ethyl methacrylate, 2-dimethylethyl acrylate, 2-dimethylethyl methacrylate, 2-propyl acrylate, 2-propyl methacrylate, 3-propyl acrylate, 3-propyl Alkyl esters of unsaturated carboxylic acids such as methacrylate, 3-dimethylpropyl acrylate and 3-dimethylpropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and arylglycidyl ether; Vinyl cyanide compounds such as acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylate; Unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Dienes of aliphatic compounds such as 1,3-butadiene, isoprene and chloroprene; Macro having acryloyl group or methacryloyl group at the terminal of polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane Monomers; These may be used alone or in combination of two or more, but the present invention is not limited thereto.

In the present invention, as the carboxyl group-containing copolymer, acrylic acid and / or methacrylic acid are essential components, and (2-acryloyloxyethyl) -amber acid and (2-methacryloyloxyethyl) are optionally Carboxyl group-containing unsaturated monomer components further comprising at least one compound selected from -amber, ω-carboxy polycaprolactone acrylate and ω-carboxy polycaprolactone methacrylate, and styrene, methyl acrylate and methyl methacrylate. , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol acrylate, glycerol methacrylate, N-phenylmaleimide , Polystyrene macro monomers, polymethyl methacrylate macro monomers and polymethyl methacrylate macro monomers. The copolymer (hereinafter referred to as the carboxyl group-containing copolymer (α)) of the at least one member selected from the group eojineun preferred.

Specific examples of the carboxyl group-containing copolymer (α) include copolymers of (meth) acrylic acid / methyl (meth) acrylate, copolymers of (meth) acrylic acid / benzyl (meth) acrylate, and (meth) acrylic acid / 2-hydroxy Copolymer of ethyl (meth) acrylate / benzyl (meth) acrylate, copolymer of (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl Copolymer of methacrylate macromonomer, copolymer of (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer, air of (meth) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate macromonomer Copolymer, copolymer of (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer, (meth) acrylic acid / 2-hydroxyethyl (meth) Copolymer of methacrylate / benzyl (meth) acrylate / polymethylmethacrylate macromonomer, copolymer of methacrylic acid / benzyl (meth) acrylate / N-phenylmaleimide, (meth) acrylic acid / [2- ( (Meth) acrylic acid / [2- (meth) acryloyloxyethyl] -amber acid / styrene (meth) acryloyloxyethyl] -amber acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide Copolymer of / allyl (meth) acrylate / N-phenylmaleimide, copolymer of (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol (meth) acrylate / N-phenylmaleimide, (meth) And copolymers of acrylic acid /?-Carboxy polycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol (meth) acrylate / N-phenylmaleimide.

The first copolymer has an average molecular weight of 8,000 to 30,000 and an acid value of 50 to 150 mg / g KOH. When the average molecular weight of the first copolymer is less than 8,000, the resolution of the photosensitive resin for the spacer is lowered. When the average molecular weight of the first copolymer is more than 30,000, the developability of the photosensitive resin for the spacer is lowered. In addition, if the acid value of the first copolymer is less than 50 mg / g KOH, the developability of the photosensitive resin for the spacer is lowered. If the acid value of the first copolymer is more than 150 mg / g KOH, the adhesiveness of the spacer is lowered. .

The polyfunctional monomer used in the present invention is a monomer having two or more polymerizable unsaturated bonds. As said polyfunctional monomer, For example, Diacrylate or dimethacrylate of alkylene glycol, such as ethylene glycol and propylene glycol; Diacrylates or dimethacrylates of polyalkylene glycols such as polystyrene glycol and polypropylene glycol; Polyacrylates or polymethacrylates of trivalent or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, or dicarboxylic acid modified substances thereof; Tris- (2-acryloyloxyethyl) phosphate, tris- (2-methacryloyloxyethyl) phosphate, and the like.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trivalent or higher polyhydric alcohols or their dicarboxylic acid modified substances, specifically trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Methacrylate and the like are preferred, and in particular, trimethylolpropane triacrylate and dipentaerythritol hexaacrylate are excellent in the strength and surface flatness of the coating layer, and also the contamination and residual on the substrate and the light shielding layer of the unexposed portion. Generating water It is preferable in that it does not make it.

In addition, in this invention, a part of polyfunctional monomer can also be replaced by the monofunctional monomer which has one polymerizable unsaturated bond. As said monofunctional monomer, the same monomer as the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer which were illustrated about alkali-soluble resin, N-acryloyl morpholine, N-methacryloyl morpholine, N-vinylpyrroli, for example DON and N-vinyl-ε-caprolactam (M-5300, M-5400, M-5600 of Toa Synthetics, Japan) are mentioned as a brand name. These monofunctional monomers can be used individually or in mixture of 2 or more types.

The photoinitiator used by this invention has the effect | action which produces the active species which initiates superposition | polymerization of the monofunctional monomer used in the case of the said polyfunctional monomer by exposure by radiation. As such a photoinitiator, a biimidazole type compound, a benzoin type compound, an acetophenone type compound, a benzophenone type compound, the (alpha)-diketone type compound, a phosphine type compound, a polynuclear quinone type compound, a triazine type compound, etc. are mentioned, for example. However, the present invention is not limited thereto.

Specific examples of the biimidazole compound include 2,2-bis (2-chlorophenyl) -4,4,5,5-tetrakis (4-ethoxycarbonylphenyl) -1,2-biimidazole, 2,2-bis (2-bromophenyl) -4,4,5,5-tetrakis (4-ethoxycarbonylphenyl) -1,2bidiimidazole, 2,2-bis (2-chlorophenyl ) -4,4,5,5-tetraphenyl-1,2-biimidazole, 2,2-bis (2,4-dichlorophenyl) -4,4,5,5-tetraphenyl-1,2- Biimidazole, 2,2-bis (2,4,6-trichlorophenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole, 2,2-bis (2-bromo Phenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole, 2,2-bis (2,4-dibromophenyl) -4,4,5,5-tetraphenyl-1 , 2-biimidazole, 2,2-bis (2,4,6-tribromophenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole, etc. are mentioned.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin-i-butyl ether, methyl 2-benzoylbenzoate and the like. Moreover, as a specific example of the said acetophenone type compound, 2, 2- dimethoxy acetophenone, 2, 2- diethoxy acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, 2-hydroxy-2-methyl- 1-phenylpropane-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methylpropane-2 -Morpholinopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxypropan-1-one, 1- (4-morpholinophenyl) -2 -Benzyl-2-dimethylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

Moreover, 3, 3- dimethyl-4- methoxy benzophenone is mentioned as a specific example of the said benzophenone type compound. In addition, specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl hallmethodiketone, and the like. In addition, specific examples of the phosphine-based compound include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,4-trimethylpentylbis (2,6-dimethoxybenzoyl) phosphine oxide, 2,4 , 6-trimethylbenzoyldiphenyl phosphine oxide and the like. Moreover, anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1, 4- naphthoquinone etc. are mentioned as a specific example of the said polynuclear quinone type compound. In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethyl-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2 -[2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trickle) Roromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4, The compound which has halomethyl groups, such as 6-bis (trichloromethyl) -s-triazine, is mentioned. In this invention, a photoinitiator can be used individually or in mixture of 2 or more types.

Moreover, in this invention, 1 or more types of sensitizers can also be used together with a photoinitiator as needed. As said sensitizer, some are included also in a donor, For example, 4, 4-bis (dimethyl) benzophenone, 4, 4-bis (diethyl) benzophenone, 4-diethyl acetophenone, 4-dimethylamino Organic amino compounds such as propiophenone, methyl 4-dimethylaminobenzoate, 4-dimethylbenzoic acid i-amyl, 4-dimethylbenzoic acid and 4-dimethylbenzoic acid nitrile; Xanthone type compounds, such as diethyl thioxanthone and di-i-propyl thioxanthone, etc. are mentioned.

Among these sensitizers, 4,4-bis (dimethyl) benzophenone, 4,4-bis (diethyl) benzophenone, diethyl thioxanthone, di-i-propyl thioxanthone, and the like are preferable, and in particular 4,4 -Bis (dimethyl) benzophenone, 4, 4-bis (diethyl) benzophenone, di-i-propyl thioxanthone, etc. are preferable. The said sensitizer can be used individually or in mixture of 2 or more types.

Specific examples of the solvent used in the present invention include ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, and di Ethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, propylene glycol n-propyl ether, propylene glycol polyalkylene glycol dialkyl ethers such as n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol diethyl ether; Polyalkylene glycol diethyls such as ethylene glycol monomethyl ether acetate, ethylene glycol diethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol diethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol diethyl ether acetate Alkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol ether, tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as 2-hydroxy-2-methylpropionate and the like; 2-hydroxy-2-methylpropionate, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethoxy draft ethyl, ethyl hydroxyacetate, 2 Hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvate n Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxo butyrate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; Etc. can be mentioned.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol methyl ether ether from the viewpoint of solubility, pigment dispersibility, coating property, and the like. , Cyclohexanone, hexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl- Preference is given to 3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like. . The said solvent can be used individually or in mixture of 2 or more types.

In addition, the present invention may further include additives. Preferably, the additive may further include a silane coupling agent in the range of 0.01 to 1% by weight based on 100% by weight of the total composition. When the amount of the silane coupling agent added is less than 0.01% by weight based on 100% by weight of the total composition, the adhesion of the spacer is lowered. When the amount of the silane coupling agent is added by more than 1% by weight based on 100% by weight of the total composition of the liquid crystal display. Afterimage driving is likely to occur.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example  One

To the photosensitive resin composition was prepared using the ingredients and contents shown in Table 1 below.

The above components were used, first, the photoinitiator was dissolved in a solvent, stirred at room temperature for 2 hours, and then stirred at room temperature for 2 hours by adding a polyfunctional monomer, a cardo-based binder resin, and a first copolymer. Subsequently, other additives, etc. were added to the reaction, and the mixture was stirred at room temperature for 1 hour. Impurity was removed by three times of leisure to prepare the photosensitive resin composition of the present invention, and the compression displacement, elastic recovery rate and residual film rate were evaluated according to the physical property evaluation method described below, and the results are shown in Table 2 below.

Example  2

The same procedure as in Example 1 was carried out except that the first copolymer 20g was used alone as the resin.

Comparative example

The same procedure as in Example 1 was carried out except that 20 g of PRG-300 (manufactured by Showa Polymer, Japan) was used as the binder resin.

Experimental Example

Spacer  Formation of patterns

The photosensitive resin composition was applied onto a glass substrate using a spin coater, and then dried at 80 ° C. for 80 seconds to form a coating film. The pattern film was used for the coating film thus obtained, and the light having a wavelength of 365 nm was irradiated for 4 seconds at an intensity of 25 mA / cm 2. Subsequently, the solution was developed at 30 DEG C for 1 minute in an aqueous solution diluted with 1 wt% of potassium hydroxide, and then washed with pure water for 1 minute. By this operation, unnecessary parts could be removed and only the spacer pattern could be left. The formed spacer pattern was cured by heating at 220 ° C. for 30 minutes in an oven to obtain a spacer pattern having a height of 4 μm.

Spacer  Evaluation of strength

The compression characteristic of the obtained spacer pattern was evaluated using a microhardness machine (Fisher H-100, Germany). The degree of compression was measured by applying a load to the spacer with a planar indenter having a diameter of 50 μm (4.55 mN / sec), and the elastic recovery rate was measured from the height restored after removing the load at the same speed.

Residual rate  Measure

When forming the spacer pattern, the ratio of the thickness of the coating film after drying at 80 ° C. and the thickness of the coating film after drying at 220 ° C. was measured.

As can be seen from Table 2, the photosensitive resin composition for spacers of the present invention, unlike the conventional photosensitive resin composition, not only has excellent compression characteristics and strength, but also shows a good residual film ratio and excellent pattern stability when forming a film. have.

As described above, the photosensitive resin composition according to the present invention is excellent in elasticity, strength, heat stability, and the like. Therefore, when the spacer is formed using the photosensitive resin composition of the present invention, a uniform cell gap can be maintained regardless of the size of the liquid crystal display device, and a change in the cell gap due to movement, vibration, shock, etc. of the liquid crystal panel is achieved. Can be prevented. In particular, the photosensitive resin composition according to the present invention has excellent strength, and the liquid crystal display device employing the same may prevent the spacer pattern from being destroyed by an external impact.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (6)

A photosensitive resin composition comprising a binder resin, a polyfunctional monomer and a photoinitiator, wherein the binder resin is used as the binder resin. A copolymer of the formula (1); And Unsaturated carboxylic acid or unsaturated carboxylic anhydride; Unsaturated hydrocarbons; And one first copolymer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid derivatives and methacrylic acid derivatives; Photosensitive resin composition comprising a. [Formula 1]

The method of claim 1, A photosensitive resin composition comprising copolymerizing monomers of the following Chemical Formula 2: Chemical Formula 3: 1 mol: 2 to 4 mol: 8 mol as a binder resin and having a molecular weight of 1,000 to 20,000; [Formula 2]

[Formula 3]

Wherein R is-(CH ₂ ) m-, where m is an integer from 1 to 10,

Or -O (CH ₂ ) n- (where n is an integer of 1 to 8) and X is a halogen atom.) [Formula 4]

Wherein R is-(CH ₂ ) m-, where m is an integer from 1 to 10,

Or -O (CH ₂ ) n- (where n is an integer of 1 to 8) and X is a halogen atom.) delete The method of claim 1, The average molecular weight of the first copolymer is 8,000 to 30,000, the acid value is 50 to 150 mg / g KOH photosensitive resin composition. The method of claim 1, wherein the composition, (a) 10 to 40% by weight of the binder resin; (b) 1 to 20% by weight of the multifunctional monomer; (c) 0.5 to 10% by weight of the photoinitiator; And (d) A photosensitive resin composition comprising a solvent as a filtrate. The photosensitive resin composition according to claim 1, further comprising a silane coupling agent as an additive in the composition, the content of which is 0.01 to 1% by weight based on the total composition.