KR100911889B1 - Photosensitive resin composition with organic~inorganic hybrid and liquid display devices using - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid photosensitive resin composition, and more particularly, to a liquid crystal display device comprising an organic-inorganic hybrid photosensitive resin composition formed of photosensitive resin and a hydrophobized inorganic material and a cured body thereof, particularly as a) a colloidal inorganic sol. An inorganic sol hydrophobized by adding 1 to 120 parts by weight of an organosilane to the colloidal inorganic material to remove water while reacting the organic silane on the surface of the nanoparticle inorganic material and adding an organic solvent to hydrophobize the reaction medium; And, b) an acrylic copolymer obtained by copolymerizing i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, and ii) at least one acrylic unsaturated compound; And c) photoinitiators; And d) polyfunctional monomers having ethylenically unsaturated bonds; And e) a silicone compound comprising an epoxy group or an amine group; And an organic-inorganic hybrid photosensitive resin composition containing a solvent and f) a cured product thereof. Accordingly, the organic-inorganic hybrid photosensitive resin composition is excellent in low dielectric properties, adhesive strength, heat resistance, insulation, flatness, chemical resistance, and the like, and is suitable as an image forming material for liquid crystal display devices. Its excellent dielectric constant, flatness, sensitivity, residual film ratio, and UV transmittance make it suitable for use as a low-passivation passivation organic insulating film, and at the same time for overcoat resist resins, black matrix resist resins, column spacer resist resins, or color filters. Used as a resist resin has the advantage of being suitable for improving low dielectric constant, high heat resistance, adhesion.

Low dielectric photosensitive resin organic insulating film liquid crystal display device resist resin organic-inorganic hybrid

Description

Photosensitive resin composition with organic ~ inorganic hybrid and liquid display devices using}

The present invention relates to a liquid crystal display device using an organic-inorganic hybrid photosensitive resin composition for passivation and a cured body thereof, and more particularly, liquid crystal display having excellent performances such as low dielectric properties, adhesive strength, heat resistance, insulation, flatness, chemical resistance, and the like. It is suitable as an image forming material of a display element, and in particular, it is not only suitable for use as an organic insulating film because it has excellent low dielectric constant, moisture resistance, adhesion and heat resistance when forming a passivation film of a liquid crystal display element, and at the same time, a resist resin for overcoat, The present invention relates to a photosensitive resin composition which can be used as a resist resin for a black matrix, a resist resin for a column spacer, or a resist resin for a color filter to improve heat resistance, adhesion, and the like.

In general, the most popular organic insulator is SiO ₂ . This is because it can be easily formed on Si, which has a high insulation rate and is most often used as a substrate. However, due to its amorphous structure and high dielectric constant of about 3.9, it is true that an optimal low dielectric constant organic insulator is insufficient in performance.

 The passivation organic insulator should have a low dielectric constant in order to reduce the transfer of charge even at a low thickness, thereby improving insulation and increasing on / off ratio, thereby improving TFT driving characteristics.

Current acrylic organic insulating layer used as passivation organic insulation film for the inde side is low as 280 in heat resistance, which is stable and, conventional SiO ₂ and the acrylic insulator having at least 300 heat resistance in reliability terms are high-cost, high dielectric constant, insufficient heat resistance There are disadvantages such as poor moisture resistance, adhesion, heat resistance, and the like.

The present invention is to solve the problems of the prior art as described above, and excellent in the performance of low dielectric constant, adhesion, heat resistance, insulation, flatness, chemical resistance, etc. is suitable as an image forming material of the liquid crystal display device, in particular liquid crystal display In forming the organic-inorganic hybrid insulating film for the passivation of the device is excellent in low dielectric properties, moisture resistance, adhesive strength, heat resistance to provide an organic-inorganic hybrid photosensitive resin composition suitable for use as an insulating film for passivation and a liquid crystal display device using a cured body thereof We assume problem to do.

In order to solve the above problems, the present invention is an organic-inorganic hybrid photosensitive resin composition, the present invention is a) colloidal inorganic sol; b) an acrylic copolymer obtained by copolymerizing i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and ii) at least one acrylic unsaturated compound; And c) photoinitiators; And d) polyfunctional monomers having ethylenically unsaturated bonds; And e) a silicone compound comprising an epoxy group or an amine group; And an organic-inorganic hybrid photosensitive resin composition containing a solvent and a cured product thereof, and f) a liquid crystal display device.

In addition, the a) colloidal inorganic sol, by adding 1 to 120 parts by weight of the organic silane to the colloidal nanoparticle inorganic material, while removing the water while reacting the organic silane on the surface of the nanoparticle inorganic material, the organic solvent is added to hydrophobize the reaction medium In addition, the colloidal nanoparticle inorganic material, the water-soluble colloid containing at least one of the inorganic material capable of reacting with silica, alumina, titania, zirconia, tin oxide, zinc oxide, organosilane or surface-modified with silica It is preferably formed of an inorganic phase.

Here, it is preferable that the addition of the organosilane, the removal of water, and the addition of the organic solvent to the water-dispersible colloidal inorganic material are repeatedly performed a plurality of times with a single or time difference.

Herein, the organosilane is R ¹ _{0 to 3} Si (OR ² ) _{1 to 4} wherein R ¹ is an alkyl group, a phenyl group, a fluorocarbon group, an acryl group, a methacryl group, an allyl group, a vinyl group, or an epoxy group. At least one is selected and mixed, and R ² is at least one selected from methyl, ethyl, isopropyl, n-propyl, or en-butyl; , OR ² is preferably used 1 to 95 parts by weight of a colloidal inorganic material having a general formula consisting of an alkoxy group.

And b) i) 5 to 45 parts by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof; And ii) 100 parts by weight of an acrylic copolymer obtained by copolymerizing 5 to 95 parts by weight of one or more acrylic unsaturated compounds; c) 0.001 to 30 parts by weight of photoinitiator; d) 10 to 100 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond; e) 0.0001 to 5 parts by weight of a silicon compound containing an epoxy group or an amine group; And f) a solvent so that the content of solids in the photosensitive resin composition is 10 to 50 parts by weight.

The shape of the colloidal nanoparticle inorganic material of a) is preferably formed in a spherical size of 1 ~ 100nm or in a fiber shape of 100 ~ 1000nm size. The surface of the colloidal nanoparticle inorganic material is surface-treated with an organosilane having a reactive group, so that the nanoparticles of the inorganic material are stably dispersed in an organic solvent, thereby having excellent storage properties and chemically bonding at an organic resin with a molecular level.

And, the acrylic copolymer of b) may be prepared by radical reaction in the presence of a solvent and a polymerization initiator iii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, and ii) an acrylic unsaturated compound as a monomer. .

The unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof of b) i) used in the present invention may be selected from unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid and itaconic acid; Or anhydrides of these unsaturated dicarboxylic acids, or the like, may be used alone or in combination of two or more thereof. Particularly, acrylic acid, methacrylic acid, or maleic anhydride may be used in terms of copolymerization reactivity and solubility in aqueous alkali solution. Do.

The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably included in 5 to 40 parts by weight, more preferably 10 to 40 parts by weight of the total monomers. If the content is less than 5 parts by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, if it exceeds 40 parts by weight there is a problem that the solubility in the aqueous alkali solution is too large.

As the b) ii) acrylic unsaturated compound used in the present invention, an epoxy group-containing unsaturated compound and an olefinically unsaturated compound are used.

As the epoxy group-containing unsaturated compound, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, glycidyl acrylate-β- Methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3 , 4-Epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. can be used, The said compound can be used individually or in mixture of 2 or more types.

In particular, the epoxy group-containing unsaturated compounds are methacrylic acid glycidyl, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl It is more preferable to use glycidyl ether or p-vinylbenzyl glycidyl ether in improving the copolymerization reactivity and the heat resistance of the obtained pattern.

The epoxy group-containing unsaturated compound is preferably contained in 10 to 70 parts by weight, more preferably 20 to 60 parts by weight of the total monomers. If the content is less than 10 parts by weight, there is a problem that the heat resistance of the resulting pattern is lowered, and if it exceeds 70 parts by weight, there is a problem that the storage stability of the copolymer is lowered.

The olefinically unsaturated compound is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate Latex, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-a Monomethyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboroyl acrylate , Phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-meth Styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3-butadiene, and the like may be used. Or it can mix and use 2 or more types.

In particular, the olefinically unsaturated compound is more preferable in terms of solubility in aqueous alkali solution which is copolymerization reactivity and developer using styrene, dicyclopentanylmethyl methacrylate, or p-methoxy styrene.

The olefinically unsaturated compound is preferably included in 10 to 70 parts by weight, more preferably 20 to 50 parts by weight based on the total total monomers. When the content is in the above range, it is possible to simultaneously solve the problem of lowering the preservation safety of the acrylic copolymer and the acrylic copolymer being difficult to dissolve in the aqueous alkali solution.

Solvents used to polymerize such monomers into acrylic copolymers include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol mono. Methyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene Glycol Methyl Ether Acetate, Propylene Glycol Ethyl Acetate, Propylene Glycol Propyl Ether Acetate, Propylene Glycol Butyl Ether Acetate, Propylene Glycol Methyl Ethyl Propionate, Propylene Glycol Ethyl Propionate Nitrate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate , Butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, lactic acid Ethyl, propyl lactate, butyl lactate, methyl 3-hydroxy propionate, ethyl 3-hydroxy propionate, propyl 3-hydroxy propionate, butyl 3-hydroxy propionate, methyl 2-hydroxybutyrate, methoxyacetic acid To methyl, ethyl methoxy acetate, methoxy methoxy acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, propoxy acetate Propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate,Ethers such as methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, etc. may be used, and the compounds may be used alone or in combination of two or more thereof. have.

The polymerization initiator used to polymerize such monomers into an acrylic copolymer may use a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethyl Valeronitrile), 2,2-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2-azobis Isobutylate and the like can be used.

In addition, the photoinitiator of c) used in the present invention may use compounds such as Irgacure 369, Irgacur 651, Irgacure 907, Darocur TPO, Irgacure 819, triazine, benzoin, acetophenone, imidazole, or thanthone. Can be.

Specifically, the photoinitiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-tri Azine, 2,4-trichloro methyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenoneno, 2, 2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, or 2,2 Compounds, such as -bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, can be used individually or in mixture of 2 or more types.

The photoinitiator is preferably included in 0.001 to 30 parts by weight, more preferably 0.01 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.001 part by weight, there is a problem in that the residual film ratio is deteriorated due to the low sensitivity. If the content is more than 30 parts by weight, there may be a problem in storage stability. There is a problem.

The polyfunctional monomo having an ethylenically unsaturated bond of d) used in the present invention is generally a crosslinkable monomer having at least two ethylenic double bonds, and is 1,4-butanedioldiacrylate, 1,3-butyl Lenglycol diacrylate, ethylene glycol diacrylate, trimethylol propane diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate , Dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, or methacrylates thereof And the like can be used.

The polyfunctional monomer having an ethylenically unsaturated bond is preferably contained in 10 to 100 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer. If the content is less than 10 parts by weight, there is a problem in that the contact hole and the pattern is difficult to implement due to the low degree of curing with the photosensitive resin.If the content exceeds 100 parts by weight, the resolution of the contact hole and the pattern is reduced during development. There is a problem.

The silicone compound containing the epoxy group or the amine group of e) used in the present invention is (3-glycidoxy propyl) trimethoxy silane, (3-glycidoxy propyl) triethoxy silane, (3-gly Seedoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane Phosphorus, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxy silane, aminopropyl trimethoxy silane, etc. can be used individually or in mixture of 2 or more types.

The silicone compound including the epoxy group or the amine group is preferably included in an amount of 0.0001 to 5 parts by weight, and more preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.0001 parts by weight, the adhesion between the ITO electrode and the photosensitive resin is inferior, and there is a problem in that the heat resistance property is inferior after curing. There is a problem that a scum of a hole or a pattern is generated.

The solvent of f) used in the present invention does not generate flatness and coating stain of the insulating film to form a uniform pattern profile.

The solvent is alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3-methyl butyrate, methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, propoxy acetate Methyl, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxy Propyl propionate, butyl 2-methoxy propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-part Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate 3-ethyl propylpropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl Propionate, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Ethyl Propoxypropionate, 3-Propoxy Propionate, 3-Propyl Propionate, 3-Butoxypropionate Esters such as methyl, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate, and the like can be used.

In particular, it is preferable to select and use at least 1 type of said solvent from the group which consists of solubility, reactivity with each component, and easy to form a coating film, glycol ethers, ethylene alkyl ether acetates, and diethylene glycols.

The solvent is preferably included so that the solid content of the entire photosensitive resin composition is 10 to 50% by weight, the composition having a solid content of the above range is preferably used after filtering with a Millipore filter of 0.1 ~ 0.2 ㎛. More preferably, it is included to be 15 to 40% by weight. If the solid content of the total composition is less than 10% by weight, there is a problem in that the coating thickness is thin, and coating flatness is lowered. When the content of the solid composition exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is hard to coat. There is a problem that can give.

Moreover, the photosensitive resin composition of this invention can add compatible additives, such as a thermal polymerization inhibitor and an antifoamer, to the said composition as needed, and can add a pigment according to a use. For example, a resist for a black matrix and a resist for a color filter, which are one of the image forming materials of a TFT type liquid crystal display device, is obtained by blending a pigment with the composition, wherein the pigment is a resist of a black matrix resist and a color filter resist. It can be appropriately selected according to the use, and both inorganic and organic pigments can be used.

In addition, the present invention provides a TFT type liquid crystal display device using the cured body of the organic-inorganic hybrid photosensitive resin as described above and a TFT type liquid crystal display device using the negative photosensitive resin composition.

The TFT-type liquid crystal display device may be formed by forming a passivation organic-inorganic photosensitive resin composition using an organic insulating film, an overcoat resist, a black matrix resist, a column spacer resist, or a color filter resist. In the method of forming, the said organic-inorganic hybrid photosensitive resin composition is used.

Specifically, an example of a method of forming a pattern of a TFT type liquid crystal display device using the organic-inorganic hybrid photosensitive resin composition is as follows.

First, the photosensitive resin composition of this invention is apply | coated to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, etc., A solvent is removed by prebaking, and a coating film is formed. At this time, it is preferable to perform the said prebaking for 1 to 15 minutes at the temperature of 70-110 degreeC.

Then, a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like on the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10 parts by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, the pattern is applied to a heating apparatus such as an oven. By heating at a temperature of 150 to 250 ° C. for 30 to 90 minutes to obtain a final pattern.

The organic-inorganic hybrid insulating film according to the present invention as described above is excellent in low dielectric properties, moisture resistance, adhesion, heat resistance, insulation, flatness, chemical resistance, etc., is suitable as an image forming material of the liquid crystal display device, in particular, liquid crystal display When forming organic-inorganic hybrid insulating film for device passivation, it is suitable for use as insulating film for passivation because it has excellent low dielectric property, moisture resistance, adhesive strength and heat resistance, and is suitable for overcoat resist resin, black matrix resist resin, column spacer resist resin, Or it is used as the resist resin for color filters, and becomes suitable for improving heat resistance, strength, etc.

The organic-inorganic hybrid photosensitive resin composition according to the present invention has excellent performances such as low dielectric properties, heat resistance, insulation, flatness, chemical resistance, and high hardness, and thus is suitable as an image forming material for liquid crystal display devices, and in particular, passivation of liquid crystal display devices. It is suitable for use as a passivation insulating film because it has excellent hardness, heat resistance, insulation, and flatness when forming an insulating film, and is used as an overcoat resist resin, black matrix resist resin, column spacer resist resin, or color filter resist resin. And the hardness can be improved.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1 (Formation of Mineral Sol)

The colloidal nanoparticle inorganic material is adjusted to acidity between pH 3-5, and 1 to 120 parts by weight of methyltrimethoxysilane (MTMS) or vinyltrimethoxysilane (VTMS), which is an organic silane diluted in alcohol, is added to the nano The reaction medium is hydrophobized by removing water while reacting the organosilane on the surface of the inorganic particles and adding an organic solvent.

At this time, when the methoxy group reacts to the surface of the colloidal inorganic particles, the methyl group is exposed to the surface, so that the colloidal inorganic material is changed into a form that can be dispersed in the organic resin, thereby controlling the degree of hydrophobicity at the inorganic surface. Do it. VTMS condensation reaction of methoxy groups of the hydroxy group of the hydrophobized colloidal inorganic interface of the three methoxy groups exposed to the vinyl group, so that the hydrophobized colloidal inorganic particles will form a colloidal inorganic sol formed with a vinyl group or other reactive groups Can be.

Example 2 (Preparation of Acrylic Copolymer)

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, methacrylic acid in a flask equipped with a cooling tube and a stirrer 35 parts by weight of glycidyl, 15 parts by weight of methyl methacrylate, and 30 parts by weight of styrene were added, followed by nitrogen substitution, followed by gentle stirring. The reaction solution was heated to 62 ° C. to prepare a polymer solution containing an acrylic copolymer while maintaining this temperature for 5 hours.

        The acrylic copolymer prepared as described above was added dropwise to 5,000 parts by weight of hexane, precipitated, and separated by filtration. Then, 200 parts by weight of propionate was added thereto and heated to 30 ° C. to obtain a solid content of 45 parts by weight, and a weight average of the polymer. The molecular weight was 11,000. At this time, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

Example 3 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

100 parts by weight of the polymer solution containing the acrylic copolymer prepared above, 15 parts by weight of Irgacure 819 as a photoinitiator, 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, 10 parts by weight of trimethylolpropane triacrylate, a silicone compound 1 part by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2 parts by weight of F171 in a silicon-based surfactant were mixed. Diethylene glycol dimethyl ether was added and dissolved in the mixture so that the solid concentration was 35% by weight.

The acrylic copolymer prepared as described above and the inorganic sol prepared in Example 1 were prepared such that the mixing weight ratio was 95: 5.

The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed.

Example 4 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

The production method of the acrylic copolymer is the same as in Example 2, the production method of the inorganic sol is the same as in Example 1. The organic-inorganic hybrid photosensitive resin composition thus prepared was prepared such that the mixed weight ratio of the acrylic copolymer and the inorganic sol was 80:20. The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed. .

Example 5 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

The production method of the acrylic copolymer is the same as in Example 2, the production method of the inorganic sol is the same as in Example 1. The organic-inorganic hybrid photosensitive resin composition thus prepared was prepared such that the mixed weight ratio of the acrylic copolymer and the inorganic sol was 60:40. The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed. .

Example 6 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

The production method of the acrylic copolymer is the same as in Example 2, the production method of the inorganic sol is the same as in Example 1. The organic-inorganic hybrid photosensitive resin composition thus prepared was prepared such that the mixed weight ratio of the acrylic copolymer and the inorganic sol was 40:60. The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed. .

Example 7 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

The production method of the acrylic copolymer is the same as in Example 2, the production method of the inorganic sol is the same as in Example 1. The organic-inorganic hybrid photosensitive resin composition thus prepared was prepared such that the mixing weight ratio of the acrylic copolymer and the inorganic sol was 20:80. The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed. .

Example 8 (Manufacture of organic-inorganic hybrid photosensitive resin composition)

The production method of the acrylic copolymer is the same as in Example 2, the production method of the inorganic sol is the same as in Example 1. The organic-inorganic hybrid photosensitive resin composition thus prepared was prepared such that the mixed weight ratio of the acrylic copolymer and the inorganic sol was 10:90. The organic-inorganic hybrid resin composition thus prepared was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was obtained, and when a film was formed, a thickness of 0.5 to 5.0 microns was obtained according to the coating speed. .

Using the organic-inorganic hybrid photosensitive resin composition coating solution prepared in Examples 3 to 8 after evaluating the physical properties in the following manner, the results are shown in Table 1 below.

After applying the photosensitive resin composition solution prepared in Examples 1 to 8 using a spin coater on a glass substrate, a film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes.

The film | membrane obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15 microseconds / cm <2> for 6 second using the predetermined pattern mask. Thereafter, the solution was developed at 25 ° C. for 2 minutes in an aqueous solution of 0.38 parts by weight of tetramethyl ammonium hydroxide, and then washed with ultrapure water for 1 minute.

Subsequently, the developed pattern was irradiated with ultraviolet rays having a intensity of 15 mA / cm 2 at 365 nm for 34 seconds, midbaked at 120 ° C. for 3 minutes, and then cured by heating at 220 ° C. for 60 minutes in an oven. A membrane was obtained.

A) Heat resistance-5wt% weight loss temperature through TGA is measured by scraping the final coating of the pattern film formed in the measurement, 5wt% reduction temperature is very good at 300 degrees or more, excellent at 280 degrees or more, normal at 250 degrees or more, It was shown as bad below 250 degrees.

B) Hardness is measured using a pencil hardness tester after coating the coating film on glass. The measurement method was carried out by measuring the hardness of the film by a pencil described in ADTM D3363.

C) Transmittance-In the measurement of a), the optical absorption spectrum of visible light of the coating film after prebaking thickness of 3 microns is measured. In the case of 98%, the cases were excellent, in the case of 92-94%, and in the case of 92% or less, they were shown as bad.

D) Adhesion is shown by tapping test using MoM, Al, ITO substrate, 3M tape on the coating film after the final curing. After dividing the coating film into 100 cells at regular intervals, attaching 3M tape, and then slowly detaching them, the number of remaining cells out of 100 cells is very good at 95 or more, good at 90 or more, and normal at 80 or more. It was 80 or less and represented as bad.

ㅁ) Flatness is measured after coating the coating on glass, and the thickness of about 100 points is measured by thickness measuring device such as optical equipment, and the difference is very good when the difference is less than 1%, excellent when less than 2%, and less than 3% If it is more than that, it represented with bad. Through this method it is possible to determine the dispersion stability between the metal compound dispersion and the acrylic copolymer prepared by the ball mill through the ball mill and the possibility of precipitation of the metal compound.

Iii) The dielectric constant was measured by measuring the capacitance of the capacitor and obtained by the following equation. First, the dielectric thin film was coated to a predetermined thickness, and then the capacitance was measured through an impedance analyzer. Each dielectric constant was calculated by the following equation.

C (capacitance) =

ε ₀ (vacuum dielectric constant) * ε _r (dielectric dielectric constant) * A (effective area) / d (dielectric thin film thickness)

division Example 3 4 5 6 7 8 Hardness 3H 4H 5H 6H 7H 8H Transmittance Very good Very good Great Great Bad  Bad Heat resistance usually Great Very good Very good Very good Very good Adhesion Great Great Great usually usually Bad Flatness Great Great Great Great Great Bad Dielectric constant 3.4 3.4 3.3 3.3 3.2 3.2

Table 1 shows the characteristics of the organic-inorganic hybrid photosensitive resin prepared according to the present invention, Examples 3 to 8 have excellent heat resistance and hardness, good flatness and dielectric constant, good transmittance and adhesion properties Seemed.

Above all, the inorganic sol compound was stably mixed to secure the flatness of the coating and the storage stability of the photosensitive resin. An inorganic sol was used to prepare an organic-inorganic hybrid photosensitive resin composition having a low dielectric constant.

From this, when the organic-inorganic hybrid photosensitive resin composition according to the present invention is used as a passivation insulating film for TFT-LCD, it was confirmed that the heat resistance, hardness and flatness and dielectric constant are good and the transmittance and adhesion are excellent.

Claims (11)

In the photosensitive resin composition, a) acidically controlled colloidal nanoparticles having a pH between 3 and 5, including at least one of silica, alumina, titania, zirconia, tin oxide, zinc oxide, inorganic materials capable of reacting with organosilanes, and inorganically surface modified with silica 1 to 95 parts by weight of a colloidal inorganic sol obtained by adding 1 to 120 parts by weight of an organosilane having a general formula represented by <Formula 1> to the particle inorganic material, removing water while hydrophobizing the inorganic surface, and adding an organic solvent. ,  <Formula 1> R ¹ _{0 ~ 3} Si (OR ² ) _{1 ~ 4} , Here, at least one selected from R ¹ : an alkyl group, a phenyl group, a fluorocarbon group, an acryl group, a methacryl group, an allyl group, a vinyl group, and an epoxy group is selected and mixed, R ² : at least one selected from methyl, ethyl, isopropyl, n-propyl or n-butyl, OR ² : alkoxy group; b) i) 5 to 40 parts by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof; And ii) 100 parts by weight of an acrylic copolymer obtained by copolymerizing 5 to 95 parts by weight of one or more acrylic unsaturated compounds; c) 0.001 to 30 parts by weight of photoinitiator; d) 10 to 100 parts by weight of a multifunctional monomer having an ethylenically unsaturated bond; e) 0.0001 to 5 parts by weight of a silicon compound containing an epoxy group or an amine group; And f) An organic-inorganic hybrid photosensitive resin composition comprising a solvent such that the content of solids in the photosensitive resin composition is 10 to 50 parts by weight. delete The method of claim 1, The unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof of b) i) consists of anhydrides of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof The organic-inorganic hybrid photosensitive resin composition, characterized in that at least one selected from the group. The method of claim 1, B) ii) Glycidyl acrylate, Glycidyl methacrylate, Glycidyl α-ethyl acrylate, Glycidyl α-propyl acrylate, Glycidyl α-n-butyl acrylate, α-n-butyl acrylic acid Glycidyl, acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethylglycidyl, methacrylic acid-beta -ethylglycidyl, acrylic acid -3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl Organic-inorganic hybrid photosensitive resin composition, characterized in that at least one selected from the group consisting of glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether. The method of claim 1, Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate in preparing the acrylic copolymer of b) , Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylic Rate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, iso Boronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, one or more from the group consisting of s-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene B) ii) an organic-inorganic hybrid photosensitive resin composition further comprising 10 to 70 parts by weight of an olefinically unsaturated compound. The method of claim 1, The polystyrene reduced weight average molecular weight (Mw) of the acrylic copolymer of b) is 6,000 to 90,000, the organic-inorganic hybrid photosensitive resin composition. The method of claim 1, The photoinitiator of c) is Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxysty Reyl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone , p- (diethylamino) benzophenoneno, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethylthioxanthone, At least one selected from the group consisting of 2,4-diethyl thioxanthone and 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole An organic-inorganic hybrid photosensitive resin composition characterized in that. The method of claim 1, Multifunctional monomoga having an ethylenically unsaturated bond of d) 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropanediacrylate, trimethylolpropane Triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate The organic-inorganic hybrid photosensitive resin composition, which is selected from the group consisting of latex, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaarithitol polyacrylate, and methacrylates thereof. The method of claim 1, The silicone compound containing the epoxy group or the amine group of e) is (3-glycidoxy oxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxy propyl) methyl Dimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4 -Epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclo An organic-inorganic hybrid photosensitive resin composition, wherein the organic-inorganic hybrid photosensitive resin composition is selected from the group consisting of hexyl) ethyltriethoxysilane and aminopropyltrimethoxy silane. The method of claim 1, wherein the photosensitive resin composition, An organic-inorganic hybrid photosensitive resin composition, wherein at least one additive selected from the group consisting of a thermal polymerization inhibitor, an antifoaming agent, and a pigment is further added. The hardening body of the hybrid photosensitive resin composition of any one of Claims 1 and 3-10 was used. The liquid crystal display element characterized by the above-mentioned.