TWI392909B - Organic-inorganic hybrid photosensitive resin composition and liquid crystal display comprising cured body thereof - Google Patents

Description

Organic-inorganic hybrid photosensitive resin composition and liquid crystal display containing the same

The present invention relates to an organic-inorganic hybrid photosensitive resin composition for a passivation film and a liquid crystal display (LCD) containing the same, and more particularly to a photosensitive resin composition having a low dielectric constant and excellent adhesion. Properties, heat resistance, insulation, flatness, and chemical resistance, and thus are suitable as materials for forming an image of an LCD, and exhibit low dielectric constant and excellent moisture resistance after forming a passivated organic insulating film of an LCD. It is suitable for use as an organic insulating film, and is also used as a photoresist resin for an overcoat layer, a photoresist resin for a black matrix, and a photoresist resin for a column spacer. Or a photoresist resin for a color filter, thereby improving heat resistance, adhesion, and the like.

Usually, the organic insulating system mainly used for the device is made of SiO ₂ . The reason is that Si has a good insulating efficiency and mainly uses a substrate, which itself contributes to the formation of a film. However, Si has an amorphous structure and a high dielectric constant of 3.9 grade, and thus is not suitable for use as an optimum low dielectric constant organic insulator.

The organic insulator for the passivation film must have a low dielectric constant in order to reduce the charge mobility, and even at a low thickness, the insulation and the on/off ratio are increased, thereby enhancing the TFT driving property.

The passivated organic insulating film of the present invention is an acrylic organic insulating film having a low heat resistance of about 280 °C. In order to achieve the desired reliability, the insulating film is considered to be stable when heat resistance of 300 ° C or higher is ensured. However, conventional SiO ₂ and acrylic insulating systems are disadvantageous because of increased cost and dielectric constant, and reduced heat resistance, moisture resistance and adhesion.

Accordingly, the present invention has been made aware of the above problems occurring in the related art, and the present invention provides an organic-inorganic hybrid photosensitive resin composition having a low dielectric constant and excellent adhesion, heat resistance, insulation, Flatness and chemical resistance, so it can be used as a material for forming an image of an LCD, and further exhibits a low dielectric constant and excellent moisture resistance after forming an organic-inorganic hybrid passivation insulating film of an LCD. It is excellent in adhesion and heat resistance, and thus is very suitable as a passivation insulating film, and the present invention also provides an LCD including a hardened body thereof.

According to the present invention, an organic-inorganic hybrid photosensitive resin composition comprises: (a) a colloidal inorganic sol, (b) from (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof and (ii) at least one acrylic acid An acrylic copolymer produced by copolymerization of an unsaturated compound, (c) a photoinitiator, (d) a polyfunctional monomer having an ethylenically unsaturated bond, (e) an anthracene compound containing an epoxy group or an amine group, And (f) a solvent. Moreover, an LCD including a hardened body thereof is provided.

Specifically, (a) the colloidal inorganic sol is formed by adding colloidal inorganic nanoparticles and 1 to 120 parts by weight of organodecane so that the organic decane reacts with the surface of the inorganic nanoparticles to remove water and then add organic Solvent This makes the reaction medium hydrophobic. The colloidal inorganic nanoparticles are preferably composed of a water-dispersible colloidal inorganic material comprising at least one organic material selected from the group consisting of vermiculite, alumina, titania, zirconia, tin oxide, zinc oxide, and organic decane. And inorganic materials modified by the surface of meteorites.

Therefore, the method includes adding a water-dispersed colloidal inorganic material and an organic decane, removing water, and adding an organic solvent, which can be repeatedly performed once or at predetermined time intervals.

The organic decane is represented by the following formula: R ¹ _0~3 Si(OR ² ) _1~4 , wherein at least one of R ¹ is selected from the group consisting of alkyl, phenyl, fluorocarbon alkyl, acryl fluorenyl, methacryl acyl, an allyl group, a vinyl group and an epoxy group, R ² Department least one selected from methyl, ethyl, isopropyl, n-propyl and n-butyl group, and an alkoxy group OR ² based, acetate The amount of the base or sulfhydryl colloidal inorganic sol is preferably from 1 to 95 parts by weight.

Further, the resin composition comprises: (b) 100 parts by weight of an acrylic copolymer which is copolymerized (i) 5 to 40 parts by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof and (ii) 5 ~95 parts by weight of at least one acrylic acid unsaturated compound; (c) 0.001 to 30 parts by weight of a photoinitiator; (d) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond; 0.0001 to 5 parts by weight of an anthracene compound containing an epoxy group or an amine group; and (f) a solvent in an amount of 10 to 50 parts by weight based on the solid content of the photosensitive resin composition.

(a) Colloidal inorganic nanoparticles have a spherical shape of 1 to 100 nm or a fiber shape of a size of 100 to 1000 nm. When the surface of colloidal inorganic nanoparticles When treated with an organic decane having a reactive group, the inorganic nanoparticles are stably dispersed in an organic solvent, thus exhibiting high stability and chemically bonding them to the organic resin at a molecular level.

(b) an acrylic copolymer can be prepared by subjecting a monomer to a radical reaction in the presence of a solvent and a polymerization initiator, the monomer comprising (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof, and (ii) an acrylic unsaturated compound.

In the present invention, examples of (b) (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof include an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or the like; and an unsaturated dicarboxylic acid such as maleic acid. , fumaric acid, citraconic acid, sec-conic acid, itaconic acid, etc.; and its unsaturated dicarboxylic anhydride, which may be used singly or in combination of two or more thereof. Acrylic acid, methacrylic acid or maleic anhydride is particularly useful for achieving desired copolymerization reactivity and solubility in an aqueous alkaline solution used as a developer.

The unsaturated carboxylic acid, the unsaturated carboxylic anhydride or a mixture thereof is used in an amount of 5 to 40 parts by weight based on the total weight of the monomers. If the amount is less than 5 parts by weight, the component is difficult to dissolve in an alkaline aqueous solution. On the contrary, if the amount exceeds 40 parts by weight, the solubility of this component in an aqueous alkaline solution is too high.

In the present invention, (b) (ii) the acrylic unsaturated compound includes an epoxy group-containing unsaturated compound and an olefin unsaturated compound.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α-n-butyl acrylate shrinkage. Glyceryl ester, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate Oil ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylic acid 6,7- Epoxyheptyl ester, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl Ether, and p-vinylbenzyl glycidyl ether. This compound may be used singly or in combination of two or more kinds thereof.

As the epoxy group-containing unsaturated compound, in order to achieve desired copolymerization reactivity and increase the heat resistance of the resulting pattern, glycidyl methacrylate, β-methyl glycidyl methacrylate is particularly suitable. 6,6-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether.

The epoxy group-containing unsaturated compound is used in an amount of 10 to 70 parts by weight, based on the total weight of the monomers, and preferably 20 to 60 parts by weight. If the amount is less than 10 parts by weight, the heat resistance of the resulting pattern is low. On the contrary, if the amount exceeds 70 parts by weight, the storage stability of the copolymer is undesirably low.

Further, examples of the olefin unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, third butyl methacrylate, methyl acrylate, acrylic acid. Isopropyl ester, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentyl methacrylate Ester, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, Dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, acrylic acid Phenyl ester, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1, 3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. This compound may be used singly or in combination of two or more kinds thereof.

As the olefin unsaturated compound, in order to achieve desired copolymerization reactivity and solubility in an aqueous alkaline solution used as a developer, styrene, dicyclopentylmethyl methacrylate or p-methoxy is particularly suitable. Styrene.

The olefin unsaturated compound is used in an amount of 10 to 70 parts by weight, based on the total weight of the monomers, and preferably 20 to 50 parts by weight. When the amount thereof falls within the above range, the problem of the low storage stability of the acrylic copolymer and the impossibility of solubility in an aqueous alkaline solution as a developer can be avoided.

Examples of the solvent for polymerizing the above monomer into an acrylic copolymer include ethers such as methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellulolytic acetate, diethylene glycol monomethyl 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 ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol Methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxyl -4-methyl-2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 Methyl methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Ethyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propyl acetate, methyl butoxyacetate, butyl Ethyl oxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, Methyl 2-butoxypropionate, 2- Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-B Butyl oxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butyl Methyl oxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate. This compound may be used singly or in combination of two or more kinds thereof.

A polymerization initiator for polymerizing the above monomer into an acrylic copolymer is a radical polymerization initiator, and specific examples thereof include 2,2-azobisisobutyronitrile and 2,2-azo (2,4-di) Methylvaleronitrile), 2,2-azo (4-methoxy-2,4- Dimethylvaleronitrile), 1,1-azo (cyclohexane-1-carbonitrile), and dimethyl 2,2-azoisobutyrate.

In the present invention, examples of the (c) photoinitiator include Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, Mitsui, benzoin, acetophenone, imidazole, and xanthone.

Specific examples of the photoinitiator include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-tripper, 2-p-methoxystyryl-4,6-bistrichloromethyl -s-Mituto, 2,4-trichloromethyl-6-tripby, 2,4-trichloromethyl-4-methylnaphthyl-6-tripper, benzophenone, p-diethylamino Benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethyl Thioxanthone, 2,4-diethylthioxanthone, and 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole. This compound may be used singly or in combination of two or more kinds thereof.

The photoinitiator is used in an amount of 0.001 to 30 parts by weight, based on 100 parts by weight of the acrylic copolymer, and preferably 0.01 to 20 parts by weight. If the amount is less than 0.001 parts by weight, the thickness is reduced due to low sensitivity. On the other hand, if the amount exceeds 30 parts by weight, the storage stability becomes problematic, and the degree of hardening is increased, and the adhesion of the pattern is undesirably reduced after development.

In the present invention, (d) a polyfunctional single system having an ethylenically unsaturated bond, a crosslinkable monomer having at least two ethylenic double bonds, and examples thereof include 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol Diacrylate, polyethylene glycol diacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, and methacrylate thereof.

The polyfunctional monomer having an ethylenically unsaturated bond is used in an amount of 10 to 100 parts by weight, and preferably 10 to 60 parts by weight based on 100 parts by weight of the acrylic copolymer. If the amount is less than 10 parts by weight, the degree of hardening of the photosensitive resin is low, making it difficult to achieve contact holes and patterns. On the contrary, if the amount exceeds 100 parts by weight, the degree of hardening is unnecessarily increased, and the resolution of the pattern and the contact hole is undesirably reduced after development.

In the present invention, (e) examples of the oxime compound containing an epoxy group or an amine group include (3-glycidoxypropyl)trimethoxynonane, (3-glycidoxypropyl)triethoxylate. Baseline, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane, 3,4-epoxybutyltrimethoxy Decane, 3,4-epoxybutyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltri Ethoxy decane, and aminopropyl trimethoxy decane, which may be used singly or in combination of two or more kinds thereof.

The oxime compound containing an epoxy group or an amine group is used in an amount of 0.0001 to 5 parts by weight, and preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer. When the amount is less than 0.0001 part by weight, the adhesion between the ITO electrode and the photosensitive resin is reduced after the curing process, and the heat resistance is lowered. On the contrary, if the amount exceeds 5 parts by weight, whitening of the unexposed portion in the developer and scum of the pattern and the contact hole are caused after the development process.

In the present invention, (f) a solvent is used for planarizing an insulating film and preventing coating The generation of stains thus forms a uniform pattern outline.

Examples of the solvent include: alcohols such as methanol, ethanol, etc.; ethers such as tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; ethyl glycol alkyl group Ether acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, etc.; diethylene glycols, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol dimethyl ether or the like; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate , propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Methyl-2-pentanone, etc.; and esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 Methyl methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Ethyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propyl acetate, methyl butoxyacetate, oxygen Ethyl acetate, butyl oxyacetate, butyl butoxyacetate, 2-methoxy propyl Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropane Butyl acrylate, butyl 2-butoxypropionate, 3-methoxypropionate methyl, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-ethoxypropane Methyl ester, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropane Ethyl acetate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropane Acid propyl ester, butyl 3-butoxypropionate, and the like.

As the solvent, at least one selected from the group consisting of glycol ethers, ethyl ethoxide ether and diethylene glycol is used, and it is compatible with the solubility of each component, reactivity, and ease of formation of a coating film. advantageous.

The amount of the solvent is such that the solid content of the photosensitive resin composition is in the range of 10 to 50 parts by weight. The composition satisfying the above requirements of the solid content range is preferably used after being filtered using a 0.1 to 0.2 μm micropore filter. Preferably, the amount of the solvent is such that the solid content of the composition ranges from 15 to 40 parts by weight. If the solid content of the composition is less than 10 parts by weight, the coating thickness becomes low, and the flatness of the coating becomes low. Conversely, if the solid content exceeds 50 parts by weight, the coating thickness will be reduced, and the coating device may be subjected to a load during the coating process.

Further, the photosensitive resin composition of the present invention may contain an additive compatible therewith, such as a thermal polymerization inhibitor or an antifoaming agent, if necessary, and may additionally contain a pigment depending on its final use. For example, for black matrices A photoresist for a photoresist or a color filter which is a material for forming an image of a TFT-LCD is formed by combining the composition of the present invention and a pigment. Moreover, the type of the pigment may be appropriately changed depending on the final use of the photoresist for the black matrix or the color filter, and an organic pigment and an organic pigment may be applied.

Further, the present invention provides a TFT-LCD comprising a hardened body of the organic-inorganic hybrid photosensitive resin composition as described above.

A method of forming a pattern of a TFT-LCD includes an organic-inorganic hybrid photosensitive resin composition for a passivation film, a photoresist for an overcoat layer, a photoresist for a black matrix, a photoresist for a column spacer, and a color filter. The photoresist for the light sheet is used to form an organic insulating film, and thus a TFT-LCD is manufactured, and the method is characterized in that an organic-inorganic hybrid photosensitive resin composition is used.

Specifically, a method of forming a pattern of a TFT-LCD using an organic-inorganic hybrid photosensitive resin composition will be described below.

First, the photosensitive resin composition of the present invention is applied onto the surface of a substrate by spraying, roll-to-roll coating or spin coating, and then a solvent is removed by prebaking to form a coating film. Moreover, the prebaking is carried out at 70 to 110 ° C for 1 to 15 minutes.

Then, the formed coating film is irradiated with visible light, VU light, far infrared light, electron beam or X-ray through a pattern which has been created, and then developed with a developer to remove unnecessary portions to obtain a prescribed pattern.

The developer contains an alkaline aqueous solution, and examples thereof include: an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc.; a primary amine such as n-propylamine; a secondary amine such as diethylamine, n-propylamine, etc.; Alkamines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc.; alkanolamines such as dimethylamine Alcoholamine, methyldiethanolamine, triethanolamine, etc.; and quaternary ammonium salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. The developer is used by dissolving the basic compound in a concentration of 0.1 to 10 parts by weight, and a specified amount of an aqueous organic solvent such as methanol or ethanol, and a surfactant may be added.

After the development process using the above developer, ultrapure water is used for the cleaning for 30 to 90 seconds, so that the unnecessary portion is removed and then dried, thereby forming a pattern. The pattern is irradiated with UV light and then heated at 150 to 250 ° C for 30 to 90 minutes using a heater such as an oven to obtain a final pattern.

The organic-inorganic hybrid insulating film according to the present invention exhibits a low dielectric constant and excellent moisture resistance, adhesion, heat resistance, insulation, flatness, and chemical resistance, and thus is suitable as a material for forming an image for an LCD. Further, after forming an organic-inorganic hybrid passivation insulating film of an LCD, it exhibits a low dielectric constant and excellent moisture resistance, adhesion, and heat resistance, and thus is suitable as a passivation insulating film. Further, the organic-inorganic hybrid insulating film can be used as a photoresist resin for an overcoat layer, a photoresist resin for a black matrix, a photoresist resin for a column spacer, and a photoresist resin for a color filter. Therefore, high heat resistance, adhesion, and the like are achieved.

The invention is better understood by the following examples, which are intended to illustrate and not to limit the invention.

Example 1: Formation of an inorganic sol

In a colloidal inorganic material having an acidic range whose pH has been adjusted to 3 to 5, 1 to 120 parts by weight of methyltrimethoxydecane (MTMS) or vinyltrimethoxydecane (VTMS), which is ethanol The diluted organic decane is such that the organic decane reacts with the surface of the inorganic nanoparticle to remove water, and then The organic solvent is added, thus making the reaction medium hydrophobic.

Moreover, MTMS plays a role in controlling the degree of hydrophobicity of the surface of the inorganic material in such a manner that when the methoxy group of the MTMS reacts with the surface of the colloidal inorganic particles, the methyl group is exposed to the surface thereof, thereby converting the colloidal inorganic material into A form that can be dispersed in an organic resin. In addition, the function of VTMS is that when the three methoxy groups of VTMS are condensed with the OH group at the interface of the hydrophobic colloidal inorganic material, the vinyl group becomes exposed, and thus the hydrophobic colloidal inorganic particles can be formed to have a vinyl group or Colloidal inorganic sols of other reactive groups.

Example 2: Preparation of acrylic copolymer

10 parts by weight of 2,2'-azo (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 in a flask equipped with a cooling tube and a stirrer Parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 15 parts by weight of methyl methacrylate, and 30 parts by weight of styrene were washed with nitrogen and then slowly stirred. The reaction solution was heated to 62 ° C and then maintained at this temperature for 5 hours, thus preparing a polymer solution containing an acrylic copolymer.

The prepared acrylic copolymer was added dropwise to 5,000 parts by weight of hexane, precipitated, filtered, separated, and 200 parts by weight of propionate was added, followed by heating to 30 ° C, thereby obtaining 45 parts by weight of solid. The final polymer of the content and a weight average molecular weight of 11,000. The weight average molecular weight is converted to polystyrene using GPC.

Example 3: Preparation of organic-inorganic hybrid photosensitive resin composition

Mix 100 parts by weight of a polymer solution containing an acrylic copolymer, 15 parts by weight of Irgacure 819 as a photoinitiator, and 40 parts by weight as a plurality Dipentaerythritol hexaacrylate of a functional monomer and 10 parts by weight of trimethylolpropane triacrylate, 1 part by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy as a lanthanide compound Decane, and 2 parts by weight of F171 as a lanthanide surfactant. Then, in this mixture, diethylene glycol dimethyl ether was added in an amount such that the solid content became 35 parts by weight to thereby dissolve the mixture.

The obtained acrylic copolymer was mixed with the inorganic sol of Example 1 in a weight ratio of 95:5.

The obtained organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm micropore filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

Example 4: Preparation of organic-inorganic hybrid photosensitive resin composition

An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 80:20, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

Example 5: Preparation of organic-inorganic hybrid photosensitive resin composition

An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 60:40, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. Filtering organic-inorganic hybrid photosensitivity using a 0.2 μm micropore filter The resin composition was used to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

Example 6: Preparation of organic-inorganic hybrid photosensitive resin composition

An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 40:60, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

Example 7: Preparation of organic-inorganic hybrid photosensitive resin composition

An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 20:80, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

Example 8: Preparation of organic-inorganic hybrid photosensitive resin composition

An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 10:90, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. Filtering organic-inorganic hybrid photosensitivity using a 0.2 μm micropore filter The resin composition was used to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.

A coating solution of each of the organic-inorganic hybrid photosensitive resin compositions of Examples 3 to 8 was applied, and its properties were evaluated by the following methods. The results are shown in Table 1 below.

On each of the photosensitive resin composition solutions of Examples 3 to 8, the solutions of the photosensitive resin compositions of Examples 3 to 8 were applied by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes, thereby forming a film.

The film was covered with a designated pattern mask and then irradiated with UV light having a intensity of 15 mW/cm ² at 365 nm for 6 seconds. Thereafter, the film was developed with an aqueous solution of 0.38 parts by weight of tetramethylammonium hydroxide at 25 ° C for 2 minutes, and then washed with ultrapure water for 1 minute.

The developed pattern was irradiated with UV light having a intensity of 15 mW/cm ² at 365 nm for 34 seconds, intermediate baking was performed at 120 ° C for 3 minutes, and then heated in an oven at 220 ° C for 60 minutes to harden, thereby obtaining a pattern. film.

(a) Heat resistance - scratching the final pattern film, and measuring the weight loss temperature of 5 wt% using TGA. When the weight loss temperature of 5 wt% was 300 ° C or higher, the heat resistance was evaluated to be excellent, and when the weight loss temperature of 5 wt% was 280 ° C or higher, it was evaluated as good, and when the weight loss temperature of 5 wt% was 250 ° C Or higher, it was evaluated as acceptable, and when the weight loss temperature of 5 wt% was lower than 250 ° C, the evaluation was poor.

(b) Hardness - A coating film was formed on the glass, and the pencil hardness of the surface thereof was measured in accordance with ADTM D3363.

(c) Light transmittance - a visible light absorption spectrum of a coating film having a thickness of 3 μm after the prebaking process in the measurement of heat resistance as in (a). The light transmittance of light at 400 nm is 98% or higher, which is evaluated as excellent, at 94% or higher but lower than 98%, it is evaluated as good, and at 92% or higher but lower than 94%, it is evaluated as Yes, and below 92% are evaluated as poor.

(d) Adhesion - The final cured film of the Mo/Al/ITO substrate was subjected to an adhesion test using a 3M tape. The coating film was cut into 100 units having a specified size, and then adhered with 3M tape, and then slowly separated. When the number of residual units per 100 units is 95 or more, it is evaluated as excellent, when the number of residual units is 90 or more, it is evaluated as good, and when the number of residual units is 80 or more, it is evaluated as acceptable. And when the number of residual units is less than 80, it is evaluated as poor.

(e) Flatness - A coating film was formed on the glass, and each thickness of about 100 points was measured using a thickness gauge. When the thickness difference is less than 1%, the flatness is evaluated to be excellent, and when the thickness difference is less than 2%, the flatness is evaluated to be good, and when the thickness difference is less than 3%, the flatness is evaluated as acceptable. When the thickness difference is 3% or more, the flatness is evaluated. difference. Thereby, the dispersion stability and the precipitation of the metal compound between the acrylic copolymer and the metal compound dispersion obtained by using a ball mill can be confirmed.

(f) Dielectric constant - The capacitance of the capacitor was measured and determined by the following equation. For this purpose, a dielectric film is formed at a specified thickness, and an impedance is measured using an impedance analyzer, and the dielectric constant is calculated by the following equation.

Among them, the C-type capacitor, the ε _0- based vacuum dielectric constant, the specific dielectric constant of the ε _r- based dielectric film, the effective area of the A- system, and the thickness of the d- based dielectric film.

As is apparent from Table 1, it shows the properties of the organic-inorganic hybrid photosensitive resin composition prepared as described above, and the resin compositions of Examples 3 to 8 exhibit high heat resistance and hardness, excellent flatness, and dielectric constant. Grade, and good light transmittance and adhesion.

In particular, by stably mixing the inorganic sol compound, coating flatness and storage stability of the photosensitive resin can be ensured. The use of an inorganic sol produces an organic-inorganic hybrid photosensitive resin composition having a low dielectric constant.

Therefore, in the passivation insulating film of the TFT-LCD using the organic-inorganic hybrid photosensitive resin composition of the present invention, it is confirmed that excellent heat resistance, hardness, flatness, dielectric constant level, and good light transmission are observed. Rate and adhesion.

As described above, the present invention provides an organic-inorganic hybrid photosensitive resin composition and an LCD containing the same. According to the present invention, the organic-inorganic hybrid photosensitive resin composition has a low dielectric constant, excellent heat resistance, insulation, flatness, chemical resistance, and hardness, and thus is suitable as a material for forming an image of an LCD, and The passivation of the organic insulating film of the LCD exhibits high hardness, heat resistance, proper insulation, and flatness, and thus is suitable as an organic insulating film. Further, a photosensitive resin composition is used for the photoresist resin for the overcoat layer, the photoresist resin for the black matrix, the photoresist resin for the column spacer, and the photoresist resin for the color filter, in order to enhance Heat resistance, hardness, etc.

Although the preferred embodiment of the present invention has been disclosed for the purpose of illustration, it will be understood by those skilled in the art that various modifications may be made without departing from the scope and spirit of the invention as disclosed in the appended claims. Additions and alternatives.

Claims (10)

An organic-inorganic hybrid photosensitive resin composition comprising: (a) 1 to 95 parts by weight of a colloidal inorganic sol, which is a solution by adding colloidal inorganic nanoparticles and 1 to 120 parts by weight of organodecane So that the surface of the inorganic nanoparticle is hydrophobic, obtained by removing water, and adding an organic solvent, wherein the colloidal inorganic nanoparticle is a water-dispersed colloidal inorganic nanoparticle, which comprises at least one selected from the group consisting of vermiculite And aluminum oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, an inorganic material capable of reacting with organic decane, and the inorganic material modified by the surface of vermiculite, and the organic decane is represented by the following formula 1: 1 R ¹ _0~3 Si(OR ² ) _1~4 wherein R ¹ is at least one selected from the group consisting of alkyl, phenyl, fluorocarbon alkyl, acryl fluorenyl, methacryl fluorenyl, allyl, vinyl , and an epoxy group, R ² lines at least one selected from methyl, ethyl, isopropyl, n-propyl and n-butyl group, and an alkoxy group oR ² based, acetate group or oxime group; (b) 100 parts by weight of an acrylic copolymer which is copolymerized (i) 5 to 40 parts by weight of an unsaturated carboxylic acid or an unsaturated carboxylic acid An anhydride or a mixture thereof and (ii) 5 to 95 parts by weight of at least one acrylic acid unsaturated compound; (c) 0.001 to 30 parts by weight of a photoinitiator; (d) 10 to 100 parts by weight of ethylenic unsaturation a polyfunctional monomer of a bond; (e) 0.0001 to 5 parts by weight of an anthracene compound containing an epoxy group or an amine group; and (f) a solvent in an amount such that the solid content of the photosensitive resin composition becomes 10 to 50 Parts by weight. The photosensitive resin composition of claim 1, wherein (b) the (i) unsaturated carboxylic acid, the unsaturated carboxylic anhydride or a mixture thereof is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, and Fumar. A group consisting of acid, citraconic acid, seccoic acid, itaconic acid and its unsaturated dicarboxylic anhydride. The photosensitive resin composition of claim 1, wherein (b) (ii) the acrylic unsaturated compound comprises an epoxy group-containing unsaturated compound, at least one selected from the group consisting of glycidyl acrylate and methacrylic acid. Glyceryl ester, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, β-methyl glycidyl acrylate, β-methyl methacrylate Glyceride, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylic acid 6,7- Epoxyheptyl ester, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl A group of ethers and p-vinylbenzyl glycidyl ethers. The photosensitive resin composition of claim 1, wherein (b) (ii) the acrylic unsaturated compound used for preparing the (b) acrylic copolymer further comprises 10 to 70 parts by weight of an olefin unsaturated compound, At least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, methacrylic acid N-butyl ester, second butyl methacrylate, third butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, bicyclic acrylate Pentene ester, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyl methacrylate Ethyl ethyl ester, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, acrylic acid Benzyl ester, 2-hydroxyethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butyl A group consisting of alkene, isoprene, and 2,3-dimethyl-1,3-butadiene. The photosensitive resin composition of claim 1, wherein (b) the acrylic copolymer has a weight average molecular weight ranging from 6,000 to 90,000, which is converted in terms of polystyrene. The photosensitive resin composition of claim 1, wherein (c) the photoinitiator is at least one selected from the group consisting of Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, 2,4-bistrichloromethyl. -6-p-methoxystyryl-s-triple, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-tripa, 2,4-trichloromethyl-6- Mitsui, 2,4-trichloromethyl-4-methylnaphthyl-6-tripper, benzophenone, p-(diethylamino)benzophenone, 2,2-dichloro-4-benzene Oxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl A group consisting of bis-2-1,2-bisimidazole. The photosensitive resin composition of claim 1, wherein (d) at least one of a polyfunctional single system having an ethylenically unsaturated bond is selected from the group consisting of 1,4-butanediol diacrylate and 1,3-butyl Diol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, poly Ethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, and its A group consisting of acrylates. The photosensitive resin composition of claim 1, wherein (e) at least one selected from the group consisting of (3-glycidoxypropyl)trimethoxynonane, (e) containing an epoxy group or an amine group; 3-glycidoxypropyl)triethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane 3,4-epoxybutyltrimethoxydecane, 3,4-epoxybutyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-( A group consisting of 3,4-epoxycyclohexyl)ethyltriethoxydecane and aminopropyltrimethoxydecane. The photosensitive resin composition of claim 1, further comprising at least one selected from the group consisting of a thermal polymerization inhibitor, an antifoaming agent, and a pigment. A liquid crystal display comprising any one of claims 1 to 9 of the patent application scope A hardened body of a photosensitive resin composition comprising decane-modified inorganic nanoparticles and used for an insulating film.