JP2007025678A - Organic/inorganic photosensitive resin composition, tft liquid crystal display element and method of forming pattern thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic photosensitive resin composition; which is superior in adhesion, heat resistance, insulation properties, flatness, chemical resistance or the like, and suitable for image forming materials of a liquid crystal display element; which is superior in the dielectric constant, planarity, sensitivity, film-remaining rate, or UV transmittance, particularly, when forming the organic insulating film of the liquid crystal display element, and suitable for use as an organic insulating film for gate; and at the same time, which is suitable for improving the sensitivity and film-remaining ratio as resist resins for overcoat, resist resins for black matrix, resist resins for column spacer, or resist resins for color filter. <P>SOLUTION: The resin composition includes (A) metal oxides selected from among groups consisting of group 3, 4, 5, 13 metal oxides, within a periodic table or groups, consisting of similar two element metal oxides; and (B) (a) acrylic-based copolymers, (b) photoinitiators, (c) polyfunctional monomers having ethylenically unsaturated bonds, (d) silicon-based compounds containing epoxy or amine groups, and (e) solvents. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an organic-inorganic composite photosensitive resin composition, a TFT-type liquid crystal display element, and a pattern forming method thereof.

In general, the most commonly used inorganic insulator for devices is SiO ₂ . This is because the insulating rate is high and it can be easily formed on Si that is most frequently used as a substrate. However, since SiO ₂ has an amorphous structure and its dielectric constant is not as high as about 3.9, the performance as an optimum gate insulator is insufficient.

The gate insulator must have a large dielectric constant, so that a large amount of charges can be collected at a low voltage, and the device can be driven at a low voltage.
Insulation characteristics must be good together with the dielectric constant. If the insulation is poor, the charges collected at both ends of the dielectric are neutralized by the leakage current. Therefore, the charge cannot be maintained for a long time, which causes a driving problem that must be refreshed frequently.

  BCB, polyimide, PMMA, parylene, acrylate, etc. are used as conventional organic insulators, but such materials can be spin-coated alone, have good flatness, and improve coating properties. However, it has a low dielectric constant and cannot be used as an organic insulator for gates.

  In order to solve such problems of the conventional technology, the present invention is excellent in performance such as dielectric constant, insulation, coating property, transmittance, adhesive strength, heat resistance, flatness, chemical resistance, and the like. Suitable for device image forming materials, especially organic / inorganic composite photosensitivity suitable for use as gate insulating film due to excellent sensitivity, residual film rate, and UV transmittance when forming organic / inorganic composite insulating film for gate of liquid crystal display device It aims at providing the pattern formation method of the TFT type liquid crystal display element using the photosensitive resin composition, the TFT type liquid crystal display element containing the hardening body of the said photosensitive resin, and the said photosensitive resin composition.

The object of the present invention is the disadvantages of existing inorganic materials for gate insulators such as SiO _2, which are high cost, low dielectric constant, insufficient flatness, inability to spin coating, and are currently used as organic insulators. It is to provide an organic-inorganic composite material that complements disadvantages such as low dielectric constant of the organic material for passivation. Thereby, the weak point of the conventional gate insulating film can be improved, and it aims at manufacturing the organic inorganic insulating material which is excellent in coating property and flatness, and has a high dielectric constant.

  Another purpose is to use an acrylate-based photosensitive resin, which has a higher dielectric constant than materials such as BCB, polyimide, PMMA, and parylene, which are existing organic insulating films, and has excellent heat resistance, high transmittance, and adhesive strength, The object is to provide a high dielectric constant material excellent in flatness as an organic-inorganic composite insulator for a gate.

In order to achieve the above object, the present invention provides an organic-inorganic composite photosensitive resin composition,
A) one or more metal oxides selected from the group consisting of Group 3, 4, 5, 13 metal oxides in the periodic table or the group consisting of similar two-element metal oxides;
B) a) an acrylic copolymer; and b) a photoinitiator; and c) a polyfunctional monomer having an ethylenically unsaturated bond; and d) a silicon-based compound containing an epoxy group or an amine group; and e) a solvent. An organic-inorganic composite photosensitive resin composition is provided.

Preferably, the present invention provides
A) 1 to 60% by weight of one or more metal oxides selected from the group consisting of Group 3, 4, 5, 13 metal oxides in the periodic table or the group consisting of similar two-element metal oxides;
B) a) 100 parts by weight of an acrylic copolymer;
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) 0.0001 to 5 parts by weight of a silicon-based compound containing an epoxy group or an amine group; and e) an organic photosensitive resin 40 containing a solvent so that the solid content in B) is 10 to 50% by weight. The organic-inorganic composite photosensitive resin composition containing ˜99% by weight is preferable.

The present invention also provides a TFT type liquid crystal display element comprising a cured product of the organic-inorganic composite photosensitive resin composition.
Moreover, this invention provides the pattern formation method of the TFT type liquid crystal display element using the said organic inorganic composite photosensitive resin composition.

  The organic-inorganic composite photosensitive resin composition according to the present invention is excellent in performance such as high dielectric properties, adhesive strength, heat resistance, insulation, flatness, and chemical resistance, and is suitable for an image forming material for a liquid crystal display element. It is suitable for use as a gate insulating film because it has excellent sensitivity, residual film ratio, UV transmittance, dielectric properties and heat resistance when forming a gate insulating film for liquid crystal display elements. Resist resin for overcoat, resist for black matrix It is used as a resin, a resist resin for column spacers, or a resist resin for color filters, and has the effect of improving dielectric properties, heat resistance and flatness.

Hereinafter, the present invention will be described in detail.
A) The metal oxide selected from the group consisting of Group 3, 4, 5, 13 metal oxides in the periodic table or the group consisting of similar two-element metal oxides has a higher dielectric constant than other metal compounds. It has characteristics such as efficiency, thermal stability, large band gap, stability on silicon at high temperature, and low leakage current, and has an amorphous structure. The metal oxide may be at least one compound selected from the group consisting of Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Ta ₂ O ₃ , TiO ₂ , HfO ₂ and ZrO _2. preferable. The similar two-element metal oxide has a structure in which a Group 4 metal oxide and SiO ₂ form a composite. As a specific example, (ZrO ₂ ) x (SiO ₂ ) y, ( HfO ₂ ) x (SiO ₂ ) y, optionally (TiO ₂ ) x (SiO ₂ ) y (wherein, x and y are independently 0 <x <1, 0 <y <1), etc. Is mentioned. The similar two-element metal oxide can be used in combination of two or three oxides according to the purpose.

  Preferably, A) a metal oxide or metal oxide powder included in the present invention is prepared, and the powder is pulverized using a rotary ball grinder, and then used in the organic photosensitive resin composition of B). It is a metal oxide dispersion having a particle size of 50 to 200 nm, which is produced by wet-mixing in a solvent having a concentration of 5 to 50% by weight and then spray-drying. When the powder is mixed with a solvent, a dispersant or the like may be used as an additive in an amount of 500 to 20,000 ppm. The dispersant prevents aggregation and recrystallization of the powder, and the metal oxide can be easily dispersed in the photosensitive resin composition, thereby improving the dispersion stability.

  Moreover, the organic-inorganic composite photosensitive resin compound of the present invention includes B) an organic photosensitive resin composition together with the metal oxide, and the photosensitive resin composition includes a) 100 parts by weight of an acrylic copolymer, b) 0.001 to 30 parts by weight of a photoinitiator, c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond, d) 0.0001 to 5 parts by weight of a silicon compound containing an epoxy group or an amine group And e) the solvent is preferably contained so that the solid content in B) is 10 to 50% by weight.

As the acrylic copolymer of a), an ordinary acrylic copolymer can be used, and preferably i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, and ii) an acrylic. It can be produced by radical reaction in the presence of a solvent and a polymerization initiator using a system unsaturated compound as a monomer.

  The a) i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or mixture thereof used in the present invention is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citracone An unsaturated dicarboxylic acid such as an acid, metaconic acid or itaconic acid; or an anhydride of these unsaturated dicarboxylic acids may be used alone or in combination of two or more. In particular, it is more preferable to use acrylic acid, methacrylic acid, or maleic anhydride in view of copolymerization reactivity and solubility in an alkaline aqueous solution that is a developer.

The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or mixture thereof is preferably contained in the total monomer of a) at 5 to 40% by weight, more preferably 10 to 40% by weight. When it is within this range, the development is very good.
The a) ii) acrylic unsaturated compound may be an ordinary acrylic unsaturated compound, preferably an epoxy group-containing unsaturated compound and an olefinic unsaturated compound.

  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, β-methyl glycidyl acrylate, 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-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl Ether or the like can be used. These compounds can be used alone or in admixture of two or more.

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

  The epoxy group-containing unsaturated compound is preferably contained in the total total monomer of a) in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight. When it is within this range, the heat resistance of the pattern and the storage stability of the copolymer can be satisfied at the same time.

  The olefinically unsaturated compounds are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, di- Cyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclo Pentanyloxyethyl acrylate, isoboro Acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butadiene, isoprene Alternatively, 2,3-dimethyl 1,3-butadiene or the like can be used. The said compound can be used individually or in mixture of 2 or more types.

  In particular, it is more preferable to use styrene, dicyclopentanylmethyl methacrylate, or p-methoxystyrene as the olefinic unsaturated compound from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution as a developer.

  The olefinically unsaturated compound is preferably contained in an amount of 10 to 70% by weight, more preferably 20 to 50% by weight, based on a). When the content is within the above range, it is possible to simultaneously solve the problems such as the decrease in the storage safety of the acrylic copolymer and the difficulty that the acrylic copolymer is hardly dissolved in an alkaline aqueous solution as a developer. .

  Solvents used to polymerize such monomers as acrylic copolymers include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve 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 ester Teracetate, 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-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, lactate Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, methoxy Ethyl acetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate , Propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionic acid Butyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 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, - it can be used butoxy propionic acid methyl 3- butoxy-propionic acid ethyl, 3-butoxy-propionic acid propyl or 3-butoxy ethers such as acid butyl, and the like. The said compound can be used individually or in mixture of 2 or more types.

  As a polymerization initiator used for polymerizing such a monomer as an acrylic copolymer, a radical polymerization initiator can be used. Specifically, 2,2-azobisisobutyro Nitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or Dimethyl 2,2-azobisisobutyrate and the like can be used.

  In the acrylic copolymer of a), the polystyrene-equivalent weight average molecular weight (Mw) prevents deterioration of developability, residual film ratio, etc. and pattern shape, heat resistance, etc., and lowers contact holes and pattern development. From the standpoint of preventing the above, it is preferably 6,000 to 90,000, more preferably 6,000 to 40,000.

  The photoinitiator of b) used in the present invention is Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, triazine, benzoin, acetophenone, imidazole, or xanthone Etc. can be used.

  Specifically, the photoinitiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2, 4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-di Ethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-1,2- Compounds such as biimidazole can be used alone or in admixture of two or more.

  From the viewpoint of preventing the deterioration of the residual film ratio due to low sensitivity, improving the storage stability, and preventing a decrease in the adhesive force of the pattern during development due to a high degree of curing, the photoinitiator. It is preferable to contain 0.001-30 weight part with respect to 100 weight part of acrylic copolymers, More preferably, it is 0.01-20 weight part.

  The polyfunctional monomer having an ethylenically unsaturated bond of c) used in the present invention is generally a crosslinkable monomer having at least two ethylenic double bonds, which is 1,4-butanediol diene. Acrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, di Pentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol It can be used diacrylate derivatives, dipentaerythritol polyacrylate or the like these methacrylates.

  The polyfunctional monomer having an ethylenically unsaturated bond improves contact holes due to a low degree of curing with a photosensitive resin and difficulty in realizing a pattern, and contact holes during development due to a high degree of curing. From the viewpoint of preventing a reduction in the resolution of the pattern, it is preferably contained in an amount of 10 to 100 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the acrylic copolymer.

  The silicon compound containing an epoxy group or amine group of d) used in the present invention is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3 -Glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Such as ethoxysilane or aminopropyltrimethoxysilane It can be used as a mixture German or two or more.

  The silicon-based compound containing an epoxy group or an amine group ensures adhesion between the ITO electrode and the photosensitive resin, prevents a decrease in heat resistance after curing, and causes a whitening phenomenon in a non-exposed portion in the developer. From the viewpoint of preventing the occurrence of contact holes and pattern scum after development, it is preferably contained in an amount of 0.0001 to 5 parts by weight, more preferably 0.005 with respect to 100 parts by weight of the acrylic copolymer. ~ 2 parts by weight.

The solvent e) used in the present invention forms a uniform pattern profile without causing flatness of the insulating film and coating unevenness.
Examples of the solvent include alcohols 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 methyl Propylene glycol alkyl ether acetates such as ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propio , Propylene glycol alkyl ether acetates such as propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, Ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl droxypropionate, 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, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxy Butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, Methyl toxiacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, 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, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, -Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3- Esters such as propyl butoxypropionate and butyl 3-butoxypropionate can be used.

  In particular, the solvent is one or more selected from the group consisting of glycol ethers, ethylene alkyl ether acetates, and diethylene glycols that are soluble, reactive with each component, and easy to form a coating film. Is preferred.

  From the viewpoint of ensuring a suitable coating thickness, preventing a decrease in coating flatness, and preventing a load from being applied to the coating equipment during coating, B) the solid content of the organic photosensitive resin. The composition having a solid content in the above range is preferably used after being filtered through a 0.1 to 0.2 μm Millipore filter or the like. More preferably, it is 15 to 40% by weight.

The organic photosensitive resin of the present invention comprising these components can further contain f) a photosensitizer and g) a surfactant as necessary.
The photosensitizer of f) has an appropriate sensitivity for the ultraviolet wavelength to be used, and transfers the energy to the photoinitiator through a photoinitiation reaction faster than the photoinitiator to assist the photoinitiator reaction rate of the photoinitiator. .

As the photosensitizer, DETX, ITX, n-butylacridone, 2-ethylhexyl-dimethylaminobenzoate, or the like can be used alone or in admixture of two or more.
The photosensitizer is preferably contained in an amount of 0.001 to 40 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a), and when the content is within the above range, a photosensitive resin. It is even better in improving the photocuring speed of the composition.

The surfactant of g) functions to improve the coating property and developability of the photosensitive composition.
The surfactant is polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, silicon-based surface activity, for example, F171, F172, F173 (trade name: Dainippon Ink Chemical Co., Ltd.), FC430, FC431 (product) Name: Sumitomo 3M Co., Ltd.) or KP341 (trade name: Shin-Etsu Chemical Co., Ltd.) can be used.

  The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight with respect to 100 parts by weight of the acrylic polymer of a), and when the content is within the above range, It is even better in improving coatability and developability.

  In the organic-inorganic composite photosensitive resin composition of the present invention, the metal oxide of A) preferably contains 1 to 60% by weight, and B) the organic photosensitive resin preferably contains 40 to 99% by weight. When it is within the above range, there is an advantage that performances such as dielectric constant, flatness, sensitivity, residual film rate, UV transmittance, adhesive force, heat resistance, insulation, and chemical resistance can be satisfied at the same time.

  In addition, the organic-inorganic composite photosensitive resin composition of the present invention can be added with an additive having compatibility such as a thermal polymerization inhibitor and an antifoaming agent, if necessary, and a pigment can be added depending on the application. can do. For example, a black matrix resist and a color filter resist, which are one of image forming materials for TFT-type liquid crystal display elements, are obtained by blending a pigment into the above composition. At this time, the pigment can be appropriately selected depending on the application of the black matrix resist and the color filter resist, and all inorganic and organic pigments can be used.

  The present invention also provides a TFT type liquid crystal display element comprising such a cured product of the organic / inorganic composite photosensitive resin and a pattern forming method for the TFT type liquid crystal display element using the organic / inorganic composite photosensitive resin composition.

  The pattern forming method of the TFT type liquid crystal display element of the present invention comprises forming a photosensitive resin composition as an organic insulating film, an overcoat resist, a black matrix resist, a column spacer resist, or a color filter resist. In the method for forming a liquid crystal display element, the organic-inorganic composite photosensitive resin composition is used.

A specific example of a method for forming a pattern of a TFT type liquid crystal display element using the organic-inorganic composite photosensitive resin composition is as follows.
First, the organic-inorganic composite photosensitive resin composition of the present invention is applied to the substrate surface by a spray method, a roll coater method, a spin coating method or the like, and the solvent is removed by pre-baking to form a coating film. At this time, the pre-bake is preferably performed at a temperature of 70 to 110 ° C. for 1 to 15 minutes.

Thereafter, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary portions. Form a pattern.
The developer is preferably an alkaline aqueous solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; diethylamine, n-propylamine and the like. Secondary amines; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; or tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. An aqueous solution of the quaternary ammonium salt can be used. At this time, the developer is used by dissolving an alkaline compound at a concentration of 0.1 to 10% by weight, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added.

  In addition, after developing with the developer as described above, unnecessary portions are removed by washing with ultrapure water for 30 to 90 seconds, dried to form a pattern, and light such as ultraviolet rays is applied to the formed pattern. Then, the pattern can be heat-treated at a temperature of 150 to 250 ° C. for 30 to 90 minutes with a heating device such as an oven to obtain a final pattern.

  The organic-inorganic composite photosensitive resin composition according to the present invention as described above is excellent in performance such as high dielectric constant, adhesive strength, heat resistance, insulation, flatness, and chemical resistance, and is an image forming material for liquid crystal display elements. Especially suitable for use as a gate insulating film because it has excellent sensitivity, residual film rate, and UV transmittance when forming an organic-inorganic composite insulating film for gates of liquid crystal display elements, resist for overcoat, resist for black matrix It is used as a resin, a resist resin for column spacers, or a resist resin for color filters, and is a material suitable for improving sensitivity and remaining film ratio.

Hereinafter, preferred examples are presented to help understanding of the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1: (Production of metal oxide dispersion)
Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Ta ₂ O ₃ , TiO ₂ , HfO ₂ , ZrO ₂ , (ZrO ₂ ) _0.5 (SiO ₂ ) _0.5 and (HfO ₂ ) _0.5 (SiO ₂ ) _0.5 Prepare each powder, pulverize the powder using a rotary ball grinder, and mix propylene glycol monomethyl ether acetate with 5 to 50 wt% of metal oxide powder and 500 to 20,000 ppm of dispersant. Then, after wet mixing, spray drying was performed to produce a metal oxide dispersion having a particle size of 50 to 200 nm.

Example 2: (Production of acrylic copolymer)
In a flask equipped with a condenser and a stirrer, 2,2′-azobis (2,4-dimethylvaleronitrile) 10 parts by weight, propylene glycol monomethyl ether acetate 200 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 35 Part by weight, 15 parts by weight of methyl methacrylate and 30 parts by weight of styrene were added, purged with nitrogen, and then gently stirred. The reaction solution was heated to 62 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 5 hours. The acrylic copolymer prepared as described above was dropped into 5,000 parts by weight of hexane, precipitated, and filtered and separated, and then 200 parts by weight of propionate was added and heated to 30 ° C. A polymer solution containing 45 parts by weight and having a polymer weight average molecular weight of 11,000 was produced. At this time, the weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC.

Example 3: (Production of organic-inorganic composite photosensitive resin composition)
100 parts by weight of a polymer solution containing the acrylic copolymer prepared in Example 2, 15 parts by weight of Irgacure 819 as a photoinitiator, 5 parts by weight of 2-ethylhexyl-4-dimethylaminobenzoate as a photosensitizer, and n -5 parts by weight of butylacridone, 40 parts by weight of dipentaerythritol hexaacrylate and 10 parts by weight of trimethylolpropane triacrylate as the polyfunctional monomer, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as the silicon compound 1 part by weight and 2 parts by weight of F171 as a silicon-based surface activity were mixed. Diethylene glycol dimethyl ether was added to the mixture and dissolved so that the solid content concentration was 35% by weight.

An organic-inorganic composite photosensitive resin composition was prepared by mixing the Al ₂ O ₃ metal oxide dispersion produced in Example 1 and the organic photosensitive resin produced as described above at a mixing weight ratio of 5:95. The thing was manufactured.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was shown, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 4: (Production of organic-inorganic composite photosensitive resin composition)
The organic-inorganic composite photosensitive resin composition was prepared by the same method as in Example 3 so that the mixing weight ratio of the Y ₂ O ₃ metal oxide dispersion and the organic photosensitive resin was 10:90.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was shown, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 5: (Production of organic-inorganic composite photosensitive resin composition)
The organic-inorganic composite photosensitive resin composition was manufactured by the same method as in Example 3 so that the mixing weight ratio of the Ta ₂ O ₃ metal oxide dispersion and the organic photosensitive resin was 15:85.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 16 cps was exhibited, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 6: (Production of organic-inorganic composite photosensitive resin composition)
The organic-inorganic composite photosensitive resin composition was manufactured by the same method as in Example 3 so that the mixing weight ratio of the TiO ₂ metal oxide dispersion and the organic photosensitive resin was 20:80.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 15 cps was shown, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 7: (Production of organic-inorganic composite photosensitive resin composition)
The organic-inorganic composite photosensitive resin composition was manufactured by the same method as in Example 3 so that the mixing weight ratio of the HfO ₂ metal oxide dispersion and the organic photosensitive resin was 30:70.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 17 cps was shown, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 8: (Production of organic-inorganic composite photosensitive resin composition)
The organic-inorganic composite photosensitivity was prepared by the same method as in Example 3 so that the mixing weight ratio of (ZrO ₂ ) _0.5 (SiO ₂ ) _0.5 metal oxide dispersion and organic photosensitive resin was 40:60. A resin composition was produced.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, the viscosity was 18 cps, and when a film was formed, a thickness of 0.3 to 0.8 microns could be obtained depending on the coating speed.

Example 9: (Production of organic-inorganic composite photosensitive resin composition)
An organic-inorganic composite photosensitive resin produced by the same method as in Example 3 so that the mixing weight ratio of the (HfO ₂ ) _0.5 (SiO ₂ ) _0.5 metal oxide dispersion and the organic photosensitive resin is 50:50. A composition was prepared.
The organic-inorganic composite resin composition thus produced was filtered through a 0.2 μm Millipore filter to remove impurities. At this time, a viscosity of 19 cps was exhibited, and when a film was formed, a thickness of 0.4 to 0.9 microns could be obtained depending on the coating speed.

Using the organic-inorganic composite photosensitive resin composition coating solutions prepared in Examples 3 to 9, physical properties were evaluated by the following methods. The results are shown in Table 1.
A) Sensitivity—After coating the organic-inorganic composite photosensitive resin composition produced in Examples 3 to 9 on a glass substrate using a spin coater, the film was prebaked on a hot plate at 90 ° C. for 2 minutes. Formed.
The film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 15 mW / cm ² for 6 seconds using a predetermined pattern mask. Thereafter, development was performed with an aqueous solution of 0.38 parts by weight of tetramethylammonium hydroxide at 25 ° C. for 2 minutes, followed by washing with ultrapure water for 1 minute.
After that, the pattern developed above was irradiated with ultraviolet rays having an intensity of 365 m at 15 mW / cm ² for 34 seconds, mid-baked at 120 ° C. for 3 minutes, and then heated and cured in an oven at 220 ° C. for 60 minutes. Pattern film was obtained.

  B) Residual film ratio—The heights of the lowermost side of the pattern film and the uppermost side of the pattern film formed at the time of the sensitivity measurement in the above a) were measured. At this time, based on the thickness of the film obtained by pre-baking the thickness change rate, 0 to 10% is excellent, 10 to 40% is good, and 40% is bad. It showed.

  C) Transmittance-When the light absorption spectrum of visible light of a coating film having a thickness of 1 micron after pre-baking at the time of sensitivity measurement in the above a) is measured, and the light transmittance at 400 nm is 98% or more Is excellent, 94-98% is excellent, 92-94% is normal, and 92% or less is bad.

  2) Heat resistance-5 wt% weight reduction temperature is measured by TGA with the final coating film applied, and the 5 wt% reduction temperature is excellent at 300 ° C or higher, excellent at 280 ° C or higher, and normal at 250 ° C or higher. It was shown to be bad below 250 ° C.

  E) Adhesive strength-A taping test was performed on the coating film which had been finally cured with a Mo, Al, ITO substrate using 3M tape. When the coating film is divided into 100 cells at regular intervals, 3M tape is applied, and then slowly peeled off, the number of cells remaining in 100 cells is 95 or more. When the number is 90 or more, the case is excellent, when 80 or more is normal, and when the number is 80 or less, the case is bad.

  F) Flatness-after coating the glass with a coating film, the thickness with respect to about 100 points is measured with a thickness measuring instrument such as an optical equipment, and the case where the significant difference is less than 1% is excellent, and less than 2% The case where it is excellent is shown to be excellent, the case where it is less than 3% is normal, and the case where it is more than that is bad. Through this method, it is possible to confirm the dispersion stability between the metal compound dispersion produced using a ball grinder and the acrylic copolymer and the possibility of precipitation of the metal compound.

G) Dielectric constant—Capacitance of the capacitor was measured and determined by the following equation. First, after coating the dielectric thin film with a certain thickness, the electrostatic capacity was measured through an impedance analyzer, and the respective dielectric constants were calculated through the following equations.
C = (ε ₀ · ε _r · A) / d
(Where C is the capacitance, ε ₀ is the vacuum dielectric constant, ε _r is the dielectric constant of the dielectric thin film, A is the effective area, and d is the thickness of the dielectric thin film)

上記表１に示されているように、本発明の実施例３〜９の有機無機複合感光性樹脂は感度に優れており、透過度が良く、耐熱性と接着力など全ての物性が良好な特性を示した。

As shown in Table 1 above, the organic-inorganic composite photosensitive resins of Examples 3 to 9 of the present invention have excellent sensitivity, good transparency, and all physical properties such as heat resistance and adhesive strength. The characteristics are shown.

In addition, it was confirmed that excellent flatness of the coating can be secured by stably dispersing the metal compound, and that the dielectric constant can be adjusted using the metal compound.
Therefore, when the organic-inorganic composite photosensitive resin composition according to the present invention is used as a gate insulating film for TFT-LCD, it is possible to obtain very excellent sensitivity, residual film ratio, transmittance and adhesive strength. It was confirmed that high dielectric constant, flatness and heat resistance were obtained.

  Although only specific embodiments of the present invention have been described in detail above, it is obvious to those skilled in the art that various modifications and corrections are possible within the scope of the technical idea of the present invention. Belongs to the scope of the appended claims.

In fields such as semiconductor devices and semiconductor processes, it can be used extensively as insulating films, resist resins, etc., in particular, image forming materials for liquid crystal display elements, for example, organic insulating films for gate insulating films of liquid crystal display elements, It can be used as an overcoat resist resin, a black matrix resist resin, a column spacer resist resin, or a color filter resist resin.

Claims (17)

A) one or more metal oxides selected from the group consisting of Group 3, 4, 5, 13 metal oxides in the periodic table or the group consisting of similar two-element metal oxides;
B) a) an acrylic copolymer;
b) a photoinitiator;
c) a polyfunctional monomer having an ethylenically unsaturated bond;
d) a silicon-based compound containing an epoxy group or an amine group; and e) an organic-inorganic composite photosensitive resin composition containing a solvent. A) 1 to 60% by weight of one or more metal oxides selected from the group consisting of Group 3, 4, 5, 13 metal oxides in the periodic table or the group consisting of similar two-element metal oxides;
B) a) 100 parts by weight of an acrylic copolymer;
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) 0.0001 to 5 parts by weight of a silicon-based compound containing an epoxy group or an amine group; and e) an organic photosensitive resin 40 containing a solvent so that the solid content in B) is 10 to 50% by weight. ~ 99% by weight
The organic-inorganic composite photosensitive resin composition according to claim 1, comprising: The A) metal oxide is one or more compounds selected from the group consisting of Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Ta ₂ O ₃ , TiO ₂ , HfO ₂ and ZrO _2. The organic-inorganic composite photosensitive resin composition according to claim 1 or 2.   The B) a) acrylic copolymer comprises i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof, and ii) an acrylic unsaturated compound as a monomer and a solvent and a polymerization initiator. The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 3, which is produced by radical reaction in the presence of.   The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride of B) a) i) or a mixture thereof is acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, The organic-inorganic composite photosensitive resin composition according to claim 4, which is one or more compounds selected from the group consisting of anhydrides of saturated dicarboxylic acids.   The B) a) ii) the acrylic unsaturated compound is an epoxy group-containing unsaturated compound such as glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, α-n-propyl glycidyl acrylate, α-n- Glycidyl butyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, methacrylic acid 3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl The organic-inorganic composite photosensitive resin composition according to claim 4, which is one or more compounds selected from the group consisting of lysidyl ethers.   B) a) ii) The acrylic unsaturated compound is an olefinic unsaturated compound, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate. 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl Methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclo Tantanyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene The organic-inorganic composite photosensitive resin composition according to claim 4, which is at least one compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl1,3-butadiene.   The weight average molecular weight (Mw) in terms of polystyrene of the acrylic copolymer of B) a) is 6,000 to 90,000, The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 7. object.   The photoinitiator of b) is Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl- 4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2, , 2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,2-bis-2-chlorophenyl-4, 5,4,5-tetraf The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 8, which is at least one compound selected from the group consisting of phenyl-2-1,2-biimidazole.   The polyfunctional monomer having an ethylenically unsaturated bond of c) is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate. Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate Derivatives, dipentaerythritol polyacrylates and their methacrylates? The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 9 is one or more compounds selected from the group consisting of.   The silicon compound containing the epoxy group or amine group of d) is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) Methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and amino Selected from the group consisting of propyltrimethoxysilane The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 10 which is the species or more compounds.   Any one of the compounds selected from the group consisting of DETX, ITX, n-butylacridone, and 2-ethylhexyl-dimethylaminobenzoate. F) A photosensitizer is additionally included. The organic-inorganic composite photosensitive resin composition according to any one of the above.   Polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173, FC430, FC431, and one or more compounds selected from the group consisting of KP341 g) additionally containing a surfactant The organic-inorganic composite photosensitive resin composition according to any one of claims 1 to 12.   The organic-inorganic composite according to any one of claims 1 to 13, further comprising a pigment that is one or more compounds selected from the group consisting of a dispersant, a thermal polymerization inhibitor, an antifoaming agent, and a pigment. Photosensitive resin composition.   The organic-inorganic composite photosensitive resin composition according to claim 1, wherein the organic-inorganic composite photosensitive resin composition is used for forming a gate dielectric of a TFT type liquid crystal display element.   A TFT type liquid crystal display device comprising a cured product of the organic-inorganic composite photosensitive resin composition according to claim 1.   The organic-inorganic composite photosensitive resin composition as described in any one of Claims 1-15 is used, The pattern formation method of the TFT type liquid crystal display element characterized by the above-mentioned.