TWI413856B - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in such performances as sensitivity, transmittance, insulation, chemical resistance, flatness and coating property, having improved adhesiveness particularly to an inorganic material, and suitable for forming an interlayer dielectric in an LCD manufacturing process. <P>SOLUTION: The photosensitive resin composition comprises: (a) an acrylic copolymer obtained by copolymerizing (i) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a mixture of these, (ii) an epoxy group-containing unsaturated compound, (iii) an olefinically unsaturated compound and (iv) a silane monomer; (b) a 1,2-quinonediazido compound; and (c) a solvent. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

Photosensitive resin composition (1) Field of invention

The present invention relates to a photosensitive resin composition, and more particularly to an excellent property such as not only sensitivity, transmittance, insulation, chemical resistance, flatness, and coating property, but particularly adhesion to an inorganic material. The photosensitive resin composition suitable for forming an interlayer insulating film for LCD manufacturing engineering is improved.

Background of the invention

In the TFT type liquid crystal display element and the integrated circuit element, an interlayer insulating film is used to insulate between wirings disposed between the layers.

In order to form such an interlayer insulating film, a photosensitive material which is easy to form a pattern, particularly a good adhesion to an inorganic material such as a glass or a metal film of the upper and lower portions, is used.

Recently, an interlayer insulating film applied in a liquid crystal display (LCD) manufacturing process uses a step of HMDS processing or the like while adding an adhesive to enhance adhesion to a substrate. However, in this method, since the number of programs is increased in the LCD manufacturing program as described above, the number of programs is increased, and there is a problem that stability is caused in the development program and the etching program due to insufficient adhesion.

Therefore, in practice, it is necessary to further study a method for reducing the engineering steps in the LCD manufacturing process, and improving the adhesion of the interlayer insulating film pattern in the development process and etching sequence to ensure stability.

[Description of the Invention]

In order to solve such a conventional technical problem, an object of the present invention is to provide an excellent performance not only in sensitivity, transmittance, insulation, chemical resistance, flatness, coating property, but also in an LCD manufacturing process. In the developing process and the etching process, the adhesion and stability of the interlayer insulating film pattern are remarkably improved, and it is suitable for using a photosensitive resin composition as an interlayer insulating film of a thick film thickness LCD manufacturing process. And an LCD substrate including a cured body of the photosensitive resin, and a pattern forming method of the LCD substrate using the photosensitive resin composition.

In order to achieve the above object, the present invention provides a photosensitive resin composition comprising: a) an i) unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof; ii) an epoxy group-containing unsaturated compound; An olefin-based unsaturated compound; and iv) an acrylic copolymer obtained by copolymerizing a decane-based monomer; and b) a 1,2-benzoquinone azo compound (1,2-quinonediazide); and c) A photosensitive resin composition of a solvent.

The present invention preferably comprises, a) i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, 5 to 40 parts by weight; Ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound; iii) 10 to 70 parts by weight of an olefin-based unsaturated compound; and iv) 3 to 15 parts by weight of a decane-based monomer copolymerized to obtain an acrylic copolymer 100 parts by weight; and b) 5 to 100 parts by weight of the 1,2-benzoquinone azo compound; and c) a solvent having a content of the solid content in the photosensitive resin composition of 10 to 50 parts by weight.

Further, the present invention provides an LCD comprising a cured body of the above-mentioned photosensitive resin.

Furthermore, the present invention provides a pattern forming method of an LCD substrate using the above-described photosensitive resin composition.

The photosensitive resin composition of the present invention is excellent not only in sensitivity, transmittance, insulating properties, chemical resistance, flatness, coating properties, but also in engineering processes, and can be used in an LCD manufacturing process, and in a developing process and an etching process. When the interlayer insulating film is significantly improved in adhesion and stability by the pattern, it is suitable to use an interlayer insulating film which is an LCD manufacturing process having a thick film thickness. Further, the pattern forming method of the LCD substrate of the present invention using the photosensitive resin composition of the present invention has an effect of forming a good pattern of an interlayer insulating film suitable for an LCD manufacturing process after an exposure process.

Detailed description of the preferred embodiment

The invention will be described in detail below.

The photosensitive composition of the present invention is characterized by containing a) i) unsaturated a carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound, iii) 10 to 70 parts by weight of an olefinic unsaturated compound, and iv) a decane monomer 3 ~15 parts by weight of an acrylic copolymer obtained by copolymerization; b) 1,2-benzoquinone azo compound; and c) a solvent.

The acrylic copolymer of the above a) used in the present invention exhibits a function of easily forming a predetermined pattern which does not cause a scum at the time of development.

The propylene-based copolymer of the above a) may be, in the presence of a solvent and a polymerization initiator, i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, ii) an epoxy group-containing unsaturated compound, iii An olefin-based unsaturated compound and iv) are obtained by a free radical reaction using a decane-based monomer as a monomer.

The above a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or the like, used in the present invention, may be used alone as an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; Maleic acid, fumaric acid, citraconic acid, methaconic acid, methylene succinic acid (itaconic) An unsaturated dicarboxylic acid such as an acid; or an unsaturated dicarboxylic anhydride thereof or the like, or a mixture of two or more thereof, particularly in the case of using acrylic acid, methacrylic acid or maleic anhydride, in the copolymerization reactivity And, it is more preferable for the solubility of the alkaline aqueous solution of the developing solution.

The unsaturated carboxylic acid, the unsaturated carboxylic anhydride or the like is preferably contained in an amount of 5 to 40 parts by weight, more preferably 10 to 30 parts by weight per 100 parts by weight of the total of the total monomers. When the content is less than 5 parts by weight, there is a problem that it is hardly soluble in an aqueous alkaline solution, and when it exceeds 40 parts by weight, there is a problem that the solubility in an alkaline aqueous solution is too large.

The epoxy group-containing unsaturated compound of the above a) ii) used in the present invention may be a glycidyl acrylate, a glycidyl methacrylate or a glycidyl α-ethyl acrylate (glycidyl methacrylate). Glycidyl α-ethylacrylate), glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, β-methyl acrylate --methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, methacrylic acid-β- --ethylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate ), 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6, 7-ring 6,7-epoxyheptyl α-ethylacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylphenyl The above compounds may be used singly or in combination of two or more kinds thereof, such as p-vinylbenzyl glycidyl ether.

The above epoxy group-containing unsaturated compound particularly uses glycidyl methacrylate, β-methyl glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, and o-vinyl phenyl shrinkage. The glyceryl ether, m-vinylphenyl glycidyl ether or p-vinylphenyl glycidyl ether is more suitable in terms of copolymerization reactivity and improvement in heat resistance of the obtained pattern.

The epoxy group-containing unsaturated compound is preferably contained in an amount of 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, per 100 parts by weight of the total of the total monomers. When the content is less than 10 parts by weight, the heat resistance of the obtained pattern may be lowered, and when it exceeds 70 parts by weight, there is a problem that the storage stability of the copolymer is lowered.

The olefin-based unsaturated compound of the above a) iii) used in the present invention may be methyl methacylate, ethyl methacylate or n-butyl methacrylate. , sec-butyl methacry-late, tert-butyl methacrylate, methyl acylate, isopropyl acylate, methacrylic acid ring Cyclohexyl methacrylate, 2-methylcyclohexyl meth-acrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, Dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-Adamantyl acrylate, 1-adamantyl methacrylate 1-Adamantyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isobornyl methacrylate (is Obornyl methacrylate), cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethyl ethyl acrylate, isobornyl acrylate Isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, benzene Styrene, α-metylstyrene, m-metylstyrene, p-metylstyrene, vinyl toluene, p -P-methoxystyrene, 1,3-butadiene, isoprene or 2,3-dimethyl1,3-butadiene 2,3-dimethyl 1,3-butadiene), etc., These compounds can be used individually or in mixture of 2 or more types.

In the olefin-based unsaturated compound, in particular, styrene methacrylic acid dicyclopentanyl ester or p-methoxy styrene is used, and the copolymerization reactivity and the solubility surface of the alkaline aqueous solution of the developing solution are Better words.

The olefin-based unsaturated compound is preferably contained in an amount of 10 to 70 parts by weight, more preferably 20 to 50 parts by weight, based on the total amount of the total monomers. When the content is less than 10 parts by weight, there is a problem that the storage stability of the acrylic copolymer is lowered, and when it exceeds 70 parts by weight, there is a problem that the acrylic copolymer is hardly soluble in the alkaline aqueous solution of the developing solution.

The decane-based monomer of the above a) iv) used in the present invention may be a vinyl trichlorosilane, a vinyltris (β-methoxyethoxysilane) or a vinyl group. Vinyltriacetoxysilane, Vinyl-trimethoxysilane, Vinyl triethoxy-silane, 3-Methylacryloyloxyethylmethyldimethoxy 3-methacryloxyethylmethyl dimethoxysilane, 3-methacryloxypropylmethyl di-methoxysilane, 3-methylpropenyloxyethylmethyldiethoxydecane (3-methacryloxyethylmethyl diethoxysilane), 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxymethyl trimethoxysilane, 3-methacryloxyethyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane (3-methacrylox) Ypropyl trimethoxysilane), 3-methacryloxybutyl trimethoxysilane, 3-methacryloxyethyl triethoxysilane or 3-methylpropene 3-methacryloxypropyl triethoxysilane or the like.

The decane-based monomer is preferably contained in an amount of from 3 to 15 parts by weight based on the total of the total monomers. When the amount is less than 3 parts by weight, the adhesion to the substrate may not be affected, and when it exceeds 15 parts by weight, the heat resistance of the pattern formed on the substrate may be lowered.

a solvent for solution polymerization of such an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, an epoxy group-containing unsaturated compound, an olefinic unsaturated compound, and a monomer of a decane monomer. Methanol, tetrahydrofuran, toluene or dioxane or the like is used.

As the polymerization initiator used for solution polymerization of such a monomer, a radical polymerization initiator may be used, specifically, 2,2-azobisisobutylonitrile, 2,2 may be used. - 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(4-methoxy-2,4-dimethyl 1,2-azobis(4-methoxy-2,4-dimethyl-valeronitrile), 1,1-azobis(cyclohexane-1-carbonitrile) (1,1-azobis(cyclo-) Hexane-1-carbonitrile)), or dimethyl 2,2'-azobisisobutylate (dimethyl 2,2'-azobisisobutylate).

The propylene-based copolymer of the above a) obtained by subjecting the monomer to a free radical reaction in the presence of a solvent and a polymerization initiator, and precipitating and filtering, and removing the unreacted monomer by a vacuum drying procedure The converted weight average molecular weight (Mw) is preferably from 5,000 to 30,000, more preferably from 5,000 to 20,000. When the polystyrene-equivalent weight average molecular weight of the interlayer insulating film is less than 5,000, the development property, the residual film ratio, and the like are lowered, and the pattern development and heat resistance are deteriorated, and the interlayer insulating film exceeding 30,000 is used. There is a problem that the sensitivity is lowered and the pattern is displayed at the same time.

The 1,2-benzoquinone azo compound used in the above b) of the present invention is used as a photosensitive compound.

As the above 1,2-benzoquinone azo compound, 1,2-quinonediazido-4-sulfonic acid ester, 1,2-benzoquinone azo-5 can be used. - 1, quinonediazido-5-sulfonic acid ester, or 1,2-benzoquinone azo-6-sulfonate.

Such a benzoquinone azo compound can be obtained by reacting a naphthoquinone azosulfonic acid halide with a phenol compound under a weak base.

As the phenol compound, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2'-tetrahydroxybenzophenone can be used. 2,2'-tetrahydroxybenzophenone, 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone (2,3, 4,3'-tetrahydroxybenzo-phenone), 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone (2, 3,4,2'-tetrahydroxyl-4'-methylbenzo-phenone), 2,3,4,2'-pentahydroxy-benzophenone, 2,3, 4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4'-hexahydroxydi Benzophenone, 2,4,6,5'-hexahydroxybenzophenone, 3,4,5,3'-hexahydroxybenzophenone, 3,4,5,4'-hexahydroxybenzophenone, 3, 4,5,5'-hexahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane (bis(p -hydroxyphenyl)methane), tris(p-hydroxyphenyl)methane (tris(p Hydroxyphenyl)methane), 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl) Bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane 1,1,3-Tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3- Phenylpropane), 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (4,4'-[1-[4 -[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol) or bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane (bis(2,5) -dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane), etc., and the above compounds may be used singly or in combination of two or more.

When a benzoquinone azo compound is synthesized from such a phenol compound and a naphtha-quinoneazidosulfonic acid halogen compound, the degree of esterification is preferably from 5 to 85%. When the degree of esterification is less than 50%, the residual film ratio may be deteriorated, and when it exceeds 85%, there is a problem that the storage stability is lowered.

The 1,2-benzoquinone azo compound is preferably contained in an amount of 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the propylene-based copolymer of a). When the content is less than 5 parts by weight, the difference in solubility between the exposed portion and the non-exposed portion becomes small and it is difficult to form a pattern; and when it exceeds 100 parts by weight, if a short time of light is irradiated, unreacted 1,2-benzoquinone is irradiated The azo compound remains in a large amount, and the solubility in the alkaline aqueous solution of the developing solution becomes too low, so that it is difficult to develop a problem.

The solvent of the above c) used in the present invention is used to form the flatness of the interlayer insulating film and to prevent the occurrence of coating film spots, and to form a uniform pattern profile.

The solvent may be benzyl alcohol, hexyl alcohol, diethyleneglycol dimethyl-ether, diethyleneglycol methylethyl-ether or diethylene glycol. Diethyleneglycol diethylether, dipropyleneglycol dimethylether, dipropyleneglycol methylethylether, dipropyleneglycol diethylether, ethyleneglycol monomethylether, ethylene glycol methyl ether (diethyleneglycol dimethylether) Ethylene-glycol monoethylether), methyl cello-solve acetate, ethyl cellosolve acetate, diethyleneglycol monomethyl-ether, Diethyleneglycol monoethylether, ethyleneglycol methylethylether, propyleneglycol monomethylether, propylene glycol monoethylether, propylene glycol monopropylether, propylene glycol monopropylether Er), propyleneglycol methyletheracetate, propylene-glycol ethyletheracetate, propylene-glycol propyletheracetate, propylene glycol butyl ether acetate (propyleneglycol butyletheracetate), propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate Butyl ether propionate), toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropyl Ethyl acetate, methyl 2-hydroxymethylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, 3-hydroxypropyl Methyl ester, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate Ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, C Methyloxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butoxy Butyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxyl Methyl propionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxyl Butyl propionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid , butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate The ethers may be used alone or in combination of two or more.

The solvent is preferably contained in an amount of 10 to 50% by weight, more preferably 15 to 40% by weight, based on the total content of the photosensitive resin component. When the solid content of the entire composition is less than 10% by weight, the coating film thickness becomes thin and the flatness of the coating film is lowered. When the content exceeds 50% by weight, the thickness of the coating film becomes thick, and the coating equipment cannot be formed. Operational problems.

The photosensitive resin composition of the present invention comprising such a component may further contain d) an epoxy resin, e) an adhesive, f) an acrylic compound, or g) a surfactant, as needed.

The epoxy resin of the above d) can produce an effect of improving the heat resistance, sensitivity, and the like of the pattern of the photosensitive resin composition.

The epoxy resin may be a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac epoxy resin, a cycloaliphatic epoxy resin, or a glycidyl ester. (glycidyl ester) type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, or glycidyl methacrylate (glycidyl) which is different from the acrylic copolymer of a) Methacrylate (co)polymerized resin, especially bisphenol A epoxy resin, cresol-aldehyde epoxy resin or glycidyl ester epoxy resin.

The epoxy resin is preferably contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer of the above a), and if the content falls outside the above range, the compatibility with the acrylic copolymer is poor. Therefore, there is a problem that sufficient coating performance cannot be obtained.

Further, the adhesive of the above e) has an effect of improving the adhesion to the substrate, and a cyanene couple having a reactive substituent such as a carbonyl group, a methacryl group, an isocyanate group or an epoxy group can be used. Joint agent, etc. Specifically, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane can be used. , γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane or β-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane (β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane).

The pressure-sensitive adhesive is preferably contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer of a).

Further, the acrylic compound of the above f) has an effect of improving the permeability, heat resistance, sensitivity, and the like of the pattern of the photosensitive resin composition.

The acrylic compound is preferably a compound represented by the following Chemical Formula 1.

In the above Chemical Formula 1, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and 1 < a < 6 and a + b = 6.

The acrylic compound is preferably contained in an amount of 0.1 to 25 parts by weight, more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the acrylic copolymer of the above a). When the content is within the above range, it is more preferable to enhance the transmittance, heat resistance, sensitivity, and the like of the pattern.

Further, the surfactant of the above g) has an effect of improving the coatability and developability of the photosensitive composition.

As the surfactant, poly-oxyethyleneoctylphenylether, poly-oxyethylene nonylphenylether, F171, F172, and F173 (trade name: Dainippon Ink Chemical Industry Co., Ltd.) can be used. ), FC430, F431 (trade name: Sumitomo 3M Co., Ltd.), or KP341 (trade name: Shin-Etsu Chemical Co., Ltd.).

The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of the above a); when the content is within the above range, the coating property and developing property of the photosensitive composition are improved. The face is better.

The photosensitive resin composition of the present invention comprising such a component preferably has a solid content concentration of 10 to 50% by weight, and the composition having the above range is filtered by a Millipore Filter of 0.1 to 0.2 μm, and then used as should.

Further, the present invention provides an LCD substrate comprising a cured body of the photosensitive resin, and a pattern forming method of the LCD substrate using the photosensitive resin composition.

In the pattern forming method of the LCD substrate of the present invention, the photosensitive resin composition is used in a method of forming a photosensitive resin composition on an organic insulating film to form a pattern of an LCD substrate.

A method of forming a pattern of an LCD substrate using the above-mentioned photosensitive resin composition, and the details are as follows.

First, the photosensitive resin composition of the present invention is applied onto the surface of a substrate by a spray coating method, a roll coating method, a spin coating method, or the like, and a solvent is removed by prebaking to form a coating film. In this case, the prebaking is preferably carried out at 70 to 110 ° C for 1 to 15 minutes.

Then, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like is irradiated onto the formed coating film through a pattern prepared in advance, and an unnecessary portion is removed by development with a developing liquid to form an unnecessary portion. The predetermined pattern.

The above-mentioned developing solution is preferably alkaline water-soluble, and specifically, inorganic bases such as sodium hydroxide, potassium hydroxide or sodium carbonate; amines such as ethylamine and n-propylamine; diethylamine; a secondary amine such as di-n-propylamine; a tertiary amine such as trimethylamine, methyl diethylamine, dimethyl ethylamine or triethylamine; dimethylethanolamine ( An aqueous solution of dimethyl ethanolamine, methyldiethanolamine, triethanolamine or the like; or an aqueous solution of a tetra-ammonium hydroxide or tetraethylammonium hydroxide-based ammonium salt Wait. In this case, the developing solution is prepared by dissolving the basic compound at a concentration of 0.1 to 10% by weight, and a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount.

Further, after developing with such a developing solution, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions, and after drying, a pattern is formed; after ultraviolet rays or the like is irradiated onto the formed pattern, A heating device such as an oven heats the pattern at a temperature of 150 to 250 ° C for 30 to 90 minutes to obtain a final pattern.

The photosensitive resin composition of the present invention not only has excellent properties such as sensitivity, transmittance, insulation, chemical resistance, flatness, and coatability, but particularly can reduce the number of program steps in the LCD manufacturing process. In the etching process, the adhesion and stability of the interlayer insulating film pattern are remarkably improved, and it is suitable to use an interlayer insulating film which is a thick film thickness of the LCD manufacturing process. Further, the pattern forming method of the LCD substrate of the present invention using the photosensitive resin composition of the present invention has an advantage that an excellent pattern suitable for the interlayer insulating film in the LCD manufacturing process after the exposure process can be formed.

The following examples are presented to enhance the understanding of the invention, but the following examples are merely illustrative of the invention, and the scope of the invention is not limited to the following examples.

[Examples] Example 1

(Production of propylene-based copolymer) 500 parts by weight of tetrahydrofuran, 25 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and isobornyl acrylic acid were placed in a flask equipped with a cooling tube and a stirrer. 20 parts by weight of the ester, 5 parts by weight of vinyltrimethoxydecane, and 1 part by weight of 2,2-azobis(2,4-dimethylvaleronitrile) were subjected to a nitrogen substitution reaction, followed by stirring slowly. The reaction solution was heated to 55 ° C, and the polymer solution containing the acrylic copolymer was produced while maintaining the temperature for 24 hours. The weight average molecular weight of the polymer was 10,000. At this time, the weight average molecular weight is a polystyrene-converted average molecular weight measured by GPC.

(1,2-benzoquinone azo compound) 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1 Ear and 1,2-naphthoquinone azo-5-sulfonic acid [chloride] (1,2-naphthoquinonediazido-5-sulfonic acid [chloride] 2 molar condensation reaction, manufacture 4,4'-[1 -[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol 1,2-naphthoquinoneazo-5-sulfonate.

(Production of Photosensitive Resin Composition) 100 parts by weight of the above-prepared acrylic copolymer and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl) produced as described above were mixed. 30 parts by weight of 1,2-phenyl]ethylidene bisphenol 1,2-naphthoquinoneazo-5-sulfonate. After dissolving in benzyl alcohol so that the solid content of the mixture was 30% by weight, it was filtered through a 0.2 μm Millipore Filter to prepare a photosensitive resin composition.

Example 2

A photosensitive resin composition was produced in the same manner as in Example 1 except that 10 parts by weight of vinyltrimethoxydecane was used in the production of the acrylic copolymer in the above Example 1.

Example 3

The same as the foregoing examples except that 3 parts by weight of vinyltrimethoxydecane used in the production of the acrylic copolymer of the above Example 1 was replaced by 3 parts by weight of 3-methacryloxypropyltrimethoxydecane. 1 The same method was carried out to produce a photosensitive resin composition.

Example 4

In addition to 5 parts by weight of vinyltrimethoxydecane used in the production of the acrylic copolymer of the foregoing Example 1, except 6 parts by weight of 3-methacryloxypropyltrimethoxydecane, and the foregoing examples 1 The same method was carried out to produce a photosensitive resin composition.

Example 5

The same as the foregoing examples except that 10 parts by weight of vinyltrimethoxydecane used in the production of the acrylic copolymer of the above Example 1 was replaced by 10 parts by weight of 3-methacryloxypropyltrimethoxydecane. 1 The same method was carried out to produce a photosensitive resin composition.

Comparative example 1

A photosensitive resin composition was produced in the same manner as in Example 1 except that the acrylic copolymer was produced without the vinyltrimethoxydecane when the acrylic copolymer was produced in the first embodiment.

Using the photosensitive resin compositions produced in the above Examples 1 to 5 and Comparative Example 1, the physical properties were evaluated by the following methods, and the results are shown in Table 1 below.

A) Coating RPM - The photosensitive resin composition obtained in the above Examples 1 to 5 and Comparative Example 1 was applied onto a glass substrate by a spin coating method, and then prebaked on a hot plate at 90 ° C for 2 minutes. A film having a thickness of 3.0 μm was formed.

B) Sensitivity - A predetermined pattern mask was used on the film formed by the above A), and ultraviolet rays of 15 mW/cm ² at a intensity of 365 nm were irradiated for 15 seconds. Thereafter, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38 wt%) at 23 ° C for 70 seconds, and then washed with ultrapure water for 1 minute.

Then, the pattern which has been developed in the foregoing process is irradiated with ultraviolet rays having a intensity of 15 mW/cm ² at 365 nm for 34 seconds, and is hardened by heating at 220 ° C for 60 minutes in a Convection oven (Convetion Oven) to obtain a pattern. Pattern film.

C) Resolution - The minimum size of the patterned film formed by the sensitivity measurement of B) above was measured.

D) Heat resistance - The widths above, below, and to the left and right of the pattern film formed in the sensitivity measurement of the above B) were measured. At this time, based on the pre-heating of the oven, the change rate of the corner is represented by ○ when it is 0 to 20%, Δ when it is 20 to 40%, and × when it is more than 40%.

E) Transparency - Transparency evaluation The transmittance of the patterned film at 400 nm was measured using a spectrophotometer.

F) Adhesiveness - When the pattern film formed by the sensitivity measurement of the above B) is reciprocated at the same speed by a press-fitting device using a manual roller, the peeling is performed when the entire area of the substrate is divided into 100 minutes. (peel off) area, expressed as a percentage.

According to the above-mentioned Table 1, it is understood that the photosensitive resin composition produced in Examples 1 to 5 is excellent in sensitivity, resolution, heat resistance, transparency, and adhesion, and can be suitably used as an LCD required for the substrate to be enlarged. The interlayer insulating film of the process. On the other hand, in the case of Comparative Example 1, the sensitivity was as low as 58.1 mJ/cm ² and the adhesion was poor, which was difficult to apply to the interlayer insulating film.

Claims (11)

A photosensitive resin composition comprising: a) i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof; ii) an epoxy group-containing unsaturated compound; iii) an olefin-based unsaturated compound; Iv) an acrylic copolymer obtained by copolymerizing a decane-based monomer; b) a 1,2-quinonediazide; and c) a solvent, wherein the a) silane of the above a) is a single The system is selected from the group consisting of vinyl trichloromethane, vinyl tris (β-methoxyethoxydecane), vinyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methacryloyloxyethylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxyethylmethyldiethoxydecane , 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxymethyltrimethoxydecane, 3-methylpropenyloxyethyltrimethoxydecane, 3-methyl Propylene methoxypropyltrimethoxydecane, 3-methylpropenyloxybutyltrimethoxydecane, 3-methylpropenyloxyethyltriethoxydecane and 3-methylpropenyloxypropyl One kind of the group consisting of an alkoxy group of silicon or more. The photosensitive resin composition of claim 1, which comprises a) i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, 5 to 40 parts by weight; ii) an epoxy group-containing unsaturated group. 10 to 70 parts by weight of the compound; Iii) 10 to 70 parts by weight of an olefin-based unsaturated compound; and iv) 100 parts by weight of an acrylic copolymer obtained by copolymerizing 3 to 15 parts by weight of a decane-based monomer; b) 1,2-benzoquinone azo compound 5 ~100 parts by weight; and c) a solvent having a content of a solid content in the photosensitive resin composition of 10 to 50 parts by weight. The photosensitive resin composition of claim 1, wherein the unsaturated carboxylic acid, the unsaturated carboxylic anhydride, or the like of the above a) i) is selected from the group consisting of acrylic acid, methacrylic acid, and cis-butene. One or more of the group consisting of acid, fumaric acid, cis-methylbutenedioic acid, trans-methylbutenedioic acid, methylene succinic acid, and the like unsaturated dicarboxylic anhydride. The photosensitive resin composition of claim 1, wherein the epoxy group-containing unsaturated compound of the above a) ii) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and α-ethyl. Glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, acrylic acid -β-ethyl glycidyl ester, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylic-6,7 -epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidol One or more of the groups consisting of ether and p-vinylphenyl glycidyl ether. The photosensitive resin composition of claim 1, wherein the aforementioned The olefin-based unsaturated compound of a) iii) is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, acrylic acid Ester, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate , dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentyloxyethyl ethacrylate, isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2- Hydroxyethyl methacrylate, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, 1,3-butane One or more of the groups consisting of aene, isoprene and 2,3-dimethyl1,3-butadiene The photosensitive resin composition of the first aspect of the invention, wherein the propylene-based copolymer of the above a) has a polystyrene-equivalent weight average molecular weight (Mw) of 5,000 to 30,000. The photosensitive resin composition of claim 1, wherein the 1,2-benzoquinone azo compound of the above b) is selected from the group consisting of 1,2-benzoquinazozosulphonate, 1, One or more of the group consisting of 2-phenylindoleazo-5-sulfonate and 1,2-benzoquinone azo-6-sulfonate. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition further contains a resin selected from the group consisting of d) epoxy resin 0.1 to 30 1 part by weight or more of e) an adhesive, 0.1 to 20 parts by weight, f) an acrylic compound, 0.1 to 25 parts by weight, and g) a surfactant of 0.0001 to 2 parts by weight. The photosensitive resin composition of claim 1, wherein the solvent is selected from the group consisting of benzyl alcohol, hexanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, One or more of the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, and dipropylene glycol diethyl ether. An LCD substrate comprising a cured resin of the photosensitive resin according to any one of claims 1 to 9. A method of forming a pattern of an LCD substrate, which is a photosensitive resin according to any one of claims 1 to 9.