KR101057130B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, in particular an acrylic copolymer obtained by copolymerizing a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixture thereof, ii) epoxy group-containing unsaturated compound, and iii) olefinically unsaturated compound. ; b) 1,2-quinonediazide compounds; And c) relates to a photosensitive resin composition comprising a polyether compound.

The photosensitive resin composition according to the present invention not only has excellent performance in transmittance, insulation, chemical resistance, heat resistance, etc., but also is particularly suitable for forming an interlayer insulating film in an LCD manufacturing process by remarkably improving flatness, coating property, sensitivity, and resolution. Do.

Interlayer insulating film, photosensitive resin, solvent

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, and more particularly, it has excellent performances such as transmittance, insulation, chemical resistance, heat resistance, and the like, and in particular, significantly improves flatness, coating property, sensitivity, and resolution, thereby improving the interlayer of the LCD manufacturing process. A photosensitive resin composition suitable for forming an insulating film.

In the TFT type liquid crystal display device or integrated circuit device, an interlayer insulating film is used to insulate the wirings arranged between the layers.

In the case of forming such an interlayer insulating film, a photosensitive material having a small number of steps and excellent flatness is used to obtain a pattern-shaped interlayer insulating film.

Recently, the interlayer insulating film applied to a liquid crystal display (LCD) manufacturing process requires a low-resistance photoresist as the substrate is enlarged.

Conventionally, the interlayer insulating film is composed of components such as PAC, a binder, a solvent, and the like, and an acetate system has been mainly used as the solvent. However, in the case of the acetate-based, there was a problem such as non-flattening of the interlayer insulating film and coating stains, thereby causing a pattern defect after the photo process.

Therefore, there is a need for further studies to improve the flatness and coating properties of the interlayer insulating film applied to the LCD manufacturing process.

In order to solve the problems of the prior art as described above, the present invention not only has excellent performance of transmittance, insulation, chemical resistance, heat resistance, etc., but also can significantly improve flatness, coating property, sensitivity, and resolution, and thus the film thickness is increased. A photosensitive resin composition suitable for use as an interlayer insulating film of a thick LCD manufacturing process, wherein a pattern defect is not caused in an interlayer insulating film applied to an LCD manufacturing process after a photo process, an LCD substrate comprising a cured body of the photosensitive resin, and the photosensitive It is to provide a pattern formation method of an LCD substrate using a resin composition.

In order to achieve the above object, the present invention provides a photosensitive resin composition,

a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;

  Ii) epoxy group-containing unsaturated compounds; And

  Iii) olefinically unsaturated compounds

  Acrylic copolymer obtained by copolymerizing;

b) 1,2-quinonediazide compounds; And

c) polyether compounds

It provides a photosensitive resin composition comprising a.                     

Preferably the present invention

a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;

  Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And

  V) 10 to 70% by weight of olefinically unsaturated compound

  100 parts by weight of an acrylic copolymer obtained by copolymerizing;

b) 5 to 100 parts by weight of 1,2-quinonediazide compound; And

c) A solvent containing the polyether compound is included so that the solid content in the photosensitive resin composition is 10 to 50% by weight.

Also preferably the present invention

a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;

  Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And

  V) 10 to 70% by weight of olefinically unsaturated compound

  100 parts by weight of an acrylic copolymer obtained by copolymerizing;

b) 5 to 100 parts by weight of 1,2-quinonediazide compound;

c) 0.0001 to 10 parts by weight of a polyether compound as a plasticizer; And

d) The solvent is included so that the content of solids in the photosensitive resin composition is 10 to 50% by weight.

In another aspect, the present invention provides an LCD substrate comprising a cured product of the photosensitive resin.

In another aspect, the present invention provides a pattern forming method of the LCD substrate using the photosensitive resin composition.

Hereinafter, the present invention will be described in detail.

This invention is characterized by including a polyether compound as a solvent or a plasticizer in a specific photosensitive resin composition.

The photosensitive resin composition of the present invention is an acrylic copolymer obtained by copolymerizing a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixture thereof, ii) epoxy group-containing unsaturated compound, and iii) olefinically unsaturated compound, b) 1 , A 2-quinonediazide compound, and c) a polyether compound.

The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which scum does not occur when developing.

The acrylic copolymer of a) may be a radical in the presence of a solvent and a polymerization initiator, i. After reacting and synthesizing, unreacted monomers may be obtained by precipitation, filtration, and vacuum drying.

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

The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably included in 5 to 40% by weight, more preferably 10 to 30% by weight based on the total total monomers. If the content is less than 5% by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, when the content exceeds 40% by weight there is a problem that the solubility in the aqueous alkali solution is too large.

The epoxy group-containing unsaturated compound of a) ii) used in the present invention is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n- Butyl acrylate glycidyl, acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethyl glycidyl, methacrylic acid-beta -ethyl glycidyl, 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- Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like can be used, and the above compounds can be used alone or in combination of two or more thereof.

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

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

The olefinically unsaturated compounds of a) iii) used in the present invention 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, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1 -Adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxy Ethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl meth Relate, 2-hydroxyethylacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, or 2,3- Dimethyl 1,3-butadiene and the like can be used, and the compounds can be used alone or in combination of two or more thereof.

In particular, the olefinically unsaturated compound is more preferably in terms of solubility in alkaline water solution of copolymerization reactivity and developer, using styrene, dicyclopentanyl methacrylate, or p-methoxy styrene.

The olefinically unsaturated compound is preferably included in 10 to 70% by weight, more preferably 20 to 50% by weight relative to the total total monomers. If the content is less than 10% by weight, there is a problem that the storage stability of the acrylic copolymer is lowered. If the content exceeds 70% by weight, the acrylic copolymer is difficult to be dissolved in an aqueous alkali solution.

Solvents used for solution polymerization of such monomers 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 methylethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl 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-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, propyl acetate Butyl, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, Lactic acid propyl, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propyl propionate, 3-hydroxy butyl propionate, 2-hydroxy 3-methyl methyl carbonate, methyl methoxy acetate, Methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, prop Propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Butyl 2-methoxy propionate, methyl 2-ethoxy propionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2 Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-part Toxi Ethers such as methyl propionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, and the like can be used, and the compounds can be used alone or in combination of two or more thereof.

The polymerization initiator used for solution polymerization of such monomers may use a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile ), 2,2-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2'-azobisisobutyl Rate and the like can be used.

The acrylic copolymer of a) obtained by synthesizing the monomer as described above by radical reaction in the presence of a solvent and a polymerization initiator, and then removing the unreacted monomer through a precipitation, filtration and vacuum drying process has a polystyrene equivalent weight average molecular weight (Mw). ) Is 5,000 to 30,000, more preferably 5,000 to 20,000. In the case of the interlayer insulating film having a polystyrene reduced weight average molecular weight of less than 5,000, there is a problem in that developability, residual film ratio, etc. are deteriorated, or pattern development, heat resistance, etc. are deteriorated. There is a problem that this is lowered.

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

As the 1,2-quinonediazide compound, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1,2-quinonediazide 6-sulfonic acid ester may be used. have.

The quinonediazide compound as described above may be prepared by reacting a naphthoquinonediazide sulfonic acid halogen compound and a phenol compound under a weak base.

Examples of the phenolic compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2'-tetrahydroxybenzophenone, and 4,4'-tetrahydroxybenzophenone. , 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2'-pentahydroxybenzophenone, 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4'-hexahydroxybenzophenone, 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, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxy Phenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimeth Methyl 4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, or bis ( 2,5-dimethyl 4-hydroxyphenyl) -2-hydroxyphenylmethane etc. can be used, The said compound can be used individually or in mixture of 2 or more types.

When the quinone diazide compound is synthesized with the phenol compound and the naphthoquinone diazide sulfonic acid halogen compound as described above, the esterification degree is preferably 50 to 85%. When the esterification degree is less than 50%, the residual film rate may be worse, and when the esterification degree is more than 85%, there is a problem that the storage stability is lowered.

The 1,2-quinonediazide compound is preferably included in an amount of 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the acrylic copolymer of a). If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed parts becomes small, and if it exceeds 100 parts by weight, a large amount of unreacted 1,2-quinonediazide compound is produced when irradiated with light for a short time. There is a problem that the development is difficult because the solubility in the alkali aqueous solution remaining as a developer is too low.

The polyether compound of c) used in the present invention may be included as a solvent or plasticizer of the photosensitive resin composition of the present invention.

The polyether-based compound is preferably an alkylene glycol-type ether compound containing alkylene glycol as a repeating unit. Particularly, the alkylene glycol-type ether compound may be a polyalkylene glycol (eg, polyethylene glycol, tetramethylene glycol Polyalkylene glycols having alkyl groups at both ends obtained by alkyl-etherification of both terminals, or alkylene glycol at one end of polyalkylene glycol (for example, polyethylene glycol, tetramethylene glycol, etc.) It is preferable that it is a polyester ether which has a dicarboxylic acid in the other terminal.

In particular, the polyether compound contained in the photosensitive resin composition of the present invention as a solvent or a plasticizer is more preferably an isobutyrate alkylene glycol type ether compound, most preferably 2,2,4-trimethyl-1, Preference is given to 3-pentanediol monoisobutylate.

When the polyether-based compound of the present invention is included as a solvent, the polyether-based compound generates planarization and coating spots of the interlayer insulating film when coating on substrates of various sizes through a large substrate, slit, spinless, or spin method. To form a uniform pattern profile.

In addition, when the polyether compound of the present invention is included as a solvent, the polyether compound may be used alone, or may be mixed with other solvents.

As a solvent which can be mixed with the said polyether type compound, Alcohol, such as methanol, ethanol, benzyl alcohol, hexyl alcohol; 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, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Dipropylene glycol diethyl ether such as dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; Aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy 4-methyl 2-pentanone, or methyl acetate, ethyl acetate, propyl acetate, butyl acetate and 2-hydroxy propionic acid Ethyl, 2-hydroxy 2-methylpropionate, 2-hydroxy ethyl 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, butoxy Methyl acetate, Ethyl oxyacetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethoxy ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , 3-Methoxypropionate Methyl 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, butyl 3-ethoxypropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, propyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionate, 3- Butoxypro Esters such as butyl pionate; and the like. In particular, the mixed solvent is benzyl alcohol, hexyl alcohol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, or dipropylene glycol It is preferable that it is diethyl ether.

When the polyether-based compound of the present invention is included as a solvent and used in combination with the blendable solvent, the polyether-based compound is preferably included in at least 5% by weight based on the total solvent content, more preferably at least 30% by weight. It is to be included.

When the polyether compound is included as a solvent, the polyether compound is preferably included so that the solid content of the entire photosensitive resin composition is 10 to 50% by weight, more preferably 15 to 40% by weight. . If the solid content of the total composition is less than 10% by weight, there is a problem that the coating thickness becomes thin, and the coating flatness is lowered. When the content of the solid composition exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is impaired during coating. There is a problem that can be.

In addition, when the polyether compound of the present invention as described above is included as a plasticizer, the polyether compound improves wettability by inhibiting separation of the blended photosensitive resin composition component of the present invention and facilitates the formation of a continuous phase. It acts to improve the coating properties. In addition, it serves to lower the viscosity while maintaining the properties of the photosensitive resin composition to the maximum.

When the polyether compound is included as a plasticizer, the polyether compound is preferably included in an amount of 0.0001 to 10 parts by weight, and more preferably 0.0001 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is out of the above range, there is a problem that can lower the heat resistance of the photosensitive resin composition.

In addition, when the polyether-based compound of the present invention is included as a plasticizer, a solvent that can be mixed with the above-described polyester-based compound may be used, and preferably alcohols, diethylene glycols, or dipropylene glycol diethyl ether. Solvents such as the solvents and the like.

Specifically, the solvent is benzyl alcohol, hexyl alcohol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, or dipropylene glycol di Ethyl ether and the like can be used, the content of which is preferably included so that the solids content of the entire photosensitive resin is 10 to 50% by weight.

The photosensitive resin composition of this invention which consists of such a component as needed may further contain d) epoxy resin, e) adhesive agent, f) acrylic compound, and g) surfactant as needed.

The epoxy resin of said d) functions to improve heat resistance, sensitivity, etc. of the pattern obtained from the photosensitive resin composition.

The epoxy resin is bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, heterocyclic epoxy resin, Or a resin obtained by co-polymerizing glycidyl methacrylate different from the acrylic copolymer of a), in particular, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a glycidyl ester type epoxy. It is preferable to use 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 a). If the content is outside the above range, compatibility with the acrylic copolymer may be insufficient to obtain sufficient coating performance. There is a problem that can not be.

In addition, the adhesive of e) serves to improve the adhesion to the substrate, it is preferably included in 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer of a).

As the adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group can be used. Specifically, the adhesive may be γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3,4-epoxy cyclohexyl) ethyltrimethoxysilane and the like can be used.

Furthermore, the said ac compound of f) functions to improve the transmittance | permeability, heat resistance, a sensitivity, etc. of the pattern obtained from the photosensitive resin composition.

Preferably, the acrylic compound is a compound represented by the following formula (1).

[Formula 1]

In the formula of Formula 1,

R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or an alkanoyl group of 1 to 5 carbon atoms,

1 <a <6 and a + b = 6.

The acrylic compound is preferably included in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight based on 100 parts by weight of the acrylic copolymer. When the content is in the above range, it is better in improving the transmittance, heat resistance, sensitivity, and the like of the pattern.

In addition, the surfactant of g) serves to improve the applicability and developability of the photosensitive composition.

The surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem, Inc.), or KP341 (trade name: Shinwol) Chemical industry) and the like.

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 copolymer of a), and when the content is in the above range, it is more preferable in improving the coating property and developability of the photosensitive composition.

It is preferable that the solid content concentration of the photosensitive resin composition of this invention which consists of the above components is 10 to 50 weight%, and the composition which has a solid content of the said range is used after filtering with a 0.1-0.2 micrometer millipore filter etc. good.

In another aspect, the present invention provides an LCD substrate comprising a cured body of the photosensitive resin as described above, and a pattern forming method of the LCD substrate using the photosensitive resin composition.

The pattern formation method of the LCD substrate of this invention uses the said photosensitive resin composition in the method of forming the pattern of an LCD substrate by forming the photosensitive resin composition into an organic insulating film.

Specifically, the method of forming the pattern of the LCD substrate using the photosensitive resin composition is as follows.

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

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

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developing solution is used by dissolving the 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 and ethanol and a surfactant may be added.

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

The photosensitive resin composition and the cured product obtained by curing the photosensitive resin composition according to the present invention not only have excellent performances such as transmittance, insulation, chemical resistance and heat resistance, but also can significantly improve flatness, coating property, sensitivity, and resolution. Not only is it suitable for use as an interlayer insulating film of a thick LCD manufacturing process, but also the pattern formation method of the LCD substrate of the present invention using the photosensitive resin composition provides an excellent pattern of the interlayer insulating film applied to the LCD manufacturing process after a photo process. There is an advantage that can be formed.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1

(Acrylic copolymer production)

In a flask equipped with a cooling tube and a stirrer, 20 parts by weight of methacrylic acid, 25 parts by weight of glycidyl methacrylate, 40 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and isoboroylacrylate 10 200 parts by weight of tetrahydrofuran as a solvent and 10 parts by weight of 2,2'-azobis (2,4-bimethylvaleronitrile) were added to the monomer by weight, followed by nitrogen substitution, followed by gentle stirring. The reaction solution was heated to 62 ° C. to prepare a polymer solution containing an acrylic copolymer while maintaining this temperature for 5 hours.

In order to remove the unreacted monomer of the polymer solution, 100 parts by weight of the polymer solution was precipitated based on 100 parts by weight of the poor solvent in which ether and n-hexane were mixed in a 1: 1 ratio. Then, the poor solvent in which the unreacted material was dissolved was removed through a filtering process using a mesh. Thereafter, vacuum drying at 30 ° C. or lower completely removed the solvent containing the unreacted monomer remaining after the filtering process, thereby preparing an acrylic copolymer having a solid content concentration of 45 wt% and a weight average molecular weight of 10,000. At this time, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

(1,2-quinonediazide compound preparation)

1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid [ Chloride] condensation reaction of 2 moles to give 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide -5-sulfonic acid ester was prepared.

(Photosensitive resin composition production)

100 parts by weight of the prepared acrylic copolymer and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2- 25 parts by weight of naphthoquinonediazide-5-sulfonic acid ester was mixed. 50 parts by weight of propylene glycol monomethyl ethyracetate and 20 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate as solvents in 30 parts by weight of the mixture so that the solid content of the mixture was 30% by weight. After the parts were dissolved, the resultant was filtered with a 0.2 μm Millipore filter to prepare a photosensitive resin composition.

Example 2

Except that 30 parts by weight of propylene glycol monomethyl ether acetate and 40 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate were used as a solvent in the preparation of the photosensitive resin composition of Example 1 It carried out by the same method as Example 1, and prepared the photosensitive resin composition.

Example 3

Except that 20 parts by weight of propylene glycol monomethyl ether acetate and 50 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate were used in the preparation of the photosensitive resin composition of Example 1 It carried out by the same method as 1, and manufactured the photosensitive resin composition.

Example 4

In preparing the photosensitive resin composition of Example 1, 5 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate was used as a plasticizer, and benzyl alcohol was added so that the solid content of the mixture was 20% by weight. A photosensitive resin composition was prepared in the same manner as in Example 1, except that the solvent was used as a solvent.

Comparative Example 1

Example 1 except that propylene glycol methyl ether acetate was used instead of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate as a solvent in the preparation of the photosensitive resin composition of Example 1 It carried out by the same method and manufactured the photosensitive resin composition.

After evaluating the physical properties by the following method using the photosensitive resin composition prepared in Examples 1 to 4 and Comparative Example 1, the results are shown in Table 1 below.

A) Coating RPM-After applying the photosensitive resin composition prepared in Examples 1 to 4 and Comparative Example 1 using a spin coater on a glass substrate, and prebaked on a hot plate for 2 minutes at 90 ℃ thickness Formed a film having a thickness of 3.0 mu m.

B) Flatness-The coating uniformity of the film formed in a) was measured using an Elipsometer. At this time, (circle) and 95-90% of the cases where the flatness exceeded 95% on the basis of the entire substrate were indicated by Δ and the case of less than 90% as x.

C) Sensitivity-The film formed in the above a) was irradiated with ultraviolet rays having a intensity of 15 mA / cm 2 at 365 nm for 15 to 25 seconds using a predetermined pattern mask. Thereafter, the solution was developed at 25 ° C. for 2 minutes in an aqueous solution of 0.4% by weight of tetramethyl ammonium hydroxide, and then washed with ultrapure water for 1 minute.

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

D) resolution—measured by the minimum size of the pattern film formed during the sensitivity measurement of c).

ㅁ) heat resistance-the width of the upper, lower, left and right of the pattern film formed when the sensitivity of the c) was measured. At this time, (circle) and the case where 20-40% of the cases where the change rate of each angle is 0-20% as a reference before midbaking were represented by (x).

Iii) Transparency-The evaluation of transparency measured the transmittance of 400 nm of the pattern film using a spectrophotometer.

G) Heat dissipation resistance-Evaluation of heat dissipation resistance The measurement substrate was heated in an oven at 220 ° C. for 1 hour, and the heat dissipation resistance was evaluated according to the change of transmittance of the pattern film before and after heating. In this case, the case where the change rate was less than 5% was represented by ○, and the case where the change rate was 5% by 10% was indicated by Δ and the case where the change rate was greater than 10%.

division Coating RPM flatness Sensitivity (mJ / ㎠) Resolution (μm) Heat resistance Transparency Heat discoloration resistance Example 1 1000 ○ 270 3 ○ 90 ○ Example 2 1050 ○ 275 3 ○ 90 ○ Example 3 1050 ○ 278 3 ○ 90 ○ Example 4 1000 ○ 272 3 ○ 90 ○ Comparative Example 1 1300 × 310 5 ○ 90 ○

Through the above Table 1, the photosensitive resin composition prepared in Examples 1 to 4 according to the present invention was excellent in sensitivity, resolution, heat resistance, transparency, and heat discoloration, and in particular, by preparing a low viscosity photosensitive resin composition, Both of the flatness was much superior to Comparative Example 1, it can be seen that it is applicable to the interlayer insulating film of the LCD process according to the size of the substrate. On the contrary, in Comparative Example 1, the sensitivity and the resolution were somewhat poor, and the flatness was not good, which made it difficult to apply the interlayer insulating film.

The photosensitive resin composition according to the present invention and the cured product cured therewith are not only excellent in performances such as transmittance, insulation, chemical resistance, heat resistance, etc., but also can significantly improve flatness, coating property, sensitivity, and resolution, and thus have a thick film thickness. Not only is it suitable for use as an interlayer insulating film in an LCD manufacturing process, but also the pattern formation method of the LCD substrate of the present invention using the photosensitive resin composition can form an excellent pattern of an interlayer insulating film applied to an LCD manufacturing process after a photo process. There is an advantage.

Claims (15)

In the photosensitive resin composition, a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And   V) 10 to 70% by weight of olefinically unsaturated compound   100 parts by weight of an acrylic copolymer obtained by copolymerizing; b) 5 to 100 parts by weight of 1,2-quinonediazide compound; And c) A photosensitive resin composition comprising a solvent containing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate such that the solid content in the photosensitive resin composition is 10 to 50% by weight. delete In the photosensitive resin composition, a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And   V) 10 to 70% by weight of olefinically unsaturated compound   100 parts by weight of an acrylic copolymer obtained by copolymerizing; b) 5 to 100 parts by weight of 1,2-quinonediazide compound; c) 0.0001 to 10 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutylate as a plasticizer; And d) The photosensitive resin composition containing a solvent so that content of solid content in the photosensitive resin composition may be 10-50 weight%. delete delete The method according to claim 1 or 3, The solvent is a polyether compound, methanol, ethanol, benzyl alcohol, hexyl alcohol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propio Hite, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate ethyl, 2-hydroxy 2-methylpropionate, 2-hydroxy 2-methylpropionate , Methyl hydroxy acetate, ethyl hydroxy acetate, butyl butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionate, 3 -Butyl hydroxypropionate, 2-hydroxy methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, propyl methoxy acetate, butyl methoxy acetate, ethoxy acetate meth Ethyl, ethoxy acetate, ethoxy propyl acetate, ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butoxy acetate Propyl, butyl butoxy acetate, 2-methoxy methyl propionate, 2-methoxy ethylpropionate, 2-methoxy propyl propionate, 2-methoxy butyl propionate, 2-ethoxy methyl propionate, 2-ethoxy fluoropropionate , 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 3-ethoxypropionate, methyl 3-propoxypropionate, 3 Propoxypropion 1 type from the group which consists of ethyl, 3-propoxy propionate, 3-propoxy propionate, 3-butoxy methyl propionate, 3-butoxy propionate, 3-butoxy propyl propionate, and 3-butyl butyl propionate The photosensitive resin composition characterized by including the solvent chosen above. The method of claim 1, The 2,2,4-trimethyl-1,3-pentanediol monoisobutylate is contained in the total solvent at least 5% by weight, the photosensitive resin composition. The method according to claim 1 or 3, A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, the group consisting of anhydrides of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, or unsaturated dicarboxylic acid thereof Photosensitive resin composition, characterized in that at least one selected from. The method according to claim 1 or 3, The epoxy group-containing unsaturated compounds of a) ii) are glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl , Acrylic acid β-methylglycidyl, methacrylic acid β-methylglycidyl, acrylic acid β-ethylglycidyl, methacrylic acid β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl At least one selected from the group consisting of ether, m-vinylbenzyl glycidyl ether, and p-vinyl benzyl glycidyl ether, characterized in that the photosensitive resin composition. The method according to claim 1 or 3, The olefinically unsaturated compound of a) iii) is 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 acrylic Rate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, iso Boronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy With ethyl acrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene 1 or more types are chosen from the group which consists of a photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 3, The polystyrene reduced weight average molecular weight (Mw) of the acryl-type copolymer of said a) is 5,000-30,000, The photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 3, The 1,2-quinonediazide compound of b) is used as 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester 1 or more types are chosen from the group which consists of a photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 3, D) 0.1 to 30 parts by weight of the epoxy resin, e) 0.1 to 20 parts by weight of the adhesive, f) 0.1 to 30 parts by weight of the acrylic compound, and g) surfactants 0.0001 to 2 with respect to 100 parts by weight of the acrylic copolymer. A photosensitive resin composition further comprising an additive selected from the group consisting of parts by weight. An LCD substrate comprising the cured product of the photosensitive resin of claim 1. The pattern formation method of the LCD substrate using the photosensitive resin composition of Claim 1 or 3.