KR101068111B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, in particular a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, ii) epoxy group-containing unsaturated compounds, iii) olefinically unsaturated compounds, and iii) silane monomers. Acrylic copolymers obtained by copolymerization; b) 1,2-quinonediazide compounds; And c) relates to a photosensitive resin composition comprising a solvent.

The photosensitive resin composition according to the present invention not only has excellent performance in sensitivity, transmittance, insulation, chemical resistance, flatness, coating property, etc., but also significantly improves adhesion to inorganic materials, thereby forming an interlayer insulating film in an LCD manufacturing process. Suitable for

Photosensitive resin, silane monomer, adhesive, interlayer insulating film

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, and more particularly, excellent performance in sensitivity, transmittance, insulation, chemical resistance, flatness, coating property, and the like, in particular, the adhesion to inorganic materials is significantly improved, and thus the LCD manufacturing process It relates to a photosensitive resin composition suitable for forming an interlayer 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 order to form such an interlayer insulating film, a pattern is easily formed, and in particular, a photosensitive material having excellent adhesion to inorganic materials such as upper and lower glass or metal films is used.

Recently, an interlayer insulating film applied to a liquid crystal display (LCD) manufacturing process is using a process such as HMDS treatment or an adhesive is added to improve adhesion to a substrate. However, the above methods require a step of treating as described above in the LCD manufacturing process, resulting in a large number of processes, and lack of adhesive force, thereby causing problems in stability during development and etching processes.                         

Therefore, there is a need for further research on a method that can reduce the process steps in the LCD manufacturing process, and improve the adhesive strength of the interlayer insulating film pattern during the developing process and the etching process to ensure stability.

In order to solve the problems of the prior art as described above, the present invention is not only excellent in the performance of sensitivity, transmittance, insulation, chemical resistance, flatness, coating properties, etc., in particular can reduce the process step in the LCD manufacturing process, development LCD substrate and photosensitive resin composition comprising a photosensitive resin composition and a cured body of the photosensitive resin suitable for use as an interlayer insulating film in an LCD manufacturing process having a thick film thickness by significantly improving the adhesion and stability of the interlayer insulating film pattern during the process and etching process. An object of the present invention is to provide a pattern forming method of an LCD substrate.

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;

  Iii) olefinically unsaturated compounds; And

  Iii) silane monomers

  Acrylic copolymer obtained by copolymerizing;

b) 1,2-quinonediazide compounds; And

c) solvent                     

It provides a photosensitive resin composition comprising a.

Preferably the present invention

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

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

  V) 10 to 70 parts by weight of olefinically unsaturated compound; And

  Iii) 3 to 15 parts by weight of silane monomers

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

The present invention also provides an LCD 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.

The photosensitive resin composition of the present invention comprises a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound, iii) 10 to 70 parts by weight of an olefinically unsaturated compound, and Vi) an acrylic copolymer obtained by copolymerizing 3 to 15 parts by weight of a silane monomer, b) a 1,2-quinonediazide compound, and c) a solvent.                     

The acrylic copolymer of a) used in the present invention functions to easily form a predetermined pattern that does not generate a scum when developing.

The acrylic copolymer of a) may be selected from the group consisting of i) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof, ii) epoxy group-containing unsaturated compounds, iii) olefinically unsaturated compounds, and iii) silane monomers as solvents, It can be synthesized by radical reaction in the presence of a polymerization initiator.

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 an amount of 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total total monomers. If the content is less than 5 parts by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, if it exceeds 40 parts by weight there is a problem that the solubility in the aqueous alkali solution is too large.

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 included in 10 to 70 parts by weight, more preferably 20 to 60 parts by weight based on 100 parts by weight of the total total monomers. If the content is less than 10 parts by weight, there is a problem that the heat resistance of the resulting pattern is lowered, and if it exceeds 70 parts by weight, there is a problem that the storage stability of the copolymer is lowered.

The olefinically unsaturated 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 Acrylate, 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 It can be used and the said compound can be used individually or in mixture of 2 or more types.

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

The olefinically unsaturated compound is preferably included in 10 to 70 parts by weight, more preferably 20 to 50 parts by weight based on 100 parts by weight of the total total monomers. If the content is less than 10 parts by weight, there is a problem that the storage stability of the acrylic copolymer is lowered. If the content exceeds 70 parts by weight, the acrylic copolymer is difficult to be dissolved in an aqueous alkali solution.

The silane monomers of a) iii) used in the present invention include vinyltrichlorosilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxyethylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxyethylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy Methyltrimethoxysilane, 3-methacryloxyethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxybutyltrimethoxysilane, 3-methacryloxyethyltriethoxysilane or 3-methacryloxypropyl triethoxysilane, etc. can be used.

The silane monomer is preferably included in 3 to 15 parts by weight based on 100 parts by weight of the total total monomers. If it is less than 3 parts by weight, there is no effect of improving adhesion to the substrate. If it exceeds 15 parts by weight, there is a problem that the heat resistance of the pattern formed on the substrate is lowered.

Such unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof; Epoxy group-containing unsaturated compounds; Olefinically unsaturated compounds; And as a solvent used for solution polymerization of the monomer of a silane monomer, methanol, tetrahydroxyfuran, toluene, dioxane, etc. can be used.

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 radical reaction of the above monomers in the presence of a solvent and a polymerization initiator, and removal of unreacted monomers through precipitation, filtration and vacuum drying processes has a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 5,000. It is preferable that it is 30,000, More preferably, it is 5,000-20,000. In the case of the interlayer insulating film having a weight average molecular weight of less than 5,000, there is a problem in that developability, residual film ratio, or the like is inferior to pattern development, heat resistance, etc., and in the case of an interlayer insulating film exceeding 30,000, the sensitivity is decreased or a pattern There is a problem that the phenomenon is inferior.

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-trihydrate Oxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-di 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 solvent of c) used in the present invention does not generate flatness and coating stain of the interlayer insulating film, thereby forming a uniform pattern profile.

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, dipropylene glycol diethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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 ethyl acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene Recall 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, 2-hydroxyethyl propionate, methyl 2-hydroxy methylpropionate, ethyl 2-hydroxy 2-methyl ethyl propionate, methyl hydroxy acetate, hydroxy acetic acid Ethyl, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy butyl propionate, 2-hydroxy Methyl oxy 3-methylbutyrate, methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy acetate, ethoxy Propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, 2 Methyl methoxy propionate, 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 2-methoxypropionate , 3-methoxy propyl propionate, 3-methoxy butyl propionate, 3-ethoxy propionate, 3-ethoxy propionate, 3-ethoxy propyl propionate, 3-ethoxy propionate, 3-propoxy propionate, 3-propoxypropy Ethers such as ethyl acid, 3-propoxypropionate, 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate It can be used and these can be used individually or in mixture of 2 or more types.

The solvent 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 in that the coating thickness is thin, and coating flatness is lowered. When the content of the solid composition exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is hard to coat. There is a problem that can give.

The photosensitive resin composition of this invention which consists of the above components can further contain d) epoxy resin, e) adhesive agent, f) acrylic compound, or 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), and in particular, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a glycidyl ester type. Preference is given to using epoxy resins.

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

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

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 0.1 to 25 parts by weight, more preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). 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 coatability 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 included in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a). If the content is in the above range, the surfactant is more preferable in coating properties 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.

The present invention also provides an LCD substrate comprising a cured product of the photosensitive resin 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 developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.

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

The photosensitive resin composition according to the present invention not only has excellent performance in sensitivity, transmittance, insulation, chemical resistance, flatness, coating property, etc., but also can reduce process steps in the LCD manufacturing process, and interlayer during development process and etching process. Significantly improve the adhesion and stability of the insulating film pattern is suitable for use as an interlayer insulating film of the LCD manufacturing process with a thick film thickness. In addition, the pattern formation method of the LCD substrate of the present invention using the photosensitive resin composition of the present invention has the advantage that it can form an excellent pattern of the interlayer insulating film applied to the LCD manufacturing process after the photo process.

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

[Example]

Example 1

(Acrylic copolymer production)

500 parts by weight of tetrahydroxyfuran, 25 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of isobornyl acrylate, and vinyltrime in a flask equipped with a cooling tube and a stirrer. 5 parts by weight of oxysilane and 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and nitrogen-substituted and stirred gently. The reaction solution was heated up to 55 ° C to maintain a temperature for 24 hours to prepare a polymer solution containing an acrylic copolymer, the weight average molecular weight of the polymer was 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- 30 parts by weight of naphthoquinonediazide-5-sulfonic acid ester was mixed. After dissolving with 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 prepared in the same manner as in Example 1, except that 10 parts by weight of vinyltrimethoxysilane was used to prepare the acrylic copolymer in Example 1.

Example 3

In the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was used in 3 parts by weight instead of 5 parts by weight of vinyltrimethoxysilane when preparing the acrylic copolymer. A resin composition was prepared.

Example 4

The photosensitive composition was carried out in the same manner as in Example 1, except that 3-methacryloxypropyltrimethoxysilane was used in place of 5 parts by weight of vinyltrimethoxysilane in Example 1 to prepare an acrylic copolymer. A resin composition was prepared.

Example 5

In the same manner as in Example 1, except that 3-methacryloxypropyltrimethoxysilane was used in place of 5 parts by weight of vinyltrimethoxysilane in the preparation of the acrylic copolymer in 10 parts by weight. The photosensitive resin composition was prepared.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the acrylic copolymer was prepared without including vinyltrimethoxysilane when preparing the acrylic copolymer in Example 1.

After evaluating the physical properties by the following method using the photosensitive resin composition prepared in Examples 1 to 5 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 5 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 film formed in the above a) was irradiated with ultraviolet rays having an intensity of 15 mA / cm 2 for 15 seconds using a pattern mask. Thereafter, the solution was developed at 23 ° C. for 70 seconds in an aqueous solution of 2.38 wt% tetramethyl ammonium hydroxide, and then washed with ultrapure water for 1 minute.

Subsequently, the developed pattern was irradiated with ultraviolet rays having an intensity of 15 mA / cm 2 at 365 nm for 34 seconds, and heated and cured at 220 ° C. for 60 minutes in a convection oven to obtain a pattern film.

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

D) heat resistance-the widths of the upper, lower, left and right sides of the pattern film formed when the sensitivity of the b) was measured. At this time, the case where the change rate of each angle was 0 to 20% based on the oven heating and (circle) and the case where 20 to 40% exceeded (triangle | delta) and 40% was represented by x.

)) Transparency—evaluation of transparency The transmittance of 400 nm of the patterned film was measured using a spectrophotometer.

Iii) Adhesiveness-After reciprocating once at the same speed using the manual roller compaction apparatus on the pattern film formed in the sensitivity measurement of b), measure the area peeled off when the total area of the substrate is divided into 100 equal parts. Marked as.

division Coating RPM Sensitivity (mJ / ㎠) Resolution (μm) Heat resistance Transparency Adhesiveness (%) Example 1 1090 54.6 3 ○ 90 35.05 Example 2 1050 51.2 3 △ 92 31.71 Example 3 1050 54.5 3 ○ 90 36.06 Example 4 1090 54.8 3 ○ 90 28.88 Example 5 1020 50.1 3 ○ 91 22.75 Comparative Example 1 1030 58.1 3 ○ 88 85.13

Through Table 1, the photosensitive resin composition prepared in Examples 1 to 5 according to the present invention was excellent in sensitivity, resolution, heat resistance, transparency, and adhesion, and applied to the interlayer insulating film of the LCD process according to the enlargement of the substrate. It was possible to find out. On the contrary, in the case of Comparative Example 1, the sensitivity was low as 58.1 mJ / cm 2, and the adhesion was poor, which makes it difficult to apply to the interlayer insulating film.

 The photosensitive resin composition according to the present invention not only has excellent performance in sensitivity, transmittance, insulation, chemical resistance, flatness, coating property, etc., but also can reduce process steps in the LCD manufacturing process, and interlayer during development process and etching process. Significantly improve the adhesion and stability of the insulating film pattern is suitable for use as an interlayer insulating film of the LCD manufacturing process with a thick film thickness. In addition, the pattern formation method of the LCD substrate of the present invention using the photosensitive resin composition of the present invention has the effect that it can form an excellent pattern of the interlayer insulating film applied to the LCD manufacturing process after the photo process.

Claims (12)

In the photosensitive resin composition, a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) epoxy group-containing unsaturated compounds;   Iii) olefinically unsaturated compounds; And   Iii) silane monomers   Acrylic copolymer obtained by copolymerizing; b) 1,2-quinonediazide compounds; And c) solvent Photosensitive resin composition comprising a. The method of claim 1, a) i) 5 to 40 parts by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound;   V) 10 to 70 parts by weight of olefinically unsaturated compound; And   Iii) 3 to 15 parts by weight of silane monomers   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) The photosensitive resin composition containing a solvent so that content of solid content in the photosensitive resin composition may be 10-50 weight%. The method of claim 1, A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof, consisting of anhydrides of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof The photosensitive resin composition, characterized in that at least one selected from the group. The method of claim 1, 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 of claim 1, 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, styrene, at least one member from the group consisting of α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The silane monomers of a) iii) include vinyltrichlorosilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxy Ethylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxyethylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxyethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxybutyltrimethoxysilane, 3-methacryloxyethyltriethoxysilane and 3-methacryloxypropyl At least 1 type is selected from the group which consists of triethoxysilane, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The acrylic copolymer of a) has a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 30,000, the photosensitive resin composition. The method of claim 1, 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 of claim 1, The photosensitive resin composition is one or more from the group consisting of d) 0.1 to 30 parts by weight of epoxy resin, e) 0.1 to 20 parts by weight of adhesive, f) 0.1 to 25 parts by weight of acrylic compound, and g) 0.0001 to 2 parts by weight of surfactant. The photosensitive resin composition, characterized in that it further comprises an additive selected. The method of claim 1, 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, and dipropylene glycol diethyl ether 1 or more types are selected from the group which consists of a photosensitive resin composition characterized by the above-mentioned. An LCD substrate comprising the cured product of the photosensitive resin of any one of claims 1 to 10. The pattern formation method of the LCD substrate using the photosensitive resin of any one of Claims 1-10.