KR101221468B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, in particular a) i) phenyl maleimide compounds, ii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof, and iii) acrylic copolymers obtained by copolymerizing epoxy group-containing unsaturated compounds. coalescence; b) 1,2-quinonediazide compounds; And c) a solvent, and a photosensitive resin composition for forming an interlayer insulating film of a liquid crystal display device.

The photosensitive resin composition according to the present invention not only has excellent performance in transmittance, insulation, flatness, chemical resistance, etc., but also minimizes outgassing that may occur in an interlayer insulating film through high heat resistance, thereby improving reliability of a post process. It is suitable for use as an interlayer insulating film in LCD manufacturing process.

Photosensitive Resin, Interlayer Insulating Film, Phenyl Malade Compound

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, and more particularly, excellent performance in transmittance, insulation, flatness, chemical resistance, etc., and in particular, minimizes outgassing that may occur in an interlayer insulating film through high heat resistance. The present invention relates to a photosensitive resin composition suitable for use as an interlayer insulating film in an LCD manufacturing process by ensuring reliability of a post process.

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 for obtaining a pattern-shaped interlayer insulating film and excellent flatness is used.

In addition, as the display quality of the liquid crystal display (LCD) is improved, the structure of the TFT type liquid crystal display device is also changed to increase the flatness by increasing the thickness of the interlayer insulating film. In addition, the interlayer insulating film applied to the LCD manufacturing process is required to have excellent high heat resistance.                         

Conventionally, the interlayer insulating film is composed of components such as PAC, a binder, a solvent, and the like, and an acrylic resin has been mainly used as the binder. However, in the case of the acrylic resin, it is difficult to exhibit the high heat resistance required for the interlayer insulating film, which causes a problem of reflectivity and adhesion of the insulating film, and causes a problem of damage to photo equipment due to outgassing. .

Therefore, there is a need for further research on a method of minimizing outgassing by improving high heat resistance of an interlayer insulating film applied to an LCD manufacturing process.

In order to solve the problems of the prior art as described above, the present invention is excellent in the performance of transmittance, insulation, flatness, chemical resistance, etc., in particular to minimize the outgassing (intergassing) that can occur in the interlayer insulating film through high heat resistance characteristics It is an object of the present invention to provide a photosensitive resin composition suitable for use as an interlayer insulating film of an LCD manufacturing process by securing process reliability, an LCD substrate including a cured body of the photosensitive resin, and a pattern forming method of an LCD substrate using the photosensitive resin composition. do.

Another object of the present invention is not only to improve the reflectivity and adhesion of the interlayer insulating film applied to the LCD manufacturing process having excellent heat resistance, but also to not damage the photo equipment due to outgassing, the photosensitive resin composition An object of the present invention is to provide an LCD substrate comprising a cured product of a resin and a pattern forming method of an LCD substrate using the photosensitive resin composition.

In order to achieve the above object, the present invention provides a photosensitive resin composition for forming an interlayer insulating film of a liquid crystal display device,

a) i) 5 to 60 parts by weight of a phenyl maleimide compound represented by Formula 1 below;

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

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

  100 parts by weight of an acrylic copolymer obtained by copolymerizing and having a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 30,000;

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

c) a photosensitive resin composition comprising a solvent such that the content of solids in the photosensitive resin composition is from 10 to 50% by weight;

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[Formula 1]

In the formula (1)

R is acetoxy (CH ₃ COO ⁻ ).

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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 is obtained by copolymerizing a) i) a phenyl maleimide compound represented by the formula (1), ii) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, and iii) an epoxy group-containing unsaturated compound. Acrylic copolymers; b) 1,2-quinonediazide compounds; And c) a solvent.

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 acryl-based copolymer of a) is a solvent containing iii) a phenyl maleimide compound represented by Formula 1, ii) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride, or a mixture thereof, and iii) an epoxy group-containing unsaturated compound as a monomer. And radical reaction in the presence of a polymerization initiator. In addition, the acrylic copolymer may further comprise iii) an olefinically unsaturated compound as a monomer.

The phenylmaleimide-based compound represented by Chemical Formula 1 of a) iii) used in the present invention functions to improve heat resistance and solubility in aqueous alkali solution.

4-carboxy phenyl maleimide may be used for the phenyl maleimide compound.

The phenylmaleimide compound is preferably included in an amount of 5 to 60 parts by weight, and more preferably 5 to 40 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 the heat resistance is lowered, and if it exceeds 60 parts by weight, there is a problem that the solubility in alkali water-soluble is lowered.

A) ii) 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, when the content 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 compounds of a) iii) used in the present invention are 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.                     

In the present invention, the acrylic copolymer may further include an olefinically unsaturated compound of a) iii) as a monomer. 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, dicyclopentanyloxyethyl meth Acrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acryl Latex, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltol Yen, p- methoxystyrene, may be used 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene, etc., it can be used by mixing the above compound alone or in combination.

In particular, the olefinically unsaturated compound is more preferable in terms of solubility in an 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. When it is in the said range, the storage stability fall of an acryl-type copolymer and the problem that an acryl-type copolymer is hard to melt | dissolve in the aqueous alkali solution which are a developer, etc. can be solved simultaneously.

Solvents used to polymerize such monomers into acrylic copolymers include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol mono. Methyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene Glycol Methyl Ether Acetate, Propylene Glycol Ethyl Acetate, Propylene Glycol Propyl Ether Acetate, Propylene Glycol Butyl Ether Acetate, Propylene Glycol Methyl Ethyl Propionate, Propylene Glycol Ethyl Propionate Hite, 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-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, lactic acid Ethyl, propyl lactate, butyl lactate, methyl 3-hydroxy propionate, ethyl 3-hydroxy propionate, propyl 3-hydroxy propionate, butyl 3-hydroxy propionate, methyl 2-hydroxybutyrate, methoxyacetic acid Methyl, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, ethoxy butyl acetate, methyl propoxy acetate, ethyl propoxy acetate Propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3 Ethers such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, and the like, and the above compounds may be used alone or in combination of two or more thereof. .

In addition, the polymerization initiator used to polymerize such monomers into an acrylic copolymer 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-azo Bisisobutylate etc. can be used.

The acrylic copolymer of a) prepared by radical reaction of such a monomer in the presence of a solvent and a polymerization initiator has a polystyrene reduced weight average molecular weight (Mw) of 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 inferior, or pattern shape and heat resistance are poor. 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'-hexahydroxy benzophenone, 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-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 alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl 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; 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, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3 Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl 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, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propionate Propionate, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Fluate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Butoxy Propionate 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, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3 Esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate. In particular, it is preferable to select and use 1 or more types from the group which consists of solubility, reactivity with each component, and easy to form a coating film, glycol ether, ethylene alkyl ether acetate, and diethylene glycol.

The solvent is preferably included so that the solid content of the entire photosensitive resin composition is 10 to 50% by weight, the composition having a solid content of the above range is preferably used after filtering with a Millipore filter of 0.1 ~ 0.2 ㎛. More preferably, it is included to be 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, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or 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.

The adhesive of e) serves to improve the adhesion with the substrate.

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, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3 , 4-epoxy cyclohexyl) ethyltrimethoxysilane and the like can be used.

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

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

Preferably, a representative example of the acrylic compound is represented by the following formula (2).

[Formula 2]

In the formula (2)

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.

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 Corporation), 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.

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, an example of a method of forming a pattern of an 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 n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. At this time, the developer is used by dissolving the alkaline compound in a concentration of 0.1 to 10 wt%, and a proper amount of a water-soluble organic solvent such as methanol, ethanol and the like 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. 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 has excellent performances such as transmittance, insulation, flatness, chemical resistance, and the like, and in particular, minimizes outgassing that may occur in an interlayer insulating layer through high heat resistance, thereby ensuring reliability of a post process. It is not only suitable for use as an interlayer insulating film in the LCD manufacturing process, but also improves the reflectivity and adhesion of the interlayer insulating film applied in the LCD manufacturing process, and does not damage photo equipment due to outgassing. There is this.

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)

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of methacrylic acid, and methacrylic acid in a flask equipped with a cooling tube and a stirrer 30 parts by weight of cydyl, 10 parts by weight of 4-hydroxy phenylmaleimide of Formula 1a, and 30 parts by weight of styrene were added thereto, 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.

Solid content concentration of the polymer solution containing the said acrylic copolymer was 45 weight%, and the weight average molecular weight of the polymer was 8,500. 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 polymer solution containing the acrylic copolymer prepared above and the prepared 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 25 parts by weight of bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester was mixed. Diethylene glycol dimethyl ether was added to dissolve so that the solid content concentration of the mixture was 35% by weight, and then filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition.

[Formula 1a]

In Formula 1a, R is OH.

Example 2

In preparing the acrylic copolymer of Example 1, using 20 parts by weight of 4-hydroxy phenylmaleimide of Formula 1a, using 20 parts by weight of styrene, the concentration of solids is 45% by weight, and the weight average molecular weight is 8,400 Except that the copolymer was prepared in the same manner as in Example 1 to prepare a photosensitive resin composition.

Example 3

In preparing the acrylic copolymer of Example 1, using methacrylic acid as 35 parts by weight, using 4-hydroxy phenylmaleimide of Formula 1a as 30 parts by weight, and using 5 parts by weight of styrene, the concentration of solids is 45 parts by weight. % And a weight average molecular weight was 8,800 except that an acrylic copolymer was prepared in the same manner as in Example 1 to prepare a photosensitive resin composition.

Example 4

In preparing the acrylic copolymer of Example 1, 40 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 40 parts by weight of 4-hydroxy phenylmaleimide of Formula 1a, and styrene A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 9,100 was prepared without using the same.

Example 5

In preparing the acrylic copolymer of Example 1, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of methacrylic acid, methacrylic acid 30 parts by weight of glycidyl, 10 parts by weight of 4-carboxy phenylmaleimide of Formula 1b, and 30 parts by weight of styrene to prepare an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 8,400 Except that was carried out in the same manner as in Example 1 to prepare a photosensitive resin composition.                     

[Chemical Formula 1b]

In Formula 1b, R is CH ₃ COO.

Example 6

In preparing the acrylic copolymer of Example 1, using 20 parts by weight of 4-carboxy phenylmaleimide of Formula 1b, using 20 parts by weight of styrene, the concentration of the solid content is 45% by weight, the weight average molecular weight of 8,600 acrylic air Except that the copolymer was prepared in the same manner as in Example 1 to prepare a photosensitive resin composition.

Example 7

In preparing the acrylic copolymer of Example 1, using methacrylic acid as 35 parts by weight, using 4-carboxy phenylmaleimide of Formula 1b as 30 parts by weight, and using styrene as 5 parts by weight of the solid content of 45% by weight The photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer having a weight average molecular weight of 9,100 was prepared.                     

Example 8

In preparing the acrylic copolymer of Example 1, 40 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 40 parts by weight of 4-carboxy phenylmaleimide of Formula 1b, and styrene A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 9,300 was prepared without using the same.

Comparative Example 1

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) without using 4-hydroxy phenylmaleimide of Formula 1a in preparing the acrylic copolymer of Example 1, propylene glycol monomethyl An acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 9,300 using 200 parts by weight of ether acetate, 40 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, and 40 parts by weight of methyl methacrylate. Except that was prepared in the same manner as in Example 1 to prepare a photosensitive resin composition.

After evaluating physical properties by the following method using the photosensitive resin composition prepared in Examples 1 to 8 and Comparative Example 1, the results are shown in Table 1 below.

A) Sensitivity—coated the photosensitive resin composition prepared in Examples 1 to 8 and Comparative Example 1 using a spin coater on a glass substrate, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a film. It was.                     

The film | membrane obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15 mW / cm <2> for 15 second using the predetermined pattern mask. Thereafter, the solution was developed at 25 DEG C for 2 minutes in an aqueous solution of 0.38 wt% 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.

B) Heat resistance-The widths of the top, bottom, left and right of the pattern film formed when the sensitivity of the a) was measured. At this time, the case where the change rate of each angle was 0 to 20% before the mid-baking was excellent, and the case of 20 to 40% was good and the case of more than 40% was indicated as bad.

C) Afterimage-In order to evaluate the afterimage, a panel was manufactured using the photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Example 1, and the panel was fixed to the frame for a predetermined time and then passed to the next frame. It was measured by observing whether the streaks or images of the previous frame remained on the screen.

The case where there was no afterimage was found to be very good, and the case where afterimages appeared and disappeared for several seconds was good.

division Sensitivity (mJ / ㎠) Heat resistance afterimage Example 1 100 Good good Example 2 115 Great good Example 3 130 Great good Example 4 150 Great Very good Example 5 110 Good good Example 6 125 Great good Example 7 145 Great good Example 8 155 Great Very good Comparative Example 1 90 Bad Bad

Through Table 1, Examples 1 to 8 using the acrylic copolymer prepared by using a phenyl maleimide compound according to the present invention has excellent sensitivity of 100 ~ 160 mJ / ㎠, in particular in the heat resistance is very good liquid crystal It was found that the afterimage formation had little effect on the interlayer insulation film. On the other hand, Comparative Example 1 was found to be difficult to apply as an interlayer insulating film because of poor sensitivity, heat resistance, and afterimage.

The photosensitive resin composition according to the present invention has excellent performances such as transmittance, insulation, flatness, chemical resistance, and the like, and in particular, minimizes outgassing that may occur in an interlayer insulating layer through high heat resistance, thereby ensuring reliability of a post process. It is not only suitable for use as an interlayer insulating film in the LCD manufacturing process, but also improves the reflectivity and adhesion of the interlayer insulating film applied in the LCD manufacturing process, and does not damage photo equipment due to outgassing. There is.

Claims (11)

In the photosensitive resin composition for forming an interlayer insulating film of a liquid crystal display device, a) i) 5 to 60 parts by weight of a phenyl maleimide compound represented by Formula 1 below;   Ii) 5 to 40 parts by weight of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof; And   Iii) 10 to 70 parts by weight of an epoxy group-containing unsaturated compound;   100 parts by weight of an acrylic copolymer obtained by copolymerizing and having a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 30,000; b) 5 to 100 parts by weight of 1,2-quinonediazide compound; And c) a photosensitive resin composition comprising a solvent such that the content of solids in the photosensitive resin composition is from 10 to 50% by weight; [Formula 1]

In the formula (1) R is acetoxy (CH ₃ COO ⁻ ). delete delete The method of claim 1, The unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof of a) ii) is composed of anhydrides of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof. Photosensitive resin composition, characterized in that at least one selected from the group. The method of claim 1, The epoxy group-containing unsaturated compound of a) iii) is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, glycidyl α-butyl acrylate , 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, Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl as monomers in the preparation of the acrylic copolymer Methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, Isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2- Hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, b 10 to 70 parts by weight of iii) an olefinically unsaturated compound selected from the group consisting of toluene, p-methoxy styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene The photosensitive resin composition characterized by the above-mentioned. delete 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, 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 30 parts by weight of acrylic compound, and g) interface with respect to 100 parts by weight of the acrylic copolymer of a). The photosensitive resin composition characterized by further including the additive selected from the group which consists of 0.0001-2 weight part of active agents. The LCD board containing the hardened | cured material of the photosensitive resin composition of any one of Claims 1, 4-6, 8, and 9. The pattern formation method of the LCD board | substrate using the photosensitive resin composition of any one of Claims 1, 4-6, 8, and 9.