KR100922843B1 - Photosensitive resin composition for dielectrics - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming an insulating film, wherein the photosensitive resin composition comprises (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) olefinic unsaturated Acrylic copolymer which makes a compound an unsaturated monomer; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) a solvent.

Organic insulating film, photosensitive resin, storage stability, p-toluene sulfonic acid / pyridine salt

Description

Photosensitive resin composition for insulating film formation {PHOTOSENSITIVE RESIN COMPOSITION FOR DIELECTRICS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming an insulating film, and more particularly, to a photosensitive resin composition for forming an insulating film having excellent performances such as transmittance, insulation, and high heat resistance, and particularly improving high sensitivity, high residual film rate, and storage stability. will be.

The existing interlayer insulating film is composed of a binder, a photoactive compound (PAC), and a solvent, and an acrylic resin has been used as a binder. However, in the case of the organic film composition as described above, there is a limit to further high sensitivity and high residual film rate characteristics. In addition, the use of epoxy acrylate-based resins also brought about problems in terms of storage stability.

The present invention is excellent in the performance of transmittance, insulation, high heat resistance and the like, and particularly to provide a photosensitive resin composition for forming an insulating film with improved high sensitivity, high residual film rate, and storage stability.

However, the technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, according to one embodiment of the present invention, (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixture thereof, ii) epoxy group-containing unsaturated compound, and iii) unsaturated olefinically unsaturated compound Acrylic copolymer made into a monomer; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) there is provided a photosensitive resin composition for forming an insulating film comprising a solvent.

According to another embodiment of the present invention, a liquid crystal display device including an insulating film made of the photosensitive resin composition for forming an insulating film is provided.

Other details of the embodiments of the present invention are included in the following detailed description.

The photosensitive resin composition for forming an insulating film according to the present invention has excellent performances such as transmittance, insulation, and high heat resistance, and particularly shows improved high sensitivity, high residual film rate, and storage stability.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is only defined by the scope of the claims to be described later.

In the photosensitive resin composition for forming an insulating film according to an embodiment of the present invention, (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound and iii) an olefinically unsaturated compound Acrylic copolymer made into; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) a solvent.

Hereinafter, each component of the photosensitive resin composition for forming an insulating film according to an embodiment of the present invention will be described in detail.

(A) Acrylic Copolymer

The acrylic copolymer is an acrylic copolymer comprising (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) an olefinic unsaturated compound as an unsaturated monomer.

Iii) said unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof

(Iii) unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid as the unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these acids; Or combinations thereof. Preferably using acrylic acid, methacrylic acid, or a combination thereof has the advantage of excellent copolymerization reactivity and solubility in aqueous alkali solution.

The acrylic copolymer preferably contains 10 to 60% by weight, more preferably 20 to 45% by weight, of the structural unit derived from the aforementioned i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof. . If it is less than 10% by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, and if not more than 60% by weight, there is a problem that the solubility in the aqueous alkali solution is too large, which is not preferable.

Ii) epoxy group-containing unsaturated compounds

As said ii) epoxy group containing unsaturated compound, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butyl acrylate, Glycidyl acrylates, such as acrylic acid (beta) -methylglycidyl, methacrylic acid (beta) -methylglycidyl, acrylic acid (beta) -ethylglycidyl, and methacrylic acid (beta) -ethylglycidyl; Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylic acid-6,7-epoxy Acrylic acid epoxy alkyls such as heptyl; vinyl benzyl glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; Or combinations thereof. Preferably methacrylic acid glycidyl, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, It is preferable to use p-vinylbenzyl glycidyl ether or a combination thereof in order to improve the copolymerization reactivity and the heat resistance of the obtained pattern.

The acrylic copolymer of the present invention preferably contains 5 to 40 wt% of the structural unit derived from the ii) epoxy group-containing unsaturated compound, and more preferably 10 to 25 wt%. If it is less than 5% by weight, there is a problem that the heat resistance of the pattern is considerably lowered, and it is not preferable. If it exceeds 40% by weight, there is a problem that the storage stability of the copolymer is lowered, which is not preferable.

Iii) olefinically unsaturated compounds

(Iii) 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 acryl Rate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate Latex, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl arc Latex, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, or these Can be used. Preferably, styrene, dicyclopentanyl methacrylate, p-methoxy styrene, or a combination thereof is used to have excellent copolymerization reactivity and solubility in aqueous alkali solution.

The acrylic copolymer of the present invention preferably contains 20 to 85% by weight, more preferably 35 to 50% by weight, of the structural unit derived from the aforementioned iv) olefinically unsaturated compound. 20 wt% If less than this, there is a problem that the preservation of the acrylic copolymer is lowered, which is not preferable. If it exceeds 85% by weight, the acrylic copolymer is difficult to dissolve in an aqueous alkali solution, which is not preferable.

The acrylic copolymer may be prepared by radical polymerization of unsaturated monomers of (i) to (i) in the presence of a solvent and a polymerization initiator.

Examples of the solvent used for the preparation of the copolymer include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Methyl vertical solvent acetate, ethyl vertical solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl 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 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, acetate Pill, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy ethyl 2-methylpropionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, Ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionic acid butyl, 2-hydroxy 3-methyl butanoate, meth Methyl methoxy acetate, methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl methoxy acetate, ethoxy propyl 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-methoxypropionic acid, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Propyl, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , 3-ethoxypropionate propyl, 3-ethoxypropionate butyl, 3-propoxypropionate methyl, 3-propoxypropionate propyl, 3-propoxypropionic acid propyl, 3-butyl propoxypropionate, 3-butoxypropionate, And ethers such as 3-butoxypropionate ethyl, 3-butoxypropionic acid propyl, and 3-butoxypropionate butyl, and combinations thereof.

In addition, a radical polymerization initiator may be used as the polymerization initiator. 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2,4 as the radical polymerization initiator -Dimethylvaleronitrile), 1,1'- azobis (cyclohexane-1-carbonitrile) dimethyl 2,2'- azobisisobutylate, etc. can be used.

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion of the said A) acrylic copolymer is 3,000-25,000, and it is more preferable that it is 5,000-15,000. If it is less than 3,000, there is a problem in that developability and residual film rate are lowered, or pattern formation, heat resistance, adhesive strength, etc. are deteriorated. It is not desirable.

(B) quinonediazide compound

The quinonediazide compound is a photosensitive compound, and may be prepared by reacting a naphthoquinone diazide sulfonic acid halogen compound and a phenolic compound under a weak base.

In the synthesis of the quinonediazide compound, the degree of esterification is preferably 45 to 90%. If the degree of esterification is less than 45%, the residual film ratio may be drastically lowered and sensitivity abnormality may occur. If the esterification degree is higher than 90%, the storage stability may decrease, which is not preferable.

The quinonediazide compound includes, for example, 1,2-quinonediazide compound, 1,4-quinonediazide compound, and the like, but is not necessarily limited thereto.

Preferably, a 1, 2- quinone diazide compound is used, and a 1, 2- quinone diazide 4- sulfonic acid ester, a 1, 2- quinone diazide 5- sulfonic acid ester among the 1, 2- quinone diazide compounds, It is more preferable to use those selected from the group consisting of 1,2-quinonediazide 6-sulfonic acid ester, and mixtures thereof.

The quinonediazide compound is preferably included in an amount of 5 to 80 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 10 to 40 parts by weight, based on 100 parts by weight of the acrylic copolymer of (A). May be included. 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 80 parts by weight, a large amount of unreacted quinonediazide compound remains when light is irradiated for a short time. There is a problem that development is difficult because the solubility in an aqueous alkali solution is too low.

(C) p-toluene sulfonic acid / pyridine salt

The p-toluene sulfonic acid / pyridine salts (PPTS) is to replace the conventional epoxy group-containing unsaturated compound, while maintaining the heat resistance, it serves to prevent the reduction of the reduction and residual film rate .

The p-toluene sulfonic acid / pyridine salt has a role of promoting acid solubility of the acrylic resin by generating an acid itself upon exposure, and having a low molecular weight effect to enhance solubility with a stone well effect. It shows an increasing sensitivity.

The p-toluene sulfonic acid / pyridine salt can maintain the residual film rate despite high sensitivity. Therefore, it is possible to solve the problem of the residual film rate change according to the ratio between the polymer and the low molecule (a phenomenon in which the sensitivity becomes slow when the residual film rate is improved).

The p-toluene sulfonic acid / pyridine salt may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer of (A). If it is less than 0.1 parts by weight, there is a problem that it is impossible to maintain high sensitivity and residual film rate, and even when used in excess of 30 parts by weight, the residual film rate and sensitivity do not increase any more.

(D) solvent

As said solvent, 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 propyl glycol glycol 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; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, 2-hydroxy ethyl 2-methylpropionate, methyl hydroxy acetate, ethyl hydroxyacetate, hydroxy Butyl oxyacetate, 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, butyl methoxy acetate, methyl 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 Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate 2-ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-part Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionic acid, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Esters such as propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and mixtures thereof Can be used. Among these, it is more preferable to select from the group which consists of solubility, reactivity with each component, and the easily formed coating film, glycol ether, ethylene glycol alkyl ether acetates, diethylene glycol, and mixtures thereof.

The solvent may be included as the remainder in the photosensitive resin composition, preferably may be included so that the solids content in the photosensitive resin composition is 10 to 60% by weight, more preferably 10 to 50% by weight, even more preferably 15 To 30% by weight. When the solid content in the photosensitive resin composition is less than 10% by weight, there is a concern that the coating flatness may decrease and the thickness of the coating may become thin.

(E) other additives

The photosensitive resin composition for forming an insulating film may further include an epoxy resin, an adhesive, an acrylic compound, or a surfactant as needed, in addition to the components (A) to (D).

The epoxy resin may be added to improve the heat resistance and sensitivity of the pattern obtained from the photosensitive resin composition for forming an insulating film. Examples of the epoxy resins include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and heterocyclic epoxy resins. And copolymers or polymers of acrylic copolymers of (A) with other glycidyl methacrylates, or combinations thereof.

It is preferable that the said epoxy resin is used in 0.1-35 weight part with respect to 100 weight part of acrylic copolymers of (A). When it exceeds 35 parts by weight, there is a problem in that the compatibility with alkali-soluble resin is poor, and sufficient coating performance cannot be obtained.

The adhesive may be added to improve the adhesion with the substrate. Examples of the adhesive include silane coupling agents having reactive substituents such as carboxyl groups, methacryl groups, isocyanate groups, and epoxy groups, and specific examples include γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and vinyl. Trimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-3,4-epoxy cyclohexyl ethyltrimethoxysilane and the like. The adhesive is preferably used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.

The acrylic compound may be added to improve the transmittance, heat resistance, or sensitivity of the pattern obtained from the photosensitive resin composition for forming an insulating film. The acrylic compound includes a compound represented by the following Chemical Formula 1, but is not limited thereto.

[Formula 1]

In Formula 1, R is selected from hydrogen, an alkyl group of C ₁ to C ₅ , an alkoxy group, and an alkanoyl group, 1 <a <6, and a + b = 6.

The acrylic compound may be used in an amount of 0.1 to 35 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the acrylic copolymer. In the said range, since a sensitivity and heat resistant UV transmittance can be improved, it is preferable.

The surfactant may be added to improve the coatability or developability of the photosensitive resin composition for forming an insulating film. Examples of the surfactants include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (India Nippon Inks Co., Ltd.), FC430, FC431 (Sumitomo Trim Co., Ltd.), KP341 (Shinwol Chemical Co., Ltd.), and the like. . It is preferable that the said surfactant is used 0.0001-2 weight part with respect to 100 weight part of acrylic copolymers of (A). In the above range, there is an advantage of the coating property of the photosensitive resin composition and the staining property at the time of the process progress, and thus it is preferable.

It is preferable to use the photosensitive resin composition for insulating film formation which has the above-mentioned structure after filtering by the Millipore filter of 0.1-0.2 micrometer.

According to another embodiment of the present invention, a liquid crystal display device including an insulating film made of the photosensitive resin composition for forming an insulating film is provided.

According to another embodiment of the present invention, there is provided a method of manufacturing a liquid crystal display device comprising the step of applying the photosensitive resin composition for forming an insulating film to a substrate, and then forming an insulating film pattern by exposing.

The insulating film of the liquid crystal display device may be manufactured by the following method.

After applying the prepared photosensitive resin composition to the surface of the substrate by a spray method, a roll coater method, a rotary coating method, etc., the solvent is removed by pre-baking to form a coating film. It is preferable to perform the said prebaking for 1 to 5 minutes at 70-120 degreeC. Thereafter, visible light, ultraviolet rays, far ultraviolet rays, electron beams, far-ultraviolet rays, electron beams, X-rays, and the like are irradiated to the formed coating film according to a pattern prepared in advance, and developed with a developer to remove an unnecessary portion to form a predetermined pattern. At this time, an aqueous alkali solution may be used as the developing solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, 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; Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; And mixtures thereof. It is preferable that the density | concentration of the alkaline compound of the said developing solution is 0.1 to 10%. In addition, an appropriate amount of a water-soluble organic solvent or a surfactant such as methanol ethanol may be added together with the solvent. In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 140 seconds to remove unnecessary parts and dried to form a pattern, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is The final pattern may be obtained by heating at 110 to 250 ° C. for 30 to 120 minutes by a heating apparatus.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Synthesis Example 1 Preparation of Acrylic Copolymer

In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 25 g of styrene, meta 10 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including an acrylic copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 10,500.

Synthesis Example 2 Preparation of Acrylic Copolymer

In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 15 g of styrene, meta 30 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 9,500.

Synthesis Example 3 Preparation of Acrylic Copolymer

In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 30 g of styrene, meta 5 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 9,800.

Synthesis Example 4 Preparation of Acrylic Copolymer

In a flask equipped with a cooling tube and a stirrer, 10 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 15 g of methacrylic acid, 30 g of styrene, meta 10 g of glycidyl acrylate and 45 g of isobornyl acrylate were added thereto, replaced with nitrogen, and slowly stirred. Thereafter, the reaction solution was raised to 60 ° C. and maintained at this temperature for 5 hours to obtain a polymer including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%, and the polystyrene conversion weight average molecular weight measured by gel permeation chromatography (GPC) with respect to the polymer was 10,300.

Synthesis Example 5 Preparation of 1,2-quinonediazide Compound

1 mol of 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid (chloride ) 2 mol condensation reaction to 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol 1,2-naphthoquinonediazide-5 -Sulfonic acid ester was prepared.

<Example 1>: Preparation of the photosensitive resin composition for insulating film formation

100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 1, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 5 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl was added so that the concentration of solid content was 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

<Example 2>: Preparation of the photosensitive resin composition for insulating film formation

100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 2, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester, and 2.5 parts by weight of p-toluene sulfonic acid / pyridine salt, and diethylene glycol dimethyl so that the concentration of solid content is 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

<Example 3>: Preparation of the photosensitive resin composition for insulating film formation

100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 3, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 10 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl ether was added so that the concentration of solid content was 30 parts by weight. After melt | dissolving in, it filtered by the 0.2 micrometer millipore filter and prepared the photosensitive resin composition for insulating film formation.

<Example 4>: Preparation of the photosensitive resin composition for insulating film formation

100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 4, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 5 parts by weight of p-toluene sulfonic acid / pyridine salt were mixed and diethylene glycol dimethyl was added so that the concentration of solid content was 30% by weight. After dissolving in ether, it was filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition for forming an insulating film.

Comparative Example 1 Preparation of Photosensitive Resin Composition for Insulating Film Formation

100 parts by weight of the acrylic copolymer mixture solution prepared in Synthesis Example 1, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) prepared in Synthesis Example 5) 20 parts by weight of ethylidene) bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester was mixed, dissolved in diethylene glycol dimethyl ether so that the concentration of solid content was 30% by weight, and filtered through a 0.2 μm Millipore filter. Thus, the photosensitive resin composition for insulating film formation was produced.

Measurement of sensitivity, residual film rate, resolution, heat resistance, and storage stability

With respect to the photosensitive resin composition for forming an insulating film prepared in Examples 1 to 4 and Comparative Example 1, a pattern film was prepared by the following method in order to measure sensitivity, residual film ratio, resolution, heat resistance, and storage stability.

Production of pattern film

After the photosensitive resin composition was applied on a glass substrate using a spin coater, a film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. The film obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15.0 mW / cm <^3> for 15 second using the predetermined | prescribed pattern mask. Thereafter, the solution was developed at 25 ° C. for 130 seconds with 0.38% aqueous tetramethyl ammonium hydroxide solution, and then washed with ultrapure water for 2 minutes. Thereafter, the pattern formed above was irradiated with ultraviolet light having an intensity of 15.0 mW / cm ³ at 365 nm for 40 seconds, and then heated to 220 ° C. for 60 minutes in an oven to obtain a pattern film.

1) Sensitivity: The sensitivity was measured at the minimum exposure amount at which the pattern is formed.

2) Residual film rate: After the photosensitive resin composition is coated on a glass substrate by using a spin coater, the solvent is removed by pre-baking the thickness of the film and post-bake. The thickness of the formed film was measured, and the residual film ratio (%) was calculated by calculating the thickness ratio of the film after solvent removal to the thickness of the film after prebaking.

3) Resolution: Based on the minimum size formed for the patterned film.

4) Heat resistance: With respect to the pattern film, the widths of the upper, lower, left and right sides of the pattern were measured, and the angle was 5 ° to 10 °, △, 10 ° or more, △, and 0 to 5 °. Marked as.

5) Storage stability: After leaving the pattern film in a clean room maintained at 23 ° C. and 40% humidity for 3 weeks, the change of sensitivity (mJ / cm ² ) and residual film rate (%) was checked. At this time, when the change rate of 3 weeks is less than 10%, (circle), when 10 to 20%, and when more than 20% is indicated by x.

TABLE 1

division Sensitivity (mJ / cm ² ) Residual Rate (%) resolution Heat resistance Storage stability Example 1 185 94 3㎛ ○ ○ Example 2 215 93 3㎛ ○ ○ Example 3 150 92 3㎛ ○ ○ Example 4 170 91 3㎛ ○ ○ Comparative Example 1 250 90 4㎛ △ ×

Looking at the Table 1, the pattern prepared from the photosensitive resin composition for forming an insulating film of the present invention is excellent in storage stability, heat resistance, and resolution compared to Comparative Example 1, it can be confirmed that particularly excellent residual film ratio compared to the sensitivity Could.

Claims (11)

(A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof, ii) an epoxy copolymer containing an epoxy group-containing unsaturated compound and iii) an olefinically unsaturated compound as an unsaturated monomer; (B) quinonediazide compounds; (C) p-toluene sulfonic acid / pyridine salt; And (D) solvent Photosensitive resin composition for insulating film formation containing a. The method of claim 1, The composition is based on 100 parts by weight of the (A) acrylic copolymer, (B) 5 to 80 parts by weight of a quinonediazide compound, (C) 0.1 to 30 parts by weight of p-toluene sulfonic acid / pyridine salt The photosensitive resin composition for insulating film formation. The method of claim 2, The composition is a photosensitive resin composition for forming an insulating film, the solid content is 10 to 60% by weight. The method of claim 1, The (A) acrylic copolymer is Iii) from 10 to 60% by weight of structural units derived from unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof, ii) from 5 to 40% by weight of structural units derived from epoxy-containing unsaturated compounds, and iii) from olefinically unsaturated compounds. The photosensitive resin composition for insulating film formation which is a copolymer containing 20 to 85 weight% of derived structural units. The method of claim 1, The unsaturated carboxylic acid and unsaturated carboxylic anhydride are formed of an insulating film that is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these acids, and combinations thereof. Photosensitive resin composition for. The method of claim 1, The epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, glycidyl acrylate-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-ethyl acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl A photosensitive resin composition for forming an insulating film, which is selected from the group consisting of benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and combinations thereof. The method of claim 1, The olefinically unsaturated compound is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate Latex, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-a Monomethyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, phenyl methacryl Latex, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate Rate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and these The photosensitive resin composition for insulating film formation is selected from the group consisting of. The method of claim 1, Said (A) acrylic copolymer has a polystyrene reduced weight average molecular weight (Mw) of 3,000-25,000, The photosensitive resin composition for insulating film formation. The method of claim 1, The (B) quinone diazide compound is 1,2-quinone diazide 4-sulfonic acid ester, 1,2-quinone diazide 5-sulfonic acid ester, 1,2-quinone diazide 6-sulfonic acid ester, and combinations thereof The photosensitive resin composition for insulating film formation chosen from the group which consists of. The method of claim 1, The photosensitive resin composition for forming an insulating film further comprises an additive selected from the group consisting of an epoxy resin, an adhesive, an acrylic compound, a surfactant, and a combination thereof. A liquid crystal display device comprising an insulating film made of the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 10.