KR100922844B1 - Photosensitive resin composition for dielectrics - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming an insulating film, wherein the composition comprises (A) i) dioxolane-based compounds, ii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof, and iii) unsaturated monomers containing epoxy groups. Acrylic copolymer made into; (B) quinonediazide compounds; And (C) a solvent.

The photosensitive resin composition according to the present invention has excellent performance in transmittance, insulation, flatness, chemical resistance, high heat resistance, and the like, and particularly, in the manufacturing process of the liquid crystal display device due to its high sensitivity, residual film rate, UV transmittance, developability and storage stability. Suitable for use as an insulating film.

Insulating film, photosensitive resin, storage stability, sensitivity, heat resistance

Description

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

The present invention relates to a photosensitive resin composition for forming an insulating film, and more particularly, excellent in transmittance, insulation, flatness, chemical resistance, and the like, and particularly, a photosensitive resin having high sensitivity, residual film rate, UV transmittance, developability, and storage stability. It relates to a composition.

In TFT-LCDs and integrated circuit devices, interlayer dielectrics are used to insulate between wirings arranged between layers.

In order to manufacture the interlayer insulating film, a specific photosensitive material is used, and there is a continuous need for a material having few processes and excellent sensitivity, residual film ratio, transmittance and storage stability. Conventional interlayer insulating film is composed of a component such as a binder, PAC, additives, solvents, the binder is an olefin unsaturated compound to control the heat resistance. However, existing olefinically unsaturated compounds have not been able to improve the liquid crystal display (LCD) manufacturing process due to problems such as sensitivity and residual film ratio of the binder. Therefore, there is a demand for developing a binder that can be easily synthesized and easily supplied, while having characteristics such as sensitivity and residual film ratio higher than that of the existing organic film.

The present invention is to solve the problems of the prior art as described above, by using a novel acrylic copolymer is excellent in performance, such as transmittance, insulation, flatness, chemical resistance, high heat resistance, in particular high sensitivity, residual film rate, The present invention provides a photosensitive resin composition for forming an insulating film that is excellent in UV transmittance, developability, and storage stability and is easy to form an interlayer insulating film in a liquid crystal display (LCD) manufacturing process.

The present invention also provides a liquid crystal display device comprising an interlayer insulating film prepared using the photosensitive resin composition.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, 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) dioxolane-based compound, ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixture thereof, and iii) epoxy group-containing unsaturated compound Acrylic copolymers having an unsaturated monomer; (B) quinonediazide compounds; And (C) It provides the photosensitive resin composition for insulating film formation containing a solvent.

According to another embodiment of the present invention provides a liquid crystal display device including an insulating film manufactured using the photosensitive resin composition.

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

The photosensitive resin composition according to the present invention has excellent performance in transmittance, insulation, flatness, chemical resistance, high heat resistance, outgassing, and the like, and in particular, it has high sensitivity, residual film ratio, UV transmittance, developability, and storage stability. In the manufacturing process of the display device, not only can the reliability be obtained, but also the effect of shortening the process progress time can be obtained.

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

The photosensitive resin composition for forming an insulating film according to an embodiment of the present invention comprises (A) i) a dioxolane-based compound, ii) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof, and iii) an epoxy group-containing unsaturated compound. Acrylic copolymer made into; (B) quinonediazide compounds; And (C) a solvent.

More preferably, the composition contains 5 to 50 parts by weight of (B) quinonediazide compound based on 100 parts by weight of (A) acrylic copolymer.

Hereinafter, each component included in the photosensitive resin composition according to the exemplary embodiment of the present invention will be described in detail.

(A) Acrylic Copolymer

The acrylic copolymer acts to easily form a predetermined pattern that does not occur scum during development, i) dioxolane compound, ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof, And iii) a copolymer comprising an epoxy group-containing unsaturated compound as an unsaturated monomer.

Iii) dioxolane compounds

The dioxolane-based compound serves to improve the sensitivity, residual film ratio, heat resistance, and storage stability of the copolymer of the insulating film, and preferably has a structure of Formula 1 below.

[Formula 1]

Where

R ₁ and R ₂ are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aliphatic ring compound group or are linked to each other to form a ring,

R ₃ is a hydrogen atom or a methyl group,

R and R 'are hydrogen or a substituted or unsubstituted alkyl group,

n is 1-5.

Specifically 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate, 2-isobutyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate, 1, 4-dioxaspiro- [4,5] -de-2yl-methyl acrylate, 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl methacrylate, 2-isobutyl-2 -Methyl-1,3-dioxolan-4yl-methyl methacrylate, 1,4-dioxaspiro- [4,5] -dec-2yl-methacrylate, 2,2-dimethyl-1,3 Dioxolane-4yl-methacrylate and mixtures thereof can be used.

The acrylic copolymer of the present invention preferably comprises 10 to 80% by weight of the structural unit derived from i) the dioxolane-based compound in the copolymer, and more preferably 30 to 60% by weight. If the content is less than 10% by weight, the heat resistance may be lowered. If the content is more than 80% by weight, the solubility to alkali water solubility and the storage stability of the copolymer may be lowered.

 Ii) unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof

Examples of the unsaturated carboxylic acid and unsaturated carboxylic anhydride include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of unsaturated dicarboxylic acids; may be selected from the group consisting of. Among these, it is more preferable to use those selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof having better copolymerization reactivity and solubility in aqueous alkali solution.

In the acrylic copolymer of the present invention, the structural unit derived from the above ii) unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably contained in the copolymer at 5 to 40% by weight, and is used at 10 to 30% by weight. It is more preferable. If it is less than 5% by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, and if not more than 40% by weight, there is a problem that the solubility in the aqueous alkali solution is too large, which is not preferable.

Viii) epoxy group-containing unsaturated compounds

(Iv) The epoxy group-containing unsaturated compound is glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid acrylic acid glycidyls such as-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethyl glycidyl, and 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-ethyl acrylic acid-6,7- Acrylic acid epoxy alkyls such as epoxyheptyl; vinyl benzyl glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; And mixtures thereof. Of these, methacrylic acid glycidyl, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p It is preferable to use those selected from the group consisting of -vinylbenzyl glycidyl ether, and mixtures thereof because it can improve the copolymerization reactivity and the heat resistance of the obtained pattern.

The acrylic copolymer of the present invention preferably comprises 5 to 50% by weight of the structural unit derived from the above-mentioned i) epoxy group-containing unsaturated compound in the copolymer, and more preferably 10 to 40% by weight. If the content is less than 5% by weight, the heat resistance of the resulting pattern may be lowered, which is not preferable. If the content is higher than 50% by weight, the storage stability of the copolymer may be lowered, which is not preferable.

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

At this time, as a solvent used for the production of the copolymer, a solvent used for the production of the copolymer, methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl Longitudinal solution acetate, ethyl vertical solution 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 Recall 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-hydroxy ethyl propionate, 2-hydroxy methyl methyl propionate, 2-hydroxy ethyl 2-methyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate , Methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy propionate methyl, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionate butyl, 2-hydroxy 3-methylbutanoic acid Methyl, methyl methoxy acetate, ethyl methoxy acetate, methoxy methoxy acetate, methoxy methoxy acetate, methyl ethoxy acetate, ethyl methoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, propoxy Methyl, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxypropionic acid propyl, 2-ethoxypropionic acid butyl, 2-butoxypropionic acid methyl, Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3 Methyl ethoxypropionate, ethyl 3-ethoxypropionate propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Ethers such as acid propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate, or a combination thereof. have.

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

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion of said A) acrylic copolymer is 3,000-30,000, and it is more preferable that it is 5,000-15,000. If the weight average molecular weight is less than 3,000, developability and residual film ratio may decrease, or pattern shape, heat resistance, adhesive strength, etc. may be deteriorated, and if the weight average molecular weight exceeds 30,000, sensitivity decreases, pattern shape defect, decrease in transmittance, etc. It is not preferable because there is a problem.

(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 there may be a sensitivity abnormality.

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-quinonediazide compound is used, and among the 1,2-quinonediazide compounds, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, More preferably, those selected from the group consisting of 1,2-quinonediazide 6-sulfonic acid esters, and mixtures thereof are used.

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 is small, and pattern formation is difficult. If the content exceeds 80 parts by weight, unreacted 1,2-quinonediazide is applied when light is irradiated for a short time. There is a problem that development is difficult because a large amount of the compound remains and the solubility in the aqueous alkali solution is too low.

(C) solvent

The solvent serves to form a uniform pattern profile by preventing flatness of the insulating film and coating stains, and alcohols 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 ethyl, 2-hydroxy 2-methylpropionate, 2-hydroxy 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-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropy Esters such as acid propyl, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and mixtures thereof You can use what is selected. Among them, it is more preferable to use those selected from the group consisting of solubility, reactivity with each component, and easy to form a coating film, glycol ethers, ethylene alkyl ether acetates, diethylene glycols, and mixtures thereof.

The solvent may be included as the remainder in the photosensitive resin composition, preferably may be included in an amount such that the solid content in the photosensitive resin composition is 10 to 60% by weight, more preferably 10 to 50% by weight, even more preferred Preferably from 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.

(D) other additives

In addition to the components (A) to (C), the photosensitive resin composition may further include an epoxy resin, an adhesive, an acrylic compound, or a surfactant as necessary.

The epoxy resin may be added to improve the heat resistance and sensitivity of the pattern obtained from the photosensitive resin composition. 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 (A) copolymers or polymers of acrylic copolymers with other glycidyl methacrylates, or mixtures thereof.

The epoxy resin is preferably used in 0.1 to 35 parts by weight based on 100 parts by weight of the (A) acrylic copolymer. When it exceeds 35 parts by weight, there is a problem in that compatibility with alkali-soluble resin is poor and sufficient coating performance cannot be obtained, which is not preferable.

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, (gamma) -isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (beta) -3, 4- epoxy cyclohexyl ethyl trimethoxysilane, etc. can be used. 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, sensitivity and the like of the pattern obtained from the photosensitive resin composition. The acrylic compound includes a compound represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

(In Formula 2, R is selected from the group consisting of hydrogen, an alkyl group of C1 to C5, 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 40 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the acrylic copolymer. Within this range, the sensitivity and heat resistance UV transmittance can be improved, which is preferable.

The surfactant may be added to improve the applicability and developability of the photosensitive resin composition. As the surfactant, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173 (Tokyo Ink Corp.), FC430, FC431 (Sumitomo Trim Co., Ltd.), KP341 (Shinwol Chemical Co., Ltd.) and the like can be used. Can be. The surfactant is preferably used in 0.0001 to 2 parts by weight based on 100 parts by weight of the (A) acrylic copolymer. The said range is preferable because there exists an advantage about the coating property of the photosensitive resin composition, and the stain characteristic at the time of a process progress.

It is preferable to use, after filtering the photosensitive resin composition which has the above-mentioned structure with the Millipore filter of 0.1-0.2 micrometer.

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, LCD manufacturing by minimizing a process time delay problem that may occur in an insulating film through characteristics of a residual film ratio relative to sensitivity. It is suitable for use as the insulating film of the process.

Accordingly, according to another embodiment of the present invention provides a liquid crystal display device including an insulating film manufactured using the photosensitive resin composition.

The insulating film may be manufactured by the following method.

The photosensitive resin composition prepared above is applied to the substrate surface by a spray method, a roll coater method, a rotary coating method, or the like, and the solvent is removed by prebaking to form a coating film. At this time, the prebaking is preferably performed for 1 to 10 minutes at a temperature of 70 to 110 ℃. Thereafter, visible light, ultraviolet light, far ultraviolet rays, electron beams, X-rays, and the like are irradiated onto the formed coating film according to a pre-prepared pattern, and developed with a developing solution to form a predetermined pattern by removing unnecessary portions. In this case, an aqueous alkali solution may be used as the developer, and specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like; 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 dimethyl ethanol amine, methyl diethanol amine and triethanol amine; Or 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 in the said developing solution is 0.1 to 10 weight%. In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added to the aqueous alkali solution. 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, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is heated in an oven or the like. By heat treatment at a temperature of 150 to 250 ℃ for 30 to 90 minutes to obtain a final pattern.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Production Example  1: Preparation of Acrylic Copolymer

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 2-ethyl-2 of the formula 45 parts by weight of -methyl-1,3-dioxolane-4yl-methyl acrylate, 15 parts by weight of methacrylic acid, and 20 parts by weight of glycidyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. After raising the reaction solution to 60 ° C. was maintained at this temperature for 5 hours to prepare a polymer solution comprising an acrylic copolymer.

 In order to remove the unreacted monomer in the polymer solution including the acrylic copolymer, 100 parts by weight of the polymer solution is precipitated in 1,000 parts by weight of an ether solvent, and a filtering process using a mesh is performed. The poor solvent in which the unreacted substance was dissolved was removed. Thereafter, vacuum drying at 30 ° C. or lower completely removes the solvent containing the unreacted monomer remaining after the filtering process, thereby preparing an acrylic copolymer having a weight average molecular weight of 8,000. At this time, the weight average molecular weight is the polystyrene reduced average molecular weight measured using gel permeation chromatography (GPC).

[Formula 3]

Production Example  2: 1,2- Quinonediazide  Preparation of the compound

1 mol 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 mol [4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide-5 Sulfonic acid esters].

Example  1: Preparation of Photosensitive Resin Composition

[4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] prepared in Preparation Example 2 with respect to 100 parts by weight of the acrylic copolymer obtained in Preparation Example 1 above. Phenyl] ethylidene] bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester] 20 parts by weight, and dissolved in diethylene glycol dimethyl ether added so that the solid content concentration in the photosensitive resin composition is 28% by weight. A photosensitive resin composition was prepared by filtration with a 0.2 μm Millipore filter.

Example  2: Preparation of Photosensitive Resin Composition

Substituted 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of the general formula (3) as a monomer during the polymerization of the acrylic copolymer in Preparation Example 1 2-isobutyl- A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using 2-methyl-1,3-dioxolane-4yl-methyl acrylate was used.

[Formula 4]

Example  3: Preparation of Photosensitive Resin Composition

1,4-di of formula (5) instead of 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of formula (3) as a monomer in the acrylic copolymer polymerization in Preparation Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using oxaspiro- [4,5] -dec-2yl-methyl acrylate was used.

[Formula 5]

Example  4: Preparation of Photosensitive Resin Composition

2-ethyl-2 of Chemical Formula 6, replacing 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of Chemical Formula 3 as a monomer during the polymerization of the acrylic copolymer in Preparation Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using -methyl-1,3-dioxolane-4yl-methyl methacrylate was used.

[Formula 6]

Example  5: Preparation of Photosensitive Resin Composition

Substituted 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of Chemical Formula 3 as a monomer during polymerization of the acrylic copolymer in Preparation Example 1, 2-isobutyl- A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using 2-methyl-1,3-dioxolane-4yl-methyl methacrylate was used.

[Formula 7]

Example  6: Preparation of Photosensitive Resin Composition

1,4-di of formula 8 in place of 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of formula 3 as a monomer in the polymerization of the acrylic copolymer in Preparation Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using oxaspiro [[4,5] -dec-2yl-methacrylate was used.

[Formula 8]

Example  7: Preparation of Photosensitive Resin Composition

2,2-dimethyl of formula (9) instead of 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of formula (3) as a monomer during polymerization of the acrylic copolymer in Preparation Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylic copolymer prepared using -1,3-dioxolane-4yl-methacrylate was used.

[Formula 9]

Comparative example  1: Preparation of Photosensitive Resin Composition

Dicycloropentenyl methacrylate is used as a monomer in the polymerization of the acrylic copolymer in Preparation Example 1 in place of 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate of Formula 3 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the acrylic copolymer prepared in the above was used.

Comparative example  2: Preparation of Photosensitive Resin Composition

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 25 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and dicyclo Photosensitive resin composition was carried out in the same manner as in Example 1, except that an acrylic copolymer having a concentration of 40 wt% and a weight average molecular weight of 9,300 prepared using 25 parts by weight of pentenyl methacrylate was used. Was prepared.

[Property evaluation]

In order to evaluate the sensitivity, residual film ratio, heat resistance and storage stability of the photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 2, a pattern film was prepared as follows.

Patterned  Produce

After the photosensitive resin composition was applied using a spin coater, a film was formed by preliminary heat treatment 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 20.0 mW / cm <^3> for 15 second using the predetermined | prescribed pattern mask. Thereafter, the mixture was developed at 25 ° C. for 130 seconds with an aqueous 0.4% tetramethyl ammonium hydroxide solution, washed with ultrapure water for 90 seconds, and blown with compressed air. Thereafter, the formed pattern was irradiated with ultraviolet light having a strength of 25.0 mW / cm ³ at 365 nm for 32 seconds, and then heated to 220 ° C. for 60 minutes in an oven to obtain a pattern film. With respect to the prepared pattern film, sensitivity, residual film ratio, heat resistance and storage stability were measured by the following method, and the results are shown in Table 1 below.

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

2) Residual film ratio: The photoresist composition is coated on a glass substrate using a spin coater, and the thickness of the film formed after pre-baking and the removal of solvent through post-bake of the film formed. The thickness 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 preliminary heat treatment.

3) Heat resistance: The width of the upper, lower, left, and right sides of the pattern was measured for the pattern film, and the heat resistance was evaluated by the following three-point reference method from the rate of change of the reference angle before curing.

When the change rate of the reference angle before curing is 0 to 20%: Excellent (○)

When the change rate of the reference angle before curing is 20 to 40%: Good (△)

If the rate of change of the reference angle before curing exceeds 40%: poor (X)

4) Storage stability: After leaving the pattern film in a clean room maintained at 23 ° C. and 40% humidity for 3 weeks, the sensitivity (mJ / cm ² ) was checked. At this time, after measuring the change rate for three weeks, the storage stability was evaluated by the following three-point reference method.

If change rate is less than 10% in 3 weeks: ○

If change rate is 10-20% for 3 weeks: △

If the rate of change over three weeks exceeds 20%: ×

TABLE 1

As shown in Table 1, the pattern prepared from the photosensitive resin composition of the present invention was significantly superior in heat resistance and storage stability compared to Comparative Examples 1 and 2, in particular exhibited an excellent effect in terms of sensitivity.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (12)

(A) i) 10 to 80% by weight of the structural unit derived from the dioxolane compound; Ii) 5 to 40% by weight of structural units derived from unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof; And iii) 5 to 50% by weight of a structural unit derived from an epoxy group-containing unsaturated compound; (B) quinonediazide compounds; And (C) solvent Photosensitive resin composition for insulating film formation containing a. The method of claim 1, Said composition is 5 to 50 weight part of (B) quinonediazide compounds with respect to 100 weight part of (A) acrylic copolymers. The photosensitive resin composition for insulating film formation. The method of claim 1, The composition is a photosensitive resin composition for forming an insulating film comprising a solid content of 10 to 60% by weight in the photosensitive resin composition. delete The method of claim 1, Wherein i) Dioxolane-based compound is a photosensitive resin composition for forming an insulating film having a structure of formula (1). [Formula 1]

(Wherein R ₁ and R ₂ are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aliphatic ring compound group or are linked to each other to form a ring, R ₃ is a hydrogen atom or a methyl group, R and R 'are hydrogen or a substituted or unsubstituted alkyl group, n is 1 to 5) The method of claim 1, The dioxolane-based compound is 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate, 2-isobutyl-2-methyl-1,3-dioxolan-4yl-methyl acrylate , 1,4-dioxaspiro- [4,5] -dec-2yl-methyl acrylate, 2-ethyl-2-methyl-1,3-dioxolan-4yl-methyl methacrylate, 2-iso Butyl-2-methyl-1,3-dioxolan-4yl-methyl methacrylate, 1,4-dioxaspiro- [4,5] -dec-2yl-methacrylate, 2,2-dimethyl- 1,3-dioxolane-4yl-methacrylate and a photosensitive resin composition for forming an insulating film selected from the group consisting of The method of claim 1, Said unsaturated carboxylic acid and unsaturated carboxylic anhydride are photosensitive resin compositions for insulating film formation chosen from the group which consists of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and these anhydrides. The method of claim 1, The epoxy group-containing unsaturated compound may be glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-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 ether, m-vinyl A photosensitive resin composition for forming an insulating film, which is selected from the group consisting of benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and mixtures thereof. The method of claim 1, Said (A) acrylic copolymer has a polystyrene reduced weight average molecular weight (Mw) of 3,000-30,000, 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 mixtures 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 further comprises an additive selected from the group consisting of epoxy resins, adhesives, acrylic compounds, surfactants, and mixtures thereof. A liquid crystal display device comprising an insulating film made of the photosensitive resin composition according to any one of claims 1 to 3 and 5 to 11.