KR20120036330A - Photosensitive resin composition for organic insulating film and organic insulating film made therefrom - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition for an organic insulating film, an organic insulating film manufactured by the same, a method for manufacturing the same, and a semiconductor device and a liquid crystal display including the same are provided to improve the storage stability and photographic characteristic. CONSTITUTION: A photo-sensitive resin composition for an organic insulating film includes alkali soluble resin, photo-sensitive acid generator, adhesive thickener, surfactant, and organic solvent. The alkali soluble resin includes resin of 7,000 to 60,000 molecular weights and resin of 2,000 to 7,000 molecular weights. The resins include the following components: unsaturated compound with unsaturated carboxylic acid, unsaturated dicarboxlic anhydride, or hydroxyl group, or the mixture of the same; unsaturated compound with steric hindered bulky alkyl cyclic group; and unsaturated compound with epoxy group.

Description

Photosensitive resin composition for organic insulating films and organic insulating film manufactured therefrom {PHOTOSENSITIVE RESIN COMPOSITION FOR ORGANIC INSULATING FILM AND ORGANIC INSULATING FILM MADE THEREFROM}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for an organic insulating film used in the manufacture of a flat panel display device including a semiconductor device and a liquid crystal display device, and an organic insulating film prepared therefrom. The synergistic effect of mixing allows for optimal improvement of residual film ratio, heat resistance, chemical resistance, photo properties, permittivity, transmittance and storage stability, which are in a trade-off relationship with each other, and sufficient margin for each property. It relates to a photosensitive resin composition for an organic insulating film having an advantage of having an organic insulating film prepared therefrom.

As battery efficiency is less than that of the larger size and high resolution required in the TFT-LCD field, attention has been focused on improving liquid crystal transmittance to solve this problem. One method for improving the transmittance of the liquid crystal is a method of improving the aperture ratio of the liquid crystal panel. In other words, the ITO (Indium Tin Oxide) electrode on the TFT structure is arranged over the entire pixel region to arrange the pixels to increase the area of the pixel electrode. In this method, the TFT-LCD aperture ratio can be improved from the existing 50 to 60% to 80 to 85%. At this time, an interlayer organic insulating film is used for the purpose of insulating the pixel electrode and the data line and for the planarization of the lower layer.

In order to be used as a material of the interlayer organic insulating film, the basic properties that the composition should have are as follows.

Basically, it has to have high sensitivity, high transmittance, excellent coating properties, and storage stability, and heat resistance is required because it is exposed to high temperature when the liquid crystal alignment layer forming process and the ITO electrode forming process are performed in a later process. In addition, in order to realize high productivity, it is necessary to have the ability of uniformity of coatings, which is important for substrate sizes that are increasingly large. In addition, there should be no foreign matter that is completely dissolved in the alkaline developer during the development process so that the photosensitive resin composition stays in the developer and is adsorbed onto the substrate. In addition, the adhesion between the photosensitive composition for organic insulating films and the substrate should be excellent. Insufficient adhesion may cause a defect in which the etching solution penetrates between the lower substrate and the organic insulating film during the microcircuit pattern transfer process through etching, and the pattern CD (critical dimension) may vary, and in severe cases, an open defect may occur in which the entire pattern is lost. In some cases. In addition, since the exposure to the photoresist stripper when forming the electrode pattern, the development of a material that satisfies characteristics such as chemical resistance and etching resistance is required. However, the photosensitive resin composition for organic insulating films which fully satisfy these requirements is not known very much.

The technical problem to be achieved by the present invention is a synergistic effect due to the mixing of a resin having a high molecular weight and a resin having a low molecular weight, the remaining film ratio, heat resistance, chemical resistance, photo properties, dielectric constant, The present invention provides a photosensitive resin composition for an organic insulating film and an organic insulating film prepared therefrom, which can optimally improve transmittance, storage stability, and the like, and have sufficient margin for each characteristic.

In order to achieve the above object, the present invention

A) a) i) unsaturated carboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds with hydroxy groups or mixtures thereof, ii) unsaturated compounds comprising bulky alkylcyclo groups with steric hindrance and iii) epoxy groups A resin having a molecular weight of 7,000 to 60,000 polymerized with an unsaturated compound having a; b) an alkali soluble resin consisting of a mixture of resins having a molecular weight of 2,000 to 7,000 polymerized with the same composition as a); B) photosensitive acid generators; C) adhesion promoter; D) It provides the photosensitive resin composition for organic insulating films which consists of surfactant and E) organic solvent.

As described above, the organic insulating film prepared according to the present invention is a synergistic effect due to the mixing of a resin having a high molecular weight and a resin having a low molecular weight, and has a residual film ratio, heat resistance, and chemical resistance in a trade-off relationship with each other. In addition, the photo-property, dielectric constant, transmittance and storage stability can all be optimally improved and have sufficient margin for each characteristic. Therefore, it can be usefully used for forming TFT circuits of metal films, semiconductor films, protective films and the like of semiconductor devices and liquid crystal display devices.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention relates to A) a) i) unsaturated carboxylic acid, unsaturated dicarboxylic anhydride, 3 to 40 parts by weight of an unsaturated compound having a hydroxy group or a mixture thereof, and ii) a bulky alkylcyclo group with steric hindrance. 3 to 60 parts by weight of an unsaturated compound and iii) a resin having a molecular weight of 7,000 to 60,000 polymerized into 3 to 60 parts by weight of an unsaturated compound having an epoxy group; b) an alkali soluble resin consisting of a mixture of resins having a molecular weight of 2,000 to 7,000 polymerized with the same composition as a); B) photosensitive acid generators; C) adhesion promoters; D) Surfactant and E) Provide the photosensitive resin composition for organic insulating films containing an organic solvent.

The alkali-soluble resin of A) used in the photosensitive resin composition for organic insulating films of this invention is a matrix resin which forms an organic insulating film, and uses acrylic resin containing the component which has a dissolution characteristic in alkaline developing solution. In the present invention, A) a) i) is unsaturated carboxylic acid such as (meth) acrylic acid or crotonic acid; Unsaturated dicarboxylic anhydrides such as maleic acid, fumaric acid, citraconic acid, metaconic acid or itaconic acid; And (meth) acrylic acid hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, di Unsaturated compounds having a hydroxy group such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] glycoside or 4-hydroxyphenyl (meth) acrylate It can be used alone or in combination of two or more compounds selected from the group consisting of.

Among the above-mentioned A) a) i), unsaturated carboxylic acid, unsaturated dicarboxylic anhydride and the like are preferable, and (meth) acrylic acid and maleic anhydride are particularly preferable in view of copolymerization reactivity and solubility in alkaline developer.

It is preferable to use the said unsaturated carboxylic acid, unsaturated dicarboxylic acid anhydride, and the unsaturated compound which has a hydroxyl group at 3-40 weight part with respect to 100 weight part of total monomers. When using the monomer in the said range, it is preferable at the point of copolymerization reactivity and the solubility to alkaline developing solution.

A) a) ii) unsaturated compounds containing a bulky alkylcyclo group having steric hindrance used in the present invention include (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5.2.1.0] decane-8-yl (meth) acrylate, (meth) acrylic acid 2 A single or two or more compounds selected from the group consisting of (tricyclo [5.2.1.0] decane-8-yloxy) ethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate; It can be mixed and used.

The unsaturated compound including a bulky alkylcyclo group having the steric hindrance is preferably used in an amount of 3 to 60 parts by weight based on 100 parts by weight of the total monomers. When using the monomer in the said range, it is preferable at the point of copolymerization reactivity, heat resistance, and storage stability.

A) a) iii) unsaturated compounds having an epoxy group for use in the present invention include (meth) glycidyl acrylate, (meth) acrylic acid 3,4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) ) Acrylic acid 2,3- epoxycyclopentyl, (meth) acrylic acid 3,4- epoxycyclohexyl, (alpha)-ethyl acrylate glycidyl, the (alpha)-ethyl acrylate 6,7-epoxyheptyl, (alpha)-n-propyl acrylate glycidyl And it can be used individually or in mixture of 2 or more types of compounds chosen from the group which consists of (alpha)-n-butyl acrylate acrylate.

The unsaturated compound having an epoxy group is preferably used in 3 to 60 parts by weight based on 100 parts by weight of the total monomers. When the monomer within the above range is used, it is preferable in view of copolymerization reactivity, heat resistance, surface hardness, and adhesion to the substrate.

When radical copolymerization with the above components it is sometimes possible to use a molecular weight modifier to control the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, mercaptans such as 3-mercapto propionic acid, and α-methyl styrene dimer. Can be. These molecular weight modifiers can be used individually or in mixture of 2 or more types.

Alkali-soluble resins of the present invention comprise i) unsaturated carboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds having hydroxy groups, or 3 to 40 parts by weight of mixtures thereof, ii) bulky alkylcyclo groups with steric hindrance. 3 to 60 parts by weight of an unsaturated compound comprising; and iii) an alkali-soluble resin having a composition of 3 to 60 parts by weight of an unsaturated compound having an epoxy group, by adjusting polymerization conditions, respectively, a resin having a molecular weight of 7,000 to 60,000 (a) and a molecular weight of 2,000 having the same composition. The resin (b) of 7,000 is synthesize | combined, and then used by mixing.

The content of the alkali-soluble resin is 40 to 99.5 parts by weight of the resin (a) having a molecular weight of 7,000 to 60,000 based on 100 parts by weight of the total resin amount, and 0.5 to 60 parts by weight of the resin (b) having a molecular weight of 2,000 to 7,000 having the same composition. It is preferable.

When the resin is mixed within the above range, the remaining film ratio, heat resistance, chemical resistance and chemical resistance, dielectric constant, transmittance, and storage stability of the high molecular weight resin and the low molecular weight resin are in a trade-off relationship. It shows synergistic effects that can be optimally improved and have sufficient margin for each characteristic.

The photosensitive acid generator of B) used in the photosensitive resin composition for an organic insulating film of the present invention serves to insolubilize the alkali-soluble resin in an alkaline developer, and after exposure, has a structure that dissolves well in the alkaline developer. It is a key photosensitive component that changes so that the exposed part can be developed. The photosensitive acid generator is generally called PAC (Photo Active Compound), and is prepared by esterifying quinonediazides and polyphenols. The quinone diazides include 1,2-diazidonaphthoquinone-4-sulfonyl chloride, 1,2-diazidonaphthoquinone-5-sulfonyl chloride and 1,2-diazidonaphthoquinone-6- Sulfonyl chloride is used, and polyphenols are 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,3 , 4,3 ', 4', 5'-hexahydroxybenzophenone, 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) Bisphenol, bisphenol-A, methyl gallate, propyl gallate, pyrogallol-acetone reaction condensate, phenol novolak resin, m-cresol novolak resin, p-cresol novolak resin, polyvinyl phenol resin and the like are used. The reaction is prepared by mixing quinonediazides and polyphenols in a specific molar ratio in the presence of a solvent such as dioxane or acetone, followed by dropwise addition of a catalyst such as triethylamine, followed by esterification. In general, the esterification rate is 10 to 90 mol% of the molar ratio of the quinonediazides to the hydroxyl groups of the polyphenols, but preferably 40 to 80 mol% of the reactant is used. This photosensitive acid generator can generally be used individually or in mixture of 2 or more types of compounds.

The adhesion promoter of C) used in the photosensitive resin composition for organic insulating films of the present invention is a component having an effect of improving the adhesion to the substrate, for example, a carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group, etc. The silane coupling agent which has a reactive functional group of is preferable. Specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltri A methoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. can be used individually or in mixture of 2 or more types. The amount of the adhesion promoter used is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

Surfactant of D) used in the photosensitive resin composition for organic insulating films of the present invention is a component having an effect of improving the coating property and coating property, uniformity and stain removal on the substrate, fluorine-based surfactants, silicone-based surfactants and nonionics It can be used alone or in combination of two or more compounds selected from the group consisting of a surfactant.

The organic solvent of E) used in the photosensitive resin composition for organic insulating films of the present invention dissolves an alkali-soluble resin, a photosensitive acid generator, an adhesion promoter, and a surfactant to enable coating on a substrate. Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene Glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol mono Glycol ethers such as methyl ether, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, 3-methoxymethyl propionate, ethyl lactate, ethylene glycol monomethyl ether acetate, and ethylene glycol mono Ethyl ether acetate, ethylene glycol Nopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate And dipropylene glycol monomethyl ether acetate, and the like, or a mixture of two or more compounds selected from the group consisting of acetates.

The photosensitive resin composition for organic insulating films of this invention may further contain additives, such as a film | membrane improvement agent and a sensitizer, as needed. The film improver is added to improve the thermal and mechanical properties of the organic insulating film, and plasticizers, acrylic resins, polystyrene derivatives, polyvinyl methyl ether, and the like are used. A sensitizer is used to improve the sensitivity of the organic insulating film, and may be 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone or 4,4 '-(1- ( 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and the like.

The solid content concentration of the photosensitive resin composition for organic insulating films of the present invention comprising the above components is preferably 5 to 65 parts by weight based on 100 parts by weight of the total photosensitive resin composition for organic insulating films, and the final composition has a pore size of about 0.2 μm before use. It is preferable to filter by a filter.

When the concentration of the solid content of the photosensitive resin composition for the organic insulating film is less than 5 parts by weight, a sufficient thickness of the organic insulating film may not be formed, and when it exceeds 65 parts by weight, coating properties and storage stability may be reduced.

In addition,

A) coating a photosensitive resin composition for an organic insulating film of the present invention on a substrate;

B) prebaking the composition to form an organic insulating film;

C) exposing and developing the organic insulating film to pattern the same; and

D) post-exposure and post-baking the patterned organic insulating layer

It provides a method of manufacturing an organic insulating film comprising a,

The above a) is a step of coating the photosensitive resin composition for an organic insulating film of the present invention on a substrate. The substrate is not particularly limited, and a plastic substrate, a glass substrate, a metal substrate, a silicon wafer, or a SiO ₂ wafer may be used.

The method of coating the photosensitive resin composition for an organic insulating film of the present invention may use a roll coating, spin coating, slit & spin coating or a slit coating method.

B) is a step of prebaking the coated photosensitive resin composition for an organic insulating film. After the coating, the organic insulating film is formed by prebaking to remove the organic solvent. The prebaking is preferably performed at 60 to 115 ° C. for 1 to 17 minutes, and the thickness of the organic insulating film formed by the prebaking is preferably 3 to 6 μm.

(C) is a step of patterning by exposing and developing the organic insulating film. The exposure is performed by exposing a single or mixed light source of g-line (436nm), h-line (405nm) i-line (365nm) through a pattern mask using exposure equipment such as a mask aligner, stepper or scanner on the organic insulating layer. Can be done. The exposure energy is determined according to the sensitivity of the organic insulating film and usually 5 to 200 mJ / cm ² is used.

After the exposure is completed, the substrate may be dip or sprayed with a developer to remove the organic insulating layer of the exposed part to form a desired pattern. The developing solution may be an inorganic alkali compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, or potassium silicate or an aqueous organic alkali solution such as triethylamine, triethanolamine, tetramethylammonium hydroxide, or tetraethylammonium hydroxide. Although it can be used, tetramethylammonium hydroxide is widely used in the manufacture of liquid crystal display devices due to metal contamination, metal corrosion and the like. Tetramethylammonium hydroxide is used in the form of 0.1 to 10 parts by weight of an aqueous solution, and is preferably developed at 20 to 30 ° C. for 30 to 120 seconds, followed by washing and drying with ultrapure water for 60 to 120 seconds.

D) post-exposure and post-bake the patterned organic insulating layer. After completion of the development, the entire surface of the organic insulating layer may be post-exposured at 200 to 500 mJ / cm ² to decompose the remaining B) photosensitive acid generator to remove color, and may be post-baked using a heating apparatus such as a hot plate or an oven. have. The post-baking conditions are performed for 10 to 60 minutes at 120 to 250 ℃, through which a final pattern can be obtained.

Moreover, this invention provides the organic insulating film manufactured from the photosensitive resin composition for organic insulating films of this invention.

The organic insulating film prepared according to the present invention has a synergistic effect due to a mixture of a resin having a high molecular weight and a resin having a low molecular weight, and has a residual film rate, heat resistance, chemical resistance and photo characteristic, and dielectric constant in a trade-off relationship with each other. It has the advantage of being able to optimally improve both permeability, storage stability and having sufficient margin for each property. Therefore, it can be usefully used for forming TFT circuits of metal films, semiconductor films, protective films and the like of semiconductor devices and liquid crystal display devices.

In addition, the present invention provides a semiconductor device and a liquid crystal display device comprising the organic insulating film of the present invention.

The semiconductor device and the liquid crystal display device may be manufactured using a general method known in the art, except for including the organic insulating film of the present invention.

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

Synthesis of Alkali-Soluble Resin (A)

< Synthetic example  1>

23 parts by weight of methacrylic acid, 33 parts by weight of cyclopentyl methacrylate, 14 parts by weight of cyclohexyl methacrylic acid, tricyclo [5.2.1.0] decane-8-yl, methacryl to a reaction vessel equipped with a cooling tube and a stirrer 7 parts by weight of acid 2- (tricyclo [5.2.1.0] decane-8-yloxy) ethyl, 23 parts by weight of glycidyl methacrylate, 15 parts by weight of α-methylstyrene dimer and diethylene glycol as a solvent 300 parts by weight of methyl ethyl ether was added. The solution was heated to 60 ° C. in a nitrogen atmosphere while mixing at 300 rpm, and 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to initiate polymerization, followed by polymerization for 15 hours. After completion of the reaction, air was removed while cooling to room temperature, and 0.4 parts by weight of hydroxyquinone was added to terminate the polymerization to obtain an alkali-soluble resin.

 < Synthetic example  2 to 10>

In Synthesis Example 1, only the composition and composition ratio were changed as shown in Table 1 below, and polymerization was performed in the same manner as in Synthesis Example 1 to prepare an alkali-soluble resin. The weight average molecular weight (Mw) and molecular weight distribution (PDI) of the alkali strongly soluble resin prepared above were measured by GPC (standard material; polystyrene).

< Example >

The resins for the organic insulating film prepared above were mixed in the ratio as shown in Table 2, and performance evaluation as the organic insulating film was performed.

week)

A (a, b): Resin of Table 1 superposed | polymerized according to the method of the synthesis example.

B: 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 3 mol of 1,2-diazidonaphthoquinone-5-sulfonyl chloride

C: γ-methacryloyloxypropyltrimethoxysilane

D: fluorine-based surfactant (R30 from DIC Corporation)

PGMEA: propylene glycol monomethyl ether acetate

One) Photo  Property evaluation

The photo characteristic evaluation was performed about the said photosensitive resin composition for organic insulating films by the following method. First, the photosensitive resin composition for an organic insulating film was spin coated on a 4 "silicon wafer, and then prebaked on a hot plate at 100 ° C. for 90 seconds to form a film having a thickness of about 5 μm. was from 100 mJ / cm ² to 50 mJ / cm ² intervals up to 700 mJ / cm ² exposure in sequence to 1505 G4, the time mask lines with 1 ㎛ interval from 1 to 10 ㎛ used / space patterns and circular patterns are repeated The pattern was developed by developing in 0.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds at 23 ° C., followed by washing and drying for 60 seconds with ultrapure water. When the exposure energy is 500 mJ / cm ² or less, ○ (good sensitivity), 500 to 1000 mJ / cm ² is indicated by Δ, and 1000 mJ / cm ² or more.

2) Residual film ratio  evaluation

After the development, the residual film ratio of the film in the non-exposed part was measured and represented by ○ when the residual film rate was 90% or more, △ when 80 to 90%, and X when less than 80%.

3) Permeability Evaluation

A film having a thickness of about 5 μm was formed on the glass substrate to form a pattern in the same manner as in the above evaluation of photo properties, and then the transmittance at 400 nm was measured using a UV-Vis spectrophotometer. In this case, when the transmittance is 90% or more, ○, 80 to 90% is indicated by △, and less than 80% by X.

4) Heat resistance evaluation

A film having a thickness of about 5 μm was formed on the glass substrate, and the transmittance at 400 nm was measured in the same manner as in the above evaluation of the transmittance. After heating at 230 ° C. for 30 minutes, the transmittance was measured again. ○ or more, 80 to 90%, △, less than 80% is represented by X.

5) permittivity evaluation

Aluminum was deposited on the glass by about 150 nm, the photosensitive resin composition for organic insulating film was coated thereon, and aluminum was further deposited to prepare a specimen. The dielectric constant of this specimen was measured using an Impedance / gain-phase analyzer (HP 4194A). In this case, when the dielectric constant is 4 or less, ○, 4 to 5, △, 5 or more represented by X.

6) storage stability evaluation

After leaving the photosensitive resin composition for organic insulating films in a refrigerator for 6 months, the sensitivity was measured according to 1) photo characteristic evaluation and storage stability was evaluated by comparing with the value at the time of liquid preparation. At this time, the change amount of sensitivity was indicated by (circle) when 10% or less of initial value, (triangle | delta) when 10-20%, and X when 20% or more.

7) Chemical resistance evaluation

The photosensitive resin composition for organic insulating films was spin-coated on a 4 "silicon wafer, and then prebaked on a hot plate at 100 ° C. for 90 seconds to form a film having a thickness of about 5 μm. Mask aligner Karl Suss MA- Each material was exposed to optimal energy using 8, and cured by heating at 230 ° C. for 30 minutes, at which time the film thickness (T1) was measured, and the thickness (T2) after soaking in NMP for 1 hour was measured. In this case, the film thickness change rate is | T2-T1 | / T1 × 100, and when the value is 95% or more, ○ (good chemical resistance),?

As shown in Table 3, in the case of the photosensitive resin composition for the organic insulating film of Examples 1 to 5 by mixing and preparing a resin having a molecular weight of 7,000 to 60,000 and a resin having a molecular weight of 2,000 to 7,000, trade-off (trade- off) can improve the photo properties, residual film ratio, transmittance, heat resistance in relation to each other and have sufficient margin for each property. Thus, it was found that the residual film rate, heat resistance, chemical resistance, photo properties, permittivity, transmittance, and storage stability were superior to those of Comparative Examples 3 or 4 using a resin having a constant molecular weight alone. It was found that the transmittance and heat resistance were very excellent.

Claims (20)

A) a) i) unsaturated carboxylic acids, unsaturated dicarboxylic anhydrides, unsaturated compounds having hydroxy groups or mixtures thereof, ii) unsaturated compounds comprising bulky alkylcyclo groups with steric hindrance and iii) epoxy groups A resin having a molecular weight of 7,000 to 60,000 polymerized with an unsaturated compound having a; b) an alkali soluble resin consisting of a mixture of resins having a molecular weight of 2,000 to 7,000 polymerized with the same composition as a);
B) photosensitive acid generators;
C) adhesion promoter;
D) surfactants and
E) organic solvent
Photosensitive resin composition for organic insulating films containing a. The method according to claim 1, wherein A) a) i) unsaturated carboxylic acid, unsaturated dicarboxylic anhydride, unsaturated compound having a hydroxy group or a mixture thereof are (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, Itaconic acid, (meth) acrylic acid hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl , Diethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] glycoside and (meth) acrylic acid 4-hydroxyphenyl The photosensitive resin composition for organic insulating films characterized by using individually or in mixture of 2 or more types of compounds. The photosensitive resin of claim 1, wherein the unsaturated compound having an unsaturated carboxylic acid, an unsaturated dicarboxylic anhydride, and a hydroxyl group of A) a) i) is used in an amount of 3 to 40 parts by weight based on 100 parts by weight of the total monomers. Composition. The method of claim 1, wherein the A) a) ii) unsaturated compounds containing a bulky alkylcyclo group having sterically hindered is cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methyl (meth) acrylate Cyclohexyl, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5.2.1.0] decane-8-yl (meth) acrylate, 2- (tricyclo (meth) acrylate) [5.2.1.0] Decane-8-yloxy) ethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate, or a mixture of two or more compounds selected from the group consisting of benzyl (meth) acrylate Photosensitive resin composition for organic insulating films characterized by the above-mentioned. The method of claim 1, wherein the A) a) ii) unsaturated compound containing a bulky alkylcyclo group having a steric hindrance is used for the organic insulating film, characterized in that 3 to 60 parts by weight based on 100 parts by weight of the total monomers Photosensitive resin composition. The method of claim 1, wherein the A) a) iii) unsaturated compounds having an epoxy group include (meth) glycidyl acrylate, (meth) acrylic acid 3,4-epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) 2,3-epoxycyclopentyl acrylate, 3,4-epoxycyclohexyl (meth) acrylic acid, α-ethyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-n-propyl acrylate glycidyl and photosensitive resin composition for organic insulating films, characterized in that a mixture of one or more compounds selected from the group consisting of? -n-butyl acrylate acrylate is used. The photosensitive resin composition for organic insulating films according to claim 1, wherein the A) a) iii) unsaturated compound having an epoxy group is used in an amount of 3 to 60 parts by weight based on 100 parts by weight of the total monomers. The resin (b) according to claim 1, wherein the content of the alkali-soluble resin A) is 40 to 99.5 parts by weight of the resin (a) having a molecular weight of 7,000 to 60,000 with respect to 100 parts by weight of the total resin amount, and a molecular weight of 2,000 to 7,000 having the same composition. A photosensitive resin composition for organic insulating films, characterized by mixing 0.5 to 60 parts by weight. The photosensitive resin composition for organic insulating films according to claim 1, wherein the C) adhesion promoter is 0.5 to 10 parts by weight based on A) 100 parts by weight of the alkali-soluble resin. The method of claim 1, wherein the organic solvent of E) is acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol mono Methyl ether, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, 3-methoxymethyl propionate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monopropyl ether acetate, Tylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol monoacetate The photosensitive resin composition for organic insulating films characterized by using individually or 2 or more types of compounds selected from the group which consists of methyl ether acetate. The solid content concentration of the said photosensitive resin composition for organic insulating films is 5-65 weight part with respect to 100 weight part of total photosensitive resin compositions for organic insulating films, The photosensitive resin composition for organic insulating films of Claim 1 characterized by the above-mentioned. A) coating a photosensitive resin composition for an organic insulating film of any one of claims 1 to 11 on a substrate;
B) prebaking the composition to form an organic insulating film;
C) exposing and developing the organic insulating layer to pattern the organic insulating layer; And
D) post-exposure and post-baking the patterned organic insulating layer
Method for producing an organic insulating film comprising a. The method of claim 12, wherein the substrate of a) is a plastic substrate, a glass substrate, a metal substrate, a silicon wafer, or a SiO ₂ wafer. The method of claim 12, wherein the prebaking of b) is performed at 60 to 115 ° C. for 1 to 17 minutes. The method of manufacturing an organic insulating film according to claim 12, wherein the thickness of the organic insulating film formed by the prebaking of b) is 3 to 6 µm. The method of claim 12, wherein the post-exposure of D) uses energy of 200 to 500 mJ / cm 2. The method of claim 12, wherein the post-baking of D) is performed at 120 to 250 ° C. for 10 to 60 minutes. The organic insulating film manufactured from the photosensitive resin composition for organic insulating films of any one of Claims 1-11. A semiconductor device comprising the organic insulating film of claim 18. A liquid crystal display device comprising the organic insulating film of claim 18.