KR20030010893A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: Provided is a photosensitive resin composition for photoresist, which is excellent in sensitivity, insulating property, leveling property, and chemical-resistance and can be used as an intercalation insulating membrane in an LCD producing process. CONSTITUTION: The photosensitive resin composition contains: 100pts.wt. of an acryl-based copolymer obtained by copolymerizing 5-40wt% of unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, 10-70wt% of an unsaturated compound containing epoxy, and 10-70wt% of an olefin-based unsaturated compound, wherein the acryl-based copolymer has a polystyrene reduced weight average molecular weight(Maw) of 5000-30000; 5-100pts.wt. of a 1,2-quinonediazide compound; 1-50pts.wt. of an acrylate compound represented by the formula 1. In the formula, R is hydrogen atom or C1-C6 alkyl, alkoxy, or alkanoyl and 1<a<6, and a+b is 6.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

[Industrial use]

The present invention relates to a photosensitive resin composition used as a photoresist in the LCD manufacturing process, and more particularly, including an acrylate copolymer having an ethylenically unsaturated double bond, various performances such as insulation, flatness, chemical resistance The present invention relates to a photosensitive resin composition which is excellent in formation, easy in pattern formation, and excellent in transmittance, and is suitable for forming interlayer insulating films such as liquid crystal display devices and integrated circuit devices.

[Prior art]

In the TFT type liquid crystal display device or integrated circuit device, an interlayer insulating film is used to insulate the wirings arranged between the layers.

In the case of forming such an interlayer insulating film, a photosensitive material having a small number of steps and excellent flatness is used to obtain a pattern-shaped interlayer insulating film.

In addition, as the display quality of the liquid crystal display (LCD) is improved, the structure of the TFT type liquid crystal display device is also changed, and the thickness of the interlayer insulating film is increased to increase the flatness.

However, when the thickness of the photosensitive resin composition for interlayer insulation films was used on condition that is thick as mentioned above, the fall of transparency by the increase of film thickness became a problem.

Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in various performances such as insulation, flatness, chemical resistance and the like and easily forms a pattern as an interlayer insulating film in view of the problems of the prior art as described above. .

Another object of the present invention is to provide a photosensitive resin composition which is excellent in transmittance even in a thick film and suitable for use as an interlayer insulating film in an LCD manufacturing process.

[Means for solving the problem]

In order to achieve the above object, the present invention

In the photosensitive resin composition, (A) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof; Ii) epoxy group-containing unsaturated compounds; And iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound; (B) 1,2-quinonediazide compounds; And (C) provides a photosensitive resin composition comprising an acrylate compound represented by the formula (1):

[Formula 1]

In Chemical Formula 1,

R is a hydrogen atom or a C ₁ -C ₅ alkyl group, an alkoxy group, or an alkanoyl group; And

1 <a <6 and a + b = 6.

Preferably the present invention

(A) iii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof 5

40% by weight;

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

V) 10 to 70% by weight of olefinically unsaturated compound

100 parts by weight of an acrylic copolymer obtained by copolymerizing;

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

(C) 1 to 50 parts by weight of the acrylate compound represented by Formula 1

It provides a photosensitive resin composition comprising a.

Hereinafter, the present invention will be described in detail.

(A) Acrylic Copolymer

In the photosensitive resin composition of the present invention, the (A) acrylic copolymer serves to easily form a predetermined pattern in which scum does not occur during development.

Such (A) acrylic copolymers may be selected from the group consisting of: i) unsaturated carboxylic acids, unsaturated carboxylic anhydrides, or mixtures thereof; Ii) epoxy group-containing unsaturated compounds; And iii) a radical reaction in the presence of a solvent and a polymerization initiator using the olefinically unsaturated compound as a monomer. This will be described in more detail as follows.

I) Unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof used in copolymerization in the present invention is preferably 5 to 40% by weight, more preferably 10 to 30% by weight based on the total monomers. Good to use in%. When the amount of the monomer used is less than 5% by weight, it is difficult to dissolve in the aqueous alkali solution, whereas when it exceeds 40% by weight, the solubility in the alkaline water solution tends to be too large.

Specific examples of the compound (iii) include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, citraconic acid, unsaturated dicarboxylic acids such as mesaconic acid and itaconic acid, and anhydrides of these unsaturated dicarboxylic acids. These can be used individually or in mixture of 2 or more types. Of these, acrylic acid, methacrylic acid, or maleic anhydride is preferably used, which is excellent in copolymerization reactivity and solubility in aqueous alkali solution.

In addition, the amount of the ii) epoxy group-containing unsaturated compound used for copolymerization in the present invention is preferably used in an amount of 10 to 70% by weight based on the total total monomers, and more preferably in an amount of 20 to 60% by weight. When the usage-amount of the said epoxy containing unsaturated compound is less than 10 weight%, the heat resistance of the pattern obtained tends to fall, and when it exceeds 70 weight%, the storage stability of a copolymer tends to fall.

Examples of the epoxy-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid β- -Methylglycidyl, methacrylic acid-beta -methylglycidyl, acrylic acid-beta -ethylglycidyl, 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-epoxyheptyl, o-vinylbenzyl glycidyl ether, m- Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like, and these may be used alone or in combination of two or more 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 the like in terms of enhancing copolymerization reactivity and heat resistance of the obtained pattern.

Further, the amount of i) olefinically unsaturated compound used in the copolymerization in the present invention is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, based on the total total monomers. When the amount of the olefinically unsaturated compound used is less than 10% by weight, the storage stability of the acrylic copolymer tends to be lowered. When the amount of the olefinically unsaturated compound is greater than 70% by weight, the acrylate copolymer becomes difficult to dissolve in the aqueous alkali solution.

Specific examples of the olefinically unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, isopropyl acrylate, Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl Acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl Styrene, vinyltoluene, p-methyl styrene, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, and the like, alone or in combination of two or more thereof. It can be used in combination. Preferably styrene, dicyclopentanyl methacrylate, or p-methoxystyrene is advantageous in terms of copolymerization reactivity and solubility in aqueous alkali solution.

Specific examples of the solvent used for the polymerization of the acrylic copolymer include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, propylene glycol monoethyl 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, propyl acetate, Butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate , Lactic acid propyl, butyl lactic acid, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propionic acid propyl, 3-hydroxy propionic acid butyl, 2-hydroxy 3-methyl butyrate, methyl methoxyacetate Ethyl methoxy acetate, propyl methoxy acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, Propoxy acetate propyl, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid propyl Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate propyl, 2-butoxypropionate butyl, 3-methoxypropionate methyl, 3-methoxypropionate propyl, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, 3-ethoxypropionate methyl, 3 Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid propyl, 3-propoxy Ethers such as butyl cionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate, and the like, and these may be used alone or in combination of two or more thereof. .

As the polymerization initiator used in the preparation of the acrylic copolymer, a radical polymerization initiator is used, and specific examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvalle. Ronitrile)), 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 (A) acrylic copolymer used by this invention is 5000-30,000 in polystyrene conversion weight average molecular weight (Mw), Preferably it is more preferable that it is 5000-20,000. In the case of the film obtained with Mw less than 5000, developability, residual film ratio, etc. tend to be lowered, or the pattern shape, heat resistance, and the like tend to be inferior. When Mw exceeds 30,000, sensitivity tends to be lowered or the pattern shape is inferior.

(B) 1,2-quinonediazide compound

In the photosensitive resin composition of this invention, it is preferable to use (B) 1,2-quinonediazide compound as a photosensitive compound.

Specific examples of the 1,2-quinonediazide compound include 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, and the like. have.

The quinone diazide compound is obtained by reacting a naphthoquinone diazide sulfonic acid halogen compound and a phenol compound under a weak base.

Specific examples of the phenolic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 'or 4,4'-tetrahydroxybenzophenone, 2,3 , 4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3, 4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2 'or 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3', 2 , 4,6,4 'or 2,4,6,5'-hexahydroxybenzophenone, 3,4,5,3', 3,4,5,4 'or 3,4,5,5'- Hexahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxy Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5 -Dimethyl 4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis ( 2,5- And the like, methyl 4-hydroxyphenyl) -2-hydroxyphenyl methane, it can be used as a mixture thereof alone or in combination.

In the synthesis of the compound, the esterification degree is preferably 50 to 85%, and when the esterification degree is less than 50%, the residual film ratio tends to worsen, and when it exceeds 85%, storage stability may tend to be inferior.

The amount of the 1,2-quinone diazide compound used is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer of (A). If the amount of the 1,2-quinone diazide compound is less than 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part is small, and thus, pattern formation is difficult. A large amount of the 1,2-quinonediazide compound of is left, solubility in an aqueous alkali solution becomes too low, making development difficult.

(C) an acrylate compound represented by the following formula (1)

In particular, in the photosensitive resin composition of this invention, the heat resistance, transparency, sensitivity, etc. of the pattern obtained from the photosensitive resin composition can be improved, including the acrylate compound represented by following formula (1) which has an ethylenically unsaturated double bond.

[Formula 1]

In Chemical Formula 1,

R is a hydrogen atom or a C ₁ -C ₅ alkyl group, an alkoxy group, or an alkanoyl group; And

1 <a <6 and a + b = 6.

The acrylate compound represented by the formula (1) can be used alone or in combination of two or more.

In addition, the present invention can be used in combination with the acrylate compound of the general formula (1), a monofunctional methacrylate having a different type of ethylenically unsaturated double bond, a bifunctional methacrylate or a trifunctional or higher methacrylate. Examples of the monofunctional methacrylate, bifunctional methacrylate or trifunctional or higher methacrylate include 2-hydroxyethyl methacrylate, isoboroyl methacrylate, and 3-methoxybutyl methacrylate. Monofunctional methacrylate, such as a ret, 2-methacrylyl oxyethyl 2-hydroxypropylphthalate, ethylene glycol methacrylate, 1, 6- hexanediol dimethacrylate, 1, 9- nonanedi Bifunctional metacrete such as old dimethacrylate, propylene glycol methacrylate, tetraethylene glycol methacrylate, bisphenoxyethanol fluorene dicrete, bisphenoxyethanol fluorene diacrete And trifunctional or higher methacrylates such as trimethylolpropane trimethacrylate.

The amount of the acrylate compound represented by the formula (1) of (C) is preferably used in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the (A) acrylic copolymer.

In addition, the photosensitive resin composition of this invention can further contain (D) epoxy resin, (E) adhesive agent, and (F) surfactant as needed.

The epoxy resin (D) can improve the heat resistance, sensitivity and the like of the pattern obtained from the photosensitive resin composition. Specific examples of the epoxy resins include bisphenol A epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, cycloaliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and heterocyclic compounds. And resins obtained by (co) polymerizing glycidyl methacrylate different from epoxy resins and (A) acrylic copolymers. Preferably, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or glycidyl ester type epoxy resin is used. The amount of the epoxy resin is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin, and when the amount is more than 30 parts by weight, the compatibility with the alkali-soluble resin is poor and sufficient coating performance cannot be obtained.

The adhesive (E) is used to improve adhesion to the substrate, and may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer. As such an adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, or the like may be used. Specific examples include γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3 , 4-epoxy cyclohexyl ethyltrimethoxysilane, and the like.

In addition, the said (F) surfactant is used in order to improve the applicability | paintability and developability of a photosensitive composition. Such surfactants include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name; Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem Co.), KP341 (trade name; Shinwol) Chemical industry). The amount of the surfactant is preferably used in 0.0001 to 2 parts by weight based on 100 parts by weight of the solid content.

On the other hand, the present invention includes the (A) acrylic copolymer, (B) 1,2-quinonediazide compound, and (C) the acrylate compound of the formula (1), if necessary (D) to (F) A solvent is added to the photosensitive resin composition which further contains a component, and provides the photosensitive resin composition coating solution.

It is preferable that the solid content concentration of the photosensitive resin composition coating solution of this invention is 30 to 70 weight%, and this is used after filtering using a 0.2 micrometer pore filter.

As a solvent used for manufacture of the said photosensitive resin composition coating solution, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy 3 Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, butyl methoxy acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate , Ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, butyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl acid, 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, 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionic acid, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid propyl, Esters such as butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionic acid, and butyl 3-butoxypropionate. Preferably, it is preferable to select and use from the group which consists of solubility, the reactivity with each component, and the formation of a coating film, glycol ether, ethylene glycol alkyl ether acetate, and diethylene glycol.

This invention applies the photosensitive resin composition obtained above to the surface of a board | substrate by the spray method, the roll coater method, and the rotary coating method, and removes a solvent by prebaking, and forms a coating film. It is preferable to perform the conditions of the said prebak at about 1 to 15 minutes at 70-110 degreeC. Thereafter, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like are irradiated onto the coating film and then developed with a developer to remove unnecessary portions to form a predetermined pattern.

As the developing solution, an aqueous alkali solution is used. For example, 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 triethanol amine; Aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used. The developing solution is used by dissolving an alkaline compound at a concentration of 0.1 to 10%, and an appropriate amount of a water-soluble organic organic solvent and a surfactant such as methanol and ethanol can be added.

After the development, washing with ultrapure water for 30 to 90 seconds to remove unnecessary portions and drying to form a pattern. After irradiating light, such as an ultraviolet-ray, to the formed pattern, the pattern is heat-processed at 150-250 degreeC for 30 to 90 minutes with a heating apparatus, such as an oven, and a final pattern can be obtained.

Hereinafter, the present invention will be described with reference to the following Examples and Comparative Examples. However, these examples are only for illustrating the present invention, and the present invention is not limited thereto.

EXAMPLE

Synthesis 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), 125 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, and methacrylic acid 25 parts by weight of glycidyl, 40 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate and 10 parts by weight of isobornyl acrylate were added, followed by nitrogen substitution, and gently stirring was started. The reaction solution was raised to 62 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing copolymer [A-1]. Solid content concentration of the obtained polymer solution was 45 weight%, and the weight average molecular weight of the polymer was 13000. In this case, the weight average molecular weight is a polystyrene converted average molecular weight measured using GPC.

Synthesis Example 2

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 of condensation reaction to [4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide -5-sulfonic acid ester].

Example 1

Preparation of Photosensitive Resin Composition

100 parts by weight of the polymer solution (copolymer [A-1]) obtained in Synthesis Example 1, the condensate obtained in Synthesis Example 2 [4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide 5-sulfonic acid ester] 25 parts by weight, and 15 parts by weight of the acrylate compound of the formula (1a) were mixed to obtain a solid content of 35% by weight. It was dissolved in diethylene glycol dimethyl ether to be filtered through a 0.2 μm Millipore filter to prepare a photosensitive resin composition solution.

[Formula 1a]

The physical properties of the photosensitive resin composition prepared above were evaluated by the following method, and the results are shown in Table 1 below.

1) Sensitivity: The composition solution 1 was applied on a glass substrate using a spin coater, and then prebaked at 90 ° C. on a hot plate for 2 minutes to form a film.

The film obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15 mW / cm <2> for 20 second using the predetermined pattern mask. Thereafter, the solution was developed at 25 ° C. for 1 minute in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide, and then washed with ultrapure water for 1 minute.

Thereafter, the pattern formed above was irradiated with ultraviolet light having an intensity of 15 mW / cm 2 at 365 nm for 34 seconds and then heated and cured at 220 ° C. for 60 minutes in an oven to obtain a pattern film.

2) Resolution: Evaluation of Resolution It was set as the minimum size formed in the pattern film obtained by said (I).

3) Transparency: Evaluation of Transparency The transmittance of 400 nm of the pattern film was measured using a spectrophotometer.

4) Heat discoloration resistance: Evaluation of heat dissipation resistance The measurement substrate was heated in an oven at 250 ° C. for 1 hour, and heat discoloration resistance was evaluated by changing the transmittance of the pattern film before and after heating. The case where the change rate at this time was less than 5% was represented by [(circle)] and the case where it was 5-10% [△] and the case where it exceeded 10% was represented by [x].

Example 2

Except for using the acrylate compound of Formula 1b instead of the acrylate compound of Formula 1a, to prepare a composition solution in the same manner as in Example 1 to evaluate the physical properties and the results are shown in Table 1 below.

[Formula 1b]

Example 3

Except for using the acrylate compound of Formula 1c instead of the acrylate compound of Formula 1a, to prepare a composition solution in the same manner as in Example 1 to evaluate the physical properties and the results are shown in Table 1 below.

[Formula 1c]

Comparative Example 1

Except not using the acrylate compound of Formula 1a to 1c, the composition solution was prepared in the same manner as in Example 1 to evaluate the physical properties and the results are shown in Table 1 below.

division Sensitivity (mJ / ㎠) Resolution (μm) Transparency Heat discoloration resistance Example 1 230 3 92 ○ Example 2 220 3 92 ○ Example 3 230 3 92 ○ Comparative Example 1 270 4 88 ×

In Table 1, Examples 1 to 3 including the acrylate having an ethylenically unsaturated double bond of Formula 1 according to the present invention is particularly excellent in transparency and heat discoloration resistance for high flatness It can be seen that it can be applied to an interlayer insulating film having a thick film thickness. On the contrary, in the case of 1, the sensitivity is poor, and the transparency and the heat discoloration resistance are poor, making it difficult to apply to the thick interlayer insulating film.

As described above, the photosensitive resin composition according to the present invention has excellent sensitivity, insulation, flatness, chemical resistance, etc., in particular, it is easy to form a pattern as an interlayer insulating film, and has excellent transmittance even in a thick film. Effective in

Claims (8)

In the photosensitive resin composition, (A) iii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof; Ii) epoxy group-containing unsaturated compounds; And Iii) olefinically unsaturated compounds Acrylic copolymer obtained by copolymerizing; (B) 1,2-quinonediazide compounds; And (C) an acrylate compound represented by the following formula (1) A photosensitive resin composition comprising: [Formula 1] In Chemical Formula 1, R is a hydrogen atom or a C ₁ -C ₅ alkyl group, an alkoxy group, or an alkanoyl group; And 1 <a <6 and a + b = 6. The method of claim 1, The photosensitive resin composition (A) iii) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof 5 40% by weight; Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And V) 10 to 70% by weight of olefinically unsaturated compound 100 parts by weight of an acrylic copolymer obtained by copolymerizing; (B) 5 to 100 parts by weight of the 1,2-quinonediazide compound; And (C) 1 to 50 parts by weight of the acrylate compound represented by Formula 1 Photosensitive resin composition comprising a. The method according to claim 1 or 2, The polystyrene reduced weight average molecular weight (Mw) of the said (A) acrylic copolymer is 5,000-30,000, The photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 2, The unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof of (A) ') is composed of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and unsaturated carboxylic anhydrides thereof 1 or more types are selected from the group. Photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 2, The epoxy group-containing unsaturated compound of the above (A) ii) Glycidyl acrylate, Glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid-β-methylglycidyl, meta Methacrylate-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-vinylbenzyl glycidyl ether, And p-vinylbenzyl glycidyl ether. The method according to claim 1 or 2, The olefinically unsaturated compound of (A) ') is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, isopropyl acryl Latex, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Oxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p At least one selected from the group consisting of -methyl styrene, vinyltoluene, p-methyl styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl 1,3-butadiene Photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 2, The 1,2-quinonediazide compound of (B) is a 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1,2-quinonediazide 6-sulfonic acid ester It is a photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The photosensitive resin composition is composed of 0.1 to 30 parts by weight of (D) epoxy resin, 0.1 to 20 parts by weight of (E) adhesive, and 0.0001 to 2 parts by weight of (F) surfactant based on 100 parts by weight of the acrylic copolymer of (A). The photosensitive resin composition characterized by further including the additive selected from the group of 1 or more types.