KR101694698B1 - Photosensitive resin composition - Google Patents

Abstract

More particularly, the present invention relates to a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a photopolymerization initiator and a solvent represented by the following general formula (1) And the occurrence of outgas can be minimized due to a small amount of loss of the compound under high energy conditions such as heating and exposure, so that contamination of the mask or chamber during exposure or prebaking can be suppressed .

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

The photosensitive resin is a representative functional polymer material practically used in production of various precision electronic and information industrial products and is currently being used for the production of high-tech industries, especially semiconductors and displays. Generally, a photosensitive resin means a polymer compound in which a chemical change of a molecular structure occurs within a short period of time by light irradiation, and a change in physical properties such as solubility, coloring, and curing for a specific solvent occurs. By using a photosensitive resin, fine precision processing is possible, energy and raw materials can be largely reduced as compared with a thermal reaction process, and work can be performed quickly and accurately in a small installation space, , Photocurable surface coating materials, and so on.

Among them, in the display field, the photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a color filter, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve the process yield in this process and improve the physical properties of the object to be applied, And adhesion and the like have been demanded.

As such a photosensitive resin composition, a composition containing a photopolymerizable monomer and a photopolymerization initiator together with an alkali-soluble resin is widely used. In order to satisfy excellent sensitivity characteristics, a photopolymerization initiator and a sensitizer are added together.

At this time, the commonly used photopolymerization initiator and sensitizer may be volatilized or sublimated in a process of applying high energy such as a prebake process and an exposure process, thereby generating gas, which may contaminate the bake chamber, There is a problem that the lens, the mask, etc. of the exposure machine are contaminated, and thus the pattern is distorted.

Therefore, there has been a demand for development of a photopolymerization initiator that exhibits excellent light absorption characteristics at the same time without causing a problem of loss under such a high energy condition,

Korean Patent Laid-Open Publication No. 2013-99338 discloses a chemically amplified positive photosensitive type high-sensitivity organic insulating film composition excellent in heat resistance and a method for forming an organic insulating film using the same.

Korea Patent Publication No. 2013-99338

It is an object of the present invention to provide a photosensitive resin composition capable of obtaining a pattern having excellent sensitivity, transmittance and mechanical properties.

An object of the present invention is to provide a photosensitive resin composition capable of suppressing contamination of a mask or a chamber during exposure or prebaking.

1. A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a photopolymerization initiation auxiliary represented by the following general formula (1)

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are independently of each other an alkyl group having 1 to 4 carbon atoms;

R ₃ is an alkyl group having 2 to 12 carbon atoms, a non-cycloalkyl group having 4 to 14 carbon atoms, or a tricycloalkyl group;

The alkyl group having 2 to 12 carbon atoms may be substituted with a cycloalkyl group having 4 to 14 carbon atoms).

2. The photosensitive resin composition according to 1 above, wherein the compound represented by the formula (1) is at least one compound selected from the compounds represented by the following formulas (1) - (a-1)

[Chemical Formula 1-a]

[Chemical Formula 1-b]

[Chemical Formula 1-c]

.

.

3. The photosensitive resin composition according to 1 above, wherein the compound represented by Formula 1 is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.

4. The photosensitive resin composition according to 1 above, which comprises 50 to 200 parts by weight of a photopolymerizable monomer, 1 to 40 parts by weight of a photopolymerization initiator, and 50 to 400 parts by weight of a solvent, based on 100 parts by weight of an alkali-

5. A photocurable pattern made from the composition of any one of claims 1 to 4 above.

6. The photocurable pattern as in the above item 5, which is an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern or a black column spacer pattern.

7. An image display apparatus having the photo-curing pattern of the fifth aspect.

The photosensitive resin composition of the present invention can provide a pattern excellent in sensitivity and transmittance and excellent in mechanical characteristics.

The photosensitive resin composition of the present invention can minimize the generation of outgas due to a small amount of loss of the compound under high energy conditions such as heating and exposure, so that contamination of the mask or chamber during exposure or prebaking can be suppressed. As a result, it is possible to prevent the distortion of the pattern shape and the damage of the equipment.

The present invention can provide a pattern having excellent sensitivity and transmittance and excellent mechanical properties by including an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a photopolymerization initiator, and a solvent represented by the following general formula (1) The present invention relates to a photosensitive resin composition capable of suppressing contamination of a mask or a chamber during exposure or prebaking since the loss of compound is small in an energy condition and occurrence of outgas can be minimized.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

Alkali-soluble resin

The alkali-soluble resin can be used in the resin of the present invention without limitation, as long as it is soluble in an alkaline developing solution and can be dissolved in a solvent of the present invention and has reactivity to the action of light or heat.

The alkali-soluble resin according to the present invention may be, for example, a copolymer of a carboxyl group-containing monomer and other monomer copolymerizable therewith.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. These may be used alone or in combination of two or more.

Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid and the like.

In the present specification, (meth) acrylic acid refers to at least one member selected from the group consisting of acrylic acid and methacrylic acid, and (meth) acryloyl refers to at least one member selected from the group consisting of acryloyl and methacryloyl .

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated carboxylic acid may also be mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated carboxylic acid may be a mono (meth) acrylate of the dicarboxylic polymer at both ends thereof. For example,? -Carboxypolycaprolactone monoacrylate,? -Carboxypolycaprolactone monomethacrylate, .

Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Aromatic vinyl compounds such as styrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether and p-vinyl benzyl methyl ether; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromonomers; A monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond; And the like. These may be used alone or in combination of two or more.

Specific examples of the monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond include

(Meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-glycidyl (meth) acrylate, Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl ether,? -Methyl-p-vinylbenzyl (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6 (Glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene

Vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate Acrylate (for example, Cyclorom M100, manufactured by Daicel), a compound represented by the following formula (I), a compound represented by the following formula (II) such as a compound represented by the general formula (II) and a monomer having an ethylenic unsaturated bond

[Formula (I)]

[Formula (II)

(In the formulas (I) and (II), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group,

,

또는

이고,X is a single bond, an alkylene group having 1 to 6 carbon atoms,

,

or

ego,

R ₁ to R ₃ are each independently an alkylene group having 1 to 6 carbon atoms;

Methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3- Acryloyloxyethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl- Monomers having an oxetanyl group such as cetane and 3-ethyl-3-acryloyloxyethyloxetane and a (meth) acryloyloxy group;

A monomer having an ethylenic unsaturated bond and a tetrahydrofuryl group such as tetrahydrofurfuryl acrylate (for example, Viscot V # 150, Osaka Yuki Kagaku Kogyo Co., Ltd.), tetrahydrofurfuryl methacrylate and the like; And the like.

When the alkali-soluble resin is a copolymer of a carboxyl group-containing monomer and another copolymerizable monomer, the content of the carboxyl group-containing monomer is not particularly limited and is, for example, 10 to 50% by weight, preferably 15 to 40% By weight, more preferably 25 to 40% by weight. When the content of the carboxyl group-containing monomer is within the above range, solubility in a developer is good, and an accurate pattern can be formed at the time of development.

Examples of the alkali-soluble resin include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (Meth) acrylate / polymethyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate macromonomer Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) / styrene (Meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer and the like are preferable.

The molecular weight of the alkali-soluble resin is not particularly limited and may be, for example, a polystyrene-reduced weight average molecular weight (hereinafter referred to as weight average molecular weight) of 3,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 50,000 . When the molecular weight of the alkali-soluble resin is within the above range, the colorant is easily dispersed, viscosity is low and storage stability can be improved.

Photopolymerization Monomer

Examples of the photopolymerizable monomer according to the present invention include monofunctional monomers, bifunctional monomers, and other multifunctional monomers having three or more functionalities.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Ralidon, and the like.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

 Specific examples of other trifunctional or more multifunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride Caprolactone-modified polyfunctional monomers having three or more functional groups, and trifunctional or more polyfunctional monomers having three or more alkylene oxide-modified groups.

In the present specification, caprolactone denaturation means that a caprolactone ring-opening polymer or ring opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group.

The alkylene oxide modification is a method in which an alkylene glycol or a dehydration condensation product of the alkylene glycol or a dehydration condensation product of the alkylene oxide and a ring opening polymer of the alkylene oxide are added between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group .

KAYARAD DPCA-20, KAYARAD DPCA-40, KAYARAD DPCA-60, KAYARAD DPCA-120 (Nippon Kayaku Co., Ltd.), NK ester AD- And commercially available products such as TMP-4CL (Shin Nakamura Chemical Industry Co., Ltd.).

As the alkylene oxide-modified trifunctional or more multifunctional monomer three or more times, preferred alkylene oxides include ethylene oxide and propylene oxide.

Of these, polyfunctional monomers having two or more functionalities are preferably used. These photopolymerizable monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer according to the present invention is not particularly limited and may be, for example, 50 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the photopolymerizable monomer is within the above range, the properties such as strength, smoothness and reliability are excellent.

Light curing Initiator

The photopolymerization initiator according to the present invention is not particularly limited and a photopolymerization initiator known in the art can be used. Examples thereof include an acetophenone based compound, a nonimidazole based compound, a oxime based compound, a triazine based compound, an acylphosphine oxide based Compounds and the like. These may be used alone or in combination of two or more.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- ) -Butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 (2-chlorobenzyl) - (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino- Phenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- - (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino- Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) Bromo-4- Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy- On oligomers and the like.

Examples of the non-imidazole compound include 2,2'-bis (2-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'- -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, wherein the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group Imidazole compounds (see, for example, JP-A 7-10913 and the like), and the like.

Examples of the oxime compounds include [1- (4-phenylsulfanylbenzoyl) heptylideneamino] benzoate, [1- [9- Phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butane- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- -Acetic acid ethyl ester-O-acetate, and hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

The content of the photopolymerization initiator according to the present invention is not particularly limited and may be, for example, 1 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content is within the above range, the photosensitive resin composition has a high sensitivity, and the film formed therefrom has excellent mechanical properties.

Light curing  Initiator

The photopolymerization initiator according to the present invention is represented by the following general formula (1)

[Chemical Formula 1]

(식 중, R₁ 및 R₂는 서로 독립적으로 탄소수 1 내지 4의 알킬기이고;
R₃는 탄소수 2 내지 12의 알킬기, 탄소수 4 내지 14의 비시클로알킬기 또는 트리시클로알킬기이고;
상기 탄소수 2 내지 12의 알킬기는 탄소수 4 내지 14의 시클로알킬기로 치환될 수 있음).

(Wherein R ₁ and R ₂ are independently of each other an alkyl group having 1 to 4 carbon atoms;
R ₃ is an alkyl group having 2 to 12 carbon atoms, a non-cycloalkyl group having 4 to 14 carbon atoms, or a tricycloalkyl group;
The alkyl group having 2 to 12 carbon atoms may be substituted with a cycloalkyl group having 4 to 14 carbon atoms).

delete

The photosensitive resin composition mainly contains a photopolymerization initiator or sensitizer for promoting the photoinitiation reaction. In the case of conventional photopolymerization initiator or sensitizer, the photopolymer resin composition is evaporated or sublimated by the energy in the pre-exposure heating step or the exposure step, Or the mask is contaminated, thereby causing a problem that pattern formation is distorted.

However, the compound represented by the general formula (1) of the present invention has a small amount of loss under high energy conditions such as heating and exposure, and thus the above problems can be avoided.

Further, the compound represented by the formula (1) of the present invention exhibits excellent light absorbing properties. Specifically, the maximum absorption maximum value (FWHM) at the wavelength range is 40 nm or less while exhibiting the maximum absorption value in the wavelength range of 320 to 330 nm. As a result, a pattern having an excellent mechanical property can be obtained effectively by adjusting the pattern profile.

In addition, the compound represented by the formula (1) of the present invention has excellent solubility in an organic solvent, and the time required for dissolution can be remarkably shortened.

The compound represented by the general formula (1) is not particularly limited and may be, for example, a compound represented by the following general formulas (1-a) to (1-c) And it is preferable from the viewpoint of exhibiting an excellent effect even if only a small amount is added. These may be used alone or in combination of two or more.

[Chemical Formula 1-a]

[Chemical Formula 1-b]

[Chemical Formula 1-c]

.

.

The method for preparing the compound represented by the formula (1) according to the present invention is not particularly limited and can be obtained, for example, by reacting a compound represented by the formula (2) with a compound represented by the formula (3) in the presence of an aluminum chloride catalyst.

 (2)

(Wherein R ₁ and R ₂ are independently of each other an alkyl group having 1 to 4 carbon atoms)

(3)

(Wherein R is an alkyl group having 2 to 12 carbon atoms, a non-cycloalkyl group having 4 to 14 carbon atoms, or a tricycloalkyl group;

The alkyl group having 2 to 12 carbon atoms may be substituted with a cycloalkyl group having 4 to 14 carbon atoms).

The reaction can be carried out in a known organic solvent, for example, methylene chloride, dichloroethane, chloroform and the like.

The reaction conditions are not particularly limited and may be performed at, for example, a temperature of -50 ° C to 40 ° C, and may be preferably carried out at a temperature of -30 ° C to -5 ° C in terms of maximizing the reaction yield, Preferably -20 &lt; 0 &gt; C to -10 &lt; 0 &gt; C.

The content of the photopolymerization initiator according to the present invention is not particularly limited and may be, for example, 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. If the content is less than 1 part by weight, a pattern shape and size capable of exhibiting desired mechanical properties can not be produced. If the content is more than 20 parts by weight, the pattern and height may increase to a level at which the target resolution can not be achieved. Preferably 1 to 10 parts by weight and more preferably 1 to 5 parts by weight in view of forming a pattern having better mechanical characteristics while meeting a target resolution.

menstruum

The type of the solvent is not particularly limited, and any solvent can be used as long as it can dissolve the above-mentioned components, has a proper drying rate, and can form a uniform and smooth coating film after evaporation of the solvent.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether;

Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;

Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate;

Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxy propylacetate, butyl propoxyacetate, methyl butoxyacetate, Methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, Methoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-propoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Ethoxypropionate, ethyl 3-butoxy-propionic acid propyl esters such as 3-butoxy-propionic acid butyl;

Cyclic ethers such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone. These may be used alone or in combination of two or more.

The content of the solvent according to the present invention is not particularly limited and may be, for example, 50 to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content is within the above range, the coating property is excellent.

additive

The photosensitive resin composition of the present invention may further contain additives such as fillers, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like as necessary.

Specific examples of the filler include glass, silica and alumina.

As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, Polyethylene imines and the like.

Specific examples of commercially available products include KP (Shinetsu Kagaku Kogyo Co., Ltd.), Polyflow (Kyoei Kagaku Co., Ltd.), F. top (Tochem Products Inc.), Megapak (Dainippon Ink Chemical Industry Co., (EFKA CHEMICALS), PB821 (Ajinomoto Co., Ltd.), SORPARS (ZEENKA CO., LTD.), FLORAD (Sumitomo 3M Corporation), Asahi Guard, (Trade name).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3 Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Trimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4- methylphenyl acrylate, 2- [1- Butylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3- tert -butyl-4-hydroxy- ] - 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert- butyl- Phenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (1H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5', 5'-tetramethyl- (Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

Examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

<Photocuring pattern and image display device>

The present invention also provides an image display device having the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.

The photocurable pattern prepared from the photosensitive resin composition is excellent in sensitivity and has excellent mechanical properties. Accordingly, the resist pattern can be used in various patterns such as an array planarizing film, a protective film, an insulating film pattern, and the like in an image display device, and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, But is not limited to.

The image display device having such a photo-curing pattern may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto, and all image display devices known in the art that can be applied are exemplified.

The photo-curing pattern can be produced by applying the above-mentioned photosensitive resin composition of the present invention onto a base material, and photo-curing and developing it.

The thickness of the pattern is not particularly limited and, for example, the thickness after curing is usually about 1 to 8 占 퐉.

The photocurable pattern of the present invention may be one prepared by the following exemplified method.

First, the photosensitive resin composition is coated on a substrate and then heated and dried to remove volatile components such as a solvent to obtain a smooth coated film.

After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m.

Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), j-line (313 nm) The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. The desired pattern shape can be formed by dissolving the unexposed portion and developing the coated film after the hardening is brought into contact with the developing solution.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Also, the base material may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example  1. Synthesis of alkali-soluble resin

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was caused to flow at 0.02 L / min to make a nitrogen atmosphere, and 200 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of 3-methoxybutyl acetate were added , And the mixture was heated to 70 DEG C while stirring. Subsequently, 240 parts by weight of a mixture of the following formulas (4) and (5) (molar ratio of 50:50), and 60 parts by weight of methacrylic acid and 140 parts by weight of 3-methoxybutyl acetate were dissolved to prepare a solution.

[Chemical Formula 4]

[Chemical Formula 5]

The prepared solution was dropped into a flask kept at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts by weight of 3-methoxybutyl acetate was added to a flask / RTI &gt; (Resin A) having a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content) was maintained at 70 캜 for 4 hours after the dropwise addition of the polymerization initiator solution was completed. &Lt; / RTI &gt;

The resulting resin A had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Manufacturing example  2. Synthesis of Compound Represented by Formula 1-a

[Reaction Scheme 1]

Dimethylaminobenzene and cyclohexylpropanoyl chloride were reacted in methylene chloride solvent in the presence of aluminum chloride (1.2 equivalents) at -25 ° C for 5 hours, and the reaction was quenched by addition of demineralized water. Then, the reaction solution is washed with K ₂ CO ₃ aqueous solution three times, washed twice with demineralized water and then dried with MgSO ₄ . The residue was purified by column chromatography (hexane: ethyl acetate = 95: 5 by volume) to obtain the compound represented by formula (I-a) in a yield of 35%. (GC purity of 99% or more)

Manufacturing example  3. Synthesis of Compound Represented by Formula 1-b

[Reaction Scheme 2]

The compound represented by the formula (1-b) was prepared in a yield of 40% in the same manner as in the Production Example 2.

Manufacturing example  4. Preparation of the compound represented by the formula (1-c)

[Reaction Scheme 3]

Compound (1-c) was prepared in a yield of 15% in the same manner as in Preparation Example 2.

Example  And Comparative Example

A photosensitive resin composition having the composition and the content (parts by weight) shown in Table 1 below was prepared.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Alkali-soluble resin
(A) 100 100 100 100 100 100 100 100 100 100 100 Photopolymerizable monomer
(B) 150 150 150 150 150 150 150 150 150 150 150 Photopolymerization initiator
(C) C-1 2.5 2.5 - 2.5 2.5 2.5 - - - 2.5 2.5 C-2 - - 2.5 - - - 2.5 2.5 2.5 - - C-3 3.0 3.0 - 3.0 3.0 3.0 - - - 3.0 3.0 C-4 - - 3.0 - - - 3.0 3.0 3.0 - - menstruum
(D) D-1 50 50 50 50 50 50 50 50 50 50 50 D-2 162.5 162.5 162.5 162.5 162.5 162.5 162.5 162.5 162.5 162.5 162.5 D-3 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 Photopolymerization initiator
(E) E-1 10.0 - 10.0 - - - - - - - - E-2 - 10.0 - 5.0 2.5 - - - - - - E-3 - - - - - 5.0 - - - - - E-4 - - - - - - - 5.0 10.0 - - E-5 - - - - - - - - - 10.0 - E-6 - - - - - - - - - - 5.0 additive
(F) 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50

C-4:

D-1: 디에틸렌글리콜 메틸에틸 에테르
D-2: 프로필렌글리콜모노메틸에테르아세테이트
D-3: 3-메톡시-1-부탄올
E-1: 제조예 2의 광중합 개시 보조제
E-2: 제조예 3의 광중합 개시 보조제
E-3: 제조예 4의 광중합 개시 보조제
E-4:

E-5:

E-6:

F: 4,4'-부틸리덴 비스[6-tert-부틸-3-메틸페놀](BBM-S: 스미토모정밀화학)A: The alkali-soluble resin of Production Example 1
B: dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Yakuza Co., Ltd.)
C-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM manufactured by Hodogaya Chemical Co.,
C-2: 2,2'-bis (o-methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (HABI- 107, Tronly)
C-3:

C-4:

D-1: Diethylene glycol methyl ethyl ether
D-2: Propylene glycol monomethyl ether acetate
D-3: 3-Methoxy-1-butanol
E-1: Photopolymerization initiator of Preparation Example 2
E-2: Photopolymerization initiator of Preparation Example 3
E-3: Photopolymerization initiator of Production Example 4
E-4:

E-5:

E-6:

F: 4,4'-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S: Sumitomo Fine Chemical)

Experimental Example

The photosensitive resin compositions of Examples and Comparative Examples were coated on a 0.7 mm thick glass substrate (Corning 1737, Corning) with a spinner and heated on a hot plate at 100 占 폚 for 125 seconds to volatilize the solvent to obtain a photosensitive Thereby forming a resin composition layer.

Thereafter, in order to obtain a dot pattern having a diameter of 14 mu m, the exposure portion was exposed with a composite wavelength exposure device (Ushio UX-1100SM, Ushio Inc.) using a mask having an octagonal pattern opening having a diameter of 14 mu m.

The substrate after exposure was subjected to a puddle development with a 0.06% aqueous solution of potassium hydroxide at 23 DEG C for 60 seconds using a developer, and then heated in an oven at 230 DEG C for 30 minutes to obtain a cured film.

(1) pattern Line width  Measure

The obtained dot pattern was measured for line width using a three-dimensional shape measuring instrument SIS-2000 manufactured by SNU Precision. The value of the pattern line width was defined as the value of Bottom CD at 5% of the total height from the bottom surface of the pattern.

Then, the CD-bias expressed by the following equation (1) was calculated.

[Equation 1]

CD-bias (탆) = pattern line width (탆) - mask opening size (탆)

(2) Measurement of pattern width ratio (T / B ratio)

Obtained dot pattern was observed with SIS-2000 of SNU Precision's SIS-2000, and the spot at 5% of the total height from the bottom of the pattern was defined as Bottom CD (a), and the point at 95% (b), and the length of (b) is divided by the length of (a) and then multiplied by 100 (= b / a × 100) is defined as T / B ratio.

(3) Sensitivity measurement

The size of a mask in which 100% of a pattern formed with a film thickness of 3 mu m remained 100% by a photomask having 1000 dot patterns each having a sensitivity of 5 mu m to 20 mu m with a diameter of 5 mu m to 20 mu m was evaluated with a microscope Respectively. The smaller the size of the mask, the better the sensitivity.

(4) Mechanical characteristics evaluation (total displacement and recovery rate)

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured under the following measurement conditions using a dynamic ultra-microhardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) The recovery rate (%) was calculated as follows using numerical values.

&Quot; (2) &quot;

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

The measurement conditions are as follows.

Test mode: Load-Unload test

Test force: 50.0 mN

Load speed: 4.41mN / sec

Holding time: 5sec

Indenter; Square pyramid indenter (diameter 50 μm)

(5) Measurement of transmittance

The transmittance of the obtained film at 400 nm was measured with a spectrophotometer.

(6) outgas  analysis

A cured film having a thickness of 3.0 탆 was prepared in the same manner as in the above Experimental Example, and the gas component including the sublimable substance generated by heating at 100 캜 for 15 minutes was collected and gas components were analyzed using GC / MS.

Specifically, the amount of outgas in the examples and the comparative examples was measured based on 100% volume of the compound component (outgas) detected in the gas component generated in the coating film formed of the composition of Comparative Example 1, It was confirmed whether or not the photopolymerization initiator auxiliary components of the examples and comparative examples were included.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Pattern line width
(탆) 15.8 15.1 15.3 15.2 14.3 15.1 17.5 16.7 15.4 18.2 18.2 CD-
Bias
(탆) +1.7 +1.1 +1.3 +1.2 +0.3 +1.1 +3.5 +2.4 +1.4 +4.2 +4.2 Vertical width ratio (%) 65 67 51 69 69 54 43 63 65 62 48 Sensitivity
(탆) 15 16 16 14 12 12 15 13 17 19 15 Displacements
(탆) 0.71 0.60 0.89 0.58 0.68 0.66 1.13 0.73 0.61 0.94 1.21 Recovery rate
(%) 65.2 68.5 62.5 69.0 66.2 68.8 53.2 65.7 68.3 60.4 52.6 Transmittance
(%) 97 97 96 99 99 99 99 98 94 95 93 Outgas amount
(%) 100 100 110 100 100 100 100 245 320 100 100 Whether photopolymerization initiator is detected X X X X X X - ○ ○ X X

Referring to Table 2, the films prepared from the compositions of Examples 1 to 6 including the photopolymerization initiation auxiliary represented by Chemical Formula 1 of the present invention are excellent in pattern CD-Bias and excellent in the top / bottom ratio did. Further, it was confirmed that it had excellent pattern, excellent sensitivity, small amount of displacement, and excellent recovery rate. In addition, the transmittance was high, the amount of outgass was small, and the photopolymerization initiation auxiliary in outgas was not detected.

In particular, the compositions of Examples 2, 4 and 5 including the photopolymerization initiation auxiliary of the formula (1-b) were excellent, and the photopolymerization initiator was significantly improved even when the photopolymerization initiator was contained in small amounts (Examples 5 and 6) .

However, the films prepared with the compositions of Comparative Examples 1 to 5 had poor pattern characteristics such as sensitivity, mechanical properties, or transmittance, or a large amount of out-gas was detected.

Claims (7)

A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a photopolymerization initiation auxiliary represented by the following general formula (1) or (1-b)
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are independently of each other an alkyl group having 1 to 4 carbon atoms;
R ₃ is an alkyl group having 2 to 12 carbon atoms, a non-cycloalkyl group having 4 to 14 carbon atoms, or a tricycloalkyl group;
The alkyl group having 2 to 12 carbon atoms is substituted with a cycloalkyl group having 4 to 14 carbon atoms)
[Chemical Formula 1-b]

.
The photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is at least one compound selected from the compounds represented by the following formulas (1) - (a-1)
[Chemical Formula 1-a]

[Chemical Formula 1-b]

[Chemical Formula 1-c]

.
The photosensitive resin composition according to claim 1, wherein the compound represented by Formula 1 is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition according to claim 1, which comprises 50 to 200 parts by weight of a photopolymerizable monomer, 1 to 40 parts by weight of a photopolymerization initiator, and 50 to 400 parts by weight of a solvent, based on 100 parts by weight of the alkali-soluble resin.
A photocurable pattern made from the composition of any one of claims 1 to 4.
The photocurable pattern according to claim 5, which is an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, or a black column spacer pattern.
The image display apparatus according to claim 5, wherein the photocurable pattern is formed on the substrate.