KR20170085684A - Photosensitive resin comopsition and photocurable pattern forming by the same - Google Patents

Abstract

The present invention relates to an alkali-soluble resin and a photo-curable pattern formed therefrom, and more particularly to an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound has a polyfunctional The present invention relates to a photosensitive resin composition capable of forming a pattern having excellent developability and development resistance and having excellent fine patterns and straightness by containing an acrylate compound and a photocurable pattern formed therefrom.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND PHOTOCURABLE PATTERN FORMING BY THE SAME [0002]

The present invention relates to a photosensitive resin composition and a photocurable pattern formed therefrom, and more particularly, to a photosensitive resin composition capable of forming a pattern having excellent developability and development resistance and excellent in fine pattern and straightness, It is about the Mars pattern.

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 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 and improve the physical properties of the application object in this process, a photosensitive resin having a high sensitivity A composition is required.

The pattern formation of the photosensitive resin composition is caused by photolithography, that is, a change in the polarity of the polymer caused by the photoreaction and a crosslinking reaction. Particularly, the change characteristics of the solubility in a solvent such as an aqueous alkali solution after exposure are utilized.

Pattern formation by the photosensitive resin composition is classified into a positive type and a negative type depending on the solubility of the photosensitive portion in development. In the positive type photoresist, the exposed portion is dissolved by the developing solution, and the negative type photoresist is a method in which the exposed portion is not dissolved in the developing solution and the unexposed portion is dissolved to form a pattern. In the positive type and negative type, A binder resin, a cross-linking agent, and the like.

Since the photosensitive resin composition is formed of a coating film having a thickness of 3 탆 or more and most of the coating film should be developed, a large amount of the photosensitive resin composition must be dissolved in the developing solution in a short time. In addition, if the development is not cleaned, it may cause not only a direct stain due to residues but also various display defects such as poor alignment of liquid crystals. Therefore, the photosensitive resin composition should have excellent developing properties.

In addition, if the portion to be formed in a pattern without being developed is dissolved in the developer, it is impossible to form a fine pattern, and thus excellent developing resistance is required.

Korean Patent Publication No. 2010-0063540 discloses a negative photosensitive resin composition.

Korean Patent Publication No. 2010-0063540

An object of the present invention is to provide a photosensitive resin composition which is excellent in developability and development resistance and can form a pattern having excellent fine patterns and straightness.

It is an object of the present invention to provide a photo-curable pattern formed of the photosensitive resin composition having excellent linearity.

1. A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the photopolymerizable compound comprises a polyfunctional acrylate-based compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, one of R ₃ and R ₄ is a substituted or unsubstituted And the other is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, or a structure represented by the following formula (2): wherein R ₃ and R ₄ are each independently a substituted or unsubstituted hydroxyalkyl group having 1 to 6 carbon atoms, And may form a ring having 3 to 8 carbon atoms substituted with a hydroxy group and n is an integer of 2 to 10,

(2)

(Wherein, R ₁ is a hetero atom having 1 to 10 carbon linear or branched alkylene group which may be interrupted, R ₂ is hydrogen or an alkyl group having 1 to 6, n is an integer of 2 to 10).

2. The photosensitive resin composition according to 1 above, wherein the polyfunctional acrylate compound is a compound represented by the following formula (3)

(3)

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a chain or branched alkylene group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, R ₃ and R ₄ are a group having 1 to 6 carbon atoms Lt; / RTI > hydroxyalkyl group).

3. The photosensitive resin composition according to 1 above, wherein the polyfunctional acrylate compound is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the total photopolymerizable compound.

4. The photosensitive resin composition according to 1 above, wherein the alkali-soluble resin and the photopolymerizable compound have a solid weight ratio of 3: 7 to 7: 3.

5. The photosensitive resin composition according to 1 above, wherein the photosensitive resin composition is a negative type.

6. A photocurable pattern formed from the photosensitive resin composition of any one of items 1 to 5 above.

7. The photocurable pattern according to 6 above, wherein the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern and a column spacer pattern.

8. An image display apparatus comprising the photocuring pattern of the above item 6.

The photosensitive resin composition of the present invention is excellent in developability and development resistance. Specifically, the cured region by the photolithography method is excellent in the developing resistance, and the non-developing region is excellent in developing property. Thus, it is possible to produce a pattern capable of forming a fine pattern and having excellent linearity.

1 and 2 are NMR data of a polyfunctional acrylate compound according to an embodiment of the present invention.

The present invention includes an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and the photopolymerizable compound includes a polyfunctional acrylate-based compound represented by the following formula (1) Pattern and straightness, and a photocurable pattern formed therefrom.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises an alkali-soluble resin, a photopolymerizable compound comprising a polyfunctional acrylate-based compound represented by the general formula (1), a photopolymerization initiator, and a solvent.

Alkali-soluble resin

The alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a developing process for forming a pattern.

Further, in order to ensure compatibility and storage stability of the photosensitive resin composition, the acid value of the alkali-soluble resin is 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the photosensitive resin composition. When the acid value is more than 150 mgKOH / g, the adhesion with the substrate is decreased to easily cause a short circuit, And the viscosity tends to rise.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

In order to impart a hydroxyl group to the alkali-soluble resin, an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group can be copolymerized, and a compound having a glycidyl group in a copolymer of an ethylenically unsaturated monomer having a carboxyl group Followed by further reaction. And further by reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group.

Specific examples of the glycidyl group-containing compounds include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, glycidyl glycidyl ether, Epoxycyclohexanedicarboxylic acid ester, and the like, and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds thereof can be used in combination.

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

The above monomers may be used alone or in combination of two or more.

The content of the alkali-soluble resin may be 10 to 90 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. When the above range is satisfied, the solubility in a developing solution is sufficient, and pattern formation is easy.

Photopolymerization  compound

The photopolymerizable compound according to the present invention includes a polyfunctional acrylate-based compound represented by the following formula (1) having a hydroxy group. Thus, the developability and the development resistance can be improved.

[Chemical Formula 1]

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, one of R ₃ and R ₄ is a substituted or unsubstituted And the other is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, or a structure represented by the following formula (2): R ₃ and R ₄ are each a substituted or unsubstituted hydroxyalkyl group having 1 to 6 carbon atoms, And may form a ring having 3 to 8 carbon atoms substituted with a hydroxy group and n is an integer of 2 to 10,

(2)

(Wherein, R ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, R ₂ is hydrogen or an alkyl group having 1 to 6, n is an integer of 2 to 10).

The hydrocarbon group means an aliphatic chain, an aliphatic branched chain, an aliphatic ring, an aromatic ring, or the like. A plurality of structures represented by parentheses in the formulas may be bonded to one or more carbons of the corresponding hydrocarbon group, respectively.

When a pattern is formed by a photolithographic method using a photosensitive resin composition, the cured portion for pattern formation should have excellent developing resistance and should not be dissolved in the developer. Otherwise, the portion which is not developed should be dissolved Should be removed.

The photopolymerizable compound according to the present invention includes the polyfunctional acrylate-based compound represented by the general formula (1), and has a high acrylate equivalent so that it has excellent resistance to developing.

In addition, in the case of a photosensitive resin composition which is cured by a photo radical, there is a problem that oxygen in the air absorbs radicals, so that the resin composition can not be sufficiently cured on the surface thereof. However, the present invention is not limited to the hydroxyalkyl group substituted or unsubstituted with a hydroxy group The non-covalent electron pair of the amino group, including the polyfunctional acrylate compound, can provide a radical to increase the degree of surface hardening.

At the same time, it also has an effect of improving developability by having a hydroxy group.

Specifically, the photosensitive resin composition of the present invention may be a negative type photosensitive resin composition. Accordingly, the portion cured by exposure does not dissolve in the developer, exhibits excellent developing resistance, and the unexposed portion exhibits high developability and can be dissolved in the developer.

More specifically, the polyfunctional acrylate compound according to the present invention may be a compound represented by the following formula (3).

(3)

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, R ₃ and R ₄ are a hydroxyalkyl group having 1 to 6 carbon atoms ).

The polyfunctional acrylate-based compound represented by formula (1) according to the present invention may be obtained by reacting an amine substituted with a hydrocarbon group having 1 to 10 carbon atoms having a hydroxy group with a polyfunctional acrylate. The hydrocarbon group means an alkyl group, an alkylene group, a cycloalkyl group, an aryl group and the like.

Examples of polyfunctional acrylates include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the amine substituted with a hydrocarbon group having 1 to 10 carbon atoms having a hydroxy group include the following compounds represented by the following formulas (4) to (24).

The content of the polyfunctional acrylate-based compound represented by the formula (1) according to the present invention is not particularly limited, but may be, for example, 1 part by weight or more, more specifically 10 to 60 parts by weight per 100 parts by weight of the photopolymerizable compound Is used. If the amount is less than 1 part by weight, the effect of improving the developability and developing resistance may be insignificant.

In addition to the above compounds, the photopolymerizable compound according to the present invention may further comprise polymeric compounds known in the art. Examples thereof include monofunctional monomers, bifunctional monomers and other multifunctional monomers, and the kind thereof is not particularly limited, but examples thereof include the following compounds.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. 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 polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

The content of the photopolymerizable compound is not particularly limited and may be, for example, 1 to 30 parts by weight, preferably 5 to 20 parts by weight, more preferably 5 to 12 parts by weight based on 100 parts by weight of the entire photosensitive resin composition have. When the photopolymerizable compound is contained in the above-mentioned content range, it can have excellent durability and can have excellent developability and resistance to development.

According to a more specific embodiment of the present invention, the alkali-soluble resin and the photopolymerizable compound may have a solid weight ratio of 3: 7 to 7: 3. When the amount of the alkali-soluble resin is relatively large, the effect of improving surface hardness and developing resistance may be insignificant, and if the amount of the photopolymerizable compound is too large, sufficient developability may be difficult to realize.

Light curing Initiator

The photopolymerization initiator according to the present invention is not particularly limited as long as it can polymerize the polymerizable compound, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, At least one compound selected from the group consisting of a sol-based compound, a thioxanthone compound, and an oxime ester compound can be used, and it is preferable to use an oxime ester compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific 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.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole .

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl- Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca), NCI-831 (Ciba Geigy), CGI- Adeca).

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

Examples of the photopolymerization initiator include at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.

Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator is not particularly limited and may be, for example, 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total solid content of the photosensitive resin composition. When the above range is satisfied, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened, so that the productivity is improved and high resolution can be maintained, and the strength of the formed pattern and the smoothness of the pattern surface can be improved.

menstruum

The solvent may be any solvent as long as it is commonly used in the art.

Specific examples of the solvent 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, propoxypropylacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, butyl Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as? -butyrolactone. The solvents exemplified herein may be used alone or in combination of two or more.

The solvent may be selected from esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate And more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used.

The solvent content may be included in the photosensitive resin composition in an amount of 40 to 95 parts by weight, preferably 45 to 85 parts by weight based on 100 parts by weight of the total amount. When the above-mentioned range is satisfied, it is preferable because the coating property is improved when applied by a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater), an ink jet or the like.

additive

The photosensitive resin composition according to the present invention may further contain additives such as polyfunctional thiol compounds, fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, .

The polyfunctional thiol compound can improve the durability of the photo-curable pattern and the adhesion to the substrate by improving the cross-linking density, and can prevent yellowing at high temperature.

The polyfunctional thiol compound is not particularly limited as long as it is a compound that can be used in the photosensitive resin composition, and a trifunctional or more thiol compound is more preferable, and a tetrafunctional or more thiol compound is more preferable. An example of the thiol compound according to the present invention may be represented by the following chemical formula (25).

(25)

(In the formula, Z ₁ is a methylene group having 2 to 10 carbon atoms or straight-chain or branched-chain alkyl group or a methylene group of the alkyl and, Y is a single bond, -CO-, -O-CO-, or -NHCO-, n is An n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or n is 3 and X is a trivalent group represented by the following formula (26)

(26)

(Wherein Z ₂ , Z ₃ and Z ₄ are, independently of one another, a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" represents a bonding bond).

n is preferably an integer of 4 or more, or an integer of 4 to 10, more preferably 4, 6 or 8.

Examples of X when n is 3 include trivalent groups represented by the following formula (26-1), for example,

As X in the case where n is 4, 6 or 8, for example, a 4, 6 or 8-valent group represented by the following formula (26-2) is preferably used.

[Formula 26-1]

(Where "*" represents a combined hand),

[26-2]

(Wherein m is an integer of 0 to 2, and "* " represents a bonding hand).

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

Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

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. Two or more species 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, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 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- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 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 (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- 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.

Specific 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>

An object of the present invention is to provide an image display device including 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 chemical resistance and peeling resistance. As a result, it can be used in various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, etc. in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, And is particularly suitable as a photoresist pattern.

The image display device having the light curing pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited thereto, Can be exemplified.

The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).

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

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is 70 to 150 DEG C which is a relatively low temperature. 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), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. If desired, the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, and a desired pattern shape can be formed.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate 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, the substrate is washed with water and post-baked at 70 to 100 DEG C for 10 to 60 minutes at a relatively low temperature.

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 . Multifunctional Acrylate  synthesis

100 g of PETA (Pentaerythritol Triacrylate) and 1 equivalent of DEA (Diethanolamine) were placed in a PGME (Propylene Glycol Monomethyl Ether) solvent, and reacted at a room temperature for 1 hour or more as shown in the following reaction formula 1. The reaction was terminated after 1 hour of reaction time on TLC (thin layer chromatograghy), and the same TLC was observed after 2 hours.

[Reaction Scheme 1]

The molecular weight of the reaction was calculated to be 4 equivalents (Mw: 352.34). As a result, it was confirmed that the acrylate was substituted by 30%.

Acrylate (3.56 eq.) And NMR data after 2 hours are shown in Figs. 1 and 2.

Example  And Comparative Example

A photosensitive resin composition having the composition and content shown in Table 1 below was prepared.

division Alkali-soluble resin Photopolymerizable compound Photopolymerization initiator menstruum ingredient Weight portion ingredient Weight portion ingredient Weight portion ingredient Weight portion Example 1 A-1 35 B-1 11 C-1 3 D-1 51 Example 2 A-1 53 B-1 7 C-1 3 D-1 37 Example 3 A-1 26 B-1 12 C-1 3 D-1 59 Example 4 A-1 61 B-1 5 C-1 3 D-1 31 Example 5 A-1 13 B-1 15 C-1 3 D-1 69 Example 6 A-1 75 B-1 3 C-1 3 D-1 21 Comparative Example 1 A-1 53 B-2 7 C-1 3 D-1 37 Comparative Example 2 A-1 53 B-3 7 C-1 3 D-1 37 Comparative Example 3 A-1 53 B-4 7 C-1 3 D-1 37 Comparative Example 4 A-1 53 B-5 7 C-1 3 D-1 37

A-1: Propylene glycol monomethyl ether acetate solution (20%, weight average molecular weight: 16000) of benzyl methacrylate / methacrylic acid (70:30 molar ratio)

B-1: The polyfunctional acrylate prepared in Preparation Example 1

B-2:

B-3:

B-4:

B-5:

C-1: I-184

D-1: Propylene glycol monomethyl acetate

Experimental Example

One. Developability  evaluation

The photosensitive resin compositions of the examples and comparative examples were dried in two 10 cm x 10 cm soda glasses and then bar-coated to a thickness of 5 탆 and dried in an oven at 100 캜 for 1 minute to remove the solvent. And the other sample was exposed so that the accumulated light quantity of the 313 nm wavelength of the Fusion LAMP was 2000 mJ, to give a sample after exposure.

The sample thus prepared before the exposure was immersed in a KOH aqueous solution prepared by dissolving KOH in distilled water for 1 minute and then taken out of the sample. The sample was then immersed in distilled water for 1 minute and then taken out. After drying for 1 minute, the surface condition was confirmed.

<Criteria>

No residue of resin is observed on the surface at all:

Residual surface resin visible, but slightly visible:

The remaining surface resin was visually observed: x

2. Phenotypic resistance evaluation

The samples after the exposure were immersed in a KOH aqueous solution prepared by dissolving KOH in distilled water and having a pH of 14 for 10 minutes, taken out of the sample, immersed in distilled water for 1 minute and then dried in a 100 degree seed drying oven for 1 minute, The surface state of the sample was confirmed.

<Criteria>

Haze is not visible on the surface at all: ○

Surface haze is visible, but slightly visible: △

Surface haze visually observed: x

division Developability Developmental resistance Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 △ ○ Example 6 ○ △ Comparative Example 1 × ○ Comparative Example 2 × ○ Comparative Example 3 ○ × Comparative Example 4 ○ ×

Referring to Table 2 above, it can be confirmed that the photosensitive resin composition of the examples is excellent in developing property and the produced pattern has excellent developing resistance.

However, in the case of the comparative example, it can be confirmed that the developing property or the developing resistance is poor.

Claims (8)

An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
Wherein the photopolymerizable compound comprises a polyfunctional acrylate-based compound represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, one of R ₃ and R ₄ is a substituted or unsubstituted And the other is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, or a structure represented by the following formula (2): R ₃ and R ₄ are each a substituted or unsubstituted hydroxyalkyl group having 1 to 6 carbon atoms, And may form a ring having 3 to 8 carbon atoms substituted with a hydroxy group and n is an integer of 2 to 10,
(2)

(Wherein, R ₁ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, R ₂ is hydrogen or an alkyl group having 1 to 6, n is an integer of 2 to 10).
The photosensitive resin composition according to claim 1, wherein the polyfunctional acrylate compound is a compound represented by the following formula (3)
(3)

(Wherein R ₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₂ is a hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a hetero atom, R ₃ and R ₄ are a hydroxyalkyl group having 1 to 6 carbon atoms ).
The photosensitive resin composition according to claim 1, wherein the polyfunctional acrylate compound is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the total photopolymerizable compound.
The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin and the photopolymerizable compound are contained in a weight ratio of solid content of 3: 7 to 7: 3.
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a negative type.
A photocurable pattern formed from the photosensitive resin composition of any one of claims 1 to 5.
7. The photocurable pattern according to claim 6, wherein the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern and a column spacer pattern.
7. An image display apparatus comprising the photocurable pattern of claim 6.

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