KR20200110059A - Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising: an alkali-soluble resin; a polymerizable compound; a photoinitiator; a tertiary amine compound; and a thiol-based compound having difunction or less. The sensitivity, resolution, and storage stability at room temperature of the photosensitive resin composition are excellent, and the physical properties of the photo-curable pattern prepared therefrom may be improved.

Description

A photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same.

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same. More specifically, it relates to a photosensitive resin composition containing a curable resin or a compound, a photocurable pattern formed therefrom, and an image display device including the same.

In the display field, the photosensitive resin composition is used to form various photocurable patterns such as photoresist, insulating film, protective film, black matrix, and column spacer. For example, the photosensitive resin composition may be selectively exposed and developed by a photolithography process to form a desired photocurable pattern. In order to secure the physical properties of a desired photocurable pattern, the photosensitive resin composition has high sensitivity, and the pattern formed therefrom needs to have improved heat resistance, chemical resistance, and the like.

The photosensitive resin composition is classified into a positive type and a negative type according to the photocuring type. The photoresist formed by the positive composition is dissolved by a developer by modifying the chemical structure of the exposed portion, and the photoresist formed by the negative composition is cured due to an increase in the degree of polymerization of the exposed portion, or remains without melting during the development process. The positive-type and negative-type compositions may each contain different binder resins, crosslinking agents, and the like.

Recently, the use of a touch screen having a touch panel is increasing, and accordingly, a display device including a flexible touch screen has been actively developed. Accordingly, the need for a resist composition having excellent sensitivity and resolution and sufficient storage stability at room temperature has increased.

Korean Patent Registration No. 10-1302508 discloses a negative photosensitive resin composition comprising a copolymer polymerized using a cyclohexenyl acrylate monomer.

However, a curable composition having excellent sensitivity and resolution and sufficient storage stability at room temperature has not been disclosed.

Korean Patent Registration No. 10-1302508

One object of the present invention is to provide a photosensitive resin composition having excellent curability and stability.

An object of the present invention is to provide a photocurable pattern formed from the photosensitive resin composition and an image display device including the same.

1. alkali-soluble resin; Polymerizable compounds; Photopolymerization initiator; A tertiary amine compound represented by the following formula (1); And a photosensitive resin composition comprising a bifunctional or less thiol-based compound:

[Formula 1]

(In Formula 1, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 4 carbon atoms, and R ₃ is a linear or cyclic alkyl group having 1 to 12 carbon atoms).

2. In the above 1, wherein the bifunctional or less thiol-based compound is a dithiol-based compound, photosensitive resin composition.

3. The photosensitive resin composition of the above 1, wherein the bifunctional or less thiol-based compound comprises at least one of the compounds represented by Formula 2 or Formula 3:

[Formula 2]

(In Formula 2, m is an integer of 1 to 5)

[Formula 3]

(In Chemical Formula 3, n is an integer of 1 to 11).

4. In the above 1, the content of the tertiary amine compound is 0.1 to 1% by weight based on the total weight of the photosensitive resin composition, photosensitive resin composition.

5. In the above 1, wherein the content of the bifunctional or less thiol-based compound is 0.1 to 1% by weight based on the total weight of the photosensitive resin composition, photosensitive resin composition.

6. In the above 1, the content ratio of the tertiary amine compound to the bifunctional or less thiol-based compound is 1 to 4.2, the photosensitive resin composition.

7. The photosensitive resin composition according to the above 1, wherein the alkali-soluble resin comprises at least one repeating unit of an epoxy group-containing unit or a terminal double bond-containing unit.

8. The photosensitive resin composition according to the above 1, wherein the photopolymerization initiator comprises at least one of a biimidazole-based compound and an oxime ester-based compound.

9. A photocurable pattern formed of the photosensitive resin composition of any one of 1 to 8 above.

10. The photocuring pattern according to the above 9, wherein the photocuring pattern is selected from the group consisting of an array planarization layer pattern, a passivation layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer.

11. An image display device including the photocuring pattern of 9 above.

The photosensitive resin composition according to the embodiments of the present invention may have excellent sensitivity, resolution, and storage stability at room temperature, including a tertiary amine compound and a bifunctional or less thiol-based compound, and the photocurable pattern prepared therefrom Physical properties can be improved.

The bifunctional or less thiol-based compound may improve storage stability of the photosensitive resin composition while maintaining crosslinking performance.

The tertiary amine compound can promote a radical crosslinking reaction and effectively prevent oxygen inhibition by donating hydrogen present at the alpha position of the tertiary amine.

The photosensitive resin composition according to the embodiments of the present invention simultaneously improves the sensitivity, resolution and storage safety at room temperature by adjusting the content ratio of the tertiary amine compound to the bifunctional or less thiol-based compound. I can make it.

1 is a schematic diagram for explaining a method of measuring a line width of a hole pattern in an experimental example.
2 to 7 are photographs sequentially showing cases of 5B, 4B, 3B, 2B, 1B, and 0B according to the chemical resistance evaluation in the experimental example.
8 and 9 are SEM photographs showing the case where the boundary surface residue according to the storage stability evaluation did not occur and the case where it occurred, respectively.

Embodiments of the present invention provide a photosensitive resin composition comprising a tertiary amine compound and a thiol-based compound having a bifunctional or lower level. Accordingly, the photosensitive resin composition may have excellent sensitivity, resolution, and storage safety at room temperature at the same time.

In addition, there is provided a photocurable pattern formed from the photosensitive resin composition and an image display device including the photocurable pattern.

Hereinafter, a photosensitive resin composition according to embodiments of the present invention will be described in detail. When there is an isomer of a compound or resin represented by the formula used in the present application, the compound or resin represented by the formula refers to a representative formula including the isomer.

In addition, these embodiments are only illustrative of the present invention and do not limit the scope of the appended claims, and it is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the present invention. It is natural that such modifications and modifications fall within the appended claims.

<Photosensitive resin composition>

The photosensitive resin composition according to the embodiments of the present invention may include an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a tertiary amine compound represented by Formula 1 below, and a thiol-based compound having a bifunctional or lower level.

Tertiary amine compounds

The photosensitive resin composition according to embodiments of the present invention may include a tertiary amine compound represented by Formula 1 below.

The tertiary amine compound is a compound that promotes a radical crosslinking reaction occurring in an exposure process, and may compensate for the reduced photocuring sensitivity of the bifunctional or less thiol-based compound described below. Accordingly, the photosensitive resin composition may have excellent sensitivity, resolution, and storage stability at the same time.

[Formula 1]

In Formula 1, R ₁ and R ₂ may be a linear or branched alkyl group having 1 to 4 carbon atoms, and R ₃ may be a linear or cyclic alkyl group having 1 to 12 carbon atoms.

The compound represented by Chemical Formula 1 is a tertiary amine compound, and contains an alpha hydrogen (acidic proton) that is highly reactive to carbon (alpha position) adjacent to a nitrogen atom in a molecule. The alpha hydrogen may react with a photopolymerization initiator to be described later to generate an alkyl radical. The radical crosslinking reaction may be initiated by the alkyl radical, and sensitivity inhibition by oxygen may be effectively alleviated. Accordingly, the sensitivity and resolution of the photosensitive resin composition may be improved.

In some embodiments, R ₁ and R ₂ may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. Preferably, R ₁ and R ₂ in Formula 1 may be a methyl group having the largest number of alpha hydrogens while having less steric hindrance.

In some embodiments, R ₃ is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclodecyl group, cyclododecyl group, methylcyclopropyl group, methylcyclobutyl group, methylcyclopentyl group, methyl Cyclohexyl group, methylcycloheptyl group, methylcyclooctyl group, methylcyclononyl group, methylcyclodecyl group, methylcyclodecyl group, ethylcyclopropyl group, ethylcyclobutyl group, ethylcyclopentyl group, ethylcyclohexyl group, ethyl It may be a cycloheptyl group, an ethylcyclooctyl group, an ethylcyclononyl group, or an ethylcyclodecyl group.

In addition, R ₃ may not contain an aromatic structure. When R ₃ includes an aromatic structure, the sensitivity of the tertiary amine compound is excessively improved, and the unexposed portion may be cured by scattered light. Accordingly, the developability of the pattern may be deteriorated. Therefore, since R ₃ does not contain an aromatic structure, it is possible to prevent the photosensitive resin composition from being over-cured and deteriorating the developability of the pattern.

According to exemplary embodiments, the content of the tertiary amine compound may be about 0.1 to 1% by weight, and preferably about 0.5 to 0.8% by weight, based on the total weight of the photosensitive resin composition. As the content of the tertiary amine compound satisfies the above range, the sensitivity, resolution, and storage stability at room temperature of the photosensitive resin composition may be further improved.

Thiol-based compounds of difunctional or less

According to exemplary embodiments, the photosensitive resin composition may include a thiol-based compound of difunctional or less. The bifunctional or less thiol-based compound may function as a crosslinking agent participating in a polymerization or curing reaction together with the polymerizable compound.

The bifunctional or less thiol-based compound may be provided, for example, as an agent that accelerates or activates the crosslinkable curing of the polymerizable compound described later. For example, radically active species (for example, peroxy radicals, etc.) are generated through the initiation reaction of a photopolymerization initiator and the polymerizable compound, and a crosslinking or polymerization reaction by a chain reaction by the radically active species Can proceed.

In addition, the bifunctional or less thiol-based compound may react with the disappeared radical active species to revive the radical active species again. Accordingly, it is possible to prevent the end of the crosslinking or polymerization reaction because the radically active species meets with oxygen penetrating into the composition or coating film in the atmosphere and disappears. Therefore, it is possible to form a desired crosslinked network without being affected by external oxygen inhibition.

In addition, since the bifunctional or less thiol-based compound has relatively low reactivity compared to the trifunctional or more polyfunctional thiol-based compound, a problem in which the thiol-based compound reacts with the polymerizable compound at room temperature can be prevented. Accordingly, storage stability of the photosensitive resin composition may be improved.

According to exemplary embodiments, the bifunctional or less thiol-based compound may be a dithiol-based compound including two thiol groups. The dithiol-based compound may include two thiol groups bonded to the ends of the linker group.

In some embodiments, the dithiol-based compound may include an ethylene oxide (EO) group or an alkylene group as a linker group.

In one embodiment, the bifunctional or less thiol-based compound may be a thiol-based compound represented by the following Formula 2 including the EO linker group.

[Formula 2]

In Formula 2, m may be an integer of 1 to 5. When m is an integer of 6 or more, the cured properties of the photocurable pattern prepared from the photosensitive resin composition may be deteriorated.

In one embodiment, the bifunctional or less thiol-based compound may be a thiol-based compound represented by Formula 3 below including the alkylene linker group.

[Formula 3]

In Formula 3, n may be an integer of 1 to 11. When n is an integer of 12 or more, the cured physical properties of the photocurable pattern prepared from the photosensitive resin composition may be deteriorated.

Preferably, n may be 6 to 10. When n decreases and the length of the alkylene linker group is shortened, sulfur (S) having an off-flavor may cause harm to the human body or the environment.

In some embodiments, as exemplarily described in Formulas 2 and 3, the linker group may have a linear structure and may not include a branch. Accordingly, it is possible to prevent the deterioration of the crosslinking promoting property due to steric hindrance according to the branch structure.

In some embodiments, the photosensitive resin composition may include only a thiol-based compound having less than or equal to bifunctionality, and may not include a polyfunctional thiol compound having more than or equal to trifunctionality.

When the trifunctional or higher polyfunctional thiol-based compound is included, a thiol group having nucleophilicity reacts with an alkali-soluble resin and/or a polymerizable compound at room temperature, and storage stability of the photosensitive resin composition may be deteriorated.

However, since the photosensitive resin composition contains a bifunctional or less thiol-based compound, it may have excellent storage stability at room temperature and excellent crosslinking accelerating property.

According to exemplary embodiments, the content of the bifunctional or less thiol-based compound may be about 0.1 to 1.5% by weight, and preferably about 0.2 to 0.5% by weight, based on the total weight of the photosensitive resin composition. As the content of the bifunctional or less thiol-based compound satisfies the above range, not only the curing reaction of the photosensitive resin composition may be accelerated, but storage stability at room temperature may be further improved.

According to exemplary embodiments, the content ratio of the tertiary amine compound to the bifunctional or less thiol-based compound may be 1 to 4.2. In the content ratio range, the photosensitive resin composition has excellent storage stability, and sensitivity and resolution of the photosensitive resin composition may be improved together. If the content ratio of the tertiary amine compound to the bifunctional or less thiol-based compound is more than 4.2, there is a concern that the sensitivity may be lowered by UV absorption by the tertiary amine compound, and if it is less than 1, it is preserved by the thiol-based compound Stability and stability over time may deteriorate.

Alkali-soluble resin

The alkali-soluble resin is a component that imparts solubility to an alkali developer used in the development treatment process when forming a pattern, and is a component that provides adhesion to the substrate to enable formation of a coating film. For example, the alkali-soluble resin can function as a binder resin for the photosensitive resin composition.

In exemplary embodiments, the alkali-soluble resin according to the present invention is used together with the tertiary amine compound and the bifunctional or less thiol-based compound mentioned above to form a highly reliable pattern with excellent reactivity even under low temperature curing conditions. I can.

The low-temperature curing conditions may be, for example, 70 to 150°C, and preferably 70 to 100°C.

The kind of alkali-soluble resin is not particularly limited as long as it is generally used in the field of the art, for example, in the field of photosensitive resin composition and does not depart from the purpose of the present invention, and a polymer of monomers commonly used in the art Or it may be a copolymer of two or more monomers, the polymerization order and arrangement of the monomers is not particularly limited.

The alkali-soluble resin may include, for example, a unit derived from a monomer represented by the following formula (4).

[Formula 4]

In Formula 4, R ₄ is a hydrogen atom or a methyl group, and R ₅ is a hydrogen atom, or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a tetrahydrofuranyl group, a tetrahydropyra An alkoxy group having 1 to 6 carbon atoms substituted or unsubstituted with an yl group, an oxirane group, an oxetane group, an oxiranyl alkoxy group having 1 to 6 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, or a tricycloalkyl group having 6 to 18 carbon atoms , A C 1 to C 6 alkyl group, a C 4 to C 8 cycloalkyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group, a C 4 to C 12 bicycloalkyl group or a C 6 to C 18 tricyclo It may be an alkyl group.

For example, the alkali-soluble resin may include a repeating unit including an epoxy group derived from a glycidyl group represented by the following Formula 4-1.

[Formula 4-1]

In Formula 4-1, R ₆ is hydrogen or a methyl group, and R ₇ is a direct bond or an alkylene group having 1 to 5 carbon atoms.

In the present invention, "direct bond" refers to a structure in which an oxygen atom and a carbon atom such as an epoxy group are directly bonded without the mediation of other atoms.

For example, the alkali-soluble resin may include a repeating unit including a terminal double bond represented by the following Formula 4-2.

[Formula 4-2]

In Formula 4-2, R ₈ is hydrogen or a methyl group.

For example, the alkali-soluble resin may include a repeating unit including a tricycloalkyl group and an epoxy group represented by the following Formula 4-3.

[Chemical Formula 4-3]

In Formula 4-3, R ₉ is hydrogen or a methyl group.

For example, the alkali-soluble resin may include a repeating unit including an oxetane group represented by the following Formula 4-4.

[Formula 4-4]

In Formula 4-4, R ₁₀ is hydrogen or a methyl group, R ₁₁ is a direct bond or an alkylene group having 1 to 5 carbon atoms, and R ₁₂ is a linear or branched alkyl group or an alkenyl group having 1 to 4 carbon atoms.

The alkali-soluble resin may include, for example, a unit derived from a monomer represented by the following formula (5).

[Formula 5]

In Formula 5, R ₁₃ is a hydrogen atom, or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, oxetane Group, an alkoxy group having 1 to 6 carbon atoms, unsubstituted or substituted with a bicycloalkyl group having 4 to 12 carbon atoms or a tricycloalkyl group having 6 to 18 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, tetrahydro It may be a furanyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group, a bicycloalkyl group having 4 to 12 carbon atoms, or a tricycloalkyl group having 6 to 18 carbon atoms.

For example, the alkali-soluble resin may include a repeating unit represented by Formula 5-1 below.

[Chemical Formula 5-1]

In Formula 5-1, R ₁₄ is hydrogen or a methyl group, R ₁₅ is bonded at one or more of the ortho, meta and para positions, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

In addition to the above monomers, the alkali-soluble resin may further contain an acrylate-based monomer known in the art and commonly used to be polymerized.

The arylate-based monomer is, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylic Rate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth) )Acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-meth Toxoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylic Rate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monophenyl ether (meth)acrylate, triethylene glycol monomethyl Ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, cyclopentanyl (meth)acrylate, dicyclo Pentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate , Tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, glycidyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

In some exemplary embodiments, the alkali-soluble resin may be an alkali-soluble resin including at least one repeating unit of an epoxy group-containing unit or a terminal double bond-containing unit.

The photosensitive resin composition according to some exemplary embodiments may include an alkali-soluble resin including the epoxy group-containing repeating unit or an alkali-soluble resin including the terminal double bond-containing repeating unit.

In one embodiment, the photosensitive resin composition may contain 1 to 10% by weight, preferably 5 to 7% by weight, based on the total weight of the photosensitive resin composition, the alkali-soluble resin containing the epoxy group-containing unit. In the above range, the solubility in a developer is sufficient, so that developability is excellent, and a photocuring pattern having excellent mechanical properties can be formed.

In one embodiment, the photosensitive resin composition may contain an alkali-soluble resin including the terminal double bond-containing repeating unit in 1 to 10% by weight, preferably 1.5 to 5% by weight, based on the total weight of the photosensitive resin composition. have. Within the above range, the resolution and pattern uniformity of the photosensitive resin composition may be excellent, and adhesion to a substrate may be excellent.

Polymerizable compound

The polymerizable compound contained in the photosensitive resin composition according to the embodiments of the present invention is a compound that can be polymerized or crosslinked by the action of a polymerization initiator described below, and increases the crosslinking density during the manufacturing process and improves the mechanical properties of the photocurable pattern. Can be strengthened.

The polymerizable compound may be used without particular limitation as long as it is used in the art. For example, it is a monofunctional monomer, a difunctional monomer, and other polyfunctional monomers, and the kind is not particularly limited, but the following compounds are examples. Can be lifted.

The monofunctional monomer compound is, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinyl It may be at least any one selected from the group consisting of pyrrolidone and the like.

The bifunctional monomer is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate may be at least one selected from the group consisting of.

Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri(meth)acrylate, oxylated trimethylolpropane tri(meth)acrylate, lopoxylated trimethylolpropanetri(meth)acrylate, and taerythritol Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaeryte It may be at least one selected from the group consisting of litolehexa (meth)acrylate and pentaerythritol hexa (meth)acrylate.

In some embodiments, the unsaturated polymerizable compound may not include a tetrafunctional or higher (meth)acrylate compound. In the case of the tetrafunctional or higher (meth)acrylate compound, due to the bulky molecular structure, the viscosity of the composition may be rapidly increased due to intermolecular interaction.

According to exemplary embodiments, the content of the polymerizable compound in the total weight of the photosensitive resin composition may be about 5 to 15% by weight, preferably 7 to 12% by weight. When the above range is satisfied, the hardness and mechanical properties of the photocurable pattern formed from the photosensitive resin composition may be excellent.

Photopolymerization initiator

The photosensitive resin composition according to an embodiment of the present invention may include a photopolymerization initiator.

The photopolymerization initiator is a compound that generates a radical capable of initiating polymerization of the above-described polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays. The photoinitiator may be, for example, an acetophenone compound, a benzophenone compound, a biimidazole compound, a triazine compound, an oxime ester compound, or a thioxanthone compound. The photopolymerization initiator may be used alone or in combination of two or more.

In exemplary embodiments, the photopolymerization initiator may include at least one of a biimidazole-based compound and an oxime ester-based compound.

The biimidazole-based compound reacts with the tertiary amine compound mentioned above to improve the sensitivity and resolution of the photosensitive resin composition, and may improve the surface curability of the photocurable pattern.

The oxime ester-based compound may supplement the radical reaction initiation property of the non-imidazole-based compound, and may improve adhesion between the substrate and the photocuring pattern.

In one embodiment, the biimidazole-based compound is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group, etc. I can.

In one embodiment, the oxime ester-based compound may include at least one or more of the compounds represented by the following Chemical Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 14 to 16, R ₁₆ , R _17, R ₁₉ , R ₂₀ and R ₂₁ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms. R ₁₈ may be an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group.

According to exemplary embodiments, the photopolymerization initiator may be about 0.01 to 10% by weight, preferably about 0.1 to 1% by weight, based on the total weight of the photosensitive resin composition. In the above range, the photosensitive resin composition may have excellent resolution of an exposure process and hardness of a cured film.

The content ratio of the biimidazole-based compound to the oxime ester-based compound included in the photosensitive resin composition according to exemplary embodiments may be 2 to 8. In the above range, since the reactivity of the biimidazole-based compound and the tertiary amine compound is excellent, the photocuring reaction of the photosensitive resin composition may be accelerated, and the adhesion to the substrate may be further improved by the oxime ester-based compound. .

solvent

In the photosensitive resin composition of the present invention, solvents commonly used in the art may be used without particular limitation.

Examples of the solvent include ethylene glycol monoalkyl ethers; Diethylene glycol dialkyl ethers; Ethylene glycol alkyl ether acetates; Alkylene glycol alkyl ether acetates; Propylene glycol monoalkyl ethers; Propylene glycol dialkyl ethers; Propylene glycol alkyl ether propionates; Butyldiol monoalkyl ethers; Butanediol monoalkyl ether acetates; Butanediol monoalkyl ether propionates; Dipropylene glycol dimethyl ether, dipropylene glycol dialkyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones; Alcohols; Esters; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. These may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, and may be included in the remaining amount excluding the above-described components and other additive components. For example, it may be included in an amount of 40 parts by weight to 95 parts by weight, preferably 45 parts by weight to 85 parts by weight, based on 100 parts by weight of the photosensitive resin composition in consideration of coating properties and drying properties of the composition.

additive

Additives may be included in the photosensitive resin composition to additionally improve properties such as curing degree, smoothness, adhesion, solvent resistance, and chemical resistance of the photosensitive resin composition according to embodiments of the present invention or a photocurable pattern formed therefrom. For example, the additive may include a curing agent, a leveling agent, a surfactant, an adhesion promoter, an antioxidant, a filler, an ultraviolet absorber, an anti-aggregation agent, a chain transfer agent, and the like.

The curing agent is used to increase deep curing and mechanical strength, and the curing agent may be an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, or an oxetane compound.

As the leveling agent, a commercially available surfactant may be used, and for example, surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, etc. can be used. Two or more types 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, In addition to polyethyleneimines, under brand names, KP (manufactured by Shin-Etsu Chemical Industries, Ltd.), Polyflow (manufactured by Kyei Chemical Corporation), Ftop (manufactured by Tochem Products), Megapak (manufactured by Tochem Products), Megapak (manufactured by Dai Nippon Ink Chemical Industries, Ltd.) Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sor Spas (manufactured by Geneca Co., Ltd.), EFKA (EFKA Chemicals Co. Manufactured), PB821 (manufactured by Ajinomoto Co., Ltd.) or SH8400 Fluid (manufactured by GE Toshiba-Toray), and the like may be used.

As the adhesion promoter, a silane-based compound is preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical), 3-mercaptopropyltrimethoxysilane, and the like may be used.

As the antioxidant, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxyl) Roxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) Propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphospepine, 3,9-bis[2-{3-(3- tert-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-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5 -Methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropio Nate, distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl) -4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3``,5,5',5'' -Hexa-tert-butyl-a,a',a''-(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 can be used.

Photocuring pattern

The present invention provides a photocurable pattern with improved cured properties prepared from the photosensitive resin composition described above.

The photocurable pattern may be used as various film structures or patterns of an image display device, for example, as 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. However, it is not limited thereto.

In forming the photocurable pattern, the photosensitive resin composition may be coated on a substrate, then exposed and developed to form a pattern, and a pre-baking or post-baking process may be performed between each step. .

First, the photosensitive resin composition may be coated on a substrate and then dried to form a coating film.

The substrate may be, for example, a glass substrate, a silicon wafer, a silicon wafer, or a plastic. The coating may use a conventional wet coating method such as inkjet printing, spin coating, flexible coating, roller coating, and spray coating. The coating thickness may vary depending on the use of the photosensitive resin composition, and may be, for example, about 0.5 to 10 μm.

The drying is a process of removing a solvent or volatile component in the composition, and the drying temperature and time may vary depending on the type of solvent used. The coating film may be made of solid components of the photosensitive resin composition, and may contain almost no volatile components.

After drying, if necessary, a pre-baking process can be performed. Pre-baking can be performed by heating with an oven, hot plate, or the like. The heating temperature and heating time in the pre-baking are selected according to the type of solvent to be used, and may be performed at a temperature of about 80 to 150° C. for about 1 to 30 minutes.

Next, a photocuring pattern may be formed by performing an exposure process of irradiating light rays through a photomask on the coating layer, and a post exposure baking (PEB) process may be further performed.

In the exposure process, a magnetic ray light source such as a UV-A region (320 to 400 nm), a UV-B region (280 to 320 nm), and a UV-C region (200 to 280 nm) of a high-pressure mercury lamp, an electron ray light source or X-ray A light source can be used. For example, a g-line (wavelength: 436 nm) light source or an i-line (wavelength: 365 nm) light source may be used in the exposure process. The photomask is for blocking light rays, and an exposed/non-exposed area is defined according to the shape of the photomask.

Next, the coating layer may be treated with an alkali developer to dissolve the non-exposed part and form a pattern made of the exposed part.

The alkali developer is, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethyl It may be an aqueous solution of organic alkalis such as ethanolamine.

The alkali developer may be used, for example, in a concentration of about 0.01 to 5% by weight, preferably about 0.05 to 2.5% by weight of the organic alkali aqueous solution.

The alkaline developer may include, for example, a surfactant such as a nonionic surfactant having an action of promoting the removal of the development residue, or a water-soluble organic solvent such as methanol or ethanol.

The developing process may be a dipping method, a shower method, or a spray method, and may be performed for about 30 to 60 seconds, and the non-exposed region region is removed, and only the exposed region region is selectively left to form a pattern.

After development, it is washed with water and then dried, and if necessary, a post-baking process, which is a heat treatment, may be performed at a temperature of about 200 to 250°C.

Image display device

The present invention provides an image display device including a photocurable pattern prepared from the photosensitive resin composition described above.

Specifically, the image display device may include, but is not limited to, a liquid crystal display device, an OLED, and a flexible display.

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid in understanding of the present invention, but this is only illustrative of the present invention and does not limit the scope of the appended claims, and the scope and technology of the present invention It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope of the spirit, and it is natural that such modifications and modifications fall within the appended claims.

Synthesis Example 1: Synthesis of alkali-soluble resin (A-1)

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 200 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Then, a mixture of the following Chemical Formulas 9 and 10 (molar ratio is 50:50), 132.2 g (0.60 mol), glycidyl methacrylate 42.6 g (0.30 mol), and 8.6 g (0.10 mol) methacrylic acid were dissolved Was prepared.

[Formula 9]

[Formula 10]

After dropping the prepared solution into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 150 g of diethylene glycol methyl ethyl ether. The solution dissolved in was dripped into the flask over 5 hours using a separate dropping funnel. After the dropping of the polymerization initiator solution was completed, it was maintained at 70° C. for 10 hours, and then cooled to room temperature, and an alkali-soluble resin (A-) having a solid content of 32.0 mass% and an acid value of 65 mgKOH/g (in terms of solid content) The solution of 1) was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 15,500, and the molecular weight distribution (Mw/Mn) was 1.97.

Synthesis Example 2: Synthesis of alkali-soluble resin (A-2)

In a 1 L flask equipped with a reflux condenser, dropping funnel, and stirrer, nitrogen was flowed at 0.02 L/min to create a nitrogen atmosphere, and 250 g of propylene glycol monomethyl ether acetate was introduced, and after heating to 100°C, 21.6 g (0.30 mol) of acrylic acid ), 3-ethyl-3-oxetanyl methacrylate 73.7 g (0.40 mol), vinyl toluene 34.5 (0.30 mol) and propylene glycol monomethyl ether acetate 150 g in a mixture containing 2,2'-azobis (2 A solution to which 3.6 g of ,4-dimethylvaleronitrile) was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 100°C for 5 hours.

Then, the atmosphere in the flask was made from nitrogen to air, and 26.3 g of glycidyl methacrylate [0.15 mol (50 mol% based on acrylic acid used in this reaction)] was added into the flask, and the reaction was continued at 110° C. for 6 hours. , An alkali-soluble resin (A-2) having a solid acid value of 65 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 8,400, and the molecular weight distribution (Mw/Mn) was 1.85.

Examples and Comparative Examples

A photosensitive resin composition was prepared with the composition and content (% by weight) shown in Tables 1 and 2 below.

division Example One 2 3 4 5 6 7 8 9 10 Alkali soluble
Resin (A) A-1 7.27 7.27 7.27 7.27 7.27 7.27 7.27 7.27 7.27 7.27 A-2 1.82 1.82 1.82 1.82 1.82 1.82 1.82 1.82 1.82 1.82 Polymerizable compound (B) 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 Light polymerization
Initiator
(C) C-1 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 C-2 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Tertiary amine
compound
(D) D-1 0.55 - - 0.55 - - - - - - D-2 - 0.55 - - 0.55 - 0.73 0.45 0.36 0.18 D-3 - - 0.55 - - 0.55 - - - - D-4 - - - - - - - - - - D-5 - - - - - - - - - - Thiol
compound
(E) E-1 0.36 0.36 0.36 - - - 0.18 0.45 0.55 0.73 E-2 - - - 0.36 0.36 0.36 - - - - E-3 - - - - - - - - - - E-4 - - - - - - - - - - E-5 - - - - - - - - - - additive
(F) F-1 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 F-2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 F-3 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Solvent (S) S-1 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 S-2 55.85 55.85 55.85 55.85 55.85 55.85 55.85 55.85 55.85 5.85

division Comparative example One 2 3 4 5 6 7 8 9 10 Alkali soluble
Resin (A) A-1 7.62 7.27 7.27 7.27 7.27 7.27 7.27 7.27 7.27 7.27 A-2 1.90 1.82 1.82 1.82 1.82 1.82 1.82 1.82 1.82 1.82 Polymerizable compound (B) 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 9.09 Light polymerization
Initiator
(C) C-1 0.57 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 C-2 0.10 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Tertiary amine
compound
(D) D-1 - - - 0.91 - - - - - - D-2 - - - - 0.91 0.55 0.55 0.55 - - D-3 - - - - - - - - - - D-4 - - - - - - - - 0.55 - D-5 - - - - - - - - - 0.55 Thiol
compound
(E) E-1 - 0.91 - - - - - - 0.36 0.36 E-2 - - 0.91 - - - - - - - E-3 - - - - - 0.36 - - - - E-4 - - - - - - 0.36 - - - E-5 - - - - - - - 0.36 - - additive
(F) F-1 0.19 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 F-2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 F-3 0.10 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Solvent (S) S-1 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 S-2 55.85 55.85 55.85 55.85 55.85 55.85 55.85 55.85 55.85 55.85

[화학식 12]

[화학식 13]

[화학식 14]

[화학식 15]

[화학식 16]

A-1: Alkali-soluble resin of Synthesis Example 1
A-2: Alkali-soluble resin of Synthesis Example 2

B: 5-functional acrylate compound (A-9570: manufactured by Sustainable Industries, Inc.)

C-1: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (B-CIM: manufactured by Hodogaya Chemical Industries, Ltd.)
C-2: oxime ester compound represented by Formula 11

D-1: compound represented by formula 12
D-2: compound represented by Chemical Formula 13
D-3: compound represented by formula 14
D-4: compound represented by formula 15
D-5: compound represented by formula 16

E-1: 3,6-dioxa-1,8-octanedithiol (manufactured by TCI)
E-2: 1,10-decanedithiol (manufactured by TCI)
E-3: pentaerythritol tetrakis[3-mercaptopropionate] (PEMP: manufactured by SC Chemical Co., Ltd.)
E-4: Tris-[(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC: manufactured by SC Chemical Co., Ltd.)
E-5: pentaerythritol hexakis [3-mercaptopropionate] (DPMP: manufactured by SC Chemical Co., Ltd.)

F-1: 4,4'-butylidene bis[6-tert-butyl-3-methylphenol] (BBM-S: Antioxidant manufactured by Sumitomo Co., Ltd. tablets
F-2: SH8400 Fluid (manufactured by GE Toshiba-Toray) surfactant
F-3: KBM-503 (manufactured by Shin-Etsu Chemical) adhesion promoter

S-1: diethylene glycol methylethyl ether
S-2: Propylene glycol monomale ether acetate

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

Experimental example

A 2 inch wide glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol, and then dried. Each of the photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated on the glass substrate, and then prebaked at 80° C. for 125 seconds using a hot plate. After cooling the prebaked substrate to room temperature, light was irradiated with an exposure amount of 30 mJ/cm 2 (based on 365 nm) using an exposure machine (MA6 manufactured by MICOSUSS) with an interval of 50 μm with the quartz glass photomask. At this time, a photomask having a square pattern with a side of 7 μm and a pattern having a mutual spacing of 100 μm on the same plane was used. After light irradiation, the coating was developed by immersing the coating film in a 2.38% tetraammonium hydroxide aqueous solution at 25° C. for 60 seconds, washing with water and drying, and post-baking at 85° C. for 60 minutes using a clean oven. The obtained pattern height was 2.0 µm. The obtained pattern was evaluated for physical properties as follows, and the results are shown in Table 3 below.

(1) Pattern Bottom-CD size measurement

The obtained hole pattern was observed with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision). As shown in FIG. 1, a point at 5% of the total height from the bottom surface of the hole pattern was defined as the bottom line width (Bottom CD), and the average value of the measured values in the horizontal and vertical directions was defined as the line width of the hole pattern. .

(2) CD-bias measurement of pattern

As described above, the difference between the bottom line width value of the obtained hole pattern and the photomask size was calculated as CD-bias. CD-bias is better as it approaches 0, and (+) means that the bottom line width value of the hole pattern is larger than that of the photomask, and (-) means that the hole size is smaller than that of the photomask.

(3) Chemical resistance evaluation

SS사 MA6)를 사용하여 30mJ/㎠의 노광량(365㎚ 기준)으로 도막의 전면에 광을 조사하였다. 광조사 후 2.38% 테트라암모늄 히드록시드 수용액에 상기 도막을 25℃ 에서 60초간 침지하여 현상하고, 수세 후 오븐 중에서, 수세 및 건조 후, 클린 오븐을 이용하여 85℃에서 120분간 포스트베이크를 실시하였다.The photosensitive resin composition prepared in Examples and Comparative Examples was applied to a glass substrate on which amorphous ITO was deposited to a thickness of 1200Å, spin-coated, and prebaked at 80° C. for 120 seconds using a hot plate. After cooling the prebaked substrate to room temperature. Exposure machine (MICOS

SS MA6) was used to irradiate the entire surface of the coating film with an exposure dose of 30 mJ/cm 2 (based on 365 nm). After light irradiation, the coating film was immersed in a 2.38% tetraammonium hydroxide aqueous solution at 25° C. for 60 seconds to develop, washed with water, washed with water and dried in an oven, and post-baked at 85° C. for 120 minutes using a clean oven. .

The prepared coating film was immersed in a positive resist stripper (produced by dissolving 60 g of 2-amino-1-propanol in 60 g of N-methyl-2-pyrrolidone and 80 g of diethylene glycol methylbutyl ether) and treatment for 45 minutes/2 minutes After that, according to ASTM D-3359-08 standard test conditions, after cutting the coating film with a cutter, the adhesion was confirmed by attaching a tape to the surface and then removing it. In the cutting/tape test after chemical treatment, the degree of peeling of the coating film is defined as 0B to 5B based on the standard test method, and 5B is judged to have the best performance (5B peeling 0%, 4B peeling less than 5%, 3B peeling 5 to 15%, 2B peeling 15 to 35%, 1B peeling 35 to 65%, 0B 65% or more) Figures 2 to 7 are patterns photos in the case of 5B, 4B, 3B, 2B, 1B, and 0B in order. .

(4) Storage stability evaluation

After the photosensitive resin compositions prepared in Examples and Comparative Examples were allowed to stand at 23° C. for 72 hours, exposure/development processes were performed as specified in the experimental method to produce a hole pattern.

Storage stability was evaluated based on the degree of progression of residues occurring at the boundary between the hole bottom surface corresponding to the unexposed part and the pattern. A pattern made of a newly prepared photosensitive resin composition and a pattern made of a photosensitive resin composition left at 23°C for 72 hours were compared, and if there was no difference between the two, the storage stability was judged as good (OK), and at 23°C for 72 hours When the residue grows at the interface of the pattern made of the left photosensitive resin composition and becomes severe, it was judged as having poor storage stability (NG).

FIG. 8 is a photograph showing a case where no residue occurs at the boundary between the pattern and the bottom surface of the hole corresponding to the unexposed portion. This is an SEM photograph showing a severe case.

division Bottom-CD size(㎛) CD-bias(㎛) Chemical resistance Storage stability Example 1 6.3 -0.7 5B OK Example 2 6.7 -0.3 5B OK Example 3 6.5 -0.5 5B OK Example 4 6.2 -0.8 5B OK Example 5 6.6 -0.4 5B OK Example 6 6.4 -0.6 5B OK Example 7 6.8 -0.2 5B OK Example 8 6.3 -0.7 5B OK Example 9 5.8 -1.2 5B OK Example 10 5.6 -1.4 5B OK Comparative Example 1 7.6 0.6 0B OK Comparative Example 2 5.2 -1.8 5B NG Comparative Example 3 5.4 -1.6 5B NG Comparative Example 4 6.9 -0.1 2B OK Comparative Example 5 6.7 -0.3 2B OK Comparative Example 6 4.5 -2.5 5B NG Comparative Example 7 5.4 -1.6 4B NG Comparative Example 8 4.1 -2.9 5B NG Comparative Example 9 Not open Not open 5B NG Comparative Example 10 Not open Not open 5B NG

Referring to Table 3, in the case of the photosensitive resin composition according to the embodiments of the present invention, a comparison without including the tertiary amine compound represented by Chemical Formula 1 and the thiol-based compound having difunctionality or less The resolution, chemical resistance, and storage stability at room temperature are better than those of the examples. Comparative Examples 2 and 3 containing a thiol-based compound having a bifunctional or lower function, but not containing a tertiary amine compound represented by Formula 1, are stored at room temperature Stability deteriorates.

Comparative Examples 9 and 10, which include a bifunctional or less thiol-based compound and a tertiary amine compound, but in which the tertiary amine compound does not satisfy the structure of Formula 1, were too high in sensitivity to scattered light. The hole pattern was not formed due to the hardening of the miner.

Comparative Examples 4 and 5 including a tertiary amine compound represented by Formula 1, but including a thiol-based compound having a trifunctional or higher function, have deteriorated chemical resistance.

Comparative Examples 6 to 8 including the tertiary amine compound represented by Chemical Formula 1 and including a thiol-based compound but containing a trifunctional or higher thiol-based compound exhibited deterioration in storage stability at room temperature.

Claims (11)

Alkali-soluble resin;
Polymerizable compounds;
Photopolymerization initiator;
A tertiary amine compound represented by the following formula (1); And
A photosensitive resin composition containing a bifunctional or less thiol-based compound:
[Formula 1]

(In Formula 1, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 4 carbon atoms, and R ₃ is a linear or cyclic alkyl group having 1 to 12 carbon atoms).
The photosensitive resin composition according to claim 1, wherein the bifunctional or less thiol-based compound is a dithiol-based compound.
The photosensitive resin composition according to claim 1, wherein the bifunctional or less thiol-based compound comprises at least one of compounds represented by Formula 2 or Formula 3:
[Formula 2]

(In Formula 2, m is an integer of 1 to 5)
[Formula 3]

(In Chemical Formula 3, n is an integer of 1 to 11).
The photosensitive resin composition of claim 1, wherein the content of the tertiary amine compound is 0.1 to 1% by weight based on the total weight of the photosensitive resin composition.
The photosensitive resin composition of claim 1, wherein the content of the bifunctional or less thiol-based compound is 0.1 to 1% by weight based on the total weight of the photosensitive resin composition.
The photosensitive resin composition of claim 1, wherein a content ratio of the tertiary amine compound to the bifunctional or less thiol-based compound is 1 to 4.2.
The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin contains at least one repeating unit of an epoxy group-containing unit or a terminal double bond-containing unit.
The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator contains at least one of a biimidazole-based compound and an oxime ester-based compound.
A photocurable pattern formed of the photosensitive resin composition of any one of claims 1 to 8.
The photocurable pattern of claim 9, wherein the photocuring pattern is selected from the group consisting of an array planarization layer pattern, a passivation layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer.
An image display device comprising the photocuring pattern of claim 9.

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