KR20160095763A - Photosensitive resin comopsition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and, more specifically, to a photosensitive resin composition which can effectively implement high sensitivity through reducing oxygen inhibition by comprising an amine additive of a specific structure and an ultraviolet absorber having maximum absorption wavelength (max) of 335 to 365 nm and can implement high resolution when being applied to a product after inhibiting the expansion of the line width in a pattern.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same.

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.

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

More specifically, the photolithography process is performed by radical polymerization of a photopolymerizable monomer or a polymer containing an unsaturated group capable of photopolymerization using a radical generated in the photoinitiator.

On the other hand, the coating film on which the photosensitive resin composition capable of performing the photolithography process is applied has oxygen diffused in the atmosphere. When oxygen reacts with the generated radical, there is a problem that it is stabilized with peroxy radical. That is, the radicals become inactivated and can no longer participate in the polymerization reaction, so that the crosslinking density of the entire cured composition is significantly lowered. This phenomenon is called oxygen inhibition, and various studies are under way to improve it.

In order to prevent oxygen inhibition, various studies have been conducted using additives capable of activating stabilized peroxy radicals. However, when these additives are used, high sensitivity can be realized, but the pattern size becomes excessively large, There is a difficult problem to implement.

Japanese Patent Laid-Open No. 2000-095896

It is an object of the present invention to provide a photosensitive resin composition capable of simultaneously realizing high sensitivity and high resolution.

It is an object of the present invention to provide a photocuring pattern that can be realized in a fine pattern and has excellent adhesion, residual film ratio and mechanical properties.

It is still another object of the present invention to provide an image display device having the photocurable pattern.

1. An amine resin composition comprising an amine additive comprising at least one of compounds represented by the following formulas (1) and (2) and an ultraviolet absorber having a maximum absorption wavelength (? _Max ) of 335 to 365 nm:

[Chemical Formula 1]

(2)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a straight or branched alkyl group having 1 to 10 carbon atoms, At least one atom may be contained,

n and m are each independently an integer of 6 to 20).

2. The photosensitive resin composition according to 1 above, wherein the ultraviolet absorber is at least one selected from the group consisting of compounds represented by the following formulas (3) to (5)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a halogen atom, An alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

The aryl group may be substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms and a tricycloalkyl group having 6 to 12 carbon atoms Lt; / RTI > may be substituted with at least one substituent selected from the group consisting of < RTI ID = 0.0 >

3. The photosensitive resin composition according to item 1, wherein the ultraviolet absorber is contained in an amount of 10 to 80 parts by weight based on 100 parts by weight of the amine additive.

4. The photosensitive resin composition according to 1 above, wherein the amine additive is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition.

5. The photosensitive resin composition according to 1 above, wherein the ultraviolet absorber is contained in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition.

6. The photosensitive resin composition according to 1 above, further comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

7. A photocurable pattern produced from the photosensitive resin composition according to any one of items 1 to 6 above.

8. The photopolymerizable composition according to 7 above, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern and a column spacer pattern. pattern

9. An image display device having the photocuring pattern of the above 8.

The photosensitive resin composition of the present invention can realize high sensitivity by relaxing oxygen inhibition and at the same time suppressing the enlargement of the line width of the pattern and realizing a high resolution by the fine pattern.

The photosensitive resin composition of the present invention is excellent in developing adhesion, and has excellent residual film ratio and mechanical properties.

Since the photocurable pattern made of the photosensitive resin composition of the present invention can be formed in a fine pattern, high resolution can be realized when applied to a product.

1 is a view schematically showing the definition of a T / B ratio.

The present invention relates to a photosensitive resin composition, and more particularly, to an amine additive having a specific structure and an ultraviolet absorber having a maximum absorption wavelength (? _Max ) of 335 to 365 nm, And at the same time suppressing the enlargement of the line width of the pattern, thereby realizing a high resolution by a fine pattern when applied to a product.

Hereinafter, the present invention will be described in detail.

Conventionally, various additives have been used in the photolithography process to suppress the problem of lowering the reactivity (oxygen inhibition) due to oxygen present in the coating film. However, such an additive can improve the curing reactivity, but it can not control the directionality in which the reaction takes place, thereby increasing not only the height of the pattern but also the width (line width) of the pattern during formation of the pattern.

Accordingly, by using an amine additive having a specific structure and a specific ultraviolet absorber at the same time, the present invention can simultaneously realize high sensitivity and high resolution by controlling the directionality of the curing reaction while alleviating the oxygen inhibition.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises an amine additive having a specific structure and an ultraviolet absorber having a maximum absorption wavelength (? _Max) of 335 to 365 nm.

Amine additive

The amine additive used in the present invention includes at least one of the compounds represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a straight or branched alkyl group having 1 to 10 carbon atoms, At least one atom may be contained,

n and m are each independently an integer of 6 to 20).

The compounds represented by the general formulas (1) and (2) are tertiary amine compounds, and include hydrogen (acidic proton) having excellent reactivity to carbon (alpha position) adjacent to a nitrogen atom in the molecule. The acidic proton reacts with a stable peroxy radical to generate an alkyl radical capable of initiating polymerization, thereby effectively relaxing the oxygen inhibition, thereby realizing high sensitivity in pattern formation.

In the above formulas, the substituents (R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ ) of the amine are preferably methyl groups, ethyl groups, butyl groups or propyl groups And more preferably a methyl group having the largest number of acdic proton while having few steric hindrance.

When the molecular weight of the amine additive is too small (n is less than 6), the amine additive is inadequate to use due to its low boiling point, and can escape from the coating film during curing reaction, resulting in outgas. The acdic proton number per molecule of the complex may be reduced and the overall reactivity may be lowered somewhat. In the above formula, when the unit number (n) of repeating alkyl chains in the molecule is 6 to 10, the above-mentioned problem can be most effectively compensated.

Ultraviolet absorber

The ultraviolet absorber used in the present invention is a component which realizes a fine pattern by suppressing an increase in line width (width) by the above-mentioned additive.

In the case of using only the amine additive, the acceleration of the curing reaction occurs only in the same direction, and the height and width (line width) of the pattern are both increased. In the present invention, by using the ultraviolet absorbent at the same time, Sensitivity) can be effectively controlled while reducing the light energy reaching the deep portion of the coating film while maintaining the appropriate range, thereby increasing the width (line width) of the base portion of the pattern (horizontal direction sensitivity).

On the other hand, when only the ultraviolet absorber is used, a fine pattern can be realized, but the density of the curing may be lowered and the pattern adhesion and mechanical characteristics may be deteriorated. In the present invention, by using the amine additive and the ultraviolet absorber at the same time, The adhesion and the mechanical properties of the film can be remarkably improved.

The ultraviolet absorber exhibits a maximum absorption wavelength (? _Max ) of 335 to 365 nm, and when the maximum absorption wavelength is less than 335 nm, the sensitivity is excessively increased so that the increase of the line width of the pattern can not be controlled. And the T / B ratio and adhesion can be lowered by decreasing the line width. When the maximum absorption wavelength of the ultraviolet absorbent is from 355 nm to 360 nm, the above-mentioned problem can be more effectively compensated.

Examples of the ultraviolet absorber include hydroxybenzophenone compounds, benzotriazole compounds, and triazine compounds. Examples of the ultraviolet absorber include ortho It is preferred that the position contains hydroxy.

Specific examples of the ultraviolet absorber may be compounds represented by the following formulas (3) to (5), which may be used alone or in combination.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a halogen atom, An alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

The aryl group may be substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms and a tricycloalkyl group having 6 to 12 carbon atoms Lt; / RTI &gt; may be substituted with at least one substituent selected from the group consisting of &lt; RTI ID = 0.0 &gt;

In the present invention, the content ratio of the amine additive to the ultraviolet absorber is not particularly limited, but may be 10 to 80 parts by weight, preferably 20 to 60 parts by weight, per 100 parts by weight of the amine additive. When included in the above range, the effect of the present invention can be further improved, and the T / B ratio of the pattern can be remarkably improved.

The T / B ratio is a value obtained by dividing the diameter of the upper portion of the pattern by the diameter of the lower portion, and a larger T / B ratio is preferable. In the present invention, the upper part of the pattern is defined as a horizontal plane at a point 95% of the total height from the bottom plane with respect to the total height of the pattern, and the lower part of the pattern is 5% (See Figure 1).

The content of the amine additive in the composition is not particularly limited, but it may be 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition. When the content is within the above range, a high sensitivity of the pattern can be realized, The mechanical strength can be further improved.

The content of the ultraviolet screening agent is not particularly limited, but may be in the range of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition. When the ultraviolet screening agent is included in the above range, it is suitable to form a fine pattern, Can,

The photosensitive resin composition according to the present invention may further comprise an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent in addition to the above-mentioned amine additive and ultraviolet absorber.

Alkali-soluble resin

The alkali-soluble resin which can be used in the present invention is not particularly limited, but may include, for example, a repeating unit represented by the following formula (6).

[Chemical Formula 6]

(Wherein R ₁ ', R ₂ ', R ₃ 'and R ₄ ' each independently represents a hydrogen atom or a methyl group,

R ₅ 'is at least one selected from the group consisting of benzyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (2-phenyl) phenoxyethoxy (Meth) acrylate, (meth) styrene, vinyltoluene, vinyltoluene, vinyltoluene, vinyltoluene, vinyltoluene, Vinyl naphthalene, N-benzyl maleimide, methyl (meth) acrylate, ethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (Meth) acrylate, methoxy tetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl The structure derived from the monomer selected from the group true,

R ₆ 'is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7)

R ₇ 'is selected from the group consisting of (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethylhexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate and 2 - (meth) acryloyloxyethyl succinate, wherein the structure is derived from a monomer selected from the group consisting of

a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 30 mol%.

In the present invention, "(meth) acrylic-" refers to "methacryl- "," acrylic- "

In the present invention, each of the repeating units represented by the formula (7) should not be construed as being limited to the display, and the sub-repeating units in the parentheses can freely be positioned at any position of the chain within a predetermined mole% range. That is, although the parentheses in the formula (7) are represented by one block for expressing the mol%, each sub-repeating unit may be placed in blocks or separately in any resin within the resin.

Preferable examples of the repeating unit represented by the formula (6) include repeating units represented by the following formula (7).

(7)

(Wherein R ₁ ', R ₂ ', R ₃ ', R ₄ ' and a, b, c and d are the same as described above).

The binder resin preferably has a weight average molecular weight of from 10,000 to 30,000 from the standpoint of exhibiting the most excellent pattern formation property and developability. It is possible to exhibit the best pattern formation property and developability in the above molecular weight range.

The alkali-soluble binder resin according to the present invention may further comprise, in addition to the repeating unit represented by the formula (6), a repeating unit formed of another monomer known in the art, and may be formed only of the repeating unit represented by the formula (6).

Examples of the monomer forming the repeating unit that can be further added include, but are not limited to, monocarboxylic acids such as crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m- vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinyl Aromatic vinyl compounds such as 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; Alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate and 2-dicyclopentanyloxyethyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (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; Unsaturated oxirane compounds such as methyl glycidyl (meth) acrylate; A (meth) acrylate substituted with a cycloalkane or a dicycloalkane ring having 4 to 16 carbon atoms; And the like. These may be used alone or in combination of two or more.

The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, it can have excellent developability and long-term stability

The content of the alkali-soluble resin is not particularly limited and may be, for example, 10 to 80 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the total solid content of the composition. When it is contained within the above-mentioned range, it is possible to form a photo-curable pattern having good solubility in developer and excellent developing property, good adhesion to the lower substrate and excellent mechanical properties.

Photopolymerization  compound

The photopolymerizable compound used in the photosensitive resin composition of the present invention increases the crosslinking density during the manufacturing process and can enhance the mechanical properties of the photocuring pattern.

The photopolymerizable compound usable in the present invention can be used without any particular limitation in the art, and examples thereof include monofunctional monomers, bifunctional monomers and other polyfunctional monomers, and the kind thereof is not particularly limited, For example.

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, 30 to 80% by weight, preferably 40 to 60% by weight based on the total solid content of the composition. When the photopolymerizable compound is contained in the above content range, the adhesion to the lower substrate is good, the durability can be improved, and the developability of the composition can be improved.

Light curing Initiator

The photopolymerization initiator usable in the present invention can be used without any particular limitation as long as it is a compound capable of polymerizing a photopolymerizable compound. Examples of the photopolymerization initiator include a triazine-based compound, an acetophenone-based compound, a non- May be used. The photosensitive resin composition containing the photopolymerization initiator has high sensitivity, and the strength and surface smoothness of the spacer pattern formed using the composition are improved.

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

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one oligomers and the like.

Examples of the acetophenone compound include compounds represented by the following formula (8).

[Chemical Formula 8]

In Formula (8), R ₁ to R ₄ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 8 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl- 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one 2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino .

Examples of the imidazole compound include 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetra (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and imidazole compounds in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, and the following chemical formulas 9, 10 and 11.

[Chemical Formula 9]

[Chemical formula 10]

(11)

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylchloroxylate, Titanocene compounds and the like can be mentioned as other photopolymerization initiators.

Further, a photopolymerization initiator having a group capable of chain transfer as a photopolymerization initiator may be used. Examples of such a photopolymerization initiator include those described in Japanese Patent Application Laid-Open No. 2002-544205.

Examples of the photopolymerization initiator having a group capable of causing chain transfer include the compounds represented by the following formulas (12) to (17).

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

In the present invention, a photopolymerization initiator may be used in combination with the photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the photosensitive resin composition containing the photopolymerization initiator is more preferable because productivity can be improved when the spacer is formed.

As the photopolymerization initiation auxiliary, an amine compound or a carboxylic acid compound is preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, , 4-dimethylaminobenzoic acid (2-ethylhexyl) benzoate, N, N-dimethylparatoluidine, And aromatic amine compounds such as bis (diethylamino) benzophenone. Of these, an aromatic amine compound is preferably used as the amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenyl And aromatic heteroacetic acids such as thioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the photoinitiator is not particularly limited and may be, for example, 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight based on 100 parts by weight of the total amount of the photosensitive resin composition based on the solid content . When the above-mentioned range is satisfied, it is preferable that the photosensitive resin composition is highly sensitized and the strength and smoothness of the spacer formed using the composition become good.

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 content of the solvent may be 40 to 90 parts by weight, preferably 50 to 85 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition containing the same. When the content of the solvent is within the above range, the coating property is improved when applied by a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater) Do.

additive

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents and the like.

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 capable of CD-Bias control and has excellent T / B ratio, developability, adhesion, and mechanical properties. 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 well suited as a spacer 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 method for producing the photocurable pattern according to the present invention is not particularly limited and may be a known method in the art. For example, the photosensitive resin composition of the present invention may be applied on a substrate, Followed by a development step) to form a photo-curable pattern.

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 coat method or a slit coat method. 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 100 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 subjected to post-baking at a relatively low temperature of 100 to 150 DEG C for 10 to 60 minutes.

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

Manufacturing example

Synthesis of alkali-soluble resin (A)

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 make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 63.7 g of benzyl maleic anhydride 26.1 g (0.25 mol) of styrene and 20.6 g (0.10 mol) of tricyclo [5.2.1.02,6] decanyl acrylate were added and stirred. Thereafter, a solution prepared by adding 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to a mixture containing 150 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel Stirring was continued at 100 &lt; 0 &gt; C for additional 5 hours.

Next, 75.4 g (0.58 mol (90 mol% relative to maleic anhydride used in the present reaction)) of hydroxyethyl methacrylate was charged into the flask, and the reaction was carried out at 110 DEG C for 6 hours To obtain an unsaturated group-containing resin A having a solid content of 38.4% by mass and a solid acid value of 168 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,400 and the molecular weight distribution (Mw / Mn) was 2.2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC-8120GPC (manufactured by TOSOH CORPORATION), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL connected in series , The column temperature was 40 占 폚, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 占, and the detector RI was used. The concentration of the test sample was 0.6 mass% (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used.

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

Example  And Comparative Example

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

division
(Parts by weight) The alkali-soluble resin (A) Photopolymerization
compound
(B) Light curing
Initiator (C) Amine
Additive (D) Ultraviolet absorber (E) Additive (F) Solvent (G) ingredient content ingredient content ingredient content Example 1 30 50 C-1 /
C-2 2/4 D-1 3 E-1 One 0.3 100 Example 2 30 50 C-1 /
C-2 2/4 D-2 3 E-1 One 0.3 100 Example 3 30 50 C-1 /
C-2 2/4 D-3 3 E-1 One 0.3 100 Example 4 30 50 C-1 /
C-2 2/4 D-4 3 E-1 One 0.3 100 Example 5 30 50 C-1 /
C-2 2/4 D-3 3 E-2 One 0.3 100 Example 6 30 50 C-1 /
C-2 2/4 D-3 3 E-3 One 0.3 100 Example 7 30 50 C-1 /
C-2 2/4 D-3 3 E-4 One 0.3 100 Example 8 30 50 C-1 /
C-2 2/4 D-3 3 E-5 One 0.3 100 Example 9 30 50 C-1 /
C-2 2/4 D-3 3 E-1 0.5 0.3 100 Example 10 30 50 C-1 /
C-2 2/4 D-3 3 E-1 1.5 0.3 100 Example 11 30 50 C-1 /
C-2 2/4 D-3 1.5 E-1 One 0.3 100 Comparative Example 1 30 50 C-1 /
C-2 2/4 - - - - 0.3 100 Comparative Example 2 30 50 C-1 /
C-2 2/4 D-3 4 - - 0.3 100 Comparative Example 3 30 50 C-1 /
C-2 2/4 - - E-1 4 0.3 100 Comparative Example 4 30 50 C-1 /
C-2 2/4 D-3 3 E-6 One 0.3 100 Comparative Example 5 30 50 C-1 /
C-2 2/4 D-3 3 E-7 One 0.3 100 Comparative Example 6 30 50 C-1 /
C-2 2/4 D-3 3 E-8 One 0.3 100

A: The alkali binder resin

B: dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Chemical Co., Ltd.)

C: Photopolymerization initiator

)C-1: Non-imidazole-based compound (

)

)C-2: Oxime ester compound (

)

D: Amine additive

D-1:

D-2:

D-3:

D-4:

E: Ultraviolet absorber

(λ_{max = 354 nm )} E-1:

(? _{max = 354 nm )}

(λ_{max = 361 nm )} E-2:

(? _{max = 361 nm )}

(λ_{max = 353 nm )} E-3:

(? _{max = 353 nm )}

(λ_{max = 348 nm )} E-4:

(? _{max = 348 nm )}

(λ_{max = 335 nm )} E-5:

(? _{max = 335 nm )}

(λ_{max = 295 nm )} E-6:

(? _{max = 295 nm )}

(λ_{max = 298 nm )} E-7:

(? _{max = 298 nm )}

(λ_{max = 332 nm )} E-8:

(? _{max = 332 nm )}

F: Additive (antioxidant)

4,4'-butylidenebis [6-tert-butyl-3-methylphenol] (BBM-S.

G: Solvent

Propylene glycol monomale ether acetate: diethylene glycol methyl ethyl ether (volume ratio of 6: 4)

Test Methods

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on the glass substrate, and then pre-baked at 90 DEG C for 125 seconds using a hot plate. After the prebaked substrate was cooled to room temperature, light was emitted at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with a distance of 150 μm from the quartz glass photomask Respectively. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

The coating film was coated on an aqueous developer having an octagonal opening (hole pattern) of 14 占 퐉 octagonal pattern and having an interval of 100 占 퐉 and containing 0.12% of a nonionic surfactant and 0.04% Followed by development and post-baking in an oven at 100 占 폚 for 1 hour. The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Table 2 below.

(1) Measurement of pattern vertical width ratio (T / B ratio)

Observing the obtained Dot pattern with a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision), a point 5% of the total height from the bottom surface of the pattern is referred to as Bottom CD (a) (B / a × 100) obtained by dividing the length of (b) by the length of (a) and then multiplying by 100 is defined as a T / B ratio.

(2) pattern of CD - bias

The pattern size obtained at the film thickness of 3.0 mu m obtained above was measured using a three-dimensional shape measuring apparatus (SIS-2000 system; SNU Precision), and the difference from the mask size was calculated by CD-bias as follows. CD-bias is better the closer to 0, (+) means that the pattern is larger in size than the mask and (-) is smaller in size than the mask.

CD-bias = (formed pattern size) - (mask size used for forming)

(3) Measurement of adhesion

The developing adhesion is determined by observing the degree of adhesion of a pattern generated by using a mask using a half-tone mask having a 25% transmittance to the substrate, The actual size of the pattern when 100% of the pattern formed with the film thickness of 3 m remained without loss by the photomask having 1000 dot patterns at intervals of 1 mu m was used by SIS-2000 of SNU Precision Co., And the line width was measured. The value of the pattern line width was defined as the value of Bottom CD at 5% of the total height from the bottom surface of the pattern. The smaller the minimum pattern size remaining without loss, the more excellent the developing adhesion.

(4) Residual film ratio evaluation

The resin compositions of Examples and Comparative Examples were applied to a substrate, spin-coated, and pre-baked at 90 DEG C for 125 seconds using a hot plate. After the prebaked substrate was cooled to room temperature. Light was irradiated onto the entire surface of the coating film with an exposure amount (based on 365 nm) of 60 mJ / cm 2 using an exposure machine (UX-1100SM; Ushio Co., Ltd.).

After light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 60 seconds and developed. After washing with water, post-baking was performed in an oven at 230 캜 for 30 minutes.

At this time, the film thickness after the exposure and the film thickness after the post-baking process were measured, and the residual film ratio was measured using the following equation.

The higher the residual film ratio, the better the performance.

(5) Mechanical properties (total displacement and recovery rate) evaluation

A pattern having a Bottom line width of 14 占 퐉 in the cured films obtained in the above-described Examples and Comparative Examples was subjected to a total displacement amount (占 퐉) and an elastic displacement amount 占 퐉 (占 퐉) using a dynamic ultrasonic microhardness meter (HM-2000; Helmut Fischer GmbH + Co.KG) ) Was measured according to the following measurement conditions, and the recovery rate (%) was calculated as follows using the measured values. The smaller the total displacement and the higher the recovery rate, the better.

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

The measurement conditions are as follows.

Test mode; Load-Unload test

Test force; 50.0 mN

Load speed; 4.41 mN / sec

Retention time; 5sec

Indenter; Square pyramid indenter (diameter 50 μm)

division
(Parts by weight) pattern CD-bias
(탆) Developability
(탆) Residual film ratio
(%) Mechanical properties Bott
om
Line width
(탆) Top line width
(탆) T / B ratio
(%) Total displacement
(탆) Shout
Recovery rate
(%) Example 1 15.0 9.6 64 1.0 12 75 1.38 63 Example 2 15.2 10.0 66 1.2 13 77 1.32 64 Example 3 14.5 10.2 70 0.5 10 79 1.12 70 Example 4 15.8 10.3 65 1.8 11 76 1.35 63 Example 5 16.3 10.4 64 2.3 11 74 1.30 65 Example 6 16.1 10.0 62 2.1 12 71 1.40 62 Example 7 15.6 9.8 63 1.6 13 75 1.45 60 Example 8 16.0 9.8 61 2.0 11 73 1.36 63 Example 9 16.5 9.6 58 2.5 9 81 1.44 60 Example 10 14.0 10.1 72 0.0 16 69 1.33 65 Example 11 14.3 8.9 62 0.3 15 73 1.41 61 Comparative Example 1 17.1 9.4 55 3.1 19 58 1.62 54 Comparative Example 2 19.5 8.4 43 5.5 13 68 1.58 56 Comparative Example 3 13.1 8.5 65 -0.9 20 52 1.51 58 Comparative Example 4 19.8 10.3 52 5.8 18 61 1.55 57 Comparative Example 5 21.3 10.2 48 7.3 15 77 1.69 51 Comparative Example 6 20.9 9.6 46 6.9 17 75 1.64 53

Referring to Table 2, it was confirmed that CB-Bias can be controlled while realizing a pattern of a small size as a whole in the case of the embodiment using the photosensitive resin composition according to the present invention.

In addition, it was confirmed that the embodiments of the present invention have excellent T / B ratio of pattern, improved adhesion to a substrate, and good developing property.

However, in the case of the comparative examples not using the amine additive and the ultraviolet absorber according to the present invention, the size of the pattern as a whole is large, the deviation of the CD-bias is large and thus it is not suitable for realizing a high resolution and remarkably deteriorates in mechanical properties from the examples .

Claims (9)

An amine additive comprising at least one of the compounds represented by the following formulas (1) and (2) and an ultraviolet absorber having a maximum absorption wavelength (? _Max ) of 335 to 365 nm:
[Chemical Formula 1]

(2)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a straight or branched alkyl group having 1 to 10 carbon atoms, At least one atom may be contained,
n and m are each independently an integer of 6 to 20).
The photosensitive resin composition according to claim 1, wherein the ultraviolet absorber is at least one selected from compounds represented by the following formulas (3) to (5)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(Wherein R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a halogen atom, An alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms, a tricycloalkyl group having 6 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
The aryl group may be substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a thioether group, a cycloalkyl group having 3 to 12 carbon atoms, a bicycloalkyl group having 4 to 12 carbon atoms and a tricycloalkyl group having 6 to 12 carbon atoms Lt; / RTI &gt; may be substituted with at least one substituent selected from the group consisting of &lt; RTI ID = 0.0 &gt;
The photosensitive resin composition according to claim 1, wherein the UV absorber is contained in an amount of 10 to 80 parts by weight based on 100 parts by weight of the amine additive.
The photosensitive resin composition according to claim 1, wherein the amine additive is included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition.
The photosensitive resin composition according to claim 1, wherein the ultraviolet absorber is contained in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the total solid content of the composition.
The photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
A photocurable pattern produced from the photosensitive resin composition according to any one of claims 1 to 6.
The method of claim 7, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern,
An image display device comprising the photocuring pattern of claim 8.

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