KR20170060726A - Negative-type photosensitive resin composition - Google Patents

Abstract

The present invention relates to a negative photosensitive resin composition, and more particularly, to an alkali-soluble resin containing repeating units represented by specific formulas. A polymerizable compound comprising a compound represented by a specific formula; A photopolymerization initiator; And a solvent, the developability can be improved.

Description

[0001] NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a negative photosensitive resin composition.

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.

On the other hand, a common display device has used a silica bead or a plastic bead having a certain diameter in order to maintain a predetermined distance between the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device. Currently, a spacer used in most display devices is formed by photolithography.

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.

Generally, after photocrosslinking, the photocurable composition for photoresist undergoes a development process. When the photoresist is developed, it is developed with an aqueous solution of TMAH (Tetramethylammonium Hydroxide) or an aqueous solution of KOH (Potassium Hydroxide) . This development process plays a very important role in forming the size (depth, height, width, etc.) of the formed structure after development.

As the size of the structure (depth, height, width, etc.) is more precisely formed, the developability of the photoresist can be improved, depending on the physical and optical technology of the process, such as narrowing the line width.

Accordingly, Korean Patent No. 10-1359470 discloses a photosensitive resin composition comprising an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor and a solvent to improve photoreactivity and light efficiency, To improve the performance of the device.

However, even in this case, there is a limit in terms of improvement in developing performance.

Korean Patent No. 10-1359470

It is an object of the present invention to provide a photosensitive resin composition which is excellent in sensitivity and reactivity and exhibits excellent sensitivity.

The present invention can improve the developability of the photocured composition to obtain a narrower line width.

It is another object of the present invention to provide a photocurable pattern formed of the photosensitive resin composition and an image display apparatus including the same.

1. An alkali-soluble first resin comprising a repeating unit represented by the following formula (1);

An alkali-soluble second resin comprising a repeating unit represented by the following formula (2);

A polymerizable compound comprising a compound represented by the following formula (3);

A photopolymerization initiator; And

A negative-working photosensitive resin composition comprising:

[Chemical Formula 1]

(2)

(Wherein R ₁ 'is a hydrogen atom or a methyl group, R ₂ ' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ 'is a hydrogen atom or a methyl group).

(3)

:

:

(Wherein,

R ₃₁ is a carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,

R ₃₂ is independently hydrogen, an acryloyloxy group, a succinate group or a linear or branched alkyl group having 1 to 5 carbon atoms,

n is an integer from 3 to 8,

Wherein the molecule represented by Formula 3 includes at least two acryloyloxy groups.

2. The negative-working photosensitive resin composition according to 1 above, wherein the first resin is represented by the following formula (1-1)

[Formula 1-1]

(Wherein R ₄ , R ₅ , R ₆ and R ₇ are independently of each other hydrogen or a methyl group,

R ₈ 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, vinyl (meth) acrylate, 2-hydroxyphenol (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ) Acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) The structure derived from the monomer selected from the group,

R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7)

R ₁₀ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of

R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,

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

3. The negative-type photosensitive resin composition according to 1 above, wherein the first resin is represented by the following formula (2-1):

[Formula 2-1]

(Wherein R ₁₆ and R ₁₇ are independently of each other hydrogen or a methyl group,

R ₁₈ is a structure derived from a monomer selected from the group consisting of the following formula (8)

(Wherein R &_lt; a _> is a single bond or an alkylene having 1 to 6 carbon atoms, and the alkylene may further contain an oxygen atom)

R ₁₉ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of

e = 40 to 95 mol%, and f = 5 to 60 mol%).

4. The negative photosensitive resin composition according to 1 above, wherein the compound represented by the formula (3) is a compound represented by the following formula (4) or (5)

[Chemical Formula 4]

[Chemical Formula 5]

.

.

5. The negative photosensitive resin composition according to 1 above, wherein the photopolymerization initiator is at least one of a nonimidazole-based and oxime ester-based photopolymerization initiator.

6. A photocurable pattern produced from the negative-working photosensitive resin composition according to any one of items 1 to 5 above.

7. The photopolymerizable composition according to 6 above, wherein said photocurable pattern is selected from the group consisting of an adhesive layer, an array planarization 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.

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

The photosensitive resin composition of the present invention is excellent in sensitivity and reactivity, and a pattern produced therefrom exhibits excellent adhesion to a substrate and exhibits excellent mechanical properties.

The present invention can improve the developability of the photocured composition to obtain a narrower line width.

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.

An embodiment of the present invention is a resin composition comprising: an alkali-soluble first resin comprising a repeating unit represented by the following formula (1); An alkali-soluble second resin comprising a repeating unit represented by the following formula (2); A polymerizable compound comprising a compound represented by the following formula (3); A photopolymerization initiator; And a solvent, thereby providing a negative photosensitive resin composition excellent in developability.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, this is merely an example and the present invention is not limited thereto.

< Negative type  Photosensitive resin composition>

The negative photosensitive resin composition of the present invention comprises: an alkali-soluble first resin comprising a repeating unit represented by the following formula (1); An alkali-soluble second resin comprising a repeating unit represented by the following formula (2); A polymerizable compound comprising a compound represented by the following formula (3); A photopolymerization initiator; And a solvent.

In the present invention, when the repeating unit, compound or resin represented by each formula contains an isomer, the repeating unit, compound or isomer represented by the formula, The term &quot; resin &quot; means a representative formula including up to its isomer.

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

Alkali-soluble resin

The alkali-soluble resin (A) used in the present invention is a component which imparts solubility to the alkali developing solution used in the development processing at the time of forming a pattern, and comprises a first resin containing a repeating unit represented by the following formula (1) And a second resin comprising a repeating unit represented by the following formula (2).

[Chemical Formula 1]

(2)

(Wherein R ₁ 'is a hydrogen atom or a methyl group, R ₂ ' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ 'is a hydrogen atom or a methyl group).

< The first resin >

The first resin according to the present invention is not particularly limited as long as it contains a repeating unit represented by the formula (1), and may include, for example, a repeating unit represented by the following formula (1-1).

[Formula 1-1]

(Wherein R ₄ , R ₅ , R ₆ and R ₇ are independently of each other hydrogen or a methyl group,

R ₈ 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, vinyl (meth) acrylate, 2-hydroxyphenol (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ) Acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) The structure derived from the monomer selected from the group,

R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7)

R ₁₀ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of

R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,

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

Preferred examples of the repeating unit represented by formula (1-1) according to the present invention include repeating units represented by the following formulas (1-2).

[Formula 1-2]

(Wherein _{among, R 12, R 13, R} 14 and R ₁₅ are independently a hydrogen or a methyl group each, a = 20 to 60mol%, b = 5 to 30mol%, c = 10 to 50mol%, d = 5 to 50mol %).

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

< The second resin >

Since the second resin according to the present invention includes the repeating unit represented by the above formula (2), a thermosetting reaction takes place through a ring-opening polymerization reaction of an epoxy functional group and a carboxylic acid in the post-baking step, The pattern can be more firmly formed through the radical polymerization of the first resin and the thermosetting reaction of the second resin.

The second resin according to the present invention is not particularly limited as long as it contains a repeating unit represented by the formula (2), and may include, for example, a repeating unit represented by the following formula (2-1).

[Formula 2-1]

(Wherein R ₁₆ and R ₁₇ are independently of each other hydrogen or a methyl group,

R ₁₈ is a structure derived from the monomer of the following formula (8)

(Wherein R &_lt; a _&gt; is a single bond or an alkylene having 1 to 6 carbon atoms, and the alkylene may further contain an oxygen atom)

R ₁₉ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of

e = 40 to 95 mol%, and f = 5 to 60 mol%).

Preferred examples of the compound of the formula (2-1) according to the present invention include compounds of the following formula (2-2).

[Formula 2-2]

(Wherein R ₁₆ and R ₁₇ are each independently hydrogen or a methyl group, e = 50 to 95 mol%, and f = 5 to 50 mol%).

From the viewpoint of further improving the adhesion, the weight average molecular weight of the second resin is preferably 2,000 to 20,000.

In the present invention, each of the repeating units represented by the formulas (1) to (2) and (1-1) to (2-2) is interpreted as being limited to the formulas (1) to (2) , And the sub-repeating unit in the parentheses can freely be positioned at any position of the chain within a predetermined mol% range. That is, although the parentheses of the formulas (1) to (2) and the formulas (1-1) to (2-2) are shown as one block for expressing the mol%, each sub-repeating unit may be divided into blocks .

If necessary, the first resin and the second resin according to the present invention may further comprise, in addition to the repeating units of the formulas (1-1) and (2-1), a repeating unit formed from other monomers known in the art, May be formed only as repeating units of formulas (2-1) and (2-1).

The monomers forming the repeating unit which can be further added to the formulas (1-1) and (2-1) are not particularly limited, and examples thereof include 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.

In the alkali-soluble resin according to the present invention, when the first resin containing the repeating unit represented by the formula (1) and the second resin including the repeating unit represented by the formula (2) are used simultaneously, the mixing weight ratio is 20:80 to 80:20 And preferably from 30:70 to 70:30. In the above range, the most excellent adhesion, developability and T / B ratio can be shown.

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 60 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, excellent mechanical properties, and narrow line width.

Polymerizable  compound

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

The polymerizable compound of the present invention is a compound represented by the following Formula 3:

(3)

:

:

(Wherein,

R ₃₁ is a carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,

R ₃₂ is independently hydrogen, an acryloyloxy group, a succinate group or a linear or branched alkyl group having 1 to 5 carbon atoms,

n is an integer from 3 to 8,

Wherein the molecule represented by Formula 3 includes at least two acryloyloxy groups.

Specifically, R ₃₂ may be any of functional groups selected from among hydrogen, acryloyloxy group, succinate group, or straight or branched chain alkyl group having 1 to 5 carbon atoms bonded to R ₃₁ through a methylene group (-CH ₂ -) , N is included in formula (3), and each of n functional groups may be independently selected from hydrogen, an acryloyloxy group, a succinate group, or a linear or branched alkyl group having 1 to 5 carbon atoms have.

On the other hand, R ₃₁ may be, for example, one carbon atom or the following formula 3-1:

[Formula 3-1]

(Where "*" represents a combined hand).

Further, preferably, the compound represented by Formula 3 may be a compound represented by Formula 4 or 5:

[Chemical Formula 4]

[Chemical Formula 5]

.

.

The content of the polymerizable compound is not particularly limited, but may be 30 to 80 parts by weight, preferably 40 to 60 parts by weight, based on 100 parts by weight of the total solid content of the composition.

In another aspect of the present invention, the polymerizable compound may be contained in an amount of 70 to 150 parts by weight based on 100 parts by weight of the total of the alkali-soluble resin based on the solid content.

When the content of the polymerizable compound is within the above range, the adhesion to the lower substrate is good, the durability can be improved, and the developability of the composition can be improved.

By including a plurality of reactors serving as bridges, it is possible to obtain a narrower line width by increasing the developability.

Other usable polymerizable compounds may be used without limitation in the art, and examples thereof include monofunctional monomers, bifunctional monomers and other polyfunctional monomers. The type of the polymerizable compound is not particularly limited, Compounds may be mentioned as examples.

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.

Light curing Initiator

The photopolymerization initiator usable in the present invention is not particularly limited as long as it is a compound capable of polymerizing a polymerizable compound, and examples thereof include a triazine-based compound, an acetophenone-based compound, a group consisting of a non- , And preferably at least one of a nonimidazole-based compound and an oxime compound.

The negative photosensitive resin composition containing the photopolymerization initiator has high sensitivity, and the strength and surface smoothness of the spacer pattern formed using the composition can be 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 (6).

[Chemical Formula 6]

In formula (6), R ₂₅ to R ₂₈ 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 6 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 compounds represented by the following formula (7), 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) 4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (4-chlorophenyl) -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5 'position being substituted by a carboalkoxy group Imidazole compounds and the like. Preferred are compounds represented by the following general formula (7), 2,2 'bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4,5,5'-tetraphenyl- '-Nonimidazole &lt; / RTI &gt;: &lt; RTI ID = 0.0 &gt;

(7)

.

.

The oxime compound is preferably selected from the group consisting of o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, 1,2-octanedione, Benzoyloxime), ethanone, 1- (9-ethyl) -6- (2-methylbenzoyl- 11, preferably at least one compound selected from the group consisting of o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, 1,2-octanedione , 1- (4-phenylthio) phenyl, 2- (o-benzoyloxime) and ethanone, 1- (9- (o-acetyloxime). &lt; RTI ID = 0.0 &gt;

[Chemical Formula 8]

[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 negative 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, 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 solid content of the composition. When the above range is satisfied, it is preferable that the negative photosensitive resin composition has a high sensitivity and the strength and smoothness of the spacer formed using the composition become favorable.

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, diethylene glycol methyl ethyl ether, etc. may be used alone or in combination of two or more.

The content of the solvent may be 60 to 1900 parts by weight, preferably 80 to 600 parts by weight, based on 100 parts by weight of the total solid content of the composition. 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 negative 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, antiflocculants, chain transfer agents and the like as needed.

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),

Butyl 4,4'- (butane-1,1-diyl) bis (2- (tert-butyl) -5-methylphenol), 4,4'-butylidenebis (6-tert- Phenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert- Thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate) , 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) , 3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a " -Cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6- . Preferably, it is 4,4 '- (butane-1,1-diyl) bis (2- (tert-butyl) -5-methylphenol).

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.

The content of the additive may be 0.1 to 10 parts by weight based on 100 parts by weight of the total solid content of the composition.

< Photocuring  Pattern and image display device>

It is an object of the present invention to provide an image display device including the photo-curable pattern made of the negative photosensitive resin composition and the photo-curable pattern.

The photocurable pattern made of the negative 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 a photocurable pattern according to the present invention is not particularly limited as long as it is a method known in the art. For example, the negative photosensitive resin composition of the present invention may be applied on a substrate, Or after coarsening) to form a photo-curable pattern.

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

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is 70 to 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

Manufacturing example  1. Synthesis of alkali-soluble resin (first 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 make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 47.3 g Azobis (2-methoxyphenyl) methane was added to a mixture containing 61.6 g (0.35 mol) of benzyl methacrylate, 22.0 g (0.10 mol) of tricyclodecanyl methacrylate and 150 g of propylene glycol monomethyl ether acetate , 4-dimethylvaleronitrile) was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate (0.30 mol (55 mol% based on the acrylic acid used in the present reaction)) was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours To obtain an unsaturated group-containing resin A-1 having a solid acid value of 109 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 25,000 and the molecular weight distribution (Mw / Mn) was 2.4.

Manufacturing example  2. Synthesis of alkali-soluble resin (second resin (A-2))

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at 0.02 L / min to make a nitrogen atmosphere. 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Next, 210.2 g (0.95 mol) of the compound of the formula (a) and 14.5 g (0.17 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ethyl ether to prepare a solution:

(A)

.

.

The resulting solution was dropped into a flask using a dropping funnel, and 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methyl ethyl ether The dissolved solution was added dropwise to the flask over 4 hours using a separate dropping funnel. (A-2) having a solid content of 41.6% by mass and an acid value of 65 mg-KOH / g (in terms of solid content) was kept at 70 캜 for 4 hours after the dropwise addition of the polymerization initiator solution was completed. ) Was obtained.

The weight average molecular weight Mw of the obtained resin (2-3) was 8,300 and the molecular weight distribution was 1.85.

Manufacturing example  3. Synthesis of alkali-soluble resin (the third resin (A-3))

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, 200 g of diethylene glycol methyl ethyl ether acetate was introduced, and after heating to 100 캜, 10.4 g ), Tricyclodecanyl acrylate (55.1 g, 0.25 mole), methacrylic acid (12.9 g, 0.15 mole) and glycidyl methacrylate (71.1 g, 0.50 mole) 2,4-dimethylvaleronitrile) in 100 g of diethylene glycol methyl ethyl ether was added dropwise to the flask over 2 hours from the dropping funnel, followed by further stirring at 100 ° C for 5 hours.

After completion of the reaction, an alkali-soluble resin A-3 having a solid acid value of 55 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 23,500 and the molecular weight distribution (Mw / Mn) was 2.3.

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 Tables 1, 2 and 3 was prepared.

division Example One 2 3 4 5 6 7 8 9 10 11 Alkali-soluble resin
(A) A-1 23.0 23.0 23.0 23.0 23.0 23.0 23.0 27.0 19.0 30.0 15.0 A-2 23.0 23.0 23.0 23.0 23.0 23.0 23.0 27.0 19.0 30.0 15.0 A-3 - - - - - - - - - - - The polymerization compound (B) B-1 48.0 - 24.0 24.0 - - - 40.0 56.0 34.0 64.0 B-2 - 48.0 - - 24.0 24.0 - - - - - B-3 - - 24.0 - 24.0 - 24.0 - - - - B-4 - - - 24.0 - 24.0 24.0 - - - - Photoinitiator
(C) C-1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 C-2 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Additive (E) One One One One One One One One One One One Solvent (F) F-1 65.0 65.0 65.0 65.0 65.0 65.0 65.0 65.0 65.0 65.0 65.0 F-2 98.0 98.0 98.0 98.0 98.0 98.0 98.0 98.0 98.0 98.0 98.0

division Comparative Example One 2 3 4 5 6 7 Alkali-soluble resin
(A) A-1 - 47.0 47.0 - 23.0 23.0 A-2 - 47.0 - 47.0 - 23.0 23.0 A-3 - - - - 47.0 - - The polymerization compound (B) B-1 95.0 - 47.0 47.0 47.0 - - B-2 - - - - - - - B-3 - - - - - 48.0 - B-4 - - - - - - 48.0 Photoinitiator
(C) C-1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 C-2 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Additive (E) - One One One One One One Solvent (F) F-1 65.0 65.0 65.0 65.0 65.0 65.0 65.0 F-2 98.0 98.0 98.0 98.0 98.0 98.0 98.0

A-1: An alkali-soluble resin represented by the general formula [1-3]

A-2: A cyclopentene oxide functional group represented by the formula [2-3]

Containing Thermoset Resin

A-3: A thermosetting resin represented by [Formula 2-4]

B-1: a tetrafunctional polymerizable compound represented by the following formula (4)

B-2: The hexafunctional polymerizable compound represented by Formula 5

B-3: A multifunctional polymerizable compound represented by the following formula (18)

B-4: A multifunctional polymerizable compound represented by the formula (19)

C-1: A photopolymerization initiator represented by Formula 6

C-2: A photopolymerization initiator represented by the following formula (7)

E: Compound of Formula 20

F-1: Diethylene glycol methyl ethyl ether

F-2: Propylene glycol monomethyl ether acetate

[Formula 1-3]

[Formula 2-3]

(e = 50 mol%, f = 50 mol%),

[Chemical Formula 2-4]

(a = 10 mol%, b = 25 mol%, c = 15 mol%, d = 50 mol%)

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

Experimental Example

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 respectively spin-coated on the glass substrate and then pre-baked at 90 DEG C for 80 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 200 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 exposed to a water-based developer having circular openings (patterns) each having a diameter of 14 mu m and having an interval of 100 mu m and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after irradiation, And after washing with water, post-baking was carried out in an oven at 235 DEG C for 15 minutes. The obtained pattern height was 3.0 占 퐉. The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Table 2 below.

(1) The phenomenon Residual film ratio  evaluation

The prepared resist solution was applied to a substrate, spin-coated, 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 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, and after post-baking at 230 캜 for 30 minutes in an oven.

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.

It is judged that the higher the residual film ratio, the better the performance.

(2) Developability  evaluation

The prepared photosensitive resin composition is spin-coated on a glass substrate, followed by pre-baking. Then, when the substrate is immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, the case where the coating film is dispersed in the form of fine particles is dissolved, and the case where the size of the fine particles is larger than that in the case of dissolution is considered to be weak. Also, if the coating is lifted as it is, it is said to be peeled off.

Fusion: O

Approx. Exfoliation: △

Peeling: X

(3) Residue  evaluation

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 respectively spin-coated on the glass substrate and then pre-baked at 90 DEG C for 80 seconds using a hot plate. After the prebaked substrate was cooled to room temperature, light was irradiated at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure machine (UX-1100SM; Ushio) at an interval of 200 m from the quartz glass photomask . At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

The coating film was exposed to a water-based developer having circular openings (patterns) each having a diameter of 14 mu m and having an interval of 100 mu m and containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after irradiation, Immersed and developed. The obtained patterns were observed using a Keyence microscope (VK-X200).

X. Residue was observed when no residue was observed.

No residue: X

It is observed before the post bake, but after the post bake the residue is gone: △

Has residue: ○

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

The photosensitive resin compositions prepared in Examples and Comparative Examples were respectively spin-coated on a glass substrate (Eagle 2000; Corning) having a size of 2 inches and a width of 2 inches, 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 amount of 80 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with a distance of 200 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.

After immersing the coating film at 25 DEG C for 60 seconds in a water-based developer having square openings each having a diameter of 12 mu m and having an interval of 100 mu m and containing 0.12% of a nonionic surfactant and 0.04% And post-baking was performed in an oven at 235 DEG C for 15 minutes. The obtained pattern height was 3.0 占 퐉. The total amount of displacement (D1, 占 퐉) and the amount of elastic displacement (D2, 占 퐉) were measured according to the following measurement conditions by using a dynamic ultra microhardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) Using the measured values, the recovery rate (%) was calculated as follows.

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 Example Comparative Example One 2 3 4 5 6 7 8 9 10 11 One 2 3 4 5 6 7 Developability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ pattern
Unformed pattern
Unformed △ △ △ X X Development residue X X X X X X X X X X X X X X ○ ○ Remaining film ratio (%) 83 81 77 79 80 75 76 75 80 86 77 68 75 65 60 76 Mechanical properties Total displacement
(탆) 1.01 1.09 1.28 1.16 1.22 1.24 1.18 1.06 1.23 1.11 1.31 1.51 1.45 1.65 1.81 1.53 Recovery rate
(%) 79.2 78.4 71.2 73.1 72.9 72.6 73.7 78.7 72.4 79.9 70.8 65.4 69.2 61.2 58.2 65.2

Referring to Tables 1 to 3, it can be confirmed that Examples 1 to 11, in which the polymerizable compound containing succinic acid is increased in composition, are excellent in developability, residual film ratio, and mechanical properties as a whole.

Claims (8)

An alkali-soluble first resin comprising a repeating unit represented by the following formula (1);
An alkali-soluble second resin comprising a repeating unit represented by the following formula (2);
A polymerizable compound comprising a compound represented by the following formula (3);
A photopolymerization initiator; And
A negative-working photosensitive resin composition comprising:
[Chemical Formula 1]

(2)

(Wherein R ₁ 'is a hydrogen atom or a methyl group, R ₂ ' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₃ 'is a hydrogen atom or a methyl group).
(3)

:
(Wherein,
R ₃₁ is a carbon or a saturated hydrocarbon group having 2 to 6 carbon atoms,
R ₃₂ is independently hydrogen, an acryloyloxy group, a succinate group or a linear or branched alkyl group having 1 to 5 carbon atoms,
n is an integer from 3 to 8,
Wherein the molecule represented by Formula 3 includes at least two acryloyloxy groups.
The negative photosensitive resin composition according to claim 1, wherein the first resin is represented by the following formula (1-1):
[Formula 1-1]

(Wherein R ₄ , R ₅ , R ₆ and R ₇ are independently of each other hydrogen or a methyl group,
R ₈ 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, vinyl (meth) acrylate, 2-hydroxyphenol (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ) Acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and tetrahydrofuryl (meth) The structure derived from the monomer selected from the group,
R ₉ is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (7)

R ₁₀ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of
R ₁₁ is hydrogen or an alkyl group having 1 to 6 carbon atoms,
a = 20 to 60 mol%, b = 5 to 30 mol%, c = 10 to 50 mol%, d = 5 to 30-> 50 mol%).
The negative photosensitive resin composition according to claim 1, wherein the second resin is represented by the following formula (2-1):
[Formula 2-1]

(Wherein R ₁₆ and R ₁₇ are independently of each other hydrogen or a methyl group,
R ₁₈ is a structure derived from a monomer selected from the group consisting of the following formula (8)

(Wherein R &_lt; a _&gt; is a single bond or an alkylene having 1 to 6 carbon atoms, and the alkylene may further contain an oxygen atom)
R ₁₉ 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, and the (meth) acryloyloxyethyl succinate is a structure derived from a monomer selected from the group consisting of
e = 40 to 95 mol%, and f = 5 to 60 mol%).
The negative photosensitive resin composition according to claim 1, wherein the compound represented by the formula (3) is a compound represented by the following formula (4) or (5)
[Chemical Formula 4]

[Chemical Formula 5]

.
The negative photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is at least one of a nonimidazole type and an oxime ester type.
A photocurable pattern produced from the negative photosensitive resin composition according to any one of claims 1 to 5.
7. The photocurable pattern according to claim 6, wherein the photocurable pattern is selected from the group consisting of an 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.
7. An image display apparatus comprising the photocuring pattern of claim 6.