KR20160029339A - Photosensitive resin comopsition - Google Patents
Photosensitive resin comopsition Download PDFInfo
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- KR20160029339A KR20160029339A KR1020140118682A KR20140118682A KR20160029339A KR 20160029339 A KR20160029339 A KR 20160029339A KR 1020140118682 A KR1020140118682 A KR 1020140118682A KR 20140118682 A KR20140118682 A KR 20140118682A KR 20160029339 A KR20160029339 A KR 20160029339A
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- acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
Abstract
Description
The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition capable of forming a pattern having excellent reactivity and excellent durability even under low-temperature curing conditions.
In the display field, the photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve the process yield and improve the physical properties of the application object in this process, a photosensitive resin having a high sensitivity A composition is required.
The pattern formation of the photosensitive resin composition is caused by photolithography, that is, a change in the polarity of the polymer caused by the photoreaction and a crosslinking reaction. Particularly, the change characteristics of the solubility in a solvent such as an aqueous alkali solution after exposure are utilized.
The pattern formation by the photosensitive resin composition is classified into a positive type and a negative type according to the solubility of the photosensitive portion in development. In the positive type photoresist, the exposed portion is dissolved by the developing solution, and the negative type photoresist is a method in which the exposed portion is not dissolved in the developing solution and the unexposed portion is dissolved to form a pattern. In the positive type and negative type, A binder resin, a crosslinking agent, and the like.
2. Description of the Related Art Recently, the use of a touch screen equipped with a touch panel has been explosively increased. Recently, a flexible touch screen has received much attention. Accordingly, it is necessary to provide a flexible characteristic for various substrates used for a touch screen, and accordingly, a usable material is also limited by a flexible polymer material, so that the manufacturing process is required to be performed under milder conditions have.
Accordingly, the curing conditions of the photosensitive resin composition also require the necessity of low-temperature curing in the conventional high-temperature curing, and the low-temperature curing has a problem in that the reactivity is lowered and the durability of the formed pattern is deteriorated.
Korean Patent No. 10-1302508 discloses a negative photosensitive resin composition which is excellent in heat resistance and light resistance and can improve sensitivity by including a copolymer polymerized by using a cyclohexenyl acrylate monomer, Conditions do not show required durability.
An object of the present invention is to provide a negative photosensitive resin composition which is curable at a low temperature, is excellent in reactivity, and has excellent durability such as chemical resistance of a formed pattern.
It is another object of the present invention to provide a negative photosensitive resin composition having an excellent pattern forming ability in a photolithography process.
It is another object of the present invention to provide a photocurable pattern formed from the photosensitive resin composition.
1. An alkali-soluble resin (A);
Polymerizable compound (B);
A thermal acid generator (C) represented by the following formula (1);
(D) a trifunctional or more polyfunctional thiol compound;
A photopolymerization initiator (E); And
A negative-working photosensitive resin composition comprising a solvent (F):
[Chemical Formula 1]
(Wherein R 1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 1 to 10 carbon atoms, and R 2 is an alkyl group having 6 to 14 carbon atoms).
2. The negative photosensitive resin composition according to 1 above, wherein R < 2 > in the general formula (1) is an alkyl group having 10 to 14 carbon atoms.
3. The negative photosensitive resin composition according to 1 above, wherein the thermal acid generator (C) is contained in an amount of 0.1 to 5% by weight based on the total weight of the composition.
4. The positive resist composition according to item 1, wherein the alkali-soluble resin (A) comprises a first resin including a repeating unit represented by the following formula (2) and a second resin including a repeating unit represented by the following formula Photosensitive resin composition:
(2)
(Wherein R 1 , R 2 and R 3 are each independently hydrogen or a methyl group,
R 4 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 5 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9)
R 6 is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12)
a = 10 to 30 mol%, b = 30 to 60 mol%, c = 20 to 50 mol%
(3)
(Wherein R 7 , R 8 , R 9 and R 10 are independently of each other hydrogen or a methyl group,
R 11 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 12 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) Gt; is a structure derived from a monomer selected from the group consisting of < RTI ID = 0.0 >
R 13 is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (21)
R 14 is a structure derived from a monomer selected from the group consisting of the following formulas (22) to (28)
d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%, g = 10 to 30 mol%).
5. The negative photosensitive resin composition according to 4 above, wherein the weight ratio of the first resin and the second resin is 70:30 to 80:20.
6. The negative-working photosensitive resin composition according to item 1, which is capable of curing at a low temperature of 100 to 150 占 폚.
7. A photocurable pattern formed from a negative-working photosensitive resin composition according to any one of items 1 to 6 above.
8. The photocurable pattern according to 7 above, wherein the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern and a black column spacer.
9. An image display device comprising the photocuring pattern of the above 7.
When the photosensitive resin composition of the present invention exhibits excellent reactivity at low temperature curing, the pattern produced therefrom exhibits high durability such as excellent chemical resistance and heat resistance.
Further, the photosensitive resin composition of the present invention shows excellent pattern forming ability.
The present invention relates to an alkali-soluble resin (A); Polymerizable compound (B); A thermal acid generator (C) represented by the general formula (1); (D) a trifunctional or more polyfunctional thiol compound; A photopolymerization initiator (E); And a solvent (F), whereby a pattern having excellent reactivity and excellent durability can be formed even under low-temperature curing conditions.
Hereinafter, the present invention will be described in detail.
<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a polymerizable compound (B), a thermal acid generator (C), a polyfunctional thiol compound (D), a photopolymerization initiator (E) and a solvent (F).
The alkali-soluble resin (A)
The alkali-soluble resin (A) used in the present invention is a component that imparts solubility to an alkali developing solution used in a developing treatment process for forming a pattern.
The alkali-soluble resin (A) according to the present invention may comprise a first resin comprising a repeating unit represented by the following formula (2) and a second resin comprising a repeating unit represented by the following formula (3).
(2)
(Wherein R 1 , R 2 and R 3 are each independently hydrogen or a methyl group,
R 4 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 5 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9)
R 6 is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12)
a = 10 to 30 mol%, b = 30 to 60 mol%, c = 20 to 50 mol%
(3)
(Wherein R 7 , R 8 , R 9 and R 10 are independently of each other hydrogen or a methyl group,
R 11 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 12 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) Gt; is a structure derived from a monomer selected from the group consisting of < RTI ID = 0.0 >
R 13 is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (21)
R 14 is a structure derived from a monomer selected from the group consisting of the following formulas (22) to (28)
d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%, g = 10 to 30 mol%).
In the present invention, each of the repeating units represented by the general formulas (2) and (3) should not be construed as being limited to the formulas (2) and (3), and the sub-repeating units in the parentheses may be freely set at any position of the chain Can be located. In other words, although the parentheses in the formulas (2) and (3) are represented as one block in order to express the mol%, each sub-repeating unit can be placed in blocks or separately as long as it is within the resin.
Preferred examples of the compound of the formula (2) according to the present invention include compounds of the following formula (2-1).
[Formula 2-1]
A = 10 to 30 mol%, b = 30 to 60 mol%, and c = 20 to 50 mol%) wherein R 1 , R 2 and R 3 are each independently hydrogen or a methyl group,
In addition, preferred examples of the compound of formula (3) according to the present invention include compounds represented by the following formula (3-1).
[Formula 3-1]
(Wherein among, R 7, R 8, R 9 and R 10 are independently hydrogen or a methyl group each, d = 10 to 30mol%, e = 10 to 20mol%, f = 30 to 60mol%, g = 10 to 30mol %).
The first resin according to the present invention has a function of improving the chemical resistance and reactivity of the photosensitive resin composition, and in this respect, the weight average molecular weight of the first resin is preferably 6,000 to 12,000. And can exhibit the most excellent reactivity and chemical resistance in the molecular weight range.
The second resin according to the present invention has a function of improving durability such as pattern forming property and heat resistance of the photosensitive resin composition, and in this respect, the weight average molecular weight of the second resin is preferably 20,000 to 30,000. It is possible to exhibit the most excellent pattern forming property and heat resistance in the molecular weight range.
The mixing weight ratio of the first resin and the second resin according to the present invention is 50:50 to 90:10, preferably 70:30 to 80:20. When the content of the first resin is smaller than that of the second resin, low-temperature curability is lowered and residues are generated after development. If the content of the first resin exceeds 9 times the weight of the second resin, the pattern formability is deteriorated.
The first resin and the second resin according to the present invention may further comprise, in addition to the repeating units of the general formulas (2) and (3), a repeating unit formed from another monomer known in the art, It is possible.
The monomers forming the repeating unit which can be further added to the formulas (2) and (3) 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.
The acid value of the alkali-soluble resin (A) 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 (A) is not particularly limited, but may be, for example, 8 to 55% by weight, preferably 25 to 50% by weight based on the solid content of the photosensitive resin composition. When it is contained within the above-mentioned range, solubility in a developing solution is sufficient, and the developing property is excellent, and a photocurable pattern having excellent mechanical properties can be formed.
Polymerizable The compound (B)
The polymerizable compound (B) used in the photosensitive resin composition of the present invention increases the crosslinking density during the production process and can enhance the mechanical properties of the photocurable pattern.
The polymerizable compound (B) can be used without any particular limitation in the art, and examples thereof include monofunctional monomers, bifunctional monomers and other multifunctional 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 polymerizable compound (B) is not particularly limited and may be, for example, 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the photosensitive resin composition. When the content of the polymerizable compound (B) is within the above range, it can have excellent durability and improve the developability of the composition.
Thermal acid generator (C)
The thermal acid generator (C) used in the present invention is a component that accelerates the curing reaction by generating an acid upon decomposition by heat, and is represented by the following chemical formula (1).
[Chemical Formula 1]
(Wherein R 1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 1 to 10 carbon atoms, and R 2 is an alkyl group having 6 to 14 carbon atoms).
The thermal acid generator (C) according to the present invention generates a large amount of acid with high efficiency and promotes curing of the composition. As a result, the low-temperature curing performance is excellent, and the durability such as the chemical resistance of the formed pattern is excellent.
This is because when the thermal acid generator (C) has a phenylsulfo group and easily generates an acid, and the alkali-soluble resin and the carbon chain are entangled in the composition during the curing, including the long chain alkyl group, and the thermally decomposed thermal acid- And the possibility of meeting them.
Further, the conventional thermal acid generators have a problem of low solubility in a non-aqueous solvent such as propylene glycol monomethyl ether acetate, which is a typical solvent used in a photosensitive resin composition, and the storage stability is lowered. However, The above-mentioned long-chain alkyl group is advantageous in that the solubility in the non-aqueous solvent is remarkably improved.
In the thermal acid generator (C) according to the present invention, the long chain alkyl group is an alkyl group having 6 to 14 carbon atoms. If the number of carbon atoms is less than 6, the entanglement effect is insignificant, and if the number of carbon atoms is more than 14, From the viewpoint of maximizing the entanglement effect, the number of carbon atoms may be more preferably from 10 to 14.
The content of the thermal acid generator (C) according to the present invention is not particularly limited, and is, for example, in the range of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the photosensitive resin composition. When the thermal acid generator (C) is included in the above content range, excellent low temperature curing performance can be exhibited.
Multifunctional Thiol Compound (D)
The multifunctional thiol compound (D) according to the present invention is a trifunctional or more thiol compound, which improves the crosslinking density and improves the durability of the photocured pattern and adhesion to the substrate, and prevents yellowing at high temperatures.
The trifunctional or more polyfunctional thiol compound according to the present invention is not particularly limited as long as it is a trifunctional or more thiol compound that can be used in the photosensitive resin composition, and a thiol compound having four or more functions is preferable. Examples of the thiol compound according to the present invention may be represented by the following formula (4).
[Chemical Formula 4]
(In the formula, Z 1 is a methylene group having 2 to 10 carbon atoms or straight-chain or branched-chain alkyl group or a methylene group of the alkyl and, Y is a single bond, -CO-, -O-CO-, or -NHCO-, n is Is an integer of 3 to 10, X is an n-valent hydrocarbon group of 2 to 70 carbon atoms which may have one or more ether bonds, or n is 3 and X is a trivalent group represented by the following formula (5)
[Chemical Formula 5]
(Wherein Z 2 , Z 3 and Z 4 are, independently of one another, a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" represents a bonding bond).
n is preferably an integer of 4 or more, or an integer of 4 to 10, more preferably 4, 6 or 8.
As X in the case where n is 3, for example, a trivalent group represented by the following formula (6)
As X in the case where n is 4, 6 or 8, for example, a 4, 6 or 8-valent group represented by the following general formula (7) is preferably used.
[Chemical Formula 6]
(Where "*" represents a combined hand),
(7)
(Wherein m is an integer of 0 to 2, and "* " represents a bonding hand).
The content of the polyfunctional thiol compound (D) according to the present invention is not particularly limited. For example, it is used in the range of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the photosensitive resin composition. When the content of the polyfunctional thiol compound (D) is within the above range, excellent low temperature curing performance can be exhibited.
Light curing Initiator (E)
The photopolymerization initiator (E) according to the present invention is not particularly limited as long as it can polymerize the polymerizable compound (B), and examples thereof include acetophenone compounds, benzophenone compounds, At least one compound selected from the group consisting of a basic compound, a non-imidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound can be used, and an oxime ester-based compound is preferably used.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole .
Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.
Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, (O-benzoyloxime), 1- (9-ethyl) -6- (2-methylbenzoyl- Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca), NCI-831 (Ciba Geigy), CGI- Adeca).
The photopolymerization initiator (E) may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.
Examples of the photopolymerization initiator include at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.
Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.
Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like can be used. .
The content of the photopolymerization initiator (E) is not particularly limited, but may be, for example, 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the photosensitive resin composition. When the above range is satisfied, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened. Thus, the productivity is improved, the resolution can be maintained, and the strength of the formed pixel portion and the smoothness on the surface of the pixel portion can be improved. good.
Solvent (F)
The solvent (F) can be used without limitation 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 (F) is preferably selected from the group consisting of diethylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate , Methyl 3-methoxypropionate and the like can be preferably used, and more preferred are diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl Acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.
The content of the solvent (F) may be in the range of 40 to 85 wt%, preferably 45 to 80 wt%, based on the total weight of the photosensitive resin composition. When the above-mentioned range is satisfied, it is preferable because the coating property is improved when applied by a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater), an ink jet or the like.
Additive (G)
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, antiflocculants and chain transfer agents.
Specific examples of the filler include glass, silica and alumina.
Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
The above-mentioned curing agent is used for enhancing deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.
The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like.
The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).
As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.
Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like.
< Photocuring Pattern and image display device>
An object of the present invention is to provide an image display device including the photo-curable pattern made of the photosensitive resin composition and the photo-curable pattern.
The photocurable pattern prepared from the photosensitive resin composition is excellent in low temperature curability and excellent in chemical resistance and heat resistance. As a result, it can be used for various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and the like in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, However, it is not limited thereto, and is particularly suitable as a photoresist pattern.
The image display device having the light curing pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited thereto, Can be exemplified.
The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).
First, a photosensitive resin composition is coated on a substrate and then heated and dried to remove a volatile component such as a solvent to obtain a smooth coated film.
The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method, or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is 70 to 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 1: Synthesis of alkali-soluble resin (first resin (A-1))
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was set to a nitrogen atmosphere, and 300 parts by mass of methylethyldiethylene glycol was added and heated to 70 DEG C with stirring. Subsequently, 300 parts by mass of a mixture of the following formulas (8) and (9) (molar ratio of 50:50), 150 parts by mass of glycidyl methacrylate and 50 parts by mass of methacrylic acid were dissolved in 140 parts by mass of methylethyldiethylene glycol, Lt; / RTI >
[Chemical Formula 8]
[Chemical Formula 9]
The prepared solution was added dropwise in a flask kept at 70 캜 using a dropping funnel over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of methylethyldiethylene glycol was added to the flask over 4 hours using a separate dropping funnel . After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (solid content: 36.7% by mass, acid value: 59 mg-KOH / g (A-1)).
The resin A-1 thus obtained had a weight average molecular weight Mw of 8,200 and a molecular weight distribution of 1.85.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured 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, 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 sample concentration 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).
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, and 300 parts by mass of methylethyldiethylene glycol was added and heated to 70 캜 with stirring. Subsequently, 30 parts by mass of styrene, 45 parts by mass of methacrylic acid, 135 parts by mass of glycidyl methacrylate, 2 parts by mass of 2- (octahydro-4,7-methano-1H-inden-5-yl) Phenoxy were dissolved in 140 parts by mass of methylethyldiethylene glycol to prepare a solution.
The prepared solution was dropped into a flask kept at 70 캜 for 4 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of methylethyldiethylene glycol was added to the flask over 4 hours using a separate dropping funnel . After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a copolymer (solid content: 32.4% by weight and acid value: 31 mg-KOH / g (A-2)).
The weight average molecular weight Mw of the obtained resin A-2 was 28,000 and the molecular weight distribution was 3.20.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured 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, 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 sample concentration 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).
Manufacturing example 3. Synthesis of alkali-soluble resin (A-3)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, nitrogen was flowed at 0.02 L / min in the flask atmosphere, 60 parts by mass of methacrylic acid, 40 parts by mass of methyl methacrylate and 20 parts by mass of 2- (octahydro-4,7-methano-1H-inden-5-yl) And 136 g of propylene glycol monomethyl ether acetate 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, 30 parts by mass of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 DEG C for 6 hours to obtain a copolymer having an acid value of solid of 110 mgKOH / g The third resin (A-3)). The weight average molecular weight measured by GPC in terms of polystyrene was 33,000 and the molecular weight distribution (Mw / Mn) was 4.0.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured 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, 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 sample concentration 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 content shown in Table 1 below was prepared.
(A)
A-2
9.6
9.6
9.6
9.6
9.6
9.6
9.6
9.6
9.6
A-2: The resin of Production Example 2
A-3: The resin of Production Example 3
B: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Yakuza Co., Ltd.)
C-1: methyl-4-dodecylbenzenesulfonate
C-2: methyl-4-hexylbenzenesulfonate
C-3: Methyl-4-tetradecylbenzenesulfonate
C-4: methyl-4-pentylbenzenesulfonate
C-5: Methyl-4-pentadecylbenzenesulfonate
D-1: 
D-2: 
E: 
F: diethylene glycol methyl ethyl ether: propylene glycol monomale ether acetate (4: 6 by volume)
G (antioxidant): SH-8400
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 respectively spin-coated on the glass substrate and then pre-baked at 90 DEG C for 125 seconds using a hot plate. The prebaked substrate was cooled to room temperature and light was irradiated at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with an interval 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.
(Hole pattern) having a square pattern of 30 mu m square and having an interval of 100 mu m and irradiated with an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide after light irradiation, Followed by development and post-baking in an oven at 90 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) Hole line width: average value of X and Y directions of bottom surface when forming a hole pattern. In the above example, pattern formation was performed using a 30 μm square pattern.
(2) CD-Bias: It can be judged that the pattern formation performance is better as the actual pattern size is smaller than the applied mask size and closer to the mask size where the actual pattern size is applied.
In this case, it is determined that the composition having a value close to 0 is better.
(3) Heat Resistance Film Ratio: After the pattern formation is completed, the cured product is heated at 90 占 폚 for 1 hour to final cure, and further heated at 230 占 폚 for 30 minutes to observe the degree of film shrinkage by further heating. It can be judged that the material having excellent curing performance under the low temperature curing condition has a small film shrinkage under the additional heating and that the high temperature curing performance is higher than that when the heat retaining film ratio after the additional heating is high.
(4) Chemical resistance evaluation: The coating film which has been cured by heating at 90 ° C for 1 hour is immersed in HNO 3 and HCl aqueous solution and treated for 45 minutes / 6 minutes.
After that, the surface was cut with a cutter according to ASTM D-3359-08 standard test conditions, and the adhesion was confirmed by attaching a tape to the tape and peeling it off.
(5B: 0% peeling, 4B: peeling 5%) was determined to be 0B to 5B according to the standard test method in the degree of peeling of the coating film in the cutting / 3B: peeling 5 or more to less than 15%, 2B: peeling 15 or more to less than 35%, 1B: peeling 35 or more to less than 65% or 0B: 65% or more).
(5) Transmittance: After the pattern formation is completed, the cured product is heated at 90 DEG C for 1 hour to final cure, and then the transmittance of the coated film portion is measured.
(Evaluation of adhesion)
Referring to Table 2, it was confirmed that the photosensitive resin composition according to the present invention was excellent in pattern formation characteristics, chemical resistance, heat resistance, and the like, of a pattern produced under low temperature curing conditions.
However, it was confirmed that the composition of the comparative example remarkably deteriorated the resistance to residual heat resistance and chemical resistance of a pattern produced by low-temperature curing and remarkably decreased pattern formation characteristics.
Claims (9)
Polymerizable compound (B);
A thermal acid generator (C) represented by the following formula (1);
(D) a trifunctional or more polyfunctional thiol compound;
A photopolymerization initiator (E); And
A negative-working photosensitive resin composition comprising a solvent (F):
[Chemical Formula 1]
(Wherein R 1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 1 to 10 carbon atoms, and R 2 is an alkyl group having 6 to 14 carbon atoms).
(2)
(Wherein R 1 , R 2 and R 3 are each independently hydrogen or a methyl group,
R 4 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 5 is a structure derived from a monomer selected from the group consisting of the following formulas (1) to (9)
R 6 is a structure derived from a monomer selected from the group consisting of the following formulas (10) to (12)
a = 10 to 30 mol%, b = 30 to 60 mol%, c = 20 to 50 mol%
(3)
(Wherein R 7 , R 8 , R 9 and R 10 are independently of each other hydrogen or a methyl group,
R 11 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 12 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) Gt; is a structure derived from a monomer selected from the group consisting of < RTI ID = 0.0 >
R 13 is a structure derived from a monomer selected from the group consisting of the following formulas (13) to (21)
R 14 is a structure derived from a monomer selected from the group consisting of the following formulas (22) to (28)
d = 10 to 30 mol%, e = 10 to 20 mol%, f = 30 to 60 mol%, g = 10 to 30 mol%).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140118682A KR20160029339A (en) | 2014-09-05 | 2014-09-05 | Photosensitive resin comopsition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140118682A KR20160029339A (en) | 2014-09-05 | 2014-09-05 | Photosensitive resin comopsition |
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| Publication Number | Publication Date |
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| KR20160029339A true KR20160029339A (en) | 2016-03-15 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017179783A1 (en) * | 2016-04-14 | 2017-10-19 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin film using same, and black column spacer |
| KR20180031112A (en) * | 2016-09-19 | 2018-03-28 | 동우 화인켐 주식회사 | Photosensitive resin comopsition and photocurable protective layer formed from the same |
| KR20180086134A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same |
| KR20190035615A (en) * | 2016-07-28 | 2019-04-03 | 닛산 가가쿠 가부시키가이샤 | Resin composition |
| WO2019146814A1 (en) * | 2018-01-26 | 2019-08-01 | 동우화인켐 주식회사 | Black photosensitive resin composition, black matrix for image display device manufactured therefrom, column spacer, and black matrix integrated column spacer |
| CN116500859A (en) * | 2022-12-29 | 2023-07-28 | 徐州博康信息化学品有限公司 | Chemical amplification type I-line photoresist and preparation and use methods thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101302508B1 (en) | 2006-02-03 | 2013-09-02 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same |
-
2014
- 2014-09-05 KR KR1020140118682A patent/KR20160029339A/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101302508B1 (en) | 2006-02-03 | 2013-09-02 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017179783A1 (en) * | 2016-04-14 | 2017-10-19 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin film using same, and black column spacer |
| KR20190035615A (en) * | 2016-07-28 | 2019-04-03 | 닛산 가가쿠 가부시키가이샤 | Resin composition |
| KR20180031112A (en) * | 2016-09-19 | 2018-03-28 | 동우 화인켐 주식회사 | Photosensitive resin comopsition and photocurable protective layer formed from the same |
| KR20180086134A (en) * | 2017-01-20 | 2018-07-30 | 동우 화인켐 주식회사 | Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same |
| KR20190024933A (en) * | 2017-01-20 | 2019-03-08 | 동우 화인켐 주식회사 | Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same |
| WO2019146814A1 (en) * | 2018-01-26 | 2019-08-01 | 동우화인켐 주식회사 | Black photosensitive resin composition, black matrix for image display device manufactured therefrom, column spacer, and black matrix integrated column spacer |
| CN116500859A (en) * | 2022-12-29 | 2023-07-28 | 徐州博康信息化学品有限公司 | Chemical amplification type I-line photoresist and preparation and use methods thereof |
| CN116500859B (en) * | 2022-12-29 | 2024-02-09 | 徐州博康信息化学品有限公司 | Chemical amplification type I-line photoresist and preparation and use methods thereof |
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