KR20140086490A - Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix - Google Patents
Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix Download PDFInfo
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- KR20140086490A KR20140086490A KR1020120157060A KR20120157060A KR20140086490A KR 20140086490 A KR20140086490 A KR 20140086490A KR 1020120157060 A KR1020120157060 A KR 1020120157060A KR 20120157060 A KR20120157060 A KR 20120157060A KR 20140086490 A KR20140086490 A KR 20140086490A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
Abstract
The present invention relates to a photosensitive composition comprising a colorant (A), an alkali-soluble resin (B), a non-reactive polyether-modified silicone compound (C), a photopolymerizable compound (D), a photopolymerization initiator (E) Soluble resin (B) comprises a monomer represented by the formula (1) and a monomer represented by the formula (2), and the non-reactive polyether-modified silicone compound (C) do.
Description
The present invention relates to a black photosensitive resin composition, a black matrix prepared by using the black photosensitive resin composition, and a color filter including the black matrix. More particularly, the present invention relates to a color filter having excellent adhesion with a substrate and storage stability, A black matrix made using the black photosensitive resin composition, and a color filter including the black matrix.
Among the color filters of the liquid crystal display, the black matrix transmits light outside the transparent pixel electrode to block uncontrolled light to improve the contrast, and is made of chromium or a resin. Chromium has excellent thin-film shading performance and pattern straightness, but resin-based black matrix is preferred because of environmental problems, high reflectance, and high cost in the process.
However, the photosensitive resin composition for producing a resin black matrix does not effectively crosslink the light due to the black pigment which greatly interferes with the photosensitivity, and causes problems such as over-erosion due to the so-called "undercut", insufficient development stability, and deterioration in photosensitivity.
In order to solve such a problem, Korean Patent Application No. 2000-0055255 discloses a photosensitive resin composition for a black matrix containing a cation resin and a silane coupling agent in which various monomers are copolymerized, but the storage stability is poor, There is a problem that a difference in optical density occurs depending on the position when the fine pattern is formed according to the heat flow at the time.
Korean Patent Application No. 2010-0032142 discloses an alkali-soluble resin (B) obtained by polymerization of a monomer containing a compound represented by the following formula (1) to improve the optical density difference as described above Discloses a black photosensitive resin composition. However, such a composition has a disadvantage in that sensitivity and adhesion are insufficient.
≪ Formula 1 >
The present invention has been conceived to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide an optical device having excellent adhesion with a substrate and storage stability and having low sensitivity to heat while minimizing heat flow during post- It is an object of the present invention to provide a black photosensitive resin composition which improves the density difference, a black matrix manufactured using the black photosensitive resin composition, a color filter including the black matrix, and a liquid crystal display device including the color filter.
It is another object of the present invention to provide a black photosensitive resin composition which is improved in spreadability to a tempered glass to prevent occurrence of a fat edge phenomenon.
According to the present invention,
(A), an alkali-soluble resin (B), a non-reactive polyether-modified silicone compound (C), a photopolymerizable compound (D), a photopolymerization initiator (E) and a solvent (F)
The alkali-soluble resin (B) comprises a monomer represented by the following formula (1) and a monomer represented by the following formula (2)
The non-reactive polyether-modified silicone compound (C) is represented by the following general formula (3): < EMI ID =
[Chemical Formula 1]
Wherein n is an integer from 2 to 4,
(2)
Wherein m is an integer of 0 to 2,
(3)
In this formula,
x, y and n are each independently a natural number of 1 to 10,
And Z is a C2-C4 alkylene glycol group.
In addition,
There is provided a black matrix formed by forming the black photosensitive resin composition in a predetermined pattern, followed by exposure and development.
In addition,
And a color filter including the black matrix.
In addition,
And a liquid crystal display device including the color filter.
The black photosensitive resin composition of the present invention not only has excellent adhesion with a substrate, but also has excellent sensitivity and can form a fine pattern.
In addition, the black photosensitive resin composition of the present invention can reduce the heat flow during post-baking without lowering the sensitivity, thereby improving the optical density difference depending on the position when forming the fine pattern. Therefore, a black matrix capable of uniformly blocking strong backlight can be produced.
In addition, the black photosensitive resin composition of the present invention improves the spreadability to a tempered glass, thereby preventing occurrence of a fat edge phenomenon.
According to the present invention,
(A), an alkali-soluble resin (B), a non-reactive polyether-modified silicone compound (C), a photopolymerizable compound (D), a photopolymerization initiator (E) and a solvent (F)
The alkali-soluble resin (B) comprises a monomer represented by the following formula (1) and a monomer represented by the following formula (2)
The non-reactive polyether-modified silicone compound (C) is represented by the following general formula (3): < EMI ID =
[Chemical Formula 1]
Wherein n is an integer from 2 to 4,
(2)
Wherein m is an integer of 0 to 2,
(3)
In this formula,
x, y and n are each independently a natural number of 1 to 10,
And Z is a C2-C4 alkylene glycol group.
The black photosensitive resin composition contains 20 to 70% by weight of a colorant (A), 4 to 30% by weight of an alkali-soluble resin (B), 0.001 to 1.5% by weight of a non-reactive polyether- ), 3 to 40% by weight of a photopolymerizable compound (D) and 0.1 to 20% by weight of a photopolymerization initiator (E)
It is preferable that the black photosensitive resin composition contains 60 to 90% by weight of the solvent (F) based on the total weight.
Hereinafter, the black photosensitive resin composition of the present invention will be described in terms of its constituent components:
The alkali-soluble resin (B)
The black photosensitive resin composition of the present invention comprises an alkali-soluble resin (B) which is a polymer containing monomers represented by the following general formulas (1) and (2)
[Chemical Formula 1]
In the above formula, n is an integer of 2 to 4.
(2)
In the above formula, m is an integer of 0 to 2.
The monomer represented by the formula (1) serves to improve the adhesion with the substrate. In addition, since the monomer is non-reactive, the storage stability of the black photosensitive resin composition is improved, thereby preventing the line width from varying according to the storage period. In addition, since the monomer has a low heat flow property during post-baking to improve the optical density difference depending on the position, it plays a role of blocking the backlight uniformly.
As the monomer represented by the above formula (1), for example, acryloxyethyl succinate and the like can be used, and preferably 4- (2- (acryloyloxy) ethoxy) -4-oxobutanoic acid, 5- (2- (acryloyloxy) ethoxy) -5-oxopentanoic acid and 6- (2- (acryloyloxy) ethoxy) -6-oxohexanoic acid. Two or more species may be used, but the present invention is not limited thereto.
The monomer of Formula 1 may be contained in an amount of 10 to 40% by weight based on the total weight of the alkali-soluble resin (B). That is, the amount of the monomer to be added for polymerization of the alkali-soluble resin (B) may be 10 to 40% by weight based on the total amount of monomers to be polymerized. When the monomer represented by the formula (1) is contained in an amount of less than 10% by weight, the effect of reducing the heat flow during post-baking when forming a pattern is insignificant, If the weight% is exceeded, problems may occur in the straightness and film uniformity due to the settling phenomenon in pattern formation.
The monomer represented by the formula (2) forms a copolymer with the monomer represented by the formula (1) to further reduce heat flow during post-baking, thereby reducing the difference in optical density due to the positional difference during the formation of the fine pattern.
As the monomer represented by the above formula (2), for example, isobornyl methacrylate may be used, preferably 1,7,7-trimethylbicyclo [2.2.1] heptan-2-yl methacrylate, Dimethyl-1-propylbicyclo [2,2,1] heptan-2-yl methacrylate, 1-ethyl-7,7-dimethylbicyclo [2.2.1] heptan- 1-ethyl-7,7-dimethylbicyclo [2.2.1] heptane-2-yl methacrylate, but is not limited thereto.
The monomer of Formula 2 may be included in an amount of 10 to 40% by weight based on the total weight of the alkali-soluble resin (B). If it is contained in an amount of less than 10% by weight, the adhesion is insufficient when the pattern is formed, and if it is more than 40% by weight, it may be difficult to form a fine pattern due to decreased developability and adhesion to a substrate.
The alkali-soluble resin (B) may further contain 20 to 80% by weight, based on the total weight of the alkali-soluble resin (B), of a compound having an unsaturated bond capable of copolymerizing with the monomer represented by the formula (1) have. That is, the alkali-soluble resin (B) of the present invention can be prepared by further adding monomer (compound) other than the monomer represented by the above-mentioned formula (1) or (2)
Specific examples of the other monomer include a (meth) acrylate compound (the (meth) acrylate includes both methacrylate and acrylate), an aromatic vinyl compound, a carboxylic acid vinyl ester compound, a vinyl cyanide compound, A monocarboxylic acid compound, a dicarboxylic acid compound, and a compound having a carboxyl group and a hydroxyl group at both terminals, may be used. have. Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) , Aminoethyl (meth) acrylate, and other unsaturated carboxylic acids; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate, and glycol monocarboxylic acid ester compounds such as oligoethylene glycol monoalkyl (meth) acrylate, but are not limited thereto. Specific examples of the aromatic vinyl compound include, but are not limited to, styrene,? -Methylstyrene, vinyltoluene, and the like. Specific examples of the carboxylic acid vinyl ester compound include, but are not limited to, vinyl acetate or vinyl propionate. Specific examples of the vinyl cyanide compound include, but are not limited to, acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and the like. Specific examples of the maleimide compound include, but are not limited to, N-cyclohexylmaleimide or N-phenylmaleimide. Specific examples of the vinyl carboxylate compound include, but are not limited to, vinyl acetate or vinyl propionate. Specific examples of the unsaturated oxetanecarboxylate compound include 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl- Methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl- 3-methyl-3-methacryloxyethyloxetane, and the like, but are not limited thereto. Specific examples of the monocarboxylic acid compound include, but are not limited to, acrylic acid, methacrylic acid, and crotonic acid. Specific examples of the dicarboxylic acid compound include fumaric acid, mesaconic acid, itaconic acid, and the like, but are not limited thereto. Specific examples of the compound having a carboxyl group and a hydroxy group at both ends include? -Carboxypolycaprolactone mono (meth) acrylate and the like, but are not limited thereto.
The alkali-soluble resin (B) may be included in the solid content of the black photosensitive resin composition in an amount of 4 to 30 wt%, preferably 5 to 27 wt%, based on the total weight of the black photosensitive resin composition. When the amount of the alkali-soluble resin (B) is in the range of 4 to 30% by weight, the pattern is easily formed due to the solubility in the developer, and the decrease in the film thickness of the exposed portion is prevented during development.
Non-reactive Polyether The modified silicone compound (C)
The black photosensitive resin composition of the present invention comprises a non-reactive polyether-modified silicone compound represented by the following general formula (3)
(3)
In this formula,
x, y and n are each independently a natural number of 1 to 10,
And Z is a C2-C4 alkylene glycol group.
The non-reactive polyether-modified silicone compound represented by Formula 3 performs leveling agent dynamics in the composition of the present invention. Further, since the ampholytic agent is used for the solvent, the surface tension can be controlled so that the pattern of the black photosensitive resin composition can be formed with a uniform film thickness. In addition, it also functions to prevent stains during coating film formation.
If y is 0, the content of the hydrophobic (= lipophilic) group is too small to cause unevenness in the formation of the coating film. If y exceeds 10, the hydrophobicity becomes too strong, Occurs.
When Z is an alkylene glycol having less than 2 carbon atoms, it is difficult to expect it to serve as a surfactant. In the case of an alkylene glycol having more than 4 carbon atoms, the hydrophobicity increases and the flatness at the time of film formation deteriorates.
The non-reactive polyether-modified silicone compound is contained in an amount of 0.001 to 1.5% by weight, more preferably 0.05 to 0.8% by weight, based on the total weight of the solid components of the black photosensitive resin composition. When the non-reactive polyether modified silicone compound is contained in an amount of 0.001 to 1.5% by weight, a black photosensitive resin composition having a uniform film thickness can be formed, and the advantage that the non-reactive polyether modified silicone compound can be uniformly mixed in the composition have.
The colorant (A)
The colorant (A) comprises a black pigment (A1) and an organic pigment (A2).
The black pigment (A1) is not particularly limited as far as it is light-shielding and can be used. Specifically, aniline black, perylene black, titanium black, carbon black and the like can be used.
The organic pigment (A2) plays a role of a color correcting agent and can be used in printing ink, ink jet ink or the like and known in the art without limitation, and specifically includes water-soluble azo pigment, insoluble azo pigment, An anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, But are not limited to, pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.
The colorant (A) may be contained in an amount of 20 to 70% by weight, and preferably 30 to 65% by weight based on the total weight of solid components of the black photosensitive resin composition. When the colorant (A) is contained in an amount of 20 to 70% by weight, optical density is sufficient for forming a thin film, and the residue of the pixel portion is reduced during development. Here, the 'solid content' means the total amount of the components other than the solvent from the black photosensitive resin composition.
Photopolymerization Compound (D)
The photopolymerizable compound (D) is a compound capable of polymerizing under the action of the photopolymerization initiator (E), and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, and preferably a bifunctional or higher functional monomer .
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.
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 or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.
Specific examples of the polyfunctional monomer 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 ) Acrylate or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.
The photopolymerizable compound (D) may be contained in an amount of 3 to 40% by weight, preferably 5 to 30% by weight based on the total solid weight of the black photosensitive composition. When the photopolymerizable compound (D) is contained in an amount of 3 to 40 parts by weight, the strength and smoothness of the exposed area are improved.
Light curing Initiator (E)
The photopolymerization initiator (E) may be a photopolymerization initiator known in the art without limitation, and specifically includes a photopolymerization initiator selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole- Mixtures may be used.
Specifically, the triazine-based compound is 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, but are not limited thereto.
Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one -One oligomers, but are not limited thereto. The acetophenone compound may be a compound represented by the following formula (4): < EMI ID =
[Chemical Formula 4]
In Formula 4, R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted by an alkyl group having 1 to 12 carbon atoms. Specific examples of the compound represented by Formula 4 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 2-dimethylamino (4-morpholinophenyl) propane-1-one, 2-methyl- But is not limited thereto.
Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group in the 4,4' (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, and the like, but not limited thereto.
Specifically, the oxime compound may be, for example, a compound represented by any one of the following formulas (5) to (7)
[Chemical Formula 5]
[Chemical Formula 6]
(7)
In addition to the above-mentioned photopolymerization initiator, other photopolymerization initiators commonly used in this field can be further used in combination so long as the effect of the present invention is not impaired. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, anthracene-based compounds, and polyfunctional thiol compounds. These may be used alone or in combination of two or more. Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, but are not limited thereto. 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. Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- However, the present invention is not limited thereto. Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene , But is not limited thereto. The polyfunctional thiol compound specifically includes tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercapto Propionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like, but are not limited thereto. In addition to these, it is also possible to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, Methyl, titanocene compounds and the like can be used as other photopolymerization initiators.
The photopolymerization initiator (E) may be contained in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight based on the total weight of the solid components of the black photosensitive resin composition. When the photopolymerization initiator (E) is contained in an amount of 0.1 to 20% by weight, the sensitivity of the black photosensitive resin composition is excellent and the exposure time is shortened so that the productivity can be improved and the fine properties can be maintained. Is preferable.
The photopolymerization initiator (E) may be used in combination with the photopolymerization initiator (E-1). When the photopolymerization initiator (E) is used in combination with the photopolymerization initiator auxiliary (E-1), the black photosensitive resin composition containing the photopolymerization initiator (E-1) has a higher sensitivity and productivity is improved when forming the black matrix or black column spacer.
The photopolymerization initiation auxiliary (E-1) may be selected from the group consisting of an amine compound and a carboxylic acid compound, or a mixture thereof.
Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4, , Aromatic amine compounds such as 4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, and the like. But is not limited thereto.
Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, Aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid, but are not limited thereto.
The photopolymerization initiation assistant (E-1) may be contained in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight based on the total weight of the solid content of the black photosensitive resin composition. When the photopolymerization initiator (E-1) is contained in an amount of 0.01 to 10% by weight, the sensitivity of the black photosensitive resin composition is increased so that the strength and smoothness of the colored layer formed using the photosensitive resin composition are increased and the productivity of the color filter is improved .
Solvent (F)
Examples of the solvent (F) include, but are not limited to, those known in the art. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Ethers; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; 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; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone, or a mixture thereof.
Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coating property and dryness can be used, more preferably an alkylene glycol alkyl ether acetate, a ketone, ethyl 3-ethoxypropionate and 3-methoxy Methyl propionate, and the like, or mixtures thereof. More preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, or a mixture thereof.
The solvent (F) may be contained in the black photosensitive resin composition in an amount of 60 to 90% by weight, preferably 70 to 88% by weight based on the total weight of the black photosensitive resin composition. When the solvent (F) is contained in an amount of 60 to 90% by weight, the coating property is good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (die coater)
The black photosensitive resin composition of the present invention may contain other additives such as fillers, other polymer compounds, curing agents, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like, as long as the object of the present invention is not impaired, It is also possible to use the additive (G) in combination.
The filler may be glass, silica, alumina, or the like, but is not limited thereto.
Specific examples of the other polymer compound include a non-reactive polyether-modified silicone compound, a curable resin such as a maleimide resin, a polyvinyl alcohol, a polyacrylic acid, a polyethylene glycol monoalkyl ether, a polyfluoroalkyl acrylate, a polyester, Thermoplastic resin or the like can be used, but the present invention is not limited thereto.
The curing agent is used for increasing the curing depth and mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound may be used, but the present invention is not limited thereto. Specifically, the epoxy compound is a bisphenol A-based non-reactive polyether-modified silicone compound, a hydrogenated bisphenol A-based non-reactive polyether-modified silicone compound, a bisphenol F-based non-reactive polyether-modified silicone compound, a hydrogenated bisphenol F- Silicone compounds, novolac-type non-reactive polyether-modified silicone compounds, other aromatic non-reactive polyether-modified silicone compounds, alicyclic non-reactive polyether-modified silicone compounds, glycidyl ester-based resins, glycidylamine- Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymeric epoxides, glycidyl (co) polymeric compounds other than the brominated derivatives of the non-reactive polyether modified silicone compounds, non- Glycidyl (meth) acrylate (co) polymer, but it can use, such as triglycidyl the SOCCIA pressing rate, and the like. Specific examples of the oxetane compound include, but are not limited to, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. It is not.
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. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The carboxylic anhydrides may be those commercially available as non-reactive polyether-modified silicone compound curing agents. Examples of the commercially available non-reactive polyether-modified silicone compound curing agent include a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rikashido HH) (MH-700) (manufactured by Shin-Etsu Chemical Co., Ltd.).
The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.
The above-mentioned pigment dispersant may be a commercially available surfactant. Specifically, it may be a surfactant selected from the group consisting of silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric surfactants, have. More specifically, examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines and the like. (Trade name: KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asahi guard, Surflon (Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol), EFKA (Nippon Ink Chemical Industries Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.) (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane, or a mixture thereof.
The adhesion promoter may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content of the black photosensitive resin composition.
The antioxidant may be a hindered phenol-based compound such as 2,2'-thiobis (4-methyl-6-t-butylphenol) or 2,6- But is not limited thereto.
Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
The anti-aggregation agent may be, for example, sodium polyacrylate, but is not limited thereto.
The black photosensitive resin composition of the present invention can be produced by the following method. The colorant (A) is mixed with the solvent (F) in advance, and the mixture is dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 탆 or less to obtain a dispersion. At this time, a pigment dispersant may be used if necessary, and some or all of the alkali-soluble resin (B) may be blended. (B), a non-reactive polyether-modified silicone compound (C), a photopolymerizable compound (D) and a photopolymerization initiator (E) in a dispersion (hereinafter sometimes referred to as a mill base) After the addition of the additive (G), the desired black photosensitive resin composition can be obtained by further adding an additional solvent so as to have a predetermined concentration as required.
Hereinafter, a color filter according to the present invention will be described.
The color filter according to the present invention includes a black matrix or black column spacer obtained by applying the above-described black photosensitive resin composition according to the present invention on a substrate, and exposing and developing it in a predetermined pattern.
More specifically, a method of forming a pattern of a black matrix or a black column spacer using a black photosensitive resin composition according to the present invention includes a coating step of applying the black photosensitive resin composition described above onto a substrate, a step of coating a part of the black photosensitive resin composition An exposure step of selectively exposing the black photosensitive resin composition and a developing step of removing the exposed area or the non-exposed area of the black photosensitive resin composition.
In the coating step, the black photosensitive composition of the present invention is coated on a substrate and preliminarily dried to remove a volatile component such as a solvent to obtain a smooth coating film. The thickness of the coating film at this time is usually about 0.5 to 5 mu m. The substrate may be a glass plate, a silicon wafer, a plate of a plastic substrate such as polyethersulfone (PES), polycarbonate (PC), or the like, and the kind thereof is not particularly limited.
The step of exposing is a step of irradiating a specific region with ultraviolet rays through a mask to obtain a desired pattern on the coating film obtained above. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel rays, and the mask and the substrate are accurately positioned.
In the developing step, the coated film after completion of the curing is contacted with an alkali aqueous solution, which is a developing solution, to dissolve and expose the non-exposed region, thereby producing a desired pattern. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.
The developing solution used in the developing step is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, Potassium, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, 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 preferable concentration of the alkaline compound is 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.
The surfactant in the developer may be selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant, or a mixture thereof. 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 sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like. 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, lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more. The surfactant may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the alkali developing solution.
Through the above process, a black matrix or a black column spacer is obtained. The configuration and manufacturing method of the color filter are well known in the art, and a detailed description thereof will be omitted.
The present invention also includes a liquid crystal display device having the above-described color filter.
The liquid crystal display device of the present invention includes a configuration known in the art except for the color filter described above. That is, all the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.
As another example, a TFT (Thin Film Transistor) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed at a position where the TFT substrate overlaps with a color filter can be given. The TFT substrate includes an outer frame made of a light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of a nematic liquid crystal placed in the outer frame, a plurality of pixel electrodes , A transparent glass substrate on which pixel electrodes are formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.
The polarizing plate has a polarization direction perpendicular to the polarizing direction and is made of an organic material such as polyvinyl alcohol. Each of the plurality of pixel electrodes is connected to a plurality of thin film transistors formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Accordingly, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.
Manufacturing example 1. Preparation of pigment dispersion (M)
20 g of carbon black, 6 g of Ajisera PB821 (Ajinomoto Fine Techno Co., Ltd.) as a dispersing agent and 74 g of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours using a bead mill to prepare a pigment dispersion (M) Respectively.
Synthetic example 1 to 20: Synthesis of alkali-soluble resin
(PGMA), AIBN, 2-acryloxyethyl succinates (B-1), n-heptafluoroisopropyl acrylate (B-1) were placed in a 1000 ml flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen- Styrene, methacrylic acid, and isobornyl methacrylate (B-2) were charged in the amounts shown in Tables 2 and 3 and replaced with nitrogen (g in Tables 2 and 3 below). Thereafter, the temperature of the reaction solution was raised to 100 DEG C with stirring, and the reaction was allowed to proceed for 7 hours. The acid value of the final solid content of the alkali-soluble resin thus synthesized and the weight average molecular weight thereof were measured by GPC, and are shown in Tables 2 and 3 below. B-1 and B-2 used in the respective synthesis examples are shown in Table 1 below.
One
2
3
4
5
6
7
8
9
10
(Unit: g)
11
12
13
14
15
16
17
18
19
20
(Unit: g)
Example 1 to 15: Preparation of black photosensitive resin composition
A black photosensitive resin composition was prepared by a method known in the art according to the compositions of Tables 4 and 5 below.
(Unit: g)
(Unit: g)
1) KAYARAD DPHA (manufactured by Nippon Kayaku)
2) Ciba Specialty Chemical
3) Ciba Specialty Chemical
4) Ciba Specialty Chemical
5) 4,4'-di (N, N'-dimethylamino) -benzophenone (Hodogaya Chemical Co., Ltd.)
6) L-1, Silsurf A008, manufacturer: Siltech
7) L-2, product name SH8700, manufacturer: Dow Corning Toray
Comparative Example 1 to 8: Preparation of black photosensitive resin composition
A black photosensitive resin composition was prepared in the same manner as in the above Examples with the composition shown in Table 6 below.
(Unit: g)
1) WR-101, Adeka
2) KAYARAD DPHA (manufactured by Nippon Kayaku)
3) Ciba Specialty Chemical
4) Ciba Specialty Chemical
5) Ciba Specialty Chemical
6) 4,4'-di (N, N'-dimethylamino) -benzophenone (Hodogaya Chemical Co., Ltd.)
7) L-1, Silsurf A008, manufacturer: Siltech
8) L-2, product name SH8700, manufacturer: Dow Corning Toray
9) L-3, trade name TF-1425, manufacturer DIC, fluorine leveling agent
10) L-4, trade name UV-3570, BYK. Reactive polyether-modified silicone
Test Example One: Heat-flowable evaluation
The black photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 8 were applied on a glass substrate by spin coating and then placed on a heating plate and maintained at a temperature of 100 캜 for 2 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 50 m was placed on the thin film, and the interval between the test photomask and the test photomask was set to 50 m. Respectively. At this time, the ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter. The film thickness of the color filter prepared above was 1.0 탆. The thickness of the remaining 20 micro-patterns of the exposed portion after the development was measured before and after post-baking, and the heat flowability was measured in the following manner. The results were evaluated on the basis of the following criteria and shown in Tables 7 and 8.
≪ Heat flow measurement formula >
(Film thickness after post-baking / film thickness before post-baking) x 100
<Evaluation Criteria>
?: More than 97%,?: 95 to 97%, X: less than 95%
As shown in Tables 7 and 8, the black photosensitive resin composition of the examples shows that heat flow is reduced and there is no significant change in the film thickness before and after post-baking. On the other hand, in the case of the black photosensitive resin composition of the comparative example, it was found that the difference in film thickness occurred before and after the post-baking because the heat flow property was large.
In Comparative Examples 5, 6, 7 and 8, the non-reactive polyether-modified silicone compound of Chemical Formula 3 was included in the range of the present invention, or was not included at all, or the fluorine leveling agent was included instead, or the reactive polyether- And the non-reactive polyether-modified silicone compound represented by the general formula (3) did not affect the heat flowability.
Test Example 2: Evaluation of storage stability
The black photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 8 were allowed to stand at 25 占 폚 for 5 days, 3 days, and 1 day, respectively. One composition was applied on a glass substrate by spin coating, then placed on a heating plate and held at a temperature of 100 캜 for 2 minutes to form a thin film. A test photomask having a 20-micrometer pattern was placed and irradiated with ultraviolet rays at a distance of 50 占 퐉 from the test photomask. At this time, the ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter. The linewidths of the patterns formed on the mask having the line width of 20 mu m in the color filters prepared above were measured, and the variation amount (DELTA CD) of the line widths according to the leaving time was measured. The results are shown in Tables 9 and 10.
? CD = linewidth of a pattern evaluated with the resin composition produced on the same day - line width of a pattern evaluated with the resin composition left at room temperature
<Evaluation Criteria>
?:? CD = less than 0.5 micrometer
?: CD = 0.5 to 1.0 micrometer
X: CD = 1.0 micrometer or more
As shown in Tables 9 and 10, the black light sensitive resin composition of the examples had no difference in pattern line width depending on the time of keeping the composition at room temperature, but the composition of Comparative Examples 1 to 4 showed a change in pattern line width .
In Comparative Examples 5, 6, 7 and 8, the non-reactive polyether-modified silicone compound of Chemical Formula 3 was included in the range of the present invention, or was not included at all, or the fluorine leveling agent was included instead, or the reactive polyether- The non-reactive polyether-modified silicone compound of the formula (3) did not affect the storage stability.
Test Example 3: Fineness And evaluation of sensitivity
The compositions of the above Examples and Comparative Examples were coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100 캜 for 2 minutes to form a thin film. A test photomask having a 20-micrometer pattern was placed and irradiated with ultraviolet rays at a distance of 50 占 퐉 from the test photomask. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 50 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, and then observed with an optical microscope to see a pattern of a few micrometers. The results are shown in Tables 11 and 12 below.
(Sensitivity)
(Sensitivity)
As shown in Tables 11 and 12, the composition of the examples remained up to a pattern of 4 탆, indicating excellent sensitivity. In the case of the compositions of Comparative Examples 1 to 7, the adhesiveness and the resulting decrease in sensitivity were confirmed as compared with the compositions of the Examples.
Test Example 4: Evaluation of adhesion
After proceeding to the development process in the same manner as in the above Test Examples 1 to 3, it was washed with distilled water for 30 seconds in an ultra-high pressure water washing process (2 MPa) and observed by an optical microscope for a pattern of a few μm, And 14, respectively.
According to Tables 13 and 14, the compositions of the examples showed finer patterns than those of the comparative examples in terms of peeling and inter-pattern connection.
As described above, the black photosensitive resin composition of the present invention is excellent in adhesion to a substrate, sensitivity and storage stability, and is less susceptible to heat flow during post-baking, thereby reducing pattern drift, Patterns and black matrices.
Experimental Example 5: Evaluation of spreadability
The compositions of the above examples and comparative examples were applied on a glass substrate by spin coating and then dried in a vacuum state by a vacuum vacuum dryer (Shindo Engineering Co., Ltd.) with steps of 10 seconds for slow vacuum and 20 seconds for fast vacuum up to 100 Pa. Then, the edge portion of the fabricated sample was observed with an optical microscope.
The criterion of judgment was NG when the coating film went inward more than 1000um from the edge of the glass, and OK when it was less than 1000um. Test results are shown in Tables 15 and 16 below.
According to Tables 15 and 16, when the non-reactive polyether-modified silicone is used, it can be seen that the substrate spreadability is excellent and the fat-edge phenomenon does not occur. The fluorine leveling agent or the reactive polyether It can be understood that the spreadability is not good.
Claims (7)
The alkali-soluble resin (B) comprises a monomer represented by the following formula (1) and a monomer represented by the following formula (2)
The non-reactive polyether-modified silicone compound (C) is represented by the following formula (3): < EMI ID =
[Chemical Formula 1]
Wherein n is an integer from 2 to 4,
(2)
Wherein m is an integer of 0 to 2,
(3)
In this formula,
x, y and n are each independently a natural number of 1 to 10,
And Z is a C2-C4 alkylene glycol group.
The black photosensitive resin composition contains 20 to 70% by weight of a colorant (A), 4 to 30% by weight of an alkali-soluble resin (B), 0.001 to 1.5% by weight of a non-reactive polyether- ), 3 to 40% by weight of a photopolymerizable compound (D) and 0.1 to 20% by weight of a photopolymerization initiator (E)
A black photosensitive resin composition characterized by containing a solvent (F) in an amount of 60 to 90% by weight based on the total weight of the black photosensitive resin composition.
The alkali-soluble resin (B) is obtained by polymerizing 10 to 40% by weight of a monomer represented by the following formula (1), 10 to 40% by weight of a monomer represented by the formula (2) And 20 to 80% by weight of a compound having an unsaturated bond capable of copolymerizing with the monomer to be displayed.
Wherein the compound having an unsaturated bond is a (meth) acrylate compound, an aromatic vinyl compound, a carboxylic acid vinyl ester compound, a vinyl cyanide compound, a maleimide compound, a vinyl carboxylate compound, an unsaturated oxetanecarboxylate compound, Wherein the compound is at least one compound selected from the group consisting of a carboxylic acid compound, a dicarboxylic acid compound, and a compound having a carboxyl group and a hydroxyl group at both terminals thereof.
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