KR20150111074A - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents
A color photosensitive resin composition, color filter and display device comprising the same Download PDFInfo
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- KR20150111074A KR20150111074A KR1020140034478A KR20140034478A KR20150111074A KR 20150111074 A KR20150111074 A KR 20150111074A KR 1020140034478 A KR1020140034478 A KR 1020140034478A KR 20140034478 A KR20140034478 A KR 20140034478A KR 20150111074 A KR20150111074 A KR 20150111074A
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- photosensitive resin
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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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
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition for a color filter used in manufacturing a color filter used for a color liquid crystal display device or the like.
Description
The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and a liquid crystal display including the same.
BACKGROUND ART Color filters are widely used in image pickup devices, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding. Particularly, the color filter is one of the most important parts for reproducing color tone in an LCD in which the use thereof is expanding, and a manufacturing method of a color filter having excellent processability and product reliability for improving productivity in a LCD manufacturing process has been continuously studied.
In recent years, the pigment concentration of the colored photosensitive resin composition used in the production of a color filter has been continuously increasing to attain a high color purity. In order to improve productivity and yield in the process, a high developing speed and a low sensitivity There is a demand for a colored photosensitive resin composition having reliability.
Korean Unexamined Patent Publication No. 2008-0077499 discloses a colored photosensitive resin composition having a high acid value and capable of accelerating the developing speed.
Conventionally, when the acid value of the above-mentioned colored photosensitive resin composition is raised to rapidly increase the developing rate, adhesion is decreased and errors in patterning at the time of development tend to occur. In addition, the colored layer formed on the background by the colored photosensitive resin composition has a serious problem that the pattern can not be maintained at a low exposure dose due to the high concentration of the pigment.
In addition to the problems of the prior art as described above, the colored photosensitive resin composition of the prior art has a problem of a decrease in shrinkage rate and an increase in viscosity.
In order to solve the above problems, the present invention provides a colored photosensitive resin composition which is excellent in sensitivity at a low exposure dose even when a pigment is contained at a high concentration and has excellent adhesion to a substrate, And to provide the above objects.
It is another object of the present invention to provide a high-quality color filter which improves the productivity and yield in the process, and which does not cause a pattern error, and a liquid crystal display device including the color filter.
(A), a binder resin (B), a photopolymerization initiator (C), a photopolymerizable monomer (D), a coloring material (E) and a solvent (F) Wherein the polyfunctional urethane acrylate (A) comprises a compound represented by the following general formula (1).
[Chemical Formula 1]
Y is a (meth) acrylate group,
R1 is a linear or branched hydrocarbon having 1 to 10 carbon atoms in which 0 to 4 (meth) acrylate groups are substituted, and oxygen may be substituted in the main chain.
According to a preferred embodiment of the present invention, the polyfunctional urethane acrylate (A) may be a urethane acrylate (A) having 9 or more functionalities.
Another aspect of the present invention provides a color filter formed using the colored photosensitive resin composition of the present invention and a liquid crystal display device including the same.
The colored photosensitive resin composition of the present invention has excellent sensitivity and adhesion to a substrate and excellent reliability even at a low exposure dose when a pixel is formed with a high concentration of pigment.
In addition, there is no peeling of the pattern during the development process, excellent heat resistance, and excellent storage stability, so that sensitivity and viscosity are not increased even when stored for a long period of time. In addition, The surface defects such as water spots are not generated.
Accordingly, the present invention can be effectively applied to a color filter having no direct surface defect, etc., in a pixel portion, and having excellent quality in terms of linearity, heat resistance and chemical resistance, and a liquid crystal display device including the same. A filter photoresist, a photoresist for a resin black matrix, a transparent photoresist or the like.
Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.
In the prior art, when the development speed is rapidly induced, the adhesiveness is lowered, and there is a serious problem that the pattern can not be maintained at a low exposure dose due to the occurrence of a pattern error at the time of development and a high concentration of pigment.
In addition, the colored photosensitive resin composition of the prior art has a problem of a decrease in shrinkage percentage and an increase in viscosity.
Accordingly, the present inventors have found that the above problems can be solved by including a specific polyfunctional urethane acrylate (A) in the colored photosensitive resin composition, and thus completed the present invention.
That is, the present invention relates to a colored photosensitive resin composition comprising a polyfunctional urethane acrylate (A), a binder resin (B), a photopolymerization initiator (C), a photopolymerizable monomer (D), a coloring material (E) Wherein the polyfunctional urethane acrylate (A) comprises a compound represented by the following general formula (1).
[Chemical Formula 1]
Y is a (meth) acrylate group,
R1 is a linear or branched hydrocarbon having 1 to 10 carbon atoms in which 0 to 4 (meth) acrylate groups are substituted, and oxygen may be substituted in the main chain.
Each component constituting the colored photosensitive resin composition for a color filter of the present invention will be described below.
The polyfunctional urethane acrylate (A)
The polyfunctional urethane acrylate (A) is represented by the following general formula (1).
[Chemical Formula 1]
Y is a (meth) acrylate group,
R1 is a linear or branched hydrocarbon having 1 to 10 carbon atoms in which 0 to 4 (meth) acrylate groups are substituted, and oxygen may be substituted in the main chain.
The polyfunctional urethane acroleate (A) of the present invention may be a polyfunctional urethane acrylate (A) having 3 to 15, inclusive of a functional group which is a methacrylate group of Y and / or R 1, Or more polyfunctional urethane acrylate.
More preferably, the polyfunctional urethane acroleate (A) is C (CH 2 OCOCR═CH 2 ) 3 , CH 2 C (CH 2 OCOCR═CH 2 ) 3 and CH 2 C (CH 2 OCOCR═CH 2 ) 2 CH 2 OCH 2 C (CH 2 OCOCR═CH 2 ) 3 , wherein R is hydrogen or a methyl group.
The polyfunctional urethane acrylate (A) of the present invention imparts mechanical strength by a urethane group and can control the developing speed by R1 attached to the urethane main chain, and improves the reactivity and adhesion by Y. At the same time, the acrylate participates in the reaction by the initiator, so that the color separation phenomenon is suppressed and the reliability is excellent.
The polyfunctional urethane acrylate (A) may be used without limitation as long as it has the structure of Formula 1. The polyfunctional urethane acrylate (A) is contained in an amount of 5 to 50 wt% based on the solid content in the colored photosensitive resin composition, By weight, more preferably 10 to 20% by weight. When the content of the polyfunctional urethane acrylate (A) is less than 5 wt% based on the above-mentioned criteria, it is difficult to expect pattern formation and adhesion enhancement. When the content exceeds 50 wt%, the viscosity of the composition increases, And the export rate is getting worse.
The binder resin (B)
The binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of the coloring material.
The binder resin (B) contained in the colored photosensitive resin composition of the present invention functions as a binder resin for the coloring material (E), and the binder resin (B) can be used without limitation as long as it is generally used in the art, Any polymer that is soluble in the alkaline developer used in the development step for the production of the color filter can be used, and more preferably an acrylic binder resin can be used.
The binder resin (B) includes, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.
Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid and the like .
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid , Itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have. The carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, Hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Nyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like. These monomers may be used alone or in combination of two or more.
When the binder resin (B) is a copolymer of a carboxyl group-containing monomer and another monomer capable of copolymerizing with the monomer, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is preferably within a range from the total weight of the constituent units constituting the copolymer By weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight, based on the weight of the composition. When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is 10 to 50% by weight based on the above-mentioned criteria, the solubility in a developer is good and a pattern is accurately formed at the time of development.
Examples of the binder resin (B) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / polymethyl (meth) acrylate / benzyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, Methacrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. (Meth) acrylic acid / methyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate / styrene copolymer, Can be used.
The binder resin (B) preferably has an acid value of 20 to 200 (mgKOH / g). When the acid value of the binder resin (B) is in the above range, the solubility in the developer is improved, the non-exposed portion easily dissolves and the sensitivity increases, and consequently the pattern of the exposed portion remains at the developing time, .
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.
The binder resin (B) has a weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) of 3,000 to 200,000, And preferably from 5,000 to 100,000. When the weight average molecular weight of the binder resin (B) is in the above range, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution is improved.
The binder resin (B) is preferably contained in an amount of 10 to 80% by weight, more preferably 20 to 70% by weight based on the solid content in the colored photosensitive resin composition. When the content of the binder resin (B) is within the above-mentioned range, it is preferable that a pattern can be formed and the resolution and the residual film ratio are improved.
The photopolymerization initiator (C)
The photopolymerization initiator (C) preferably contains an acetophenone-based compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy- 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and the like.
These acetophenone compounds may be used alone or in combination of two or more. The photopolymerization initiator (C) may be used in combination with other photopolymerization initiators other than the acetophenone-based compound.
Examples of other types of photopolymerization initiators include an active radical generator, a sensitizer, and an acid generator that generate an active radical upon irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Specific examples of the benzophenone compound include methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra Oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- -Propoxyloxanthone, 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-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4 dimethoxyphenyl) ethenyl] -1,3,5- Triazine, and the like.
Specific examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- -Imidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate and titanocene compounds .
Specific examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, di Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates and benzoin tosylates.
Among these compounds, there are compounds which simultaneously generate an active radical and an acid. For example, a triazine-based compound is also used as an acid generator.
The photopolymerization initiator (C) may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the sum of the binder resin (B) and the photopolymerizable monomer (D) based on the solid content. When the content of the photopolymerization initiator (C) is within the above range on the basis of the above criteria, the colored photosensitive resin composition becomes highly sensitive and shortens the exposure time, thereby improving the productivity and maintaining high resolution.
On the other hand, the photopolymerization initiator (C) can be used in combination with a photopolymerization initiator. The photopolymerization initiator may be used to promote the polymerization of the photopolymerizable monomer initiated by the photopolymerization initiator (C).
Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, and the like.
Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate , 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'- ) Benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable.
Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. . The photopolymerization initiation assistant may be a commercially available product, EAB-F (manufactured by Hodogaya Chemical Co., Ltd.), and the photopolymerization initiator may be used alone or in combination of two or more.
Specific examples of preferable combinations of the photopolymerization initiator (C) and the photopolymerization initiation assistant include diethoxyacetophenone and 4,4'-bis (diethylamino) benzophenone; 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; 1-hydroxycyclohexyl phenyl ketone and 4,4'-bis (diethylamino) benzophenone; Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; A combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, -Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone.
When the photopolymerization initiator (C) and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 0.01 to 5 mol per 1 mol of the photopolymerization initiator. When the photopolymerization initiator is contained within the above range, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed using the composition is improved.
The photopolymerizable compound (D)
The photopolymerizable compound (D) is a compound capable of polymerizing under the action of light and a photopolymerization initiator, and examples thereof include monofunctional monomers, bifunctional monomers, and other multifunctional monomers.
Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Ralidon, and the like.
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 (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate Neopentyl glycol diacrylate, propyloxylate neopentyl glycol diacrylate, and the like.
Specific examples of the trifunctional 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 the tetrafunctional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane tetramethacrylate, dipentaerythritol tetraacrylate, Tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerin tetraacrylate, glycerin tetramethacrylate, and the like.
Specific examples of the pentafunctional monomer include dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, and the like. .
Specific examples of the hexafunctional monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like.
Of these, the photopolymerizable compound (D) may preferably be a multifunctional monomer having a bifunctional or higher functionality, and particularly a multifunctional monomer having a functionality of 5 or more may be preferably used.
The photopolymerizable compound (D) may be contained in an amount of 5 to 50% by weight, preferably 7 to 45% by weight based on the solid content in the colored photosensitive resin composition. When the photopolymerizable monomer (D) is in the range of 5 to 50% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are improved.
The coloring material (E)
The coloring material (E) is not limited in color tone, and the color tone can be selected according to the use of the color filter to be produced. The coloring material (E) may be any one or more of a pigment, a dye, and a natural coloring material. A pigment may be preferably used because the coloring material (E) is excellent in heat resistance and coloring property.
The pigment may be an organic pigment or an inorganic pigment generally used in the art.
The organic pigment in the pigment may be subjected to surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, graft treatment of the surface of the pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method (refinement) A cleaning treatment with an organic solvent and water for removal, a removal treatment with an ion exchange method of ionic impurities, or the like.
Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Oxides and the like.
Preferably, the pigment is a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists). More specifically, pigments having a color index (C.I.) number as described below are exemplified, but are not limited thereto.
C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147 , 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264 and 265
C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.) and 60
C.I. Pigment Violet 1, 19, 23, 29, 32, 36 and 38
C.I. Pigment Violet 1, 19, 23, 29, 32, 36 and 38
C.I. Pigment Green 7, 36 and 58
C.I Pigment Brown 23 and 25
C.I Pigment Black 1 and 7, etc.
These pigments may be used alone or in combination of two or more. The coloring material (E) may be contained in an amount of 3 to 60% by weight, preferably 5 to 55% by weight based on the solid content in the colored photosensitive resin composition.
When the content of the coloring material (E) is 3 to 60% by weight on the basis of the above criteria, the color density when the color filter is produced is sufficient and the polymer may be contained in the required amount in the colored photosensitive resin composition, A sufficient pattern can be formed.
When a pigment is used as the coloring material, it is preferable to use a pigment having a uniform average particle diameter.
As a method of making the particle diameter of the pigment uniform, a method of dispersing the pigment by adding a surfactant as a pigment dispersant can be mentioned. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.
Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
The pigment dispersant is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the coloring material in the colored photosensitive resin composition. When the pigment dispersant is used within the above range on the basis of the above criteria, a pigment having a uniform average particle diameter can be obtained, which is preferable.
Solvent (F)
The solvent used in the conventional colored photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. The solvent may be selected from ethers, aromatic hydrocarbons, ketones, alcohols, esters And amides are preferred.
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 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, propylene glycol monopropyl ether acetate, 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; cyclic esters such as? -butyrolactone; And the like.
The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Decyltate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The solvents exemplified above may be used alone or in admixture of two or more. The solvent may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total amount of the colored photosensitive resin composition of the present invention have.
When the above-mentioned solvent is in the range of 60 to 90% by weight, the coating property is good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Provides a resolution effect.
Additive (G)
The additive can be cited as being optionally be added, as needed, for example, another polymer compound, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and coagulation preventing agent, and the like.
Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .
The curing agent is used for deep curing and for increasing mechanical strength. 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 Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.
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. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
The surfactant may be used to further improve film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.
Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.
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- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
The photosensitive resin composition of the present invention can be produced, for example, by the following method.
The colored curable resin composition according to the present invention comprises a polyfunctional urethane acrylate (A). The colored curable resin composition further comprises at least one component selected from the group consisting of a binder resin (B), a photopolymerization initiator (C), a photopolymerizable compound (D), a coloring material (E) and a solvent (F) May further include various additives (G) commonly used in the art.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.
First, to prepare the colored photosensitive resin composition according to the present invention, a polyfunctional urethane acrylate was prepared in the following Synthesis Examples 1, 2 and 3.
Synthetic example 1: Compound of formula (2)
Miramer M340 (Miwon, PETA) 283 g and dibutyltin dilaurate 0.25 g were placed in a three-necked reactor equipped with a mechanical stirrer, a temperature sensor and a temperature sensor, and stirred at room temperature. 153 g of N3300 (Bayer Co.) and 0.5 g of methoxyhydroquinone were charged and reacted for 3 hours while maintaining the reaction temperature at 75 캜. After the reaction was completed, 9-functional urethane acrylate was prepared. The reaction was terminated when the characteristic peak of isocyanate of 2260 cm -1 in the infrared spectrum completely disappeared.
(2)
Synthetic example 2: Compound of Formula 3
In a three-neck reactor, 401 g of dipentaerythritol hexaacrylate (KAYARD DPHA) and 0.25 g of dibutyltin dilaurate were fed into a heating device connected to a mechanical stirrer, a temperature sensor and a temperature sensor, Lt; / RTI > 98 g of N3300 (Bayer Co.) and 0.5 g of methoxyhydroquinone were charged and reacted for 3 hours while maintaining the reaction temperature at 75 캜. After the reaction was completed, a 15-functional urethane acrylate was prepared. The reaction was terminated when the characteristic peak of isocyanate of 2260 cm -1 in the infrared spectrum completely disappeared.
(3)
Example 1 to 7 and Comparative Example 1: Preparation of photosensitive resin composition
A colored photosensitive resin composition comprising the components and the ratio (% by weight) shown in Table 1 below was prepared.
In Table 1, the respective components are as follows.
(A-1) 9-functional urethane-based acrylate:
(A-2) 15-functional urethane-based acrylate:
(B-1) binder resin
: Copolymer of methacrylic acid and benzyl methacrylate (ratio of methacrylic acid unit to benzyl methacrylate unit: 31:69, acid value: 100 mgKOH / g, weight average molecular weight in terms of polystyrene: 20,000)
(C-1) a photopolymerization initiator
: 2-Benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369, manufactured by Ciba Specialty Chemicals)
(D-1) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(E-1) Coloring material: C.I. Pigment Blue 15: 6
(E-2) Coloring material: CI Pigment violet 23
(F-1) Solvent: Propylene glycol monomethyl ether acetate
(G-1) Additive: Surfactant (SH-8400 manufactured by Toray Silicone)
(G-2) Additive
: Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)
(G-3) Additive: adhesion promoter (3-methacryloxypropyltrimethoxysilane)
Manufacturing example : Manufacture of color filters
Using the colored photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Example 1, the following color filters were produced.
The prepared colored photosensitive resin composition was applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 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 was placed on the thin film, and an interval between the test photomask and the test photomask was set to 1000 mu m, and an ultrahigh pressure mercury lamp (USH-250D, (365 nm) at 40 mJ / cm 2 under the atmosphere. The ultraviolet-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 for 80 seconds using a spray developing machine. The glass substrate on which the thin film was coated was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C for 20 minutes to prepare a color filter. The pattern shape (thin film) thickness of the manufactured color filter was 1.9 to 2.1 mu m.
Experimental Example
Sensitivity, development unevenness and developing speed of the color filters in the colored photosensitive compositions and production examples of the examples and comparative examples were measured by the following methods, and the results are shown in Table 2 below.
(1) Sensitivity and development speed
During the manufacturing process of the color filter, the developing time was measured by measuring the time at which peeling of the non-exposed thin film portion occurred. Further, during the manufacturing process of the color filter, the minimum exposure amount (mJ / cm 2) necessary for forming a thin film without peeling of the pattern after development was measured.
(2) Evaluation of development stain
The prepared colored photosensitive resin composition was applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Subsequently, light was irradiated at an exposure dose (365 nm) of 40 mJ / cm 2 in an atmospheric environment using an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio DENKI CO., LTD.). The ultraviolet-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 for 80 seconds using a spray developing machine. The glass substrate coated with the thin film was washed with distilled water, and then a small amount of distilled water was added dropwise to the dried thin film by blowing nitrogen gas. The glass substrate was kept at a circular shape for 2 minutes at room temperature and then blown with nitrogen gas. Subsequently, the substrate was irradiated with an Na lamp, and the surface state of the coating film was observed to visually judge whether or not a circular spot was formed, and the evaluation was made according to the following criteria.
○: Circular water stains were not recognized on the surface of the coating film.
△: Circular water stain was finely recognized on the surface of the coating film.
X: Circular water stain clearly observed on the surface of the film.
(3) Adhesion
The prepared substrate was cut into 100 matrix structures in a region of 10 x 10 mm, and the number of dislodged matrices was marked by adhering a tape on the substrate and vertically and strongly releasing the matrix (number of dislocations / 100).
(4) Heat resistance
After the pattern was finally formed, the color change (heat resistance) around 230 ° C / 2 hr was compared and evaluated. The formula to be used at this time is calculated by the above-described equation (2) representing the color change in the three-dimensional colorimeter defined by L *, a *, b * .
Equation 1
? Eab * = (? L *) 2+ (? A *) 2+ (? B *) 2] 1/2
(5) NMP content
The prepared substrate is cut into 3 × 3 cm, and then immersed in 14.6 ml of NMP solution at 80 ° C./40 minutes. Then, the absorbance is evaluated by a UV-Vis spectrometer.
(40 mJ / cm 2)
Solvent resistance
(mJ / cm2)
As shown in Table 2, the colored photosensitive resin compositions of Examples 1 to 7 including the polyfunctional urethane acrylate represented by Formula 1 according to the present invention are superior to the colored photosensitive resin compositions of Comparative Example 1 It can be confirmed that the development unevenness is not recognized while exhibiting excellent sensitivity and developing speed. Further, it was confirmed that the adhesion was excellent and the heat resistance was excellent.
In particular, in Examples 1 to 7 including the polyfunctional urethane acrylate according to the present invention, the sensitivity was excellent, the developing speed was not lowered, and the development unevenness was more remarkable than that of the colored photosensitive resin composition of Comparative Example 1 It is possible to manufacture a color filter of excellent quality even at a low exposure dose. Further, it was confirmed that Examples 1 to 7 are excellent in adhesion and excellent in heat resistance and solvent resistance. And that the performance of the embodiment comprising the polyfunctional urethane acrylate in a preferred content is better.
Claims (9)
Wherein the polyfunctional urethane acrylate (A) comprises a compound represented by the following general formula (1)
[Chemical Formula 1]
Y is a (meth) acrylate group,
R1 is a linear or branched hydrocarbon having 1 to 10 carbon atoms in which 0 to 4 (meth) acrylate groups are substituted, and oxygen may be substituted in the main chain.
Wherein the polyfunctional urethane acrylate (A) is urethane acrylate having 9 or more functionalities.
Wherein the polyfunctional urethane acrylate (A) comprises 5 to 50% by weight based on the solid content in the colored photosensitive resin composition.
The binder resin (B) is a copolymer of a carboxyl group-containing monomer and other monomer copolymerizable with the monomer,
Wherein the carboxyl group-containing monomer is contained in an amount of 10 to 50% by weight based on the total weight of the copolymer.
Wherein the photopolymerizable compound (D) is at least five functional.
The colored photosensitive resin composition preferably contains, in a weight fraction of the solid content in the colored photosensitive resin composition,
10 to 80% by weight of a binder resin (B);
5 to 50% by weight of photopolymerizable compound (D); And
And 3 to 60% by weight of a coloring material (E)
The photopolymerization initiator (C) comprises 0.1 part by weight to 40 parts by weight based on 100 parts by weight of the sum of the binder resin (B) and the photopolymerizable compound (D)
The colored photosensitive resin composition according to claim 1, wherein the solvent (F) comprises 60 to 90% by weight based on the total amount of the colored photosensitive resin composition.
Wherein the colored photosensitive resin composition further comprises at least one additive selected from a polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an antiflocculating agent.
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