KR101486570B1 - Photosensitive resin composition and color filter using the same - Google Patents
Photosensitive resin composition and color filter using the same Download PDFInfo
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- KR101486570B1 KR101486570B1 KR20140006222A KR20140006222A KR101486570B1 KR 101486570 B1 KR101486570 B1 KR 101486570B1 KR 20140006222 A KR20140006222 A KR 20140006222A KR 20140006222 A KR20140006222 A KR 20140006222A KR 101486570 B1 KR101486570 B1 KR 101486570B1
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
Description
The present invention relates to a photosensitive resin composition for a color filter and a color filter using the same.
A color filter is used for a liquid crystal display, an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more hues on a solid-state imaging element or a transparent substrate. Such a colored thin film is usually formed by a pigment dispersion method or the like.
The colored photosensitive resin composition used for the production of a color filter according to the pigment dispersion method generally comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, a solvent, and other additives. A large amount of the pigment dispersion is used as the coloring agent. For example, a red pigment dispersion in which a red pigment and a yellow pigment are mixed is used to realize a red pixel of a color filter, and a green pigment dispersion in which a green pigment and a yellow pigment are mixed is used to realize a green pixel of a color filter.
Recent color filter manufacturing processes are being produced in a continuous process capable of mass production. In recent years, color filters having excellent color characteristics, heat resistance, and the like have been demanded in accordance with high-quality specifications. In particular, attempts have been made to improve pigments as colorants in order to improve luminance characteristics.
One embodiment is to provide a photosensitive resin composition having excellent transmittance, high brightness, and high contrast ratio and thus having excellent color characteristics.
Another embodiment is to provide a color filter using the photosensitive resin composition.
One embodiment includes (A) an acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) at least one repeating unit represented by the following formula (1), at least one repeating unit represented by the following formula (2), at least one repeating unit represented by the following formula (3), at least one repeating unit represented by the following formula A pigment dispersion comprising a functional resin and a pigment; And (E) a solvent.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
(In the above Chemical Formulas 1 to 4,
R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L 1 to L 4 each independently represents a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.)
The functional resin may include a repeating unit represented by the following formula (5).
[Chemical Formula 5]
(In the above formula (5)
a, b, c and d are each independently an integer of 1 or more.
The weight average molecular weight of the functional resin may be 5,000 g / mol to 30,000 g / mol.
In the pigment dispersion containing the functional resin and the pigment, the pigment may be a pigment in which the functional resin is adsorbed on the surface of the pigment.
The pigments may include organic pigments, inorganic pigments, or combinations thereof.
The pigment may comprise a green pigment.
The pigment may be surface-treated with the functional resin, and the photosensitive resin composition may contain 3 to 10% by weight of the acrylic binder resin; 3 wt% to 13 wt% of the photopolymerizable monomer; 0.1% by weight to 3% by weight of the photopolymerization initiator; 2 to 10% by weight of a pigment surface-treated with the functional resin; And the solvent balance.
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
The pigment surface-treated with the functional resin can be produced by pulverizing the pigment and mixing the pulverized pigment with the functional resin.
The mixing of the pulverized pigment with the functional resin may include adding the pulverized pigment and the functional resin to a solvent to prepare a solution and drying the solution.
The pulverized pigment and the functional resin may be mixed in a weight ratio of 10: 4 to 10: 2.
The mixing can be performed at a temperature of 20 ° C to 70 ° C.
Another embodiment provides a color filter using the photosensitive resin composition for a color filter.
The details of other embodiments are included in the detailed description below.
The above photosensitive resin composition is excellent in transmittance, has high brightness and high contrast ratio and is excellent in color characteristics, and thus can be usefully used in color filters.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.
&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.
"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.
Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.
In the chemical formulas described herein, "*" means the same or different atom or moiety connected to the chemical formula.
The photosensitive resin composition according to one embodiment comprises (A) an acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) at least one repeating unit represented by the following formula (1), at least one repeating unit represented by the following formula (2), at least one repeating unit represented by the following formula (3), at least one repeating unit represented by the following formula A pigment dispersion comprising a functional resin and a pigment; And (E) a solvent.
The photosensitive resin composition according to one embodiment includes a functional resin and a pigment, for example, by including a pigment surface-treated with the above-mentioned functional resin, aggregation between the pigments is suppressed and the dispersibility of the pigment is improved, And the color characteristics such as transmittance and luminance can be improved.
The functional resin includes repeating units represented by the following general formulas (1) to (4).
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
(In the above Chemical Formulas 1 to 4,
R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L 1 to L 4 each independently represents a single bond, or a substituted or unsubstituted C1 to C10 alkylene group.)
In one embodiment, the functional resin may include a repeating unit represented by the following formula (5).
[Chemical Formula 5]
(In the above formula (5)
a, b, c and d are each independently an integer of 1 or more.
The weight average molecular weight of the functional resin may be 5,000 g / mol to 30,000 g / mol.
The functional resin includes a ring structure having a large molecular weight, so that the heat resistance of the pigment surface-treated with such a functional resin can be improved.
The pigment surface-treated with the functional resin may be a pigment in which the functional resin is adsorbed on the surface of the pigment. The pigment in which the functional resin is adsorbed on the surface of the pigment can be prepared by mixing the pigment and the functional resin in a solvent at a weight ratio of 10: 4 to 10: 2 and removing the solvent therefrom.
Each component will be described in detail below.
(D) Pigment
The pigments may include organic pigments, inorganic pigments, or combinations thereof. For example, the pigment may include a green pigment.
In general, pigments are used in a finer process, that is, a process of finely pulverizing large pigment particles. Since fine pigments are likely to coagulate with each other, a pigment derivative or the like is added in pigment dispersion in order to suppress the coagulation. In the case of a pigment derivative, it has a structure similar to that of a pigment or has a structure that can be adsorbed well on the surface of a pigment physically and chemically so that aggregation between the fine pigments can be suppressed.
However, when the pigment is dispersed, the pigment derivative added may cause a color difference with the pigment, resulting in a decrease in coloring power or a decrease in dispersibility due to the cohesive force between the pigment derivatives.
In one embodiment, the surface of the fine pigment is surface-treated with the functional resin, that is, the resin containing the repeating units represented by the above Chemical Formulas (1) to (4), after the micronization process is completed. The aggregation between the fine pigments can be effectively suppressed.
The functional resin is physically chemically adsorbed on the surface of the fine pigment to prevent adsorption between the fine pigments, and further, the dispersion agent to be described later is additionally adsorbed on the surface of the fine pigment to which the functional resin is not adsorbed, thereby improving the dispersibility of the pigment. As a result, the fine pigment particles do not cohere with each other, so that the scattering of light is reduced and the transmittance can be improved.
Treating the surface of the pigment with the functional resin may include grinding the pigment and mixing the pulverized pigment with the functional resin.
Specifically, mixing the pulverized pigment with the functional resin may comprise adding the pulverized pigment and the functional resin to a solvent to prepare a solution, and drying the solution.
In this case, the pulverized pigment and the functional resin may be mixed at a weight ratio of 10: 4 to 10: 2, and the mixing may be performed at a temperature of 20 to 70 ° C.
Examples of the pigments include red pigments, blue pigments, green pigments, violet pigments, yellow pigments, cyanine pigments, magenta pigments, and black pigments.
Examples of the red pigments include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. have. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, siccone pigments, anthraquinone (sudan I, II, III, R), dianthraquinolide, Vis azo, benzopyran and the like.
Examples of the blue pigments include metal phthalocyanine pigments, indanthrone pigments, indophenol pigments, and the like. Specific examples of the blue pigments include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloroal phthalocyanine, titanyl phthalocyanine, vanadinic acid phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine and cobalt phthalocyanine.
As the green pigments, halogenated phthalocyanine pigments And the like. Specific examples thereof include polychloro copper phthalocyanine, polychlorobromophthalocyanine such as Green 58, and the like.
Examples of the violet pigment include dioxazine violet, first violet B, methyl violet, indanthrene brilliant violet, and the like.
Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Specific examples thereof include hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR).
Examples of the cyanine pigment include metal-free phthalocyanine, merocyanine, and the like.
Examples of the magenta pigment include dimethyl quinacridone, thioindigo, and the like.
Examples of the black pigment include aniline black, perylene black, titanium black and carbon black.
As mentioned above, in addition to the surface treatment with the functional resin, the pigment may further include a dispersing agent for assisting dispersion of the pigment.
As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.
DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.
The dispersant may be contained in an amount of 0.01 to 15% by weight based on the total amount of the photosensitive resin composition for a color filter. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition for a color filter is excellent, so that excellent stability, developability and patternability can be obtained.
At this time, the pigment may be contained in the photosensitive resin composition in the form of a dispersion. As the solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used. The content of the pigment dispersion may be 20% by weight to 40% by weight, for example 30% by weight to 40% by weight, based on the total weight of the photosensitive resin composition.
The average particle size of the pigment may be from 5 nm to 150 nm, for example from 10 nm to 70 nm. When the average particle diameter of the pigment is within the above range, a high contrast ratio can be realized while having excellent heat resistance and light resistance.
The pigment surface-treated with the functional resin may be contained in an amount of 2 wt% to 10 wt%, for example, 5 wt% to 8 wt% with respect to the total amount of the photosensitive resin composition. When the pigment is used within the above range, it can exhibit a high luminance and a high contrast ratio at the same color coordinates while having excellent color characteristics.
(A) Acrylic binder resin
The photosensitive resin composition according to one embodiment includes an acrylic binder resin.
The acrylic binder resin may contain a first ethylenic unsaturated monomer And a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing at least one acrylic repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.
The first ethylenically unsaturated monomer may be included in an amount of 5 to 50% by weight, for example, 10 to 40% by weight based on the total amount of the acrylic binder resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.
Specific examples of the acrylic binder resin include polybenzyl methacrylate, (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, and (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but not limited thereto, Or more may be used in combination.
The weight average molecular weight of the acrylic binder resin may be from about 3,000 g / mol to about 150,000 g / mol, such as from about 5,000 g / mol to about 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition for a color filter has excellent physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate during production of a color filter.
The acid value of the acrylic binder resin may be about 50 mgKOH / g to 200 mgKOH / g, such as about 80 mgKOH / g to 150 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.
The acrylic binder resin may be contained in an amount of 3% by weight to 15% by weight, for example, 5% by weight to 10% by weight based on the total amount of the photosensitive resin composition for a color filter. When the acrylic binder resin is contained in the above range, the sensitivity and developability are excellent, and the chemical resistance is improved, so that the pattern peeling does not occur.
(B) Photopolymerization Monomer
The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.
Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.
Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.
A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ®, the same M-111 ®, the same M-114 ®; KAYARAD TC-110S ® and TC-120S ® from Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of V-158 ®, V-2311 ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ®, copper or the like M-240 ®, the same M-6200 ®; KAYARAD HDDA ® , HX-220 ® and R-604 ® from Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of 社V-260 ®, V- 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ®, the same M-400 ®, the same M-405 ®, the same M-450 ®, Dong M -7100 ® , copper M-8030 ® , copper M-8060 ® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ®, copper DPCA-20 ®, ® copper -30, -60 ® copper, copper ® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ®, copper ® -300, -360 ® copper, copper -GPT ®, copper -3PA ®, and the like copper -400 ®. These products may be used alone or in combination of two or more.
The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.
The photopolymerizable monomer may be contained in an amount of 3 wt% to 13 wt%, for example, 4 wt% to 10 wt% based on the total amount of the photosensitive resin composition for a color filter. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in reliability, and is excellent in developability in an alkaline developer.
(C) Light curing Initiator
The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.
Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisobutyl Propyl thioxanthone and the like.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6- (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.
Examples of the oxime compounds include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.
The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.
The photopolymerization initiator may be contained in an amount of 0.1 wt% to 3 wt%, for example, 0.5 wt% to 1.0 wt% with respect to the total amount of the photosensitive resin composition for a color filter. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.
(E) Solvent
The solvent may be a material which has compatibility with the acrylic binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the pigment surface-treated with the functional resin but does not react.
The solvent is not particularly limited, but specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.
In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be contained in an amount of from about 40% by weight to about 90% by weight based on the total amount of the photosensitive resin composition for a color filter. When the solvent is contained within the above range, the photosensitive resin composition for a color filter has an appropriate viscosity, and therefore, the color filter has excellent processability in the production of the color filter.
(F) Other additives
The photosensitive resin composition for a color filter may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots and spots upon application, to improve leveling performance, 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
The additive can be easily adjusted according to desired properties.
The coupling agent may be a silane coupling agent. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used singly or in combination of two or more Can be mixed and used.
The silane coupling agent may be used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition for a color filter.
The photosensitive resin composition for a color filter may further contain a fluorine-based surfactant, if necessary.
Examples of the fluorine-based surfactant include F-482, F-484, F-478 and F-554 manufactured by DIC Corporation.
The amount of the fluorine-based surfactant is preferably 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% with respect to the total amount of the photosensitive resin composition. If it is out of the above range, spreadability is not uniform in the coating step, and it is difficult to form a film having a uniform thickness.
The photosensitive resin composition according to one embodiment is an alkali developing type which is cured by irradiation of light and can be developed into an alkaline aqueous solution. When the photosensitive resin composition is laminated on a substrate and irradiated with an active ray to form a pattern necessary for the color filter, the photosensitive resin composition is reacted with light. The reacted site is less soluble in the solvent than the unreacted site, Are selectively soluble. The solution for removing the unexposed portions is called a developer, and there are two types of such developers, organic solvent type and alkali developing type. Among them, organic solvent type causes air pollution and is harmful to human body, so it is better to use alkali developing type in environmental aspect. The photosensitive resin composition according to one embodiment can be used in an environmentally friendly manner since an alkali developing type developer can be used.
According to another embodiment, there is provided a color filter manufactured using the above-described photosensitive resin composition.
A method of manufacturing the color filter is as follows.
The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.
Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV in the range of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance, solvent resistance and the like can be improved.
Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.
(As a functional resin Surface-treated Pigment)
Manufacturing example One
(Green 58, DIC), 3 g of a resin having a molecular weight of about 12,000 g / mol containing the repeating unit represented by the following formula (6) and 82 ml of a solvent (propylene glycol methyl ethyl acetate, Sigma-aldrich) The mixture was kneaded using a homogenizer or a mechanical stirrer while maintaining the temperature at 40 占 폚. After kneading, the mixture was dried at room temperature to remove the solvent.
[Chemical Formula 6]
(Pigment dispersion)
Manufacturing example 2
A pigment, a dispersant, and an acrylic binder surface-treated with a functional resin according to Production Example 1 were dissolved in a solvent and stirred with the following composition.
Pigment according to Preparation Example 1: 15 wt%
Dispersant (BYK 2102, BYK): 6 wt%
Acrylic binder (100S, SMS): 5 wt%
Solvent (propylene glycol methyl ethyl acetate, Sigma-Aldrich): 74 wt%
Manufacturing example 3
A pigment, a dispersant, and an acrylic binder were dissolved in a solvent and stirred with the following composition.
Pigment (Green 58, DIC): 15 wt%
Dispersant (BYK 2102, BYK): 3.5 wt%
Acrylic binder (100S, SMS): 3 wt%
Solvent (propylene glycol methyl ethyl acetate, Sigma-Aldrich): 78.5 wt%
(Photosensitive resin composition for color filter)
Example 1 and Comparative Example One
The following photopolymerization initiator was dissolved in the following solvent with the composition shown in Table 1, followed by stirring at room temperature for 1 hour. To the composition shown in Table 1, the following acrylic binder resin and the following acrylic photopolymerizable monomer were added and stirred at room temperature for 2 hours. To the composition shown in Table 1, the following fluorochemical surfactant was added and stirred at room temperature for 1 hour. The pigment dispersion was added to the composition of Table 1 and stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities to obtain a photosensitive resin according to Example 1 and Comparative Example 1 A composition was prepared. The components used in the production of the photosensitive resin composition are as follows.
(A) Acrylic binder resin (polybenzyl methacrylate resin (NPR1520), Miwon Chemical Co.)
(B) Acrylic photopolymerizable monomer (dipentaerythritol hexaacrylate (DPHA), Japanese explosive)
(C) Photopolymerization initiator (oxime compound (CGI-124, BASF))
(D) Pigment dispersion
(D-1) A pigment dispersion according to Production Example 2
(D-2) The pigment dispersion according to Production Example 3
(E) Solvent (propylene glycol methyl ethyl acetate, Sigma-Aldrich)
(F) Fluorine-based surfactant (F-554, DIC)
(Fluorine-based surfactant)
Evaluation: Spectroscopic characteristics of photosensitive resin composition
The photosensitive resin composition according to Example 1 and Comparative Example 1 was coated on a glass substrate to a thickness of 3.0 mu m to 4.0 mu m using a coating machine (MIKASA), and then dried on a hot plate at 90 DEG C to form a coating film . The obtained coating film was irradiated with light at an exposure amount of 100 mJ / cm < 2 > and then baked at 230 DEG C for 30 minutes in an oven condition. The transmittance, chromaticity coordinates and luminance were measured using a colorimeter (Otsuka Co., Ltd., MCPD 3000). The results are shown in Table 2 below.
(0.240, 0.500)
It can be seen from Table 2 that in the case of Example 1 using the pigment according to one embodiment, the brightness of the photosensitive resin composition as compared with Comparative Example 1 is high and the transmittance is excellent.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (12)
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) at least one repeating unit represented by the following formula (1), at least one repeating unit represented by the following formula (2), at least one repeating unit represented by the following formula (3), at least one repeating unit represented by the following formula A pigment dispersion comprising a functional resin and a pigment; And
(E) Solvent
: ≪ EMI ID =
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In the above Chemical Formulas 1 to 4,
R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L 1 and L 2 are each independently a substituted or unsubstituted C1 to C10 alkylene group,
L 3 and L 4 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
Wherein the functional resin comprises a repeating unit represented by the following formula (5): < EMI ID =
[Chemical Formula 5]
In Formula 5,
a, b, c, and d are each independently an integer of 1 or more.
Wherein the weight average molecular weight of the functional resin is 5,000 g / mol to 30,000 g / mol.
Wherein the pigment comprises an organic pigment, an inorganic pigment, or a combination thereof.
Wherein the pigment comprises a green pigment.
The pigment is surface-treated with the functional resin,
The photosensitive resin composition
3 to 15% by weight of the acrylic binder resin;
3 wt% to 13 wt% of the photopolymerizable monomer;
0.1% by weight to 3% by weight of the photopolymerization initiator;
2 to 10% by weight of a pigment surface-treated with the functional resin; And
The solvent balance
.
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
The pigment dispersion containing the functional resin
Pulverizing the pigment; And
Mixing the pulverized pigment and the functional resin
By weight based on the total weight of the photosensitive resin composition.
The step of mixing the pulverized pigment and the functional resin
Adding the pulverized pigment and the functional resin to a solvent to prepare a solution; And
Drying the solution
By weight based on the total weight of the photosensitive resin composition.
Wherein the pulverized pigment and the functional resin are mixed in a weight ratio of 10: 4 to 10: 2.
Wherein the mixing is carried out at a temperature of 20 캜 to 70 캜.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140006222A KR101486570B1 (en) | 2014-01-17 | 2014-01-17 | Photosensitive resin composition and color filter using the same |
| CN201480073417.9A CN105934712A (en) | 2014-01-17 | 2014-04-22 | Photosensitive resin composition for color filter and color filter using same |
| PCT/KR2014/003515 WO2015108240A1 (en) | 2014-01-17 | 2014-04-22 | Photosensitive resin composition for color filter and color filter using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140006222A KR101486570B1 (en) | 2014-01-17 | 2014-01-17 | Photosensitive resin composition and color filter using the same |
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| Publication Number | Publication Date |
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| KR101486570B1 true KR101486570B1 (en) | 2015-01-26 |
Family
ID=52592648
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| KR20140006222A KR101486570B1 (en) | 2014-01-17 | 2014-01-17 | Photosensitive resin composition and color filter using the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101486570B1 (en) |
| CN (1) | CN105934712A (en) |
| WO (1) | WO2015108240A1 (en) |
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| KR20230013441A (en) * | 2021-07-19 | 2023-01-26 | 삼성에스디아이 주식회사 | Pigment dispersion, photosensitive resin composition comprising the same, photosensitive resin layer, color filter and display device |
| CN115124889B (en) * | 2022-08-31 | 2022-11-22 | 山东凯瑞尔光电科技有限公司 | Red color paste for color photoresist and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060083988A (en) * | 2003-12-01 | 2006-07-21 | 도오꾜오까고오교 가부시끼가이샤 | Thick film photoresist composition and method of forming resist pattern |
| KR100699731B1 (en) | 2002-04-22 | 2007-03-27 | 미쓰비시 가가꾸 가부시키가이샤 | Curable resin composition for die coating, color filter, process for producing color filter, and liquid crystal display device |
| KR20100072934A (en) * | 2008-12-22 | 2010-07-01 | 제일모직주식회사 | Photosensitive resin composition for color filter and color filter using same |
| KR20130036161A (en) * | 2011-10-03 | 2013-04-11 | 후지필름 가부시키가이샤 | Negative chemical amplification resist composition, resist film, and, resist-coated mask blanks, method for forming resist pattern, and photomask, each using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259876A (en) * | 1995-03-24 | 1996-10-08 | Japan Synthetic Rubber Co Ltd | Organic pigment dispersed liquid for color filter |
| JP4064681B2 (en) * | 2002-02-14 | 2008-03-19 | 富士フイルム株式会社 | Pigment dispersant, pigment dispersion composition containing the same, and colored photosensitive composition |
| KR20090031987A (en) * | 2007-09-26 | 2009-03-31 | 후지필름 가부시키가이샤 | Pigment dispersion composition, photocurable composition, color filter, liquid crystal display element, solid state image sensor and method for manufacturing color filter |
| WO2009116442A1 (en) * | 2008-03-17 | 2009-09-24 | 富士フイルム株式会社 | Pigment-dispersed composition, colored photosensitive composition, photocurable composition, color filter, liquid crystal display element, and solid image pickup element |
-
2014
- 2014-01-17 KR KR20140006222A patent/KR101486570B1/en not_active IP Right Cessation
- 2014-04-22 CN CN201480073417.9A patent/CN105934712A/en not_active Withdrawn
- 2014-04-22 WO PCT/KR2014/003515 patent/WO2015108240A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100699731B1 (en) | 2002-04-22 | 2007-03-27 | 미쓰비시 가가꾸 가부시키가이샤 | Curable resin composition for die coating, color filter, process for producing color filter, and liquid crystal display device |
| KR20060083988A (en) * | 2003-12-01 | 2006-07-21 | 도오꾜오까고오교 가부시끼가이샤 | Thick film photoresist composition and method of forming resist pattern |
| KR20100072934A (en) * | 2008-12-22 | 2010-07-01 | 제일모직주식회사 | Photosensitive resin composition for color filter and color filter using same |
| KR20130036161A (en) * | 2011-10-03 | 2013-04-11 | 후지필름 가부시키가이샤 | Negative chemical amplification resist composition, resist film, and, resist-coated mask blanks, method for forming resist pattern, and photomask, each using the same |
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|---|---|
| WO2015108240A1 (en) | 2015-07-23 |
| CN105934712A (en) | 2016-09-07 |
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