WO2015108240A1 - Photosensitive resin composition for color filter and color filter using same - Google Patents

Photosensitive resin composition for color filter and color filter using same Download PDF

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Publication number
WO2015108240A1
WO2015108240A1 PCT/KR2014/003515 KR2014003515W WO2015108240A1 WO 2015108240 A1 WO2015108240 A1 WO 2015108240A1 KR 2014003515 W KR2014003515 W KR 2014003515W WO 2015108240 A1 WO2015108240 A1 WO 2015108240A1
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WO
WIPO (PCT)
Prior art keywords
pigment
resin composition
photosensitive resin
formula
functional resin
Prior art date
Application number
PCT/KR2014/003515
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French (fr)
Korean (ko)
Inventor
형경희
김남광
이연수
이유진
정지영
최세영
최승집
Original Assignee
제일모직 주식회사
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Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Priority to CN201480073417.9A priority Critical patent/CN105934712A/en
Publication of WO2015108240A1 publication Critical patent/WO2015108240A1/en

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Classifications

    • 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
    • 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
    • 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
    • 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

Definitions

  • the present disclosure relates to a photosensitive resin composition for color filters and a color filter using the same.
  • the color filter is used in a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine region colored with three or more colors on a solid state image pickup device or a transparent substrate.
  • Such colored thin films are usually formed by a pigment dispersion method or the like.
  • the colored photosensitive resin composition used for manufacturing the color filter according to the pigment dispersion method generally consists of a binder resin, a photopolymerization monomer, a photopolymerization initiator, a colorant, a solvent, other additives, and the like.
  • Many pigment dispersions are used as the colorant.
  • a red pigment dispersion in which a red pigment and a yellow pigment are mixed is used to implement a red pixel of a color filter
  • a green pigment dispersion in which a green pigment and a yellow pigment is mixed is used to implement a green pixel of a color filter.
  • color filter manufacturing process is produced in a continuous process capable of mass production.
  • color filters having excellent color characteristics, heat resistance, etc. are required according to high quality specifications, and in particular, attempts to improve pigments, which are colorants, have been continued to improve luminance characteristics.
  • One embodiment is to provide a photosensitive resin composition having excellent transmittance and excellent color characteristics by having high brightness and high contrast ratio.
  • Another embodiment is to provide a color filter using the photosensitive resin composition.
  • One embodiment includes (A) an acrylic binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) at least one repeating unit represented by formula 1, at least one repeating unit represented by formula 2, at least one repeating unit represented by formula 3, at least one repeating unit represented by formula 4 Pigment dispersion containing a functional resin and a pigment comprising; And (E) provides a photosensitive resin composition comprising a solvent.
  • R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group
  • L 1 to L 4 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
  • the functional resin may include a repeating unit represented by Formula 5 below.
  • 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 pigment may be a pigment in which the functional resin is adsorbed on the pigment surface.
  • the pigment may comprise an organic pigment, an inorganic pigment, or a combination thereof.
  • the pigment may comprise a green pigment.
  • the pigment may be surface-treated with the functional resin
  • the photosensitive resin composition is 3 to 10% by weight of the acrylic binder resin; 3 wt% to 13 wt% of the photopolymerizable monomer; 0.1 wt% to 3 wt% of the photopolymerization initiator; 2 wt% to 10 wt% of the pigment surface-treated with the functional resin; And the balance of the solvent.
  • the photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
  • Pigments surface-treated with the functional resin can be prepared by pulverizing the pigment and mixing the pulverized pigment with the functional resin.
  • Mixing the ground pigment with the functional resin may include adding the ground 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 may be at a temperature of 20 °C to 70 °C.
  • Another embodiment provides a color filter using the photosensitive resin composition for the color filter.
  • the photosensitive resin composition is excellent in transmittance, and has a high brightness and high contrast ratio, and excellent color characteristics, it can be usefully used in color filters.
  • substituted means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, It means substituted with a substituent of C2 to C20 heterohalogen atom (F, Cl, Br, I),
  • hetero means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.
  • (meth) acrylate means that both “acrylate” and “methacrylate” are possible
  • (meth) acrylic acid means “acrylic acid” and “methacrylic acid”.
  • Photosensitive resin composition is (A) acrylic binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) at least one repeating unit represented by formula 1, at least one repeating unit represented by formula 2, at least one repeating unit represented by formula 3, at least one repeating unit represented by formula 4 Pigment dispersion containing a functional resin and a pigment comprising; And (E) a solvent.
  • the photosensitive resin composition according to the embodiment includes a functional resin and a pigment, for example, by including a pigment surface-treated with the functional resin, thereby suppressing agglomeration between pigments, thereby improving dispersibility of the pigment, and thereby scattering light. By reducing, color characteristics such as transmittance and luminance can be improved.
  • the functional resin includes repeating units represented by the following 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 are each independently 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.
  • 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 can improve the heat resistance of the pigment surface-treated with such a functional resin by including a ring structure having a large molecular weight.
  • the pigment surface-treated with the functional resin may be a pigment in which the functional resin is adsorbed onto the pigment surface.
  • the pigment in which the functional resin is adsorbed on the surface of the pigment may 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.
  • Pigments may include organic pigments, inorganic pigments, or combinations thereof.
  • the pigment may comprise a green pigment.
  • the pigment is used through a process of miniaturization, that is, finely pulverizing the large pigment particles, fine pigments are easy to aggregate with each other, a pigment derivative, etc. are added during pigment dispersion to suppress the aggregation.
  • the pigment derivative it has a structure similar to the pigment, or having a structure capable of adsorbing well on the surface of the pigment physicochemically can suppress aggregation between fine pigments.
  • the added pigment derivative may cause color difference with the pigment to cause a decrease in coloring power or to cause dispersibility deterioration due to cohesion between pigment derivatives.
  • Pigment according to an embodiment surface treatment of the surface of the fine pigment with the functional resin that is, the resin containing the repeating units represented by Formula 1 to Formula 4 after the refinement process is completed, thereby improving the treatment efficiency, Therefore, aggregation between fine pigments can be efficiently suppressed.
  • the functional resin may be physicochemically adsorbed on the surface of the fine pigment to prevent adsorption between the fine pigments, and the dispersant described later may be further adsorbed onto the surface of the fine pigment to which the functional resin is not adsorbed, thereby improving dispersibility of the pigment.
  • fine pigment particles do not aggregate with each other, so that light scattering may be reduced to improve transmittance.
  • Treating the surface of the pigment with the functional resin may include pulverizing the pigment and mixing the pulverized pigment with the functional resin.
  • mixing the ground pigment and the functional resin may include adding the ground 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 may also be carried out at a temperature of 20 °C to 70 °C.
  • pigments examples include red pigments, blue pigments, green pigments, violet pigments, yellow pigments, cyanine pigments, magenta pigments, and black pigments.
  • red pigment examples include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, anthracene pigments, and the like.
  • specific examples of the red pigment include perylene pigments, quinacridone pigments, naphthol AS, cuminamine pigments, anthraquinones (sudan I, II, III, R), dianthraquinolides, Vis azo, benzopyran, etc. are mentioned.
  • blue pigment examples include metal phthalocyanine pigments, indanthone pigments, and indophenol pigments.
  • Specific examples of the blue pigment include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloro aluminum phthalocyanine, titanyl phthalocyanine, vanadate phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, and cobalt phthalocyanine.
  • Halogenated phthalocyanine pigment dye etc. are mentioned as said green pigment.
  • polychloro bromine phthalocyanine such as polychloro copper phthalocyanine and Green 58, etc. are mentioned.
  • Examples of the violet pigment include dioxazine violet, first violet B, methyl violet, indansrene brilliant violet, and the like.
  • yellow pigment examples include a tetra chloro isoindolinone pigment, a hansa pigment, a benzidine yellow pigment, and an azo pigment.
  • hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR) etc. are mentioned.
  • cyanine pigments examples include metal-free phthalocyanine and merocyanine.
  • the magenta pigment may include dimethyl quinacridone, thio indigo, and the like.
  • black pigment aniline black, perylene black, titanium black, carbon black, etc. are mentioned.
  • the pigment may further include a dispersant for aiding the dispersion of the pigment.
  • a nonionic dispersant As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used.
  • the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.
  • Examples of commercially available products of the dispersant include, for example, DISKBY-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -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, EFKA-450, etc.
  • the dispersant may be included in an amount of 0.01 wt% to 15 wt% based on the total amount of the photosensitive resin composition for color filters.
  • the dispersant is included in the above range, excellent stability, developability and patternability can be obtained by excellent dispersibility of the photosensitive resin composition for color filters.
  • the pigment may be included in the photosensitive resin composition in the form of a dispersion.
  • 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% to 40% by weight, such as 30% to 40% by weight based on the total amount of the photosensitive resin composition.
  • the average particle diameter of the pigment may be 5 nm to 150 nm, such as 10 nm to 70 nm. When the average particle diameter of the pigment is within the above range, high contrast ratio can be realized while having excellent heat resistance and light resistance.
  • the pigment surface-treated with the functional resin may be included in an amount of 2 wt% to 10 wt%, such as 5 wt% to 8 wt%, based on the total amount of the photosensitive resin composition.
  • the pigment When used in the above range, it can have a high color and contrast ratio at the same color coordinates while having excellent color characteristics.
  • the photosensitive resin composition according to one embodiment includes an acrylic binder resin.
  • the acrylic binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.
  • the first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid,, or a combination thereof.
  • the first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt%, such as 10 to 40 wt%, based on the total amount of the acrylic binder resin.
  • the second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, ⁇ -methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxy
  • acrylic binder resin examples 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, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these alone or in combination thereof. You may mix and use the above.
  • the weight average molecular weight of the acrylic binder resin may be about 3,000 g / mol to 150,000 g / mol, such as about 5,000 g / mol to 30,000 g / mol.
  • the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition for color filters are excellent, the viscosity is appropriate, and the adhesion with the substrate is excellent in the manufacture of the 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.
  • 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 included in an amount of 3 wt% to 15 wt%, such as 5 wt% to 10 wt%, based on the total amount of the photosensitive resin composition for color filters.
  • the acrylic binder resin is included in the above range, it is excellent in sensitivity and developability, and chemical resistance is improved, so that pattern tearing does not occur.
  • a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.
  • the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.
  • photopolymerizable monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol 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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythri
  • Examples of commercially available products of the photopolymerizable monomer are as follows.
  • Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ® , M-111 ® , M-114 ®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ® , TC-120S ®, etc .; The V-158 ® and V-2311 ® of Osaka Yuki Chemical Co., Ltd. are mentioned.
  • difunctional ester of the (meth) acrylic acid examples include, but are not limited to, Aronix M-210 ® , M-240 ® , M-6200 ®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ® , HX-220 ® , R-604 ®, etc .; And V-260 ® , V-312 ® and V-335 HP ® from Osaka Yuki Kagaku Kogyo Co., Ltd.
  • Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ® , M-400 ® , M-405 ® , M-450 ® , M-450 ® from Toagosei Kagaku Kogyo Co., Ltd.
  • the photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.
  • the photopolymerizable monomer may be included in an amount of 3 wt% to 13 wt%, such as 4 wt% to 10 wt%, based on the total amount of the photosensitive resin composition for the color filter.
  • curing is sufficiently performed at the time of exposure in the pattern forming step to provide excellent reliability and excellent developability to an alkaline developer.
  • the photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.
  • acetophenone-based compound examples include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.
  • benzophenone-based compound examples include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.
  • thioxanthone-based compound examples include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso Propyl thioxanthone, etc. are mentioned.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.
  • triazine-based compound examples include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,
  • Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone and the like.
  • the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.
  • the photopolymerization initiator may be included in an amount of 0.1 wt% to 3.0 wt%, such as 0.5 wt% to 1.0 wt%, based on the total amount of the photosensitive resin composition for color filters.
  • photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and it is possible to prevent a decrease in transmittance due to the unreacted initiator.
  • the solvent may be a material having compatibility with the acrylic binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the pigment surface-treated with the functional resin but not reacting.
  • the solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl 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 methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates
  • glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.
  • the solvent may be included in a balance, such as 40 wt% to 90 wt%, based on the total amount of the photosensitive resin composition for color filters.
  • a balance such as 40 wt% to 90 wt%, based on the total amount of the photosensitive resin composition for color filters.
  • the photosensitive resin composition for color filters may include malonic acid, in order to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residue due to undeveloped; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
  • the additive can be easily adjusted according to the desired physical properties.
  • the coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, ⁇ -methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, ⁇ -isocyanate propyl triethoxysilane, ⁇ -glycidoxy propyl trimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. It can be mixed and used.
  • the silane coupling agent may be used in an amount of 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition for color filters.
  • the photosensitive resin composition for color filters may further include a fluorine-based surfactant, if necessary.
  • fluorine-based surfactants examples include F-482, F-484, F-478, F-554, etc. of DIC Corporation, but are not limited thereto.
  • the fluorine-based surfactant is preferably included in an amount of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If outside the above range, the spreading property is not uniform in the coating step, it is difficult to form a film of uniform thickness.
  • the photosensitive resin composition according to one embodiment is an alkali developing type that is curable by irradiation of light and developable with an alkaline aqueous solution.
  • the photosensitive resin composition is laminated on a substrate and irradiated with an active line to form a pattern required for a color filter, the reaction is caused by light. Only it can be selectively dissolved.
  • the solution for removing the non-exposed sites is called a developer, and there are two types of developer, an organic solvent type and an alkali developer type. Among them, organic solvent type causes air pollution and is harmful to human body, so it is better to use alkaline developing type in terms of environment. Since the photosensitive resin composition according to the exemplary embodiment may use an alkaline developing type developer, it may be usefully used in terms of environment.
  • According to another embodiment provides a color filter manufactured using the photosensitive resin composition described above.
  • the manufacturing method of the color filter is as follows.
  • the above-mentioned photosensitive resin composition is applied to a thickness of, for example, 0.5 ⁇ to 10 ⁇ to form a resin composition layer.
  • UV, an electron beam, or an X-ray can be used as a light source used for irradiation,
  • UV of 190 nm-450 nm, specifically, 200 nm-400 nm region can be irradiated. It can also be performed using a photoresist mask further at the said irradiation process.
  • the resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed part is melt
  • a color filter having a desired pattern By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained.
  • crack resistance, solvent resistance, and the like can be improved by reheating the image pattern obtained by the development in the above step or by curing by actinic radiation.
  • the pigment, dispersant, and acrylic binder surface-treated with the functional resin according to Preparation Example 1 were dissolved and stirred in a solvent.
  • Dispersant (BYK2102, BYK): 6% by weight
  • Solvent propylene glycol methyl ethyl acetate, sigma-aldrich: 74 wt%
  • a pigment, a dispersant, and an acrylic binder were dissolved and stirred in a solvent with the following composition.
  • Acrylic binder (100S, SMS company): 3% by weight
  • Solvent (propylene glycol methyl ethyl acetate, sigma-aldrich): 78.5 wt%
  • acrylic binder resin polybenzyl methacrylate resin (NPR1520), Miwon Corporation)
  • Example 1 Comparative Example 1 (A) Acrylic Binder Resin 10 10 (B) Acrylic Photopolymerizable Monomer 8 8 (C) photopolymerization initiator 0.7 0.7 (D) Pigment Dispersion (D-1) 35 - (D-2) - 35 (E) solvent 45.8 45.8 (F) Additive (Fluorinated Surfactant) 0.5 0.5 Total 100.00 100.00
  • the photosensitive resin compositions according to Example 1 and Comparative Example 1 were coated on a glass substrate using a coating apparatus (MIKASA Co., Ltd.) so as to have a film thickness of 3.0 ⁇ m to 4.0 ⁇ m, and then dried at 90 ° C. on a hot plate to coat the coating film. Obtained.
  • the obtained coating film was irradiated with light at an exposure dose of 100 mJ / cm 2, and then baked at an oven condition of 230 ° C. for 30 minutes. Transmittance, color coordinates, and luminance were measured using a colorimeter (Otsuka, MCPD 3000), and the results are shown in Table 2 below.
  • Example 1 using the pigment according to the embodiment, it can be seen that the brightness of the photosensitive resin composition compared to Comparative Example 1 has a high transmittance.

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Abstract

Provided are a photosensitive resin composition and a color filter using the same, the composition comprising: (A) an acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a pigment dispersion containing a functional resin and a pigment, the functional resin including at least one repeating unit represented by chemical formula 1, at least one repeating unit represented by chemical formula 2, at least one repeating unit represented by chemical formula 3 and at least one repeating unit represented by chemical formula 4; and (E) a solvent.

Description

컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터Photosensitive resin composition for color filters and color filter using same
본 기재는 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터에 관한 것이다.The present disclosure relates to a photosensitive resin composition for color filters and a color filter using the same.
컬러필터는 액정표시장치, 카메라의 광학필터 등에 사용되는 것으로서, 3종 이상의 색상으로 착색된 미세한 영역을 고체촬영소자 또는 투명기판 상에 코팅하여 제조된다. 　이와 같은 착색 박막은 통상 안료분산법 등에 의하여 형성된다.The color filter is used in a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine region colored with three or more colors on a solid state image pickup device or a transparent substrate. Such colored thin films are usually formed by a pigment dispersion method or the like.
상기 안료분산법에 따른 컬러필터 제조에 사용되는 착색 감광성 수지 조성물은 일반적으로 바인더 수지, 광중합 단량체, 광중합 개시제, 착색제, 용매, 기타 첨가제 등으로 이루어진다. 　상기 착색제로서 안료 분산액이 많이 사용된다. 예컨대, 컬러필터의 적색 화소를 구현하기 위해서는 적색 안료와 황색 안료를 혼합한 적색 안료 분산액을 사용하고, 컬러필터의 녹색 화소를 구현하기 위해서는 녹색 안료와 황색 안료를 혼합한 녹색 안료 분산액을 사용한다.The colored photosensitive resin composition used for manufacturing the color filter according to the pigment dispersion method generally consists of a binder resin, a photopolymerization monomer, a photopolymerization initiator, a colorant, a solvent, other additives, and the like. Many pigment dispersions are used as the colorant. For example, a red pigment dispersion in which a red pigment and a yellow pigment are mixed is used to implement a red pixel of a color filter, and a green pigment dispersion in which a green pigment and a yellow pigment is mixed is used to implement a green pixel of a color filter.
근래의 컬러필터 제조공정은 대량생산이 가능한 연속공정으로 생산되고 있다. 　또한 최근에는 고품질 사양에 따라 색특성, 내열성 등이 우수한 컬러필터가 요구되고 있으며, 특히 휘도 특성을 개선하기 위해 착색제인 안료를 개량하려는 시도가 계속되고 있다.Recently, the color filter manufacturing process is produced in a continuous process capable of mass production. In addition, in recent years, color filters having excellent color characteristics, heat resistance, etc. are required according to high quality specifications, and in particular, attempts to improve pigments, which are colorants, have been continued to improve luminance characteristics.
일 구현예는 투과도가 우수하고, 고휘도 및 고명암비를 가짐으로써 색특성이 우수한 감광성 수지 조성물을 제공하기 위한 것이다.One embodiment is to provide a photosensitive resin composition having excellent transmittance and excellent color characteristics by having high brightness and high contrast ratio.
다른 일 구현예는 상기 감광성 수지 조성물을 사용한 컬러필터를 제공하기 위한 것이다.　Another embodiment is to provide a color filter using the photosensitive resin composition.
일 구현예는 (A) 아크릴계 바인더 수지; (B) 광중합성 단량체; (C) 광중합 개시제; (D) 적어도 하나의 하기 화학식 1로 표시되는 반복단위, 적어도 하나의 하기 화학식 2로 표시되는 반복단위, 적어도 하나의 하기 화학식 3으로 표시되는 반복단위, 적어도 하나의 하기 화학식 4로 표시되는 반복단위를 포함하는 기능성 수지 및 안료를 포함하는 안료분산액; 및 (E) 용매를 포함하는 감광성 수지 조성물을 제공한다.One embodiment includes (A) an acrylic binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) at least one repeating unit represented by formula 1, at least one repeating unit represented by formula 2, at least one repeating unit represented by formula 3, at least one repeating unit represented by formula 4 Pigment dispersion containing a functional resin and a pigment comprising; And (E) provides a photosensitive resin composition comprising a solvent.
[화학식 1][Formula 1]
Figure PCTKR2014003515-appb-I000001
Figure PCTKR2014003515-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2014003515-appb-I000002
Figure PCTKR2014003515-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2014003515-appb-I000003
Figure PCTKR2014003515-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2014003515-appb-I000004
Figure PCTKR2014003515-appb-I000004
(상기 화학식 1 내지 화학식 4에서,(In Formula 1 to Formula 4,
R1 내지 R8은 각각 독립적으로 수소, 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L1 내지 L4는 각각 독립적으로 단일결합, 또는 치환 또는 비치환된 C1 내지 C10 알킬렌기이다.)L 1 to L 4 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.)
상기 기능성 수지는 하기 화학식 5로 표시되는 반복단위를 포함할 수 있다.The functional resin may include a repeating unit represented by Formula 5 below.
[화학식 5][Formula 5]
Figure PCTKR2014003515-appb-I000005
Figure PCTKR2014003515-appb-I000005
(상기 화학식 5에서,(In Chemical Formula 5,
a, b, c 및 d는 각각 독립적으로 1 이상의 정수이다.)a, b, c and d are each independently an integer of 1 or more.)
상기 기능성 수지의 중량평균 분자량은 5,000 g/mol 내지 30,000 g/mol일 수 있다.The weight average molecular weight of the functional resin may be 5,000 g / mol to 30,000 g / mol.
상기 기능성 수지 및 안료를 포함하는 안료분산액에서, 상기 안료는 상기 기능성 수지가 상기 안료 표면에 흡착된 안료일 수 있다.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 pigment surface.
상기 안료는 유기 안료, 무기 안료, 또는 이들의 조합을 포함할 수 있다.The pigment may comprise an organic pigment, an inorganic pigment, or a combination thereof.
상기 안료는 녹색 안료를 포함할 수 있다.The pigment may comprise a green pigment.
상기 안료는 상기 기능성 수지로 표면처리한 것일 수 있고, 상기 감광성 수지 조성물은 상기 아크릴계 바인더 수지 3 중량% 내지 10 중량%; 상기 광중합성 단량체 3 중량%　내지 13 중량%; 상기 광중합 개시제 0.1 중량% 내지 3 중량%; 상기 기능성 수지로 표면처리한 안료 2 중량% 내지 10 중량%; 및 상기 용매 잔부량을 포함할 수 있다.The pigment may be surface-treated with the functional resin, the photosensitive resin composition is 3 to 10% by weight of the acrylic binder resin; 3 wt% to 13 wt% of the photopolymerizable monomer; 0.1 wt% to 3 wt% of the photopolymerization initiator; 2 wt% to 10 wt% of the pigment surface-treated with the functional resin; And the balance of the solvent.
상기 감광성 수지 조성물은 말론산; 3-아미노-1,2-프로판디올; 비닐기 또는 (메타)아크릴옥시기를 포함하는 커플링제; 레벨링제; 불소계 계면활성제; 및 라디칼 중합 개시제로부터 선택되는 적어도 하나의 첨가제를 더 포함할 수 있다.The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
상기 기능성 수지로 표면처리된 안료는 안료를 분쇄하고, 상기 분쇄된 안료를 기능성 수지와 혼합함으로써 제조될 수 있다.Pigments surface-treated with the functional resin can be prepared by pulverizing the pigment and mixing the pulverized pigment with the functional resin.
상기 분쇄된 안료를 기능성 수지와 혼합하는 것은, 상기 분쇄된 안료와 기능성 수지를 용매에 첨가하여 용액을 제조하고, 상기 용액을 건조하는 것을 포함할 수 있다.Mixing the ground pigment with the functional resin may include adding the ground pigment and the functional resin to a solvent to prepare a solution, and drying the solution.
상기 분쇄된 안료와 기능성 수지는 10 : 4 내지 10 : 2 의 중량비로 혼합될 수 있다.The pulverized pigment and the functional resin may be mixed in a weight ratio of 10: 4 to 10: 2.
상기 혼합은 20℃ 내지 70℃의 온도에서 이루어질 수 있다.The mixing may be at a temperature of 20 ℃ to 70 ℃.
다른 일 구현예는 상기 컬러필터용 감광성 수지 조성물을 사용한 컬러필터를 제공한다.　Another embodiment provides a color filter using the photosensitive resin composition for the color filter.
기타 구현예들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Specific details of other embodiments are included in the following detailed description.
상기 감광성 수지 조성물은 투과도가 우수하며, 고휘도 및 고명암비를 가져 색특성이 우수함에 따라, 컬러 필터에 유용하게 사용될 수 있다.The photosensitive resin composition is excellent in transmittance, and has a high brightness and high contrast ratio, and excellent color characteristics, it can be usefully used in color filters.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 　다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.　Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 명세서에서 특별한 언급이 없는 한, "치환"이란 적어도 하나의 수소 원자가 할로겐 원자(F, Cl, Br, I), 히드록시기, C1 내지 C20의 알콕시기, 니트로기, 시아노기, 아민기, 이미노기, 아지도기, 아미디노기, 히드라지노기, 히드라조노기, 카르보닐기, 카르바밀기, 티올기, 에스테르기, 에테르기, 카르복실기 또는 그것의 염, 술폰산기 또는 그것의 염, 인산이나 그것의 염, C1 내지 C20의 알킬기, C2 내지 C20의 알케닐기, C2 내지 C20의 알키닐기, C6 내지 C30의 아릴기, C3 내지 C20의 사이클로알킬기, C3 내지 C20의 사이클로알케닐기, C3 내지 C20의 사이클로알키닐기, C2 내지 C20의 헤테로사이클로알킬기, C2 내지 C20의 헤테로사이클로알케닐기, C2 내지 C20의 헤테로사이클로알키닐기, C3 내지 C30 헤테로아릴기 또는 이들의 조합의 치환기로 치환된 것을 의미한다.Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, It means substituted with a substituent of C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group or a combination thereof.
또한 본 명세서에서 특별한 언급이 없는 한, "헤테로"란, 고리기 내에 N, O, S 및 P 중 적어도 하나의 헤테로 원자가 적어도 하나 포함된 것을 의미한다.In addition, "hetero" means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.
또한 본 명세서에서 특별한 언급이 없는 한, "(메타)아크릴레이트"는 "아크릴레이트"와 "메타크릴레이트" 둘 다 가능함을 의미하며, "(메타)아크릴산"은 "아크릴산"과 "메타크릴산" 둘 다 가능함을 의미한다. Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.
본 명세서에서 특별한 언급이 없는 한, "조합"이란 혼합 또는 공중합을 의미한다.Unless otherwise stated herein, "combination" means mixed or copolymerized.
본 명세서 내 화학식에서 별도의 정의가 없는 한, 화학결합이 그려져야 하는 위치에 화학결합이 그려져있지 않은 경우는 상기 위치에 수소 원자가 결합되어 있음을 의미한다.Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.
본 명세서에 기재된 화학식 중 "*"는 동일하거나 상이한 원자 또는 화학식과 연결되는 부분을 의미한다.In the formulas described herein, "*" means a moiety connected to the same or different atoms or formulas.
일 구현예에 따른 감광성 수지 조성물은 (A) 아크릴계 바인더 수지; (B) 광중합성 단량체; (C) 광중합 개시제; (D) 적어도 하나의 하기 화학식 1로 표시되는 반복단위, 적어도 하나의 하기 화학식 2로 표시되는 반복단위, 적어도 하나의 하기 화학식 3으로 표시되는 반복단위, 적어도 하나의 하기 화학식 4로 표시되는 반복단위를 포함하는 기능성 수지 및 안료를 포함하는 안료분산액; 및 (E) 용매를 포함한다.Photosensitive resin composition according to one embodiment is (A) acrylic binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) at least one repeating unit represented by formula 1, at least one repeating unit represented by formula 2, at least one repeating unit represented by formula 3, at least one repeating unit represented by formula 4 Pigment dispersion containing a functional resin and a pigment comprising; And (E) a solvent.
일 구현예에 따른 감광성 수지 조성물은 기능성 수지 및 안료를 포함함으로써, 예컨대 상기 기능성 수지로 표면처리한 안료를 포함함으로써, 안료 간 응집이 억제되어 안료의 분산성이 향상되고, 이로 인해 빛의 산란이 감소하여 투과율 및 휘도 등의 색특성을 개선시킬 수 있다.The photosensitive resin composition according to the embodiment includes a functional resin and a pigment, for example, by including a pigment surface-treated with the functional resin, thereby suppressing agglomeration between pigments, thereby improving dispersibility of the pigment, and thereby scattering light. By reducing, color characteristics such as transmittance and luminance can be improved.
상기 기능성 수지는 하기 화학식 1 내지 화학식 4로 표시되는 반복단위들을 포함한다.The functional resin includes repeating units represented by the following Chemical Formulas 1 to 4.
[화학식 1][Formula 1]
Figure PCTKR2014003515-appb-I000006
Figure PCTKR2014003515-appb-I000006
[화학식 2][Formula 2]
Figure PCTKR2014003515-appb-I000007
Figure PCTKR2014003515-appb-I000007
[화학식 3][Formula 3]
Figure PCTKR2014003515-appb-I000008
Figure PCTKR2014003515-appb-I000008
[화학식 4][Formula 4]
Figure PCTKR2014003515-appb-I000009
Figure PCTKR2014003515-appb-I000009
(상기 화학식 1 내지 화학식 4에서,(In Formula 1 to Formula 4,
R1 내지 R8은 각각 독립적으로 수소, 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
L1 내지 L4는 각각 독립적으로 단일결합, 또는 치환 또는 비치환된 C1 내지 C10 알킬렌기이다.)L 1 to L 4 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.)
일 실시예에서, 상기 기능성 수지는 하기 화학식 5로 표시되는 반복단위를 포함할 수 있다.In one embodiment, the functional resin may include a repeating unit represented by the following Formula 5.
[화학식 5][Formula 5]
Figure PCTKR2014003515-appb-I000010
Figure PCTKR2014003515-appb-I000010
(상기 화학식 5에서,(In Chemical Formula 5,
a, b, c 및 d는 각각 독립적으로 1 이상의 정수이다.)a, b, c and d are each independently an integer of 1 or more.)
상기 기능성 수지의 중량평균 분자량은 5,000 g/mol 내지 30,000　g/mol일 수 있다.The weight average molecular weight of the functional resin may be 5,000 g / mol to 30,000 g / mol.
상기 기능성 수지는 분자량이 큰 고리 구조를 포함함으로써, 이러한 기능성 수지로 표면 처리된 안료의 내열성을 향상시킬 수 있다.The functional resin can improve the heat resistance of the pigment surface-treated with such a functional resin by including a ring structure having a large molecular weight.
상기 기능성 수지로 표면처리된 안료는, 상기 기능성 수지가 상기 안료 표면에 흡착된 안료일 수 있다. 상기 기능성 수지가 상기 안료 표면에 흡착된 안료는, 상기 안료 및 기능성 수지를 용매 내에서 10 : 4 내지 10 : 2의 중량비로 혼합하고, 이로부터 용매를 제거함으로써 제조될 수 있다.The pigment surface-treated with the functional resin may be a pigment in which the functional resin is adsorbed onto the pigment surface. The pigment in which the functional resin is adsorbed on the surface of the pigment may 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.
이하에서 각 성분에 대하여 구체적으로 설명한다. Each component is demonstrated concretely below.
(D) 안료(D) pigment
안료는 유기 안료, 무기 안료, 또는 이들의 조합을 포함할 수 있다. 예컨대, 상기 안료는 녹색 안료를 포함할 수 있다.Pigments may include organic pigments, inorganic pigments, or combinations thereof. For example, the pigment may comprise a green pigment.
일반적으로, 안료는 미세화 과정, 즉 큰 안료 입자를 미세하게 분쇄하는 과정을 거쳐 사용하는데, 미세 안료는 서로 응집하기 쉬우므로, 상기 응집을 억제하기 위해 안료 분산 시 안료유도체 등을 첨가한다. 안료유도체의 경우, 안료와 유사한 구조를 가지거나, 물리화학적으로 안료 표면에 잘 흡착할 수 있는 구조를 가짐으로써 미세 안료 간 응집을 억제할 수 있다. In general, the pigment is used through a process of miniaturization, that is, finely pulverizing the large pigment particles, fine pigments are easy to aggregate with each other, a pigment derivative, etc. are added during pigment dispersion to suppress the aggregation. In the case of the pigment derivative, it has a structure similar to the pigment, or having a structure capable of adsorbing well on the surface of the pigment physicochemically can suppress aggregation between fine pigments.
그러나, 안료 분산 시, 첨가된 안료유도체는 안료와의 색 차이가 발생하여 착색력 감소를 유발하거나 안료유도체 간 응집력 때문에 분산성 저하를 유발할 수 있다.However, when the pigment is dispersed, the added pigment derivative may cause color difference with the pigment to cause a decrease in coloring power or to cause dispersibility deterioration due to cohesion between pigment derivatives.
일 구현예에 따른 안료는 미세화 과정이 완료된 후 미세 안료 표면을 상기한 기능성 수지, 즉, 상기 화학식 1 내지 화학식 4로 표시되는 반복단위들을 포함하는 수지로 표면처리 함으로써 처리 효율을 향상시켰으며, 이로 인해 미세 안료 간 응집을 효율적으로 억제할 수 있다.Pigment according to an embodiment surface treatment of the surface of the fine pigment with the functional resin, that is, the resin containing the repeating units represented by Formula 1 to Formula 4 after the refinement process is completed, thereby improving the treatment efficiency, Therefore, aggregation between fine pigments can be efficiently suppressed.
상기 기능성 수지는 미세 안료 표면에 물리화학적으로 흡착하여 미세 안료간 흡착을 방지하고, 또한 후술하는 분산제가 상기 기능성 수지가 흡착되지 않은 미세 안료의 표면에 추가 흡착됨으로써 안료의 분산성도 향상시킬 수 있다. 결과, 미세 안료 입자가 서로 응집되지 않아 빛의 산란이 감소하여 투과율을 향상시킬 수 있다.The functional resin may be physicochemically adsorbed on the surface of the fine pigment to prevent adsorption between the fine pigments, and the dispersant described later may be further adsorbed onto the surface of the fine pigment to which the functional resin is not adsorbed, thereby improving dispersibility of the pigment. As a result, fine pigment particles do not aggregate with each other, so that light scattering may be reduced to improve transmittance.
상기 기능성 수지로 안료의 표면을 처리하는 것은 안료를 분쇄하고, 상기 분쇄된 안료를 기능성 수지와 혼합하는 것을 포함할 수 있다.Treating the surface of the pigment with the functional resin may include pulverizing the pigment and mixing the pulverized pigment with the functional resin.
구체적으로, 상기 분쇄된 안료와 기능성 수지를 혼합하는 것은 상기 분쇄된 안료와 기능성 수지를 용매에 첨가하여 용액을 제조하고, 상기 용액을 건조하는 것을 포함하여 이루어질 수 있다.Specifically, mixing the ground pigment and the functional resin may include adding the ground pigment and the functional resin to a solvent to prepare a solution, and drying the solution.
이 때, 상기 분쇄된 안료와 기능성 수지는 10 : 4 내지 10 : 2의 중량비로 혼합될 수 있고, 또한, 상기 혼합은 20℃ 내지 70℃의 온도에서 수행될 수 있다.At this time, the pulverized pigment and the functional resin may be mixed in a weight ratio of 10: 4 to 10: 2, the mixing may also be carried out at a temperature of 20 ℃ to 70 ℃.
상기 안료로는, 예컨대, 적색계 안료, 청색계 안료, 녹색계 안료, 바이올렛계 안료, 황색계 안료, 시아닌계 안료, 마젠타(Magenta)계 안료, 흑색 안료 등이 있다. Examples of the pigments include red pigments, blue pigments, green pigments, violet pigments, yellow pigments, cyanine pigments, magenta pigments, and black pigments.
상기 적색계 안료로는 페릴렌계 안료, 안트라퀴논(anthraquinone)계 안료, 디안트라퀴논계 안료, 아조계 안료, 디아조계 안료, 퀴나크리돈(quinacridone)계 안료, 안트라센(anthracene)계 안료 등을 들 수 있다. 　상기 적색계 안료의 구체적인 예로는 페릴렌 안료, 퀴나크리돈(quinacridone) 안료, 나프톨(naphthol) AS, 시코민 안료, 안트라퀴논(anthraquinone)(sudan I, II, III, R), 디안트라퀴놀리드, 비스 아조(vis azo), 벤조피란 등을 들 수 있다. Examples of the red pigment include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, anthracene pigments, and the like. have. Specific examples of the red pigment include perylene pigments, quinacridone pigments, naphthol AS, cuminamine pigments, anthraquinones (sudan I, II, III, R), dianthraquinolides, Vis azo, benzopyran, etc. are mentioned.
상기 청색계 안료로는 금속 프탈로시아닌(phthalocyanine)계 안료, 인단스론계 안료, 인도 페놀계 안료 등을 들 수 있다. 　상기 청색계 안료의 구체적인 예로는 동 프탈로시아닌, 클로로 동 프탈로시아닌, 클로로 알루미늄 프탈로시아닌, 티타닐 프탈로시아닌, 바나딘산 프탈로시아닌, 마그네슘 프탈로시아닌, 아연 프탈로시아닌, 철 프탈로시아닌, 코발트 프탈로시아닌 등의 프탈로시아닌 금속착체 등을 들 수 있다. 　Examples of the blue pigment include metal phthalocyanine pigments, indanthone pigments, and indophenol pigments. Specific examples of the blue pigment include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloro aluminum phthalocyanine, titanyl phthalocyanine, vanadate phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, and cobalt phthalocyanine.
상기 녹색계 안료로는 할로겐화 프탈로시아닌계 안료　등을 들 수 있다. 　구체적으로는 폴리클로로 동 프탈로시아닌, Green 58 등의 폴리클로로 브롬 프탈로시아닌 등을 들 수 있다. 　Halogenated phthalocyanine pigment | dye etc. are mentioned as said green pigment. Specifically, polychloro bromine phthalocyanine, such as polychloro copper phthalocyanine and Green 58, etc. are mentioned.
상기 바이올렛계 안료로는 디옥사진바이올렛, 퍼스트 바이올렛 B, 메틸바이올렛, 인단스렌 브릴리언트 바이올렛 등을 들 수 있다. 　Examples of the violet pigment include dioxazine violet, first violet B, methyl violet, indansrene brilliant violet, and the like.
상기 황색계 안료로는 테트라 클로로 이소인돌리논(tetra chloro isoindolinone)계 안료, 한자(hansa)계 안료, 벤지딘 옐로우(benzidine yellow)계 안료, 아조계 안료 등을 들 수 있다. 　구체적으로는 한자 옐로우(hansa yellow)(10G, 5G, 3G, G, GR, A, RN, R), 벤지딘(benzidine)(G, GR), 크롬 옐로우(chrome yellow), 퍼머넌트 옐로우(permanent yellow) (FGL, H10G, HR) 등을 들 수 있다. 　Examples of the yellow pigment include a tetra chloro isoindolinone pigment, a hansa pigment, a benzidine yellow pigment, and an azo pigment. Specifically, hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR) etc. are mentioned.
상기 시아닌계 안료로는 무금속 프탈로시아닌, 메로시아닌 등을 들 수 있다. Examples of the cyanine pigments include metal-free phthalocyanine and merocyanine.
상기 마젠타(magenta)계 안료로는 디메틸 퀴나크리돈(dimethyl quinacridone), 티오인디고(thio indigo) 등을 들 수 있다. 　The magenta pigment may include dimethyl quinacridone, thio indigo, and the like.
상기 흑색 안료로는 아닐린 블랙, 퍼릴렌 블랙, 티탄 블랙, 카본 블랙 등을 들 수 있다.As said black pigment, aniline black, perylene black, titanium black, carbon black, etc. are mentioned.
상기 언급한 바와 같이, 상기 안료는 상기 기능성 수지로 표면처리하는 것 외에도, 추가로, 상기 안료의 분산을 돕기 위한 분산제를 더 포함할 수 있다.As mentioned above, in addition to the surface treatment with the functional resin, the pigment may further include a dispersant for aiding the dispersion of the pigment.
상기 분산제로는 비이온성 분산제, 음이온성 분산제, 양이온성 분산제 등을 사용할 수 있다. 　상기 분산제의 구체적인 예로는, 폴리알킬렌글리콜 및 이의 에스테르, 폴리옥시알킬렌, 다가알코올 에스테르 알킬렌 옥사이드 부가물, 알코올알킬렌 옥사이드 부가물, 술폰산 에스테르, 술폰산 염, 카르복실산 에스테르, 카르복실산 염, 알킬아미드 알킬렌 옥사이드 부가물, 알킬 아민 등을 들 수 있으며, 이들을 단독으로 또는 둘 이상 혼합하여 사용할 수 있다.As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.
상기 분산제의 시판되는 제품을 예로 들면, BYK社의 DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 등; EFKA 케미칼社의 EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450 등; Zeneka社의 Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 등; 또는 Ajinomoto社의 PB711, PB821 등이 있다.Examples of commercially available products of the dispersant include, for example, DISKBY-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -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, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.
상기　분산제는 상기 컬러필터용 감광성 수지 조성물의 총량에 대하여 0.01 중량% 내지 15 중량%로 포함될 수 있다. 　상기 분산제가 상기 범위 내로 포함될 경우, 상기 컬러필터용 감광성 수지 조성물의 분산성이 우수함에 따라, 우수한 안정성, 현상성 및 패턴성을 얻을 수 있다.The dispersant may be included in an amount of 0.01 wt% to 15 wt% based on the total amount of the photosensitive resin composition for color filters. When the dispersant is included in the above range, excellent stability, developability and patternability can be obtained by excellent dispersibility of the photosensitive resin composition for color filters.
이 때, 상기 안료는 분산액의 형태로 감광성 수지 조성물에 포함될 수 있다. 이 때, 상기 안료 분산액을 형성하는 용매로는 에틸렌글리콜 아세테이트, 에틸셀로솔브, 프로필렌글리콜 메틸에테르아세테이트, 에틸락테이트, 폴리에틸렌글리콜, 사이클로헥사논, 프로필렌글리콜 메틸에테르 등을 사용할 수 있다. 상기 안료분산액의 함량은 감광성 수지 조성물 총량에 대해 20 중량% 내지 40 중량%, 예컨대 30 중량% 내지 40 중량% 일 수 있다.In this case, the pigment may be included in the photosensitive resin composition in the form of a dispersion. In this case, 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% to 40% by weight, such as 30% to 40% by weight based on the total amount of the photosensitive resin composition.
상기 안료의 평균 입경은 5 nm 내지 150　nm, 예컨대 10 nm 내지 70 nm 일 수 있다. 　상기 안료의 평균 입경이 상기 범위 내일 경우, 우수한 내열성　및 내광성을 가지면서 고명암비를 구현할 수 있다.The average particle diameter of the pigment may be 5 nm to 150 nm, such as 10 nm to 70 nm. When the average particle diameter of the pigment is within the above range, high contrast ratio can be realized while having excellent heat resistance and light resistance.
상기 기능성 수지로 표면처리한 안료는 상기 감광성 수지 조성물 총량에 대하여 2 중량% 내지 10 중량%, 예컨대 5 중량% 내지 8 중량%로 포함될 수 있다. 상기 안료를 상기 범위 내로 사용할 경우, 우수한 색특성을 가지면서 동일한 색 좌표에서 높은 휘도 및 명암비를 나타낼 수 있다.The pigment surface-treated with the functional resin may be included in an amount of 2 wt% to 10 wt%, such as 5 wt% to 8 wt%, based on the total amount of the photosensitive resin composition. When the pigment is used in the above range, it can have a high color and contrast ratio at the same color coordinates while having excellent color characteristics.
(A) 아크릴계 바인더 수지(A) Acrylic Binder Resin
일 구현예에 따른 감광성 수지 조성물은 아크릴계 바인더 수지를 포함한다.The photosensitive resin composition according to one embodiment includes an acrylic binder resin.
상기 아크릴계 바인더 수지는 제1 에틸렌성 불포화 단량체　및 이와 공중합 가능한 제2 에틸렌성 불포화 단량체의 공중합체로, 하나 이상의 아크릴계 반복단위를 포함하는 수지일 수 있다.The acrylic binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.
상기 제1 에틸렌성 불포화 단량체는 하나 이상의 카르복시기를 함유하는 에틸렌성 불포화 단량체이며, 이의 구체적인 예로는　아크릴산, 메타크릴산, 말레산, 이타콘산, 푸마르산,　또는 이들의 조합을 들 수 있다.The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid,, or a combination thereof.
상기 제1 에틸렌성 불포화 단량체는 상기 아크릴계 바인더 수지 총량에 대하여 5 내지　50　중량%, 예컨대 10 내지　40 중량%로 포함될 수 있다.The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt%, such as 10 to 40 wt%, based on the total amount of the acrylic binder resin.
상기 제2 에틸렌성 불포화 단량체는 스티렌, α-메틸스티렌, 비닐톨루엔, 비닐벤질메틸에테르 등의 방향족 비닐 화합물; 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시 부틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 페닐(메타)아크릴레이트 등의 불포화 카르복시산 에스테르 화합물; 2-아미노에틸(메타)아크릴레이트, 2-디메틸아미노에틸(메타)아크릴레이트 등의 불포화 카르복시산 아미노 알킬 에스테르 화합물; 초산비닐, 안식향산 비닐 등의 카르복시산 비닐 에스테르 화합물; 글리시딜(메타)아크릴레이트 등의 불포화 카르복시산 글리시딜 에스테르 화합물; (메타)아크릴로니트릴 등의 시안화 비닐 화합물; (메타)아크릴아미드 등의 불포화 아미드 화합물; 등을 들 수 있으며, 이들을 단독으로 또는 둘 이상 혼합하여 사용할 수 있다.The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.
상기 아크릴계 바인더 수지의 구체적인 예로는 폴리벤질메타크릴레이트, (메타)아크릴산/벤질메타크릴레이트 공중합체, (메타)아크릴산/벤질메타크릴레이트/스티렌 공중합체, (메타)아크릴산/벤질메타크릴레이트/2-히드록시에틸메타크릴레이트 공중합체, (메타)아크릴산/벤질메타크릴레이트/스티렌/2-히드록시에틸메타크릴레이트 공중합체 등을 들 수 있으나, 이에 한정되는 것은 아니며, 이들을 단독 또는 2종 이상을 배합하여 사용할 수도 있다. 　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, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these alone or in combination thereof. You may mix and use the above.
상기 아크릴계 바인더 수지의 중량평균 분자량은 약 3,000 g/mol 내지 150,000 g/mol, 예컨대 약 5,000 g/mol 내지 30,000 g/mol 일 수 있다.　상기 아크릴계 바인더 수지의 중량평균 분자량이 상기 범위 내일 경우, 상기 컬러필터용 감광성 수지 조성물의 물리적 및 화학적 물성이 우수하고 점도가 적절하며, 컬러필터 제조시 기판과의 밀착성이 우수하다. The weight average molecular weight of the acrylic binder resin may be about 3,000 g / mol to 150,000 g / mol, such as about 5,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition for color filters are excellent, the viscosity is appropriate, and the adhesion with the substrate is excellent in the manufacture of the color filter.
상기 아크릴계 바인더 수지의 산가는 약 50 mgKOH/g 내지 200 mgKOH/g, 예컨대 약 80 mgKOH/g 내지 150 mgKOH/g　일 수 있다. 　상기 아크릴계 바인더 수지의 산가가 상기 범위 내일 경우 픽셀 패턴의 해상도가 우수하다.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.
상기 아크릴계 바인더 수지는 상기 컬러 필터용 감광성 수지 조성물 총량에 대하여 3 중량% 내지 15 중량%, 예컨대 5 중량% 내지 10 중량%로 포함될 수 있다. 　상기 아크릴계 바인더 수지가 상기 범위 내로 포함될 경우, 감도 및 현상성이 우수하고, 내화학성이 향상되어 패턴 뜯김이 발생하지 않는다.The acrylic binder resin may be included in an amount of 3 wt% to 15 wt%, such as 5 wt% to 10 wt%, based on the total amount of the photosensitive resin composition for color filters. When the acrylic binder resin is included in the above range, it is excellent in sensitivity and developability, and chemical resistance is improved, so that pattern tearing does not occur.
(B) 광중합성 단량체(B) photopolymerizable monomer
상기 광중합성 단량체는 적어도 1개의 에틸렌성 불포화 이중결합을 가지는 (메타)아크릴산의 일관능 또는 다관능 에스테르가 사용될 수 있다.As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.
상기 광중합성 단량체는 상기 에틸렌성 불포화 이중결합을 가짐으로써,　패턴 형성 공정에서 노광시 충분한 중합을 일으킴으로써 내열성, 내광성 및 내화학성이 우수한 패턴을 형성할 수 있다.Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.
상기 광중합성 단량체의 구체적인 예로는, 에틸렌 글리콜 디(메타)아크릴레이트, 디에틸렌 글리콜 디(메타)아크릴레이트, 트리에틸렌 글리콜 디(메타)아크릴레이트, 프로필렌 글리콜 디(메타)아크릴레이트, 네오펜틸 글리콜 디(메타)아크릴레이트, 1,4-부탄디올 디(메타)아크릴레이트, 1,6-헥산디올 디(메타)아크릴레이트, 비스페놀A 디(메타)아크릴레이트, 펜타에리트리톨 디(메타)아크릴레이트, 펜타에리트리톨 트리(메타)아크릴레이트, 펜타에리트리톨 테트라(메타)아크릴레이트, 펜타에리트리톨 헥사(메타)아크릴레이트, 디펜타에리트리톨 디(메타)아크릴레이트, 디펜타에리트리톨 트리(메타)아크릴레이트, 디펜타에리트리톨 펜타(메타)아크릴레이트, 디펜타에리트리톨 헥사(메타)아크릴레이트,　비스페놀A 에폭시(메타)아크릴레이트, 에틸렌 글리콜 모노메틸에테르 (메타)아크릴레이트, 트리메틸올 프로판 트리(메타)아크릴레이트, 트리스(메타)아크릴로일옥시에틸 포스페이트, 노볼락에폭시 (메타)아크릴레이트　등을 들 수 있다. 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 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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) 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.
상기 광중합성 단량체의 시판되는 제품을 예로 들면 다음과 같다. 　상기 (메타)아크릴산의 일관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-101®, 동 M-111®, 동 M-114® 등; 니혼 가야꾸(주)社의 KAYARAD TC-110S®, 동 TC-120S® 등; 오사카 유끼 가가꾸 고교(주)社의 V-158®, V-2311® 등을 들 수 있다. 　상기 (메타)아크릴산의 이관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-210®, 동 M-240®, 동 M-6200® 등; 니혼 가야꾸(주)社의 KAYARAD HDDA®, 동 HX-220®, 동 R-604® 등; 오사카 유끼 가가꾸 고교(주)社의 V-260®, V-312®, V-335 HP® 등을 들 수 있다. 　상기 (메타)아크릴산의 삼관능 에스테르의 예로는, 도아 고세이 가가꾸 고교(주)社의 아로닉스 M-309®, 동 M-400®, 동 M-405®, 동 M-450®, 동 M-7100®, 동 M-8030®, 동 M-8060® 등; 니혼 가야꾸(주)社의 KAYARAD TMPTA®, 동 DPCA-20®, 동-30®, 동-60®, 동-120® 등; 오사카 유끼 가야꾸 고교(주)社의 V-295®, 동-300®, 동-360®, 동-GPT®, 동-3PA®, 동-400® 등을 들 수 있다. 　상기 제품을 단독 사용 또는 2종 이상 함께 사용할 수 있다.Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ® , M-111 ® , M-114 ®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ® , TC-120S ®, etc .; The V-158 ® and V-2311 ® of Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ® , M-240 ® , M-6200 ®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ® , HX-220 ® , R-604 ®, etc .; And V-260 ® , V-312 ® and V-335 HP ® from Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ® , M-400 ® , M-405 ® , M-450 ® , M-450 ® from Toagosei Kagaku Kogyo Co., Ltd. -7100 ® , M-8030 ® , M-8060 ®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ® , DPCA-20 ® , East-30 ® , East-60 ® , East-120 ®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ®, copper ® -300, -360 ® copper, copper -GPT ®, copper -3PA ®, and the like copper -400 ®. The above products can be used alone or in combination of two or more.
상기 광중합성 단량체는　보다 우수한 현상성을 부여하기 위하여 산무수물로 처리하여 사용할 수도 있다.The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.
상기 광중합성 단량체는 상기 컬러 필터용 감광성 수지 조성물 총량에 대하여 3 중량% 내지 13　중량%, 예컨대 4 중량% 내지 10 중량%로 포함될 수 있다. 상기 광중합성 단량체가 상기 범위 내로 포함될 경우,　패턴 형성 공정에서 노광시 경화가 충분히 일어나 신뢰성이 우수하며, 알칼리 현상액에의 현상성이 우수하다.The photopolymerizable monomer may be included in an amount of 3 wt% to 13 wt%, such as 4 wt% to 10 wt%, based on the total amount of the photosensitive resin composition for the color filter. In the case where the photopolymerizable monomer is included in the above range, curing is sufficiently performed at the time of exposure in the pattern forming step to provide excellent reliability and excellent developability to an alkaline developer.
(C) 광중합 개시제(C) photopolymerization initiator
상기 광중합 개시제는 아세토페논계 화합물, 벤조페논계 화합물, 티오크산톤계 화합물, 벤조인계 화합물, 트리아진계 화합물, 옥심계 화합물 등을 사용할 수 있다.The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.
상기 아세토페논계의 화합물의 예로는, 2,2'-디에톡시 아세토페논, 2,2'-디부톡시 아세토페논, 2-히드록시-2-메틸프로피오페논, p-t-부틸트리클로로 아세토페논, p-t-부틸디클로로 아세토페논, 4-클로로 아세토페논, 2,2'-디클로로-4-페녹시 아세토페논, 2-메틸-1-(4-(메틸티오)페닐)-2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온 등을 들 수 있다.Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.
상기 벤조페논계 화합물의 예로는, 벤조페논, 벤조일 안식향산, 벤조일 안식향산 메틸, 4-페닐 벤조페논, 히드록시 벤조페논, 아크릴화 벤조페논, 4,4'-비스(디메틸 아미노)벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 4,4'-디메틸아미노벤조페논, 4,4'-디클로로벤조페논, 3,3'-디메틸-2-메톡시벤조페논 등을 들 수 있다.Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.
상기 티오크산톤계 화합물의 예로는, 티오크산톤, 2-클로로티오크산톤, 2-메틸티오크산톤, 이소프로필 티오크산톤, 2,4-디에틸 티오크산톤, 2,4-디이소프로필 티오크산톤 등을 들 수 있다.Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso Propyl thioxanthone, etc. are mentioned.
상기 벤조인계 화합물의 예로는, 벤조인, 벤조인 메틸 에테르, 벤조인 에틸 에테르, 벤조인 이소프로필 에테르, 벤조인 이소부틸 에테르, 벤질디메틸케탈 등을 들 수 있다.Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.
상기 트리아진계 화합물의 예로는, 2,4,6-트리클로로-s-트리아진, 2-페닐 4,6-비스(트리클로로메틸)-s-트리아진, 2-(3', 4'-디메톡시스티릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4'-메톡시나프틸)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로 메틸)-s-트리아진, 2-비페닐 4,6-비스(트리클로로 메틸)-s-트리아진, 비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시나프토1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-4-비스(트리클로로메틸)-6-피페로닐-s-트리아진, 2-4-비스(트리클로로메틸)-6-(4-메톡시스티릴)-s-트리아진 등을 들 수 있다.Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-bis (trichloro Rhomethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.
상기 옥심계 화합물의 예로는, 2-(o-벤조일옥심)-1-[4-(페닐티오)페닐]-1,2-옥탄디온, 1-(o-아세틸옥심)-1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]에탄온 등을 들 수 있다.Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone and the like.
상기 광중합 개시제는 상기 화합물 이외에도 카바졸계 화합물, 디케톤류 화합물, 술포늄 보레이트계 화합물, 디아조계 화합물, 이미다졸계 화합물, 비이미다졸계 화합물 등을 사용할 수 있다.In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.
상기 광중합 개시제는 상기 컬러 필터용 감광성 수지 조성물 총량에 대하여 0.1 중량% 내지 3.0　중량%, 예컨대 0.5 중량% 내지 1.0 중량%로 포함될 수 있다. 상기 광중합 개시제가 상기 범위 내로 포함될 경우, 패턴 형성 공정에서 노광시 광중합이 충분히 일어나고, 미반응 개시제로 인한 투과율의 저하를 막을 수 있다.The photopolymerization initiator may be included in an amount of 0.1 wt% to 3.0 wt%, such as 0.5 wt% to 1.0 wt%, based on the total amount of the photosensitive resin composition for color filters. When the photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and it is possible to prevent a decrease in transmittance due to the unreacted initiator.
(E) 용매(E) solvent
상기 용매는 상기 아크릴계 바인더 수지, 상기 광중합성 단량체, 상기 광중합 개시제, 및 상기 기능성 수지로 표면처리된 안료와의 상용성을 가지되 반응하지 않는 물질들이 사용될 수 있다.The solvent may be a material having compatibility with the acrylic binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the pigment surface-treated with the functional resin but not reacting.
상기 용매는 특별한 제한은 없으나, 구체적으로 예를 들면, 메탄올, 에탄올 등의 알코올류; 디클로로에틸 에테르, n-부틸 에테르, 디이소아밀 에테르, 메틸페닐 에테르, 테트라히드로퓨란 등의 에테르류; 에틸렌 글리콜 메틸에테르, 에틸렌 글리콜 에틸에테르, 프로필렌 글리콜 메틸에테르 등의 글리콜 에테르류; 메틸 셀로솔브 아세테이트, 에틸 셀로솔브 아세테이트, 디에틸 셀로솔브 아세테이트 등의 셀로솔브 아세테이트류; 메틸에틸 카르비톨, 디에틸 카르비톨, 디에틸렌 글리콜 모노메틸에테르, 디에틸렌 글리콜 모노에틸에테르, 디에틸렌 글리콜 디메틸에테르, 디에틸렌 글리콜 메틸에틸에테르, 디에틸렌 글리콜 디에틸에테르 등의 카르비톨류; 프로필렌 글리콜 메틸에테르 아세테이트, 프로필렌 글리콜 프로필에테르 아세테이트 등의 프로필렌 글리콜 알킬에테르 아세테이트류; 톨루엔, 크실렌 등의 방향족 탄화수소류; 메틸에틸케톤, 사이클로헥사논, 4-히드록시-4-메틸-2-펜타논, 메틸-n-프로필케톤, 메틸-n-부틸케논, 메틸-n-아밀케톤, 2-헵타논 등의 케톤류; 초산 에틸, 초산-n-부틸, 초산 이소부틸 등의 포화 지방족 모노카르복실산 알킬 에스테르류; 메틸 락테이트, 에틸 락테이트 등의 락트산 알킬 에스테르류; 메틸 히드록시아세테이트, 에틸 히드록시아세테이트, 부틸 히드록시아세테이트 등의 히드록시아세트산 알킬 에스테르류; 메톡시메틸 아세테이트, 메톡시에틸 아세테이트, 메톡시부틸 아세테이트, 에톡시메틸 아세테이트, 에톡시에틸 아세테이트 등의 아세트산 알콕시알킬 에스테르류; 메틸 3-히드록시프로피오네이트, 에틸 3-히드록시프로피오네이트 등의 3-히드록시프로피온산 알킬 에스테르류; 메틸 3-메톡시프로피오네이트, 에틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 메틸 3-에톡시프로피오네이트 등의 3-알콕시프로피온산 알킬 에스테르류; 메틸 2-히드록시프로피오네이트, 에틸 2-히드록시프로피오네이트, 프로필 2-히드록시프로피오네이트 등의 2-히드록시프로피온산 알킬 에스테르류; 메틸 2-메톡시프로피오네이트, 에틸 2-메톡시프로피오네이트, 에틸 2-에톡시프로피오네이트, 메틸 2-에톡시프로피오네이트 등의 2-알콕시프로피온산 알킬 에스테르류; 메틸 2-히드록시-2-메틸프로피오네이트, 에틸 2-히드록시-2-메틸프로피오네이트 등의 2-히드록시-2-메틸프로피온산 알킬 에스테르류; 메틸 2-메톡시-2-메틸프로피오네이트, 에틸 2-에톡시-2-메틸프로피오네이트 등의 2-알콕시-2-메틸프로피온산 알킬 에스테르류; 2-히드록시에틸 프로피오네이트, 2-히드록시-2-메틸에틸 프로피오네이트, 히드록시에틸 아세테이트, 메틸 2-히드록시-3-메틸부타노에이트 등의 에스테르류; 또는 피루빈산 에틸 등의 케톤산 에스테르류의 화합물이 있으며, 또한 N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸포름아닐리드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 디메틸술폭시드, 벤질에틸에테르, 디헥실에테르, 아세틸아세톤, 이소포론, 카프론산, 카프릴산, 1-옥탄올, 1-노난올, 벤질알코올, 초산 벤질, 안식향산 에틸, 옥살산 디에틸, 말레인산 디에틸, γ-부티로락톤, 에틸렌 카보네이트, 프로필렌 카보네이트, 페닐 셀로솔브 아세테이트 등이 있으며, 이들 단독으로 사용되거나 2종 이상을 혼합하여 사용할 수 있다.The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl 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 methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl 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-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; 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 methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl 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-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.
상기 용매 중 혼화성(miscibility) 및 반응성을 고려한다면, 좋게는 에틸렌 글리콜 모노에틸 에테르 등의 글리콜 에테르류; 에틸 셀로솔브 아세테이트 등의 에틸렌 글리콜 알킬에테르 아세테이트류; 2-히드록시에틸 프로피오네이트 등의 에스테르류; 디에틸렌 글리콜 모노메틸 에테르 등의 디에틸렌 글리콜류; 프로필렌 글리콜 모노메틸에테르 아세테이트, 프로필렌 글리콜 프로필에테르 아세테이트 등의 프로필렌 글리콜 알킬에테르 아세테이트류가 사용될 수 있다. Considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.
상기 용매는　상기 컬러필터용 감광성 수지 조성물 총량에 대하여 잔부량, 예컨대 40 중량% 내지 90 중량%로 포함될 수 있다. 　상기 용매가 상기 범위 내로 포함될 경우 상기 컬러필터용 감광성 수지 조성물이 적절한 점도를 가짐에 따라 컬러필터 제조시 공정성이 우수하다.　The solvent may be included in a balance, such as 40 wt% to 90 wt%, based on the total amount of the photosensitive resin composition for color filters. When the solvent is included in the above range, as the photosensitive resin composition for color filters has an appropriate viscosity, processability in manufacturing color filters is excellent.
(F) 기타 첨가제(F) other additives
상기 컬러필터용 감광성 수지 조성물은 도포시 얼룩이나 반점을 방지하고, 레벨링 성능을 개선하기 위해, 또한 미현상에 의한 잔사의 생성을 방지하기 위하여, 말론산; 3-아미노-1,2-프로판디올; 비닐기 또는 (메타)아크릴옥시기를 포함하는 커플링제; 레벨링제; 불소계 계면활성제; 및 라디칼 중합 개시제로부터 선택되는 적어도 하나의 첨가제를 더 포함할 수 있다.The photosensitive resin composition for color filters may include malonic acid, in order to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residue due to undeveloped; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
상기 첨가제는 원하는 물성에 따라 용이하게 조절될 수 있다.The additive can be easily adjusted according to the desired physical properties.
상기 커플링제는 실란계 커플링제일 수 있고, 상기 실란계 커플링제의 예로는, 트리메톡시실릴 벤조산, γ-메타크릴 옥시프로필 트리메톡시실란, 비닐 트리아세톡시실란, 비닐 트리메톡시실란, γ-이소 시아네이트 프로필 트리에톡시실란, γ-글리시독시 프로필 트리메톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 이들을 단독 또는 2종 이상 혼합하여 사용할 수 있다. The coupling agent may be a silane coupling agent, and examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. It can be mixed and used.
상기 실란계 커플링제는 구체적으로 상기 컬러필터용 감광성 수지 조성물 100 중량부에 대하여 0.01 중량부 내지 1 중량부로 사용될 수 있다.The silane coupling agent may be used in an amount of 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition for color filters.
또한 상기 컬러필터용 감광성 수지 조성물은 필요에 따라 불소계 계면활성제를 더 포함할 수 있다. 　In addition, the photosensitive resin composition for color filters may further include a fluorine-based surfactant, if necessary.
상기 불소계 계면활성제의 예로는 DIC社의 F-482, F-484, F-478, F-554 등이 있으며, 이에 한정되는 것은 아니다.Examples of the fluorine-based surfactants include F-482, F-484, F-478, F-554, etc. of DIC Corporation, but are not limited thereto.
상기 불소계 계면활성제는 감광성 수지 조성물 총량에 대하여 0.01 중량% 내지 5 중량%로 포함되는 것이 바람직하고 0.1 중량% 내지 2 중량%로 포함되는 것이 보다 바람직하다. 상기 범위를 벗어나는 경우 코팅 단계에서 퍼짐성이 균일하지 못하여 균일한 두께의 막 형성이 어렵다.The fluorine-based surfactant is preferably included in an amount of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt%, based on the total amount of the photosensitive resin composition. If outside the above range, the spreading property is not uniform in the coating step, it is difficult to form a film of uniform thickness.
일 구현예에 따른 감광성 수지 조성물은 빛의 조사에 의해 경화되고 알칼리성 수용액으로 현상 가능한 알칼리 현상형이다. 　상기 감광성 수지 조성물을 기판 위에 라미네이션시킨 다음 컬러필터에 필요한 패턴을 형성하도록 활성선을 조사하면 광에 의해 반응하게 되는데, 반응한 부위는 반응하지 않은 부위에 비해 용매에 대한 용해도가 급격히 떨어져 미반응 부위만 선택적으로 용해 가능하게 된다. 　이와 같이 비노광 부위를 제거하는 용액을 현상액이라 하는데, 이러한 현상액에는 유기 용매형과 알칼리 현상형의 2가지 타입이 있다. 　이들 가운데 유기 용매형은 대기오염을 유발하고 인체에 유해하므로 환경 면에서 알칼리 현상형을 사용하는 것이 좋다. 　일 구현예에 따른 감광성 수지 조성물은 알칼리 현상형　현상액을 사용할 수 있으므로, 환경 면에서 유용하게 사용할 수 있다.The photosensitive resin composition according to one embodiment is an alkali developing type that is curable by irradiation of light and developable with an alkaline aqueous solution. When the photosensitive resin composition is laminated on a substrate and irradiated with an active line to form a pattern required for a color filter, the reaction is caused by light. Only it can be selectively dissolved. The solution for removing the non-exposed sites is called a developer, and there are two types of developer, an organic solvent type and an alkali developer type. Among them, organic solvent type causes air pollution and is harmful to human body, so it is better to use alkaline developing type in terms of environment. Since the photosensitive resin composition according to the exemplary embodiment may use an alkaline developing type developer, it may be usefully used in terms of environment.
　
다른 일 구현예에 따르면 전술한 감광성 수지 조성물을 이용하여 제조된 컬러필터를 제공한다.According to another embodiment provides a color filter manufactured using the photosensitive resin composition described above.
상기 컬러필터의 제조 방법은 다음과 같다. The manufacturing method of the color filter is as follows.
유리기판 위에 스핀 도포, 롤러 도포, 스프레이 도포 등의 적당한 방법을 사용하여, 예를 들면, 0.5 ㎛ 내지 10 ㎛의 두께로 전술한 감광성 수지　조성물을 도포하여 수지 조성물 층을 형성한다.By using a suitable method such as spin coating, roller coating or spray coating on the glass substrate, the above-mentioned photosensitive resin composition is applied to a thickness of, for example, 0.5 탆 to 10 탆 to form a resin composition layer.
이어서, 상기 수지 조성물 층이 형성된 기판에 컬러필터에 필요한 패턴을 형성하도록 광을 조사한다. 　조사에 사용되는 광원으로는 UV, 전자선 또는 X선을 사용할 수 있고, 예를 들면, 190nm 내지　450㎚, 구체적으로는 200nm 내지 400㎚ 영역의 UV를 조사할 수 있다. 　상기 조사하는 공정에서 포토레지스트 마스크를 더욱 사용하여 실시할 수도 있다. 　이와 같이 조사하는 공정을 실시한 후, 상기 광원이 조사된　수지 조성물 층을 현상액으로 처리한다. 　이때 수지 조성물 층에서 비노광 부분은 용해됨으로써 컬러필터에 필요한 패턴이 형성된다. 이러한 공정을 필요한 색의 수에 따라 반복함으로써 원하는 패턴을 갖는 컬러필터를 수득할 수 있다. 　또한 상기 공정에서 현상에 의해 수득된 화상 패턴을 다시 가열하거나 활성선 조사 등에 의해 경화시키면 내크랙성, 내용제성 등을 향상시킬 수 있다.Subsequently, light is irradiated to form the pattern which a color filter requires on the board | substrate with which the said resin composition layer was formed. UV, an electron beam, or an X-ray can be used as a light source used for irradiation, For example, UV of 190 nm-450 nm, specifically, 200 nm-400 nm region can be irradiated. It can also be performed using a photoresist mask further at the said irradiation process. After performing the irradiation step in this manner, the resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed part is melt | dissolved in the resin composition layer, and the pattern required for a color filter is formed. By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained. In addition, crack resistance, solvent resistance, and the like can be improved by reheating the image pattern obtained by the development in the above step or by curing by actinic radiation.
이하, 본 발명의 바람직한 실시예를 기재한다.　　다만, 하기의 실시예는 본 발명의 바람직한 일 실시예일뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.
(기능성 수지로 표면처리한 안료)(Pigment surface-treated with functional resin)
제조예 1Preparation Example 1
미세화된 안료(Green 58, DIC社) 15g, 하기 화학식 6으로 표시되는 반복단위를 포함하는 분자량 약 12,000 g/mol의 수지 3g 및 용매(프로필렌글리콜메틸에틸아세테이트, sigma-aldrich社) 82ml 를 혼합하여 40℃로 온도를 유지하면서 Homogenizer 내지는 mechanical stirrer를 사용하여 혼련하였다. 혼련 후 상온에서 건조시켜 용매를 제거하였다.15 g of a finely pigmented pigment (Green 58, DIC), 3 g of a resin having a molecular weight of about 12,000 g / mol including a 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 ° C. After kneading, the solvent was removed by drying at room temperature.
[화학식 6][Formula 6]
Figure PCTKR2014003515-appb-I000011
Figure PCTKR2014003515-appb-I000011
(안료 분산액)(Pigment dispersion)
제조예 2Preparation Example 2
하기와 같은 조성으로, 용매에 제조예 1에 따른 기능성 수지로 표면처리된 안료, 분산제, 및 아크릴계 바인더를 용해시키고 교반하였다.With the following composition, the pigment, dispersant, and acrylic binder surface-treated with the functional resin according to Preparation Example 1 were dissolved and stirred in a solvent.
제조예 1에 따른 안료: 15 중량%Pigment according to Preparation Example 1: 15% by weight
분산제(BYK2102, BYK社): 6 중량%Dispersant (BYK2102, BYK): 6% by weight
아크릴계 바인더(100S, SMS社): 5 중량%Acrylic binder (100S, SMS): 5% by weight
용매(프로필렌글리콜메틸에틸아세테이트, sigma-aldrich社): 74 중량%Solvent (propylene glycol methyl ethyl acetate, sigma-aldrich): 74 wt%
제조예 3Preparation Example 3
하기와 같은 조성으로, 용매에 안료, 분산제, 및 아크릴계 바인더를 용해시켜 교반하였다.A pigment, a dispersant, and an acrylic binder were dissolved and stirred in a solvent with the following composition.
안료(Green 58, DIC社): 15 중량%Pigment (Green 58, DIC): 15 wt%
분산제(BYK2102, BYK社): 3.5 중량%Dispersant (BYK2102, BYK): 3.5 wt%
아크릴계 바인더(100S, SMS社): 3 중량%Acrylic binder (100S, SMS company): 3% by weight
용매(프로필렌글리콜메틸에틸아세테이트, sigma-aldrich社): 78.5 중량%Solvent (propylene glycol methyl ethyl acetate, sigma-aldrich): 78.5 wt%
(컬러필터용 감광성 수지 조성물)(Photosensitive resin composition for color filters)
실시예 1 및 비교예 1Example 1 and Comparative Example 1
하기 표 1에 기재된 조성으로, 하기 용매에 하기 광중합 개시제를 용해시킨 후 1시간 동안 상온에서 교반하였다. 　여기에, 표 1의 조성으로, 하기 아크릴계 바인더 수지, 및 하기 아크릴계 광중합성 단량체를 첨가하고, 2시간 동안 상온에서 교반하였다.　여기에, 표 1의 조성으로, 하기 불소계 계면활성제를 첨가하고 1시간 동안 상온에서 교반하였다.　여기에, 표 1의 조성으로, 안료분산액을 첨가하고 2시간 동안 상온에서 교반한 후, 상기 용액에 대하여 3회에 걸친 여과를 행하여 불순물을 제거하여 실시예 1, 및 비교예 1에 따른 감광성 수지 조성물을 제조하였다.　상기 감광성 수지 조성물의 제조시 사용된 성분은 아래와 같다.To the composition shown in Table 1, after dissolving the following photopolymerization initiator in the solvent was stirred at room temperature for 1 hour. To this, in the composition of 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 of Table 1, the following fluorine-based surfactant was added and stirred at room temperature for 1 hour. Here, in the composition of Table 1, after adding the pigment dispersion and stirring at room temperature for 2 hours, the solution was filtered three times to remove impurities to remove the photosensitive resin according to Example 1, and Comparative Example 1 The composition was prepared. Components used in the preparation of the photosensitive resin composition are as follows.
(A) 아크릴계 바인더 수지(폴리벤질메타크릴레이트 수지(NPR1520), 미원상사)(A) acrylic binder resin (polybenzyl methacrylate resin (NPR1520), Miwon Corporation)
(B) 아크릴계 광중합성 단량체(디펜타에리트리톨헥사아크릴레이트(DPHA), 일본화약)(B) Acrylic photopolymerizable monomer (Dipentaerythritol hexaacrylate (DPHA), Nippon Gunpowder)
(C) 광중합 개시제(옥심계 화합물(CGI-124, BASF社))(C) photoinitiator (oxime compound (CGI-124, BASF Co., Ltd.))
(D) 안료분산액(D) Pigment Dispersion
(D-1) 제조예 2에 따른 안료분산액  (D-1) Pigment Dispersion According to Preparation Example 2
(D-2) 제조예 3에 따른 안료분산액  (D-2) Pigment Dispersion According to Preparation Example 3
(E) 용매(프로필렌글리콜메틸에틸아세테이트, sigma-aldrich社)(E) Solvent (propylene glycol methyl ethyl acetate, sigma-aldrich)
(F) 불소계 계면활성제(F-554, DIC社)(F) Fluorine-based surfactants (F-554, DIC Corporation)
표 1 (단위: 중량%)
실시예 1 비교예 1
(A) 아크릴계 바인더 수지 10 10
(B) 아크릴계 광중합성 단량체 8 8
(C) 광중합 개시제 0.7 0.7
(D) 안료분산액 (D-1) 35 -
(D-2) - 35
(E) 용매 45.8 45.8
(F) 첨가제 (불소계 계면활성제) 0.5 0.5
총합(Total) 100.00 100.00
Table 1 (Unit: weight%)
Example 1 Comparative Example 1
(A) Acrylic Binder Resin 10 10
(B) Acrylic Photopolymerizable Monomer 8 8
(C) photopolymerization initiator 0.7 0.7
(D) Pigment Dispersion (D-1) 35 -
(D-2) - 35
(E) solvent 45.8 45.8
(F) Additive (Fluorinated Surfactant) 0.5 0.5
Total 100.00 100.00
평가: 감광성 수지 조성물의 분광 특성Evaluation: Spectral Characteristics of Photosensitive Resin Composition
유리 기판 상에 코팅기기(MIKASA社)를 사용하여 실시예 1 및 비교예 1에 따른 감광성 수지 조성물을 막두께가 3.0 ㎛ 내지 4.0 ㎛가 되도록 코팅한 후, 핫 플레이트 상에서 90℃로 건조시켜 도막을 수득하였다. 수득된 도막을 100mJ/cm2의 노광량으로 광 조사 후, 오븐조건 230℃에서 30분간 굽기를 진행하였다. 이를 측색기(오츠카社, MCPD 3000)를 이용하여 투과도, 색좌표 및 휘도를 측정하여, 그 결과를 하기 표 2에 나타내었다. The photosensitive resin compositions according to Example 1 and Comparative Example 1 were coated on a glass substrate using a coating apparatus (MIKASA Co., Ltd.) so as to have a film thickness of 3.0 μm to 4.0 μm, and then dried at 90 ° C. on a hot plate to coat the coating film. Obtained. The obtained coating film was irradiated with light at an exposure dose of 100 mJ / cm 2, and then baked at an oven condition of 230 ° C. for 30 minutes. Transmittance, color coordinates, and luminance were measured using a colorimeter (Otsuka, MCPD 3000), and the results are shown in Table 2 below.
표 2
투과도(540nm) 색특성 (0.240, 0.500)
Y(휘도) 명암비
실시예 1 93% 59 10000
비교예 1 90% 57 10000
TABLE 2
Transmittance (540nm) Color Characteristic (0.240, 0.500)
Y (luminance) Contrast Ratio
Example 1 93% 59 10000
Comparative Example 1 90% 57 10000
상기 표 2를 통하여, 일 구현예에 따른 안료를 사용한 실시예 1의 경우, 비교예 1 대비 감광성 수지 조성물의 휘도가 높고, 우수한 투과도을 가짐을 알 수 있다.Through Table 2, in the case of Example 1 using the pigment according to the embodiment, it can be seen that the brightness of the photosensitive resin composition compared to Comparative Example 1 has a high transmittance.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다.　　그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.　The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (12)

  1. (A) 아크릴계 바인더 수지;(A) acrylic binder resin;
    (B) 광중합성 단량체;(B) photopolymerizable monomers;
    (C) 광중합 개시제;(C) photoinitiator;
    (D) 적어도 하나의 하기 화학식 1로 표시되는 반복단위, 적어도 하나의 하기 화학식 2로 표시되는 반복단위, 적어도 하나의 하기 화학식 3으로 표시되는 반복단위, 적어도 하나의 하기 화학식 4로 표시되는 반복단위를 포함하는 기능성 수지 및 안료를 포함하는 안료분산액; 및(D) at least one repeating unit represented by formula 1, at least one repeating unit represented by formula 2, at least one repeating unit represented by formula 3, at least one repeating unit represented by formula 4 Pigment dispersion containing a functional resin and a pigment comprising; And
    (E) 용매(E) solvent
    를 포함하는 감광성 수지 조성물:Photosensitive resin composition comprising:
    [화학식 1][Formula 1]
    Figure PCTKR2014003515-appb-I000012
    Figure PCTKR2014003515-appb-I000012
    [화학식 2][Formula 2]
    Figure PCTKR2014003515-appb-I000013
    Figure PCTKR2014003515-appb-I000013
    [화학식 3][Formula 3]
    Figure PCTKR2014003515-appb-I000014
    Figure PCTKR2014003515-appb-I000014
    [화학식 4][Formula 4]
    Figure PCTKR2014003515-appb-I000015
    Figure PCTKR2014003515-appb-I000015
    상기 화학식 1 내지 화학식 4에서,In Chemical Formulas 1 to 4,
    R1 내지 R8은 각각 독립적으로 수소, 또는 치환 또는 비치환된 C1 내지 C10 알킬기이고,R 1 to R 8 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,
    L1 내지 L4는 각각 독립적으로 단일결합, 또는 치환 또는 비치환된 C1 내지 C10 알킬렌기이다.L 1 to L 4 are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
  2. 제1항에 있어서, The method of claim 1,
    상기 기능성 수지는 하기 화학식 5로 표시되는 반복단위를 포함하는 감광성 수지 조성물:The functional resin is a photosensitive resin composition comprising a repeating unit represented by the following formula (5):
    [화학식 5][Formula 5]
    Figure PCTKR2014003515-appb-I000016
    Figure PCTKR2014003515-appb-I000016
    상기 화학식 5에서,In Chemical Formula 5,
    a, b, c, 및 d는 각각 독립적으로 1 이상의 정수이다.a, b, c, and d are each independently an integer of 1 or more.
  3. 제1항에 있어서,The method of claim 1,
    상기 기능성 수지의 중량평균 분자량은 5,000 g/mol 내지 30,000 g/mol 인 감광성 수지 조성물.The weight average molecular weight of the functional resin is 5,000 g / mol to 30,000 g / mol of the photosensitive resin composition.
  4. 제1항에 있어서, The method of claim 1,
    상기 안료는 유기 안료, 무기 안료, 또는 이들의 조합을 포함하는 감광성 수지 조성물.The pigment is a photosensitive resin composition comprising an organic pigment, an inorganic pigment, or a combination thereof.
  5. 제1항에 있어서, The method of claim 1,
    상기 안료는 녹색 안료를 포함하는 감광성 수지 조성물.The pigment is a photosensitive resin composition comprising a green pigment.
  6. 제1항에 있어서,The method of claim 1,
    상기 안료는 상기 기능성 수지로 표면처리한 것이고,The pigment is surface-treated with the functional resin,
    상기 감광성 수지 조성물은The photosensitive resin composition
    상기 아크릴계 바인더 수지 3 중량% 내지 15 중량%;3 wt% to 15 wt% of the acrylic binder resin;
    상기 광중합성 단량체 3 중량% 내지 13 중량%;3 wt% to 13 wt% of the photopolymerizable monomer;
    상기 광중합 개시제 0.1 중량% 내지 3 중량%;0.1 wt% to 3 wt% of the photopolymerization initiator;
    상기 기능성 수지로 표면처리한 안료 2 중량% 내지 10 중량%; 및2 wt% to 10 wt% of the pigment surface-treated with the functional resin; And
    상기 용매 잔부량Residual solvent amount
    을 포함하는 감광성 수지 조성물. 　Photosensitive resin composition comprising a.
  7. 제1항에 있어서,The method of claim 1,
    상기 감광성 수지 조성물은 말론산; 3-아미노-1,2-프로판디올; 비닐기 또는 (메타)아크릴옥시기를 포함하는 커플링제; 레벨링제; 불소계 계면활성제; 및 라디칼 중합 개시제로부터 선택되는 적어도 하나의 첨가제를 더 포함하는 감광성 수지 조성물.The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; And at least one additive selected from radical polymerization initiators.
  8. 제1항에 있어서,The method of claim 1,
    상기 기능성 수지를 포함하는 안료분산액은The pigment dispersion containing the functional resin is
    안료를 분쇄하는 단계; 및Pulverizing the pigment; And
    상기 분쇄된 안료 및 기능성 수지를 혼합하는 단계Mixing the pulverized pigment and a functional resin
    를 포함하는 방법으로 제조된 감광성 수지 조성물.Photosensitive resin composition prepared by the method comprising a.
  9. 제8항에 있어서,The method of claim 8,
    상기 분쇄된 안료 및 기능성 수지를 혼합하는 단계는 Mixing the pulverized pigment and functional resin is
    상기 분쇄된 안료 및 기능성 수지를 용매에 첨가하여 용액을 제조하는 단계; 및 Preparing a solution by adding the pulverized pigment and a functional resin to a solvent; And
    상기 용액을 건조하는 단계Drying the solution
    를 포함하는 방법으로 제조된 감광성 수지 조성물.Photosensitive resin composition prepared by the method comprising a.
  10. 제8항에 있어서,The method of claim 8,
    상기 분쇄된 안료 및 기능성 수지는 10 : 4 내지 10 : 2 의 중량비로 혼합되는 감광성 수지 조성물.The pulverized pigment and functional resin is a photosensitive resin composition is mixed in a weight ratio of 10: 4 to 10: 2.
  11. 제8항에 있어서,The method of claim 8,
    상기 혼합하는 단계는 20℃ 내지 70℃의 온도에서 수행하는 감광성 수지 조성물.The mixing step is carried out at a temperature of 20 ℃ to 70 ℃ photosensitive resin composition.
  12. 제1항 내지 제11항 중 어느 한 항의 감광성 수지 조성물을 이용하여 제조된 컬러필터.The color filter manufactured using the photosensitive resin composition of any one of Claims 1-11.
PCT/KR2014/003515 2014-01-17 2014-04-22 Photosensitive resin composition for color filter and color filter using same WO2015108240A1 (en)

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