WO2012020715A1 - Composition durcissable bleue, filtre coloré et son procédé de fabrication, dispositif de capture d'images à semi-conducteur, et dispositif d'affichage à cristaux liquides - Google Patents

Composition durcissable bleue, filtre coloré et son procédé de fabrication, dispositif de capture d'images à semi-conducteur, et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2012020715A1
WO2012020715A1 PCT/JP2011/067997 JP2011067997W WO2012020715A1 WO 2012020715 A1 WO2012020715 A1 WO 2012020715A1 JP 2011067997 W JP2011067997 W JP 2011067997W WO 2012020715 A1 WO2012020715 A1 WO 2012020715A1
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group
curable composition
pigment
groups
blue curable
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PCT/JP2011/067997
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English (en)
Inventor
Shinichi Kanna
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Fujifilm Corporation
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Priority to KR1020137001472A priority Critical patent/KR20130091727A/ko
Publication of WO2012020715A1 publication Critical patent/WO2012020715A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements

Definitions

  • the invention relates to a blue curable composition, a color filter and a method for producing the same, a solid-state image pickup device, and a liquid crystal display device.
  • the pigment dispersion method produces a color filter by photolithography using a colored curable composition prepared by dispersing a pigment in a curable composition.
  • the pigment dispersion method includes patterning by photolithography, and thus is regarded as suitable for producing a color filter having a high accuracy of position, a large size, and a high definition.
  • a color filter is produced by the pigment dispersion method, a curable composition is applied to a glass substrate using a spin coater or a roll coater to form a coating film, and the coating film is subjected to pattern exposure and development to form color pixels. The procedure is repeated for the respective colors, thereby obtaining a color filter.
  • pigments used in colored curable compositions include the
  • JP-A Japanese Patent Application Laid-Open
  • phthalocyanine pigment examples include copper
  • Copper phthalocyanines having ⁇ , ⁇ , ⁇ and ⁇ crystal forms vary in robustness such as heat resistance, water resistance, solvent resistance, and light resistance, optical properties such as transmission spectrum and absorption spectrum, and apparent tint. Therefore, they are selected according to the intended use.
  • ⁇ copper phthalocyanine having fine and uniform particles is used for producing color filters.
  • the production of ⁇ copper phthalocyanine must undergo many processes and energy-wasting processes.
  • Japanese Patent No. 4461304 and JP-ANo. 2008-274062 provide a proposal for producing a copper phthalocyanine having novel properties.
  • the colored curable compositions used in the pigment dispersion method are demanded to achieve further improvements for the purposes of increasing the resolution and performance of color filters.
  • the invention has been accomplished in view of the above circumstances. It is an object of the invention to provide a blue curable composition without roughness or color unevenness.
  • the roughness herein is considered to be brightness unevenness due to nonuniformity of optical transparency of the colored cured film caused by relatively coarse pigment particles and the aggregation of particles, and the phase separation of the
  • a blue curable composition comprising:
  • a copper phthalocyanine pigment having an a crystal form and a transmission maximum at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm;
  • ⁇ 2> The blue curable composition of ⁇ 1>, further comprising a dipyrromethene metal complex compound or a tautomer thereof, obtained from a dipyrromethene compound represented by the following formula (I) and a metal atom or a metal compound:
  • R 1 to R 7 each independently represent a hydrogen atom or a monovalent substituent.
  • R 2 to R 5 and R 7 each independently represent a hydrogen atom or a monovalent substituent
  • R 10 and R 11 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, but (p+q) of R 2 to R 5 , R 10 , and R 11 are each converted to a divalent linking group bonded to L 1 or L 2 or converted to a single bond so that L 1 or L 2 is directly bonded to the dipyrromethene skeleton
  • Ma represents a metal or a metal compound
  • X 1 represents a group necessary for neutralizing a charge of Ma
  • r represents 0, 1 or 2
  • X 3 and X 4 each independently represent NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl
  • ⁇ (L')-(C0 2 M) m ⁇ s may be identical or different; when q represents 2, a plurality of
  • ⁇ 6> The blue curable composition of any one of ⁇ 1> to ⁇ 5>, wherein the copper phthalocyanine pigment is a particulate pigment obtained by mixing a solution prepared by dissolving the pigment in a good solvent for the pigment with a poor solvent for the pigment.
  • ⁇ 7> The blue curable composition of ⁇ 6>, wherein the good solvent is an acid or a mixture of an acid and another solvent.
  • a method for producing a color filter comprising a step (A) of applying the blue curable composition of any one of ⁇ 1> to ⁇ 8> to a support thereby forming a blue curable composition layer, and a step (B) of exposing the blue curable composition layer formed in the step (A) to light through a mask, followed by development to form a colored pattern.
  • a solid-state image pickup device comprising the color filter of ⁇ 10>.
  • a liquid crystal display device comprising the color filter of ⁇ 10>.
  • a blue curable composition without roughness or color unevenness is provided.
  • a color filter without roughness or color unevenness and a method for producing the same and a solid-state image pickup device and a liquid crystal display device including the color filter and achieving high color reproducibility are provided.
  • the blue curable composition of the invention includes a copper phthalocyanine pigment having an a crystal form and a transmission maximum at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm, an oxime polymerization initiator, a polymerizable compound, and a solvent.
  • the blue curable composition contains a copper phthalocyanine pigment.
  • the conventional copper phthalocyanine pigment having an a crystal form contains coarse particles, and thus the blue curable composition containing the pigment tends to be inferior because of roughness and color unevenness.
  • phthalocyanine pigment which has an a crystal form and a transmission maximum at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm, as a coloring agent and an oxime polymerization initiator in the blue curable composition.
  • the invention has been accomplished on the basis of the finding.
  • the invention may provide a blue curable composition with less roughness and color unevenness.
  • the blue curable composition of the invention contains a copper phthalocyanine pigment having an a crystal form and a transmission maximum at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm (hereinafter may be referred to as "copper phthalocyanine pigment").
  • the powder X-ray diffractometry uses a full automatic multipurpose X-ray diffractometer (trade name: X'Pert PRO MPD, manufactured by PANalytical).
  • a Cu anticathode is used, the tube voltage is 45 kV, the tube current is 40 mA, and the scanning rate is 1.6 °/min.
  • the thermogravimetry/differential thermal analysis (TG/DTA) uses TG/DTA6300 (trade name, manufactured by Seiko Instruments, Inc.).
  • TG/DTA6300 trade name, manufactured by Seiko Instruments, Inc.
  • an alumina powder is used as reference, and the temperature rising rate is 20°C/min.
  • FT-IR infrared absorption spectrometry
  • the average particle diameter of the copper phthalocyanine pigment used in the invention may be 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less in terms of the major diameter.
  • the fine particles of the copper phthalocyanine pigment used in the invention may have a spherical shape which may be not perfectly spherical, and the ratio of the major diameter to the minor diameter may be from 0.75 to 1.5, preferably from 0.8 to 1.3.
  • the copper phthalocyanine pigment used in the invention may be a particulate pigment obtained by, for example, mixing a solution of the copper phthalocyanine pigment in a good solvent with a poor solvent for the copper phthalocyanine pigment. More specifically, when mixing the solution of the copper phthalocyanine pigment in a good solvent (a copper phthalocyanine pigment solution) with the poor solvent (the second solvent), they may be added in any order, but it is preferred that the copper phthalocyanine pigment solution be jetted into and mixed with the second solvent, preferably with stirring of the second solvent.
  • the stirring speed is preferably from 100 rpm to 10000 rpm, more preferably from 150 rpm to 8000 rpm, and particularly preferably from 200 rpm to 6000 rpm.
  • the addition may optionally use a pump or other device.
  • the addition of the solution may be carried out in or over the second solvent, but is preferably carried out in the second solvent. It is more preferred that the solution be continuously fed into the solvent through a feeding pipe using a pump.
  • the inside diameter of the feeding pipe is preferably from 0.1 mm to 200 mm, and more preferably from 0.2 mm to 100 mm.
  • the feeding speed from the feeding pipe into the liquid is preferably from 1 to 10000 ml/min, and more preferably from 5 to 5000 ml/min.
  • a solution of the copper phthalocyanine pigment in a good solvent and a poor solvent for the copper phthalocyanine pigment be introduced through different branch channels into the main channel and mixed therein, thereby depositing particles to obtain a particulate copper phthalocyanine pigment.
  • the particle diameter of the nanoparticles of the copper phthalocyanine pigment to be deposited may be controlled by adjusting the Reynolds number.
  • the Reynolds number is a dimensionless number used to describe flow conditions of a fluid, and represented by the following equation:
  • Re represents the Reynolds number
  • p represents the density [kg/m 3 ] of the copper phthalocyanine pigment solution
  • U represents the relative rate [m/s] when the copper phthalocyanine pigment solution meets the second solvent
  • L represents the equivalent diameter [m] of the channel or feeding port where the copper phthalocyanine pigment solution meets the second solvent
  • ⁇ represents the coefficient of viscosity [Pa s] of the copper phthalocyanine pigment solution.
  • the equivalent diameter L is the diameter of a circular pipe corresponding to the channel or feeding port having an arbitrary cross-sectional shape.
  • the equivalent diameter L is represented by the following equation (2), wherein A represents the sectional area of the pipe, and p represents the inner circumference of the pipe or the outer circumference of the channel.
  • the copper phthalocyanine pigment solution be poured into the second solvent through a pipe to form particles.
  • the equivalent diameter agrees with the diameter of the circular pipe.
  • the opening diameter of the liquid feeding port may be changed to control the equivalent diameter.
  • the equivalent diameter L is not particularly limited, but, for example, the same as the preferred inside diameter of the above-described feeding port.
  • the relative rate U when the copper phthalocyanine pigment solution meets the second solvent is defined by the relative rate in the direction perpendicular to the surface where these liquids meet. More specifically, when the copper phthalocyanine pigment solution is poured into the second solvent in a stationary state, the feeding rate from the feeding port is equal to the relative rate U.
  • the relative rate U is not particularly limited, but is preferably, for example, from 0.5 to 100 m/s, and more preferably from 1.0 to 50 m/s.
  • the density p of the copper phthalocyanine pigment solution is defined according to the type of the selected material, and is practically, for example, from 0.8 to 2.0 kg/m .
  • the coefficient of viscosity ⁇ of the copper phthalocyanine pigment solution is defined by the material used, environmental temperature, and other factors, and the preferred range is the same as the above-described preferred viscosity of the copper phthalocyanine pigment solution.
  • Reynolds number is preferably 100 or more, and more preferably 150 or more.
  • the upper limit of the Reynolds number is not particularly limited, but is preferably, for example, 100000 or less, thereby obtaining favorable nanoparticles of the copper phthalocyanine pigment under control.
  • the Reynolds number may be increased such that the nanoparticles to be obtained have an average particle diameter of 60 nm or less. When the Reynolds number is increased within the above range, nanoparticles of the copper
  • phthalocyanine pigment having a smaller particle diameter may be obtained under control.
  • the mixing ratio between the copper phthalocyanine pigment solution and the second solvent is preferably from 1/50 to 2/3, more preferably from 1/40 to 1/2, and particularly preferably from 1/20 to 3/8, in terms of the volume ratio.
  • the particle concentration in the liquid when the copper phthalocyanine pigment fine particles are deposited is not particularly limited, but the amount of the copper phthalocyanine pigment fine particles is preferably from 10 mg to 40000 mg, more preferably from 20 mg to 30000 mg, and particularly preferably from 50 mg to 25000 mg with respect to 1000 ml of the solvent.
  • the preparation scale for the formation of the copper phthalocyanine pigment fine particles is not particularly limited, but the mixing amount of the second solvent is preferably from 10 L to 2000 L, and more preferably from 50 L to 1000 L.
  • the particle diameter of the copper phthalocyanine pigment fine particles or the fine colorant substance may be represented as the average size of a mass quantified by any measuring method.
  • Examples of commonly used particle diameter include mode diameter indicating the maximum value in a distribution, median diameter corresponding to the median value of the integral distribution curve, and various average diameters (for example, number average, length average, area average, mass average, and volume average).
  • the average particle diameter is based on the volume weighted average.
  • the average particle diameter of the copper phthalocyanine pigment fine particles is preferably from 1 nm to 1 ⁇ , more preferably from 1 nm to 200 nm, even more preferably from 2 nm to 100 nm, and particularly preferably from 5 nm to 80 nm, in terms of the volume weighted average.
  • the particles to be formed may be crystalline particles, amorphous particles, or mixtures thereof.
  • the ratio (Mv/Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used as the index indicating the monodispersity of the particles.
  • the monodispersity of the copper phthalocyanine pigment fine particles (primary particles), more specifically the Mv/Mn is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.8, and particularly preferably from 1.0 to 1.5.
  • Examples of the method for measuring the particle diameter of the copper phthalocyanine pigment fine particles include microscopic methods, mass methods, light scattering methods, light blocking methods, electric resistance methods, acoustic methods, and dynamic light scattering methods. Among them, microscopic methods and dynamic light scattering methods are particularly preferred. Examples of microscopes used in the microscopic methods include scanning electron microscopes and transmission electron microscopes. Examples of particle measuring apparatuses used in the dynamic light scattering methods include NANOTRAC UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), and dynamic light scattering photometer DLS-7000 SERIES (trade name, manufactured by Otsuka Electronics Co., Ltd.).
  • the copper phthalocyanine pigment solution and/or the second solvent may contain a compound (hereinafter may be referred to as a particle diameter regulator) for which at least the second solvent is a good solvent (solubility in the second solvent is 4.0% by mass or more).
  • polymer particle diameter regulator examples include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, partially formalized polyvinyl alcohol, partially butyralized polyvinyl alcohol, vinylpyrrolidone-vinyl acetate copolymer,
  • polyethylene oxide/propylene oxide block copolymer polyacrylic acid, sodium polyacrylate, polyvinyl sulfate, poly(4-vinylpyridine) salt, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride/diallylamine hydrochloride copolymer, diallylamine monomer/S0 2 copolymer, diallylamine hydrochloride/maleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride/acrylamide copolymer, condensed naphthalene sulfonate, cellulose derivatives, and starch derivatives.
  • Other examples include natural polymers such as alginates, gelatin, albumin, casein, gum arabic, gum tragacanth, and lignin sulfonates.
  • polyvinyl pyrrolidone, polyacrylic acid, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride/diallylamine hydrochloride copolymer, diallylamine monomer/S0 2 copolymer are preferred.
  • These particle diameter regulators may be used alone or in combination of two or more thereof.
  • the mass average molecular weight is preferably from 1,000 to 500,000, more preferably from 10,000 to 500,000, and particularly preferably from 10,000 to 100,000.
  • anionic particle diameter regulators include N-acyl-N-alkyltaurine salts, fatty acid salts, alkyl sulfate salt, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkylsulfosuccinates, alkyl phosphates, naphthalene sulfonate formalin condensate, and polyoxyethylene alkyl sulfates. Among them,
  • N-acyl-N-alkyltaurine salts are preferred.
  • Preferred examples of the N-acyl-N-alkyltaurine salts include those described in JP-ANo. 3-273067. These anionic particle diameter regulators may be used alone or in combination of two or more thereof.
  • cationic particle diameter regulators examples include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, and cationic salts of imidazoline derived from fatty acids. These cationic particle diameter regulators may be used alone or in combination of two or more thereof.
  • Amphoteric particle diameter regulators contain, within the molecules thereof, anionic and cationic groups, which are contained in the molecules of the anionic and cationic particle diameter regulators.
  • nonionic particle diameter regulators examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, and glycerol fatty acid ester.
  • polyoxyethylene alkyl aryl ether is preferred.
  • These nonionic particle diameter regulator may be used alone or in combination of two or more thereof.
  • the content of the particle diameter regulator is preferably from 0.1% to 100% by mass, more preferably from 0.1% to 50% by mass, and even more preferably from 0.1% to 20% by mass with respect to the content of the copper phthalocyanine pigment, thereby further improving the particle diameter control for the copper phthalocyanine pigment fine particles.
  • the particle diameter regulator may be used alone or in combination of two or more thereof.
  • the copper phthalocyanine pigment fine particles in the fine colorant substance are preferably buildup copper phthalocyanine pigment fine particles obtained by deposition through the contact between a copper phthalocyanine pigment solution in a good solvent and a poor solvent, which is more preferred to breakdown copper phthalocyanine pigment particles obtained by grinding a bulk pigment.
  • the fine colorant substance is not particularly limited as long as it contains the copper phthalocyanine pigment fine particles, but is preferably prepared by partially or completely removing the solvents (good solvent (the first solvent) and poor solvent (the second solvent)) from the mixed solution in which the copper phthalocyanine pigment fine particles have been deposited.
  • the process of removing the solvents from the mixed solution after depositing the copper phthalocyanine pigment fine particles is not particularly limited, and examples of the method include filtration using a filter, and sedimentation of the copper phthalocyanine pigment fine particles by centrifugation to concentrate them.
  • filtration apparatus examples include vacuum or pressure filtration apparatus.
  • filters include filter paper, nanofilter, and ultrafilter.
  • the centrifuge may be any machine as long as it sediments the copper
  • the centrifuge examples include general-purpose ones, those having skimming function (function for aspirating the supernatant layer during rotation, and exhaust it outside the system), and continuous centrifuges which continuously exhaust solids.
  • the centrifugation conditions is preferably from 50 to 10000, more preferably from 100 to 8000, and particularly preferably from 150 to 6000, in terms of the centrifugal force (a value representing how many times larger than the gravitational acceleration the centrifugal acceleration is).
  • the temperature during centrifugation is preferably from -10°C to 80°C, more preferably from -5°C to 70°C, and particularly preferably from 0°C to 60°C, according to the type of the dispersion solvent.
  • the process of removing the solvent component may use a method of concentrating the solution through sublimation of the solvent by vacuum freeze drying, a method of concentrating the solution through drying the solvent under heating or reduced pressure, or a combination of these methods.
  • the fine colorant substance may be in the form of a colorant substance dispersion (hereinafter may be referred to simply as colorant dispersion) prepared using a dispersion solvent (third solvent) whose composition is different from that of the first solvent.
  • colorant dispersion a colorant substance dispersion prepared using a dispersion solvent (third solvent) whose composition is different from that of the first solvent.
  • the third solvent is not particularly limited as to its type, but is preferably an organic solvent, and preferred examples thereof include ether solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents.
  • the third solvent may be any pure solvent selected from the above solvents, or a mixed solvent composed of plural solvents.
  • any solvents including the above-described third solvent and the below-described fourth solvent, which are used as a medium of the dispersion and different from the good solvent (first solvent) and the poor solvent (second solvent), are collectively referred to as "third solvent”.
  • Examples of the ether solvent include tetrahydrofuran and propylene glycol monomethyl ether.
  • Examples of the ester solvent include 2-(l-methoxy)propyl acetate, ethyl acetate, and ethyl lactate.
  • Examples of the ketone solvent include methyl ether ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the aromatic hydrocarbon solvent include benzene, toluene, and xylene.
  • Examples of the aliphatic hydrocarbon solvent include n-hexane and cyclohexane.
  • ethyl lactate, ethyl acetate, and 2-(l-methoxy)propyl acetate are preferred, and ethyl lactate and 2-(l-methoxy)propyl acetate are more preferred.
  • These solvents may be used alone or in combination of two or more thereof.
  • the third solvent will not be the same as the first or second solvent.
  • the addition amount of the third solvent is not particularly limited, but is preferably from 100 to 300000 parts by mass, and more preferably from 500 to 10000 parts by mass, with respect to 100 parts by mass of the copper phthalocyanine pigment fine particles,.
  • the copper phthalocyanine pigment fine particles may be used in the form of, for example, a dispersion in a vehicle.
  • the vehicle in a paint is the medium for dispersing the copper phthalocyanine pigment in the liquid, and includes a component (binder) which is bonded to the pigment and hardens the coating film, and a component (organic solvent) which dissolves and dilutes them.
  • the polymer compound used for the formation of the copper phthalocyanine pigment fine particles and/or the copper phthalocyanine pigment dispersant used for the redispersion are collectively referred to as binder.
  • the concentration of the copper phthalocyanine pigment fine particles in the dispersion after redispersion of the copper phthalocyanine pigment fine particles is selected according to the intended use.
  • the concentration of the copper phthalocyanine pigment fine particles is preferably from 2% to 30% by mass, more preferably from 4% to 20% by mass, and particularly preferably from 5% to 15% by mass, with respect to the total amount of the dispersion.
  • the amounts of the binder and the dissolving and diluting component are defined as appropriate according to the type of the copper phthalocyanine pigment.
  • the concentration of the binder is preferably from 1% to 30% by mass, more preferably from 3% to 20% by mass, and particularly preferably from 5% to 15% by mass, with respect to the total amount of the dispersion.
  • the amount of the dissolving and diluting component is preferably from 5% to 80% by mass, and more preferably from 10% to 70% by mass.
  • the content of the copper phthalocyanine pigment fine particles in the colorant dispersion is not particularly limited, but is preferably from 1.0% to 35.0% by mass, and more preferably from 5.0% to 25.0% by mass.
  • the aggregation of the copper phthalocyanine pigment fine particles in the third solvent may spontaneously dissipate without adding other dispersant or the like, so that the fine particles disperse in the medium.
  • the colorant substance having this property is regarded as "self-dispersible” or “having self-dispersibility".
  • any dispersant for the copper phthalocyanine pigment may be added before the redispersion of the colorant substance.
  • Redispersion of the aggregated fine colorant substance may be achieved by, for example, dispersion by ultrasonic or application of physical energy.
  • the ultrasonic irradiation apparatus used herein preferably has a function of applying ultrasound of 10 kHz or more, and examples thereof include ultrasonic homogenizers and ultrasonic cleaners. If the liquid temperature increases during ultrasonic irradiation, thermal aggregation of nanoparticles occur. Therefore, the liquid temperature is preferably from 1°C to 100°C, and more preferably from 5°C to 60°C.
  • the temperature control may be achieved by, for example, the control of the dispersion temperature, or the temperature control of the temperature control bath for controlling the temperature of the dispersion.
  • the disperser used for dispersing the colorant substance by applying a physical energy is not particularly limited, and examples of the disperser include kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. In addition, high pressure dispersion methods and dispersion methods using fine beads are also preferred.
  • the colorant dispersion may contain any known dispersant such as a copper phthalocyanine pigment dispersant or surfactant, without impairing the effect of the invention.
  • copper phthalocyanine pigment dispersant examples include polymeric dispersants (for example, linear polymers, block polymers, graft polymers, and terminal modified polymers), surfactants (for example, polyoxyethylene alkyl phosphate,
  • examples of preferred structures include block polymers, graft polymers, and terminal modified polymers which have anchor sites for the surface of the copper phthalocyanine pigment surface.
  • the copper phthalocyanine pigment derivative modifies the surface of the copper phthalocyanine pigment to promote the adsorption of the polymeric dispersant.
  • Examples of the block polymers as polymer compounds include DISPERBYK-2000, 2001 (trade names, manufactured by BYK Chemie), and EFKA4330, 4340 (trade names, manufactured by EFKA).
  • Examples of the graft polymers include SOLSPERSE 24000, 28000, 32000, 38500, 39000, 55000 (trade names, manufactured by The Lubrizol Corporation), and DISPERBYK-161, 171, 174 (trade names, manufactured by BYK Chemie).
  • terminal modified polymers examples include SOLSPERSE 3000, 17000, and 27000 (trade names, manufactured by The Lubrizol Corporation).
  • the good solvent is defined as a solvent which dissolves the copper phthalocyanine compound, and the solubility is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • An acid or a solvent containing an acid and another solvent used for dissolving the copper phthalocyanine compound is not particularly limited as long as it dissolves the copper phthalocyanine compound.
  • Preferable examples thereof include an inorganic acid such as sulfuric acid or an organic acid. It is more preferably alkyl sulfonic acid, alkylcarboxylic acid, alkyl halide sulfonic acid, alkyl halide carboxylic acid, aromatic sulfonic acid, aromatic carboxylic acid, or a mixture thereof, even more preferably alkyl sulfonic acid or aromatic sulfonic acid, and particularly preferably methane sulfonic acid.
  • Examples of the solvent to be combined with an acid include alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, and mixtures of these solvents.
  • alcohol compound solvents, amide compound solvents, ketone compound solvents, aromatic compound solvents, ester compound solvents are preferred.
  • the acid solvent is preferably free from water, except for unavoidable moisture.
  • Examples of the sulfoxide compound solvents include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, and sulfolane.
  • Examples of the amide compound solvents include N,N-dimethylformamide, l-methyl-2-pyrrolidone, 2-pyrrolidinone, l ,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide,
  • N-methylpropane amide N-methylpropane amide, and hexamethylphosphoric triamide.
  • the concentration of the copper phthalocyanine compound with respect to the acid solvent is preferably from 0.1% to 50% by mass, and more preferably from 1% to 10% by mass.
  • the conditions for preparing the copper phthalocyanine compound solution are not particularly limited, but the temperature under normal pressure is preferably from 5°C to 150°C, and more preferably from 20°C to 80°C.
  • the pressure is normally normal pressure, but the preparation may be carried out under a pressure of 100 kPa to 3000 kPa (1 atm to 30 atm).
  • the poor solvent is defined as a solvent in which the copper phthalocyanine compound is poorly soluble, and the solubility is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and particularly preferably 0.001% by mass or less.
  • the poor solvent is preferably pure water or any of the
  • organic solvents and particularly preferably pure water.
  • the organic solvent used as the poor solvent is preferably selected from alcohol solvents, ketone solvents, ether solvents, aromatic solvents, carbon disulfides, aliphatic solvents, nitrile solvents, sulfoxide solvents, halogen solvents, ester solvents, ionic solutions, and mixtures of two or more of these solvents.
  • Examples of the alcohol compound solvents include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and l-methoxy-2-propanol.
  • Examples of the ketone compound solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • ether compound solvents examples include dimethyl ether, diethyl ether, and tetrahydrofuran.
  • Examples of the aliphatic solvents include alkylene carbonates.
  • aromatic compound solvents examples include benzene and toluene.
  • Examples of the aliphatic compound solvents include hexane.
  • nitrile compound solvents examples include acetonitrile.
  • halogen compound solvents examples include dichloromethane and trichloroethylene.
  • sulfoxide compound solvents examples include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, and sulfolane.
  • ester compound solvents examples include ethyl acetate, ethyl lactate, and 2-(l-methoxy)propyl acetate.
  • ionic liquids examples include the salts of l-butyl-3-methylimidazolium and
  • the organic poor solvent is preferably a solvent having a dielectric constant of 20 or more, and examples thereof include alcohol compounds, alkylene carbonate compounds, nitrile compounds, and sulfoxide compounds. Among them, alkylene carbonates (for example, propylene carbonate and ethylene carbonate) are more preferred.
  • the content of the copper phthalocyanine pigment in the blue curable composition is preferably from 5% to 60% by mass, more preferably from 10% to 60% by mass, and most preferably from 35% to 50% by mass with respect to the total solid content of the blue curable composition, from the viewpoint of easiness of hue control of the color filter.
  • the invention uses a copper phthalocyanine pigment having an a crystal form and a transmission maximum at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm. Since the copper phthalocyanine pigment is composed of fine spherical particles, it improves the transmittance in a wavelength region of from 400 to 500 nm. As a result, the combination of the pigment with the below-described specific dipyrromethene metal complex compound or tautomer thereof, or specific dioxane pigment allows the provision of a blue curable composition with no roughness or color unevenness.
  • Some copper phthalocyanine pigments have an a crystal form and a transmission maximum at a wavelength of more than 475 nm in a wavelength region of from 400 nm to 500 nm, but they are not preferred, because they cause color unevenness due to coarse particles contained therein, which result in the deterioration of transparency and coloring power.
  • the blue curable composition of the invention contains an oxime polymerization initiator as a polymerization initiator.
  • the oxime polymerization initiator is not particularly limited, and examples thereof include the oxime compounds described in JP-ANo. 2000-80068 (paragraphs [0004] to [0296]), WO02/100903 Al , JP-A Nos. 2001-233842, and 2006-342166 (paragraphs [0004] to [0264]).
  • oxime-o-acyl compounds such as 2-(o-benzoyloxime)-l-[4-(phenylthio)phenyl]-l,2-octane dione and
  • polymerization initiator examples include the oxime polymerization initiators represented by the following formula (OX-1) described in JP-ANo.
  • R 1 represents a substituent containing an aromatic ring or a hetero aromatic ring.
  • R la represents an alkyl group having at least one substituent selected from the following group (A);
  • R 2a represents an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxy carbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkyl thiocarbonyl group, an aryl thiocarbonyl group, a heterocycle thiocarbonyl group, a heteroaryl thiocarbonyl group, or -CO-CO-Rd (wherein Rd represents an aromatic ring or hetero aromatic ring which may have a
  • n an integer of 1 to 6.
  • Cyano groups alkenyl groups, alkynyl groups, -NArAr', -SAr, -COOH, -CONRaRb, -NRa-CO-Rb, -O-CO-NRaRb, -NRa-CO-ORb, -NRa-CO-NRaRb, -SO-Rc, -S0 2 -Rc, -0-S0 2 -Rc, -S0 2 -NRaRb, -NRa-S0 2 -Ra, -CO-NRa-CORb, -CO-NRa-S0 2 -Rb,
  • Ar and Ar' each independently represent an aromatic ring or hetero aromatic ring which may have a substituent
  • Ra and Rb each independently represent a hydrogen atom, an alkyl group, an aromatic ring, or a hetero aromatic ring, which may have a substituent
  • Rc represents an alkyl group, an aromatic ring, or a hetero aromatic ring, which may have a substituent
  • the oxime compound is more preferably the compound represented by the following formula (OX-2), from the viewpoints of sensitivity, stability over time, and coloration during post-heating.
  • R and X each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group
  • n represents an integer of 1 to 5.
  • R is preferably an acyl group thereby achieving high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferred.
  • the A is preferably an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group), an.
  • an alkyl group for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group
  • alkylene group substituted with an alkenyl group for example, a vinyl group or an allyl group
  • an alkylene group substituted with an aryl group for example, a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, or a styryl group
  • the Ar is preferably a substituted or unsubstituted phenyl group, thereby increasing the sensitivity and preventing coloration by heating over time.
  • the Ar is a substituted phenyl group
  • preferred examples of the substituent include halogen groups such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, an arylthioxy group which may have a substituent, or an amino group which may have a substituent, thereby improving the solvent solubility and absorption efficiency in the longer wavelength region.
  • n in the formula (OX-2) is preferably an integer of 1 to 2.
  • the blue curable composition of the invention may contain, in addition to the oxime polymerization initiator, other known photopolymerization initiator described in, for example, JP-A No. 2004-295116, paragraphs [0070] to [0077], and [0079], and the like.
  • the photopolymerization initiator may be used alone or in combination of two or more thereof.
  • the content of the photopolymerization initiator in the total solid content of the blue curable composition is preferably from 3% to 20% by mass, more preferably from 4% to 19% by mass, and particularly preferably from 5% to 18% by mass, thereby more effectively achieving the effect of the invention.
  • the blue curable composition of the invention may contain a dye.
  • the dye is not particularly limited, and may be selected from known dyes used for conventional color filters. Examples of the dye include those disclosed in JP-ANos.
  • Examples of the chemical structure of the dye include pyrazole azo, anilino azo,
  • triphenylmethane anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, and pyrrolopyrazole azo methine dyes.
  • dipyrromethene metal complex compounds obtained from the compound represented by the following formula (I) and a metal atom or metal compound, or tautomers thereof (hereinafter appropriately referred to as "specific complex") are preferred, because their absorption wavelengths are close to that of a dioxazine pigment.
  • R 1 to R 7 each independently represent a hydrogen atom or a monovalent substituent.
  • substituents represented by R 1 to R 7 may be the monovalent groups listed below (the monovalent groups listed below may be generically referred to as "substituent R").
  • halogen atoms for example, a fluorine atom, a chlorine atom, and a bromine atom
  • alkyl groups linear, branched, and cyclic alkyl groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1-norbornyl group, and a
  • alkenyl groups alkenyl groups having preferably 2 to 48, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, and a 3-butene-l-yl group
  • aryl groups aryl groups having preferably 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenyl group and a naphthyl group
  • heterocyclic groups heterocyclic groups having preferably 1 to 32, more preferably 1 to 18 carbon atoms, such as a 2-thienyl group, 4-pyridyl group, a 2-furil group, a 2-pyrimidinyl group, a 1-pyridyl group,
  • silyl groups silyl groups having preferably 3 to 38, more preferably 3 to 18 carbon atoms, such as a trimethylsilyl group, a triethyl silyl group, a tributyl silyl group, a
  • t-butyldimethylsilyl group and a t-hexyl dimethylsilyl group
  • hydroxyl groups cyano groups, nitro groups
  • alkoxy groups alkoxy groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, and a cycloalkyloxy group such as a cyclopentyloxy group, a cyclohexyloxy group), aryloxy groups (aryloxy groups having preferably 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenoxy group and a
  • heterocyclicoxy groups heterocyclicoxy groups having preferably 1 to 32, more preferably 1 to 18 carbon atoms, such as a 1 -phenyl tetrazole-5-oxy group, a
  • silyloxy group silyloxy group (silyloxy groups having preferably 1 to 32, more preferably 1 to 18 carbon atoms, such as a trimethylsilyloxy group, a
  • acyloxy groups (acyloxy groups having preferably 2 to 48, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, dodecanoyloxy group), alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having preferably 2 to 48, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a
  • cycloalkyloxycarbonyloxy group such as a cyclohexyloxycarbonyloxy group
  • aryloxycarbonyloxy groups (aryloxycarbonyloxy groups having preferably 7 to 32, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group), carbamoyloxy groups (carbamoyloxy groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as an ⁇ , ⁇ -dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, an
  • N-phenylcarbamoyloxy group and an N-ethyl-N-phenyl carbamoyloxy group
  • sulfamoyloxy groups (sulfamoyloxy groups having preferably 1 to 32, more preferably 1 to 24 carbon atoms, such as an N,N-diethylsulfamoyloxy group and an N-propylsulfamoyloxy group),
  • alkylsulfonyloxy groups alkylsulfonyloxy groups (alkylsulfonyloxy groups having preferably 1 to 38, more preferably 1 to 24 carbon atoms , such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, and a cyclohexylsulfonyloxy group),
  • arylsulfonyloxy groups (arylsulfonyloxy groups having preferably 6 to 32, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), acyl groups (acyl groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, and a cyclohexanoyl group), alkoxycarbonyl groups (alkoxycarbonyl groups having preferably 2 to 48, more preferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, an
  • aryloxycarbonyl groups an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl groups
  • aryloxycarbonyl groups having preferably 7 to 32, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group carbamoyl groups (carbamoyl groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, an
  • N,N-diethylcarbamoyl group an N-ethyl-N-octylcarbamoyl group, an N,N-dibutylcarbamoyl group, an N-propyl carbamoyl group, an N-phenylcarbamoyl group, an
  • N,N-dimethylureide group and an N-phenyl ureide group
  • imide groups imide groups having preferably 36 or less, more preferably 24 or less carbon atoms, such as an
  • alkoxycarbonylamino groups alkoxycarbonylamino groups having preferably 2 to 48, more preferably 2 to 24 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a
  • aryloxycarbonylamino groups aryloxycarbonylamino groups having preferably 7 to 32, more preferably 7 to 24 carbon atoms, such as a
  • sulfonamide groups sulfonamide groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methane sulfonamide group, a butane sulfonamide group, a benzene sulfonamide group, a hexadecane sulfonamide group, and a cyclohexane sulfonamide group
  • sulfamoylamino groups sulfamoylamino groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms , such as an
  • azo groups (azo groups having preferably 1 to 32, more preferably 1 to 24 carbon atoms, such as a phenylazo group and a 3-pyrazolyl azo group),
  • alkylthio groups alkylthio groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group
  • arylthio groups arylthio groups having preferably 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenylthio group
  • heterocyclic thio groups alkylthio groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group
  • arylthio groups arylthio groups having preferably 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenylthio group
  • heterocyclic thio groups alkylthio groups having
  • heterocyclic thio groups having preferably 1 to 32, more preferably 1 to 18 carbon atoms such as a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group
  • alkylsulfinyl groups alkylsulfinyl groups having preferably 1 to 32, more preferably 1 to 24 carbon atoms, such as a dodecanesulfinyl group
  • arylsulfinyl groups arylsulfinyl groups having preferably 6 to 32, more preferably 6 to 24 carbon atoms, such as a phenylsulfinyl group
  • alkylsulfonyl groups alkylsulfonyl groups having preferably 1 to 48, more preferably 1 to 24 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a
  • propylsulfonyl group a butylsulfonyl group, an isopropylsulfonyl group, a
  • arylsulfonyl groups arylsulfonyl groups having preferably 6 to 48, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyl group and a
  • sulfamoyl groups (sulfamoyl groups having preferably 32 or less, more preferably 24 or less carbon atoms, such as a sulfamoyl group, an
  • R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , and R 5 and R 6 may be each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.
  • the ring to be formed may be a saturated or unsaturated ring.
  • Examples of the 5-membered, 6-membered, or 7-membered saturated or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, and pyridazine ring.
  • a benzene ring and a pyridine ring are preferred.
  • the 5-membered, 6-membered, or 7-membered ring is a group which may be further substituted, it may be substituted with any of the above-described substituent R, and when substituted with two or more substituents, these substituents may be identical or different.
  • the R 1 and R 7 are each preferably, among the above-described groups, an alkylamino group, an arylamino group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, or a sulfonamide group, more preferably a carbonamide group, an ureide group, an alkoxycarbonylamino group, or a sulfonamide group, even more preferably a carbonamide group, an ureide group, an alkoxycarbonylamino group, or a sulfonamide group, and particularly preferably a carbonamide group or an ureide groups.
  • the R 2 and R 5 are each preferably, among the above-described groups, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an
  • alkylsulfonyl group an arylsulfonyl group, a nitrile group, an imide group, or a
  • carbamoylsulfonyl group more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group, even more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group, and particularly preferably an alkoxycarbonyl group, an aryloxycarbonyl groups, or a carbamoyl group.
  • the R 3 and R 4 are each preferably, among the above-described groups, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group.
  • the alkyl group is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a benzyl group, and more preferably a branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, such as an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, a cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms,
  • the aryl groups are each preferably a substituted or unsubstituted phenyl group or a substituted or
  • unsubstituted naphthyl group and more preferably a substituted or unsubstituted phenyl group.
  • the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted
  • 4-pyridyl group a substituted or unsubstituted 3-pyridyl group, a substituted or unsubstituted 2-pyridyl group, a substituted or unsubstituted 2-furil group, a substituted or unsubstituted 2-pyrimidinyl group, a substituted or unsubstituted 2-benzothiazolyl group, a substituted or unsubstituted 1-imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group, a substituted or unsubstituted benzotriazole-l-yl group, and more preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 2-furil group, a substituted or unsubstituted 2-pyrimidinyl group, or a
  • the metal or metal compound used herein may be any metal atom or metal compound as long as it forms a complex, and may be a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.
  • Examples thereof include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, metal chlorides such as AlCl, InCl, FeCl, TiCl 2 , SnCl 2 , SiCl 2 , and GeCl 2 , metal oxides such as TiO and VO, and metal hydroxides such as Si(OH) 2 .
  • R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a heterocyclic amino group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an
  • R and R each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfamoyl group; R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an ary
  • R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, a heterocyclic amino group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R and R each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an an alkoxycarbonyl group, an phosphinoyla
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R 7 represents a hydrogen atom, a halogen atom, an alkyl group,
  • R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carbonamide group, an ureide group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; R and R each independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an
  • R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group
  • R 7 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group
  • the metal atom or metal compound represents Zn, Cu, Co, or VO.
  • R 3 and R 4 are each preferably a phenyl group, thereby achieving good robustness.
  • the reason for this may be as follows: (1) when R and R 4 are each a phenyl group, the spectrum of the compound shifts toward the long wavelength region, and overlap thereof with the spectrum of the phthalocyanine pigment used in combination (near 550 nm) increases, and thus energy transfer readily occurs; and (2) the presence of sterically-bulky substituents improves the robustness of the compound.
  • R and/or R is preferably a 2,6-di-tert-butyl-4-methylcyclohexyl oxycarbonyl group, thereby achieving good solvent solubility.
  • the specific complex in the invention is the compound represented by the following formula (II- 1).
  • R 1 to R 6 each independently represent a hydrogen atom or a substituent;
  • R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;
  • Ma represents a metal atom or a metal compound,
  • X represents a group necessary for neutralizing the charge of Ma;
  • X 1 represents a group capable of being bonded to Ma.
  • the X 1 and X 2 may be bonded to each other to form a 5-membered,
  • R 1 to R 6 in the formula (II- 1) have the same definitions as R 1 to R 6 in the formula (I), and preferred embodiments thereof are the same.
  • the Ma in the formula (II- 1) represents a metal atom or metal compound, which has the same definition as the above-described metal atom or metal compound for composing the specific complex, and the preferred ranges thereof are the same.
  • R 7 in the formula (II- 1) has the same definition as R 7 in the formula (I), and preferred examples thereof are the same.
  • the X 1 in the formula (II- 1) may be any group capable of being bonded to Ma, and examples thereof include water, alcohols (for example, methanol, ethanol, and propanol), and the groups derived from the compounds described in "Metal Chelate” [1], written by Takeichi Sakaguchi and Keihei Ueno (1995, Nankodo Co., Ltd.), [2] (1996), [3] (1997).
  • Methodal Chelate [1] written by Takeichi Sakaguchi and Keihei Ueno (1995, Nankodo Co., Ltd.)
  • water, carboxylic acid compounds, and alcohols are preferred, and water and carboxylic acid compounds are more preferred.
  • the X 2 in the formula (II- 1) represents a group necessary for neutralizing the charge of Ma, and examples thereof include a halogen atom, a hydroxyl group, a carboxylate group, a phosphate group, a sulfonate group. Among them, from the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylate group, a sulfonate group are preferred, and a hydroxyl group and a carboxylate group are more preferred.
  • the 5-membered, 6-membered, or 7-membered ring together with Ma may be a saturated or unsaturated ring.
  • the 5-membered, 6-membered, and 7-membered ring may be consisted of carbon atoms and hydrogen atoms, or a heterocycle containing at least one atom selected from nitrogen, oxygen, and sulfur atoms.
  • the specific complex in the invention is the compound represented by the following formula ( ⁇ -2).
  • R 1 to R 6 and R 8 to R 13 each independently represent a hydrogen atom or a substituent
  • R 7 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group
  • Ma represents a metal atom or a metal compound.
  • R 1 to R 6 in the formula (II-2) have the same definitions as R 1 to R 6 in the formula (I), and preferred embodiments thereof are the same.
  • the substituents represented by R 8 to R 13 have the same definitions as the substituents represented by R 1 to R 6 in the compound represented by the formula (I), and preferred examples thereof are the same.
  • the substituents represented by R 8 to R 13 in the compound represented by the formula ( ⁇ -2) may be further substituted, they may be substituted with any of the above-described substituents R, and when substituted with two or more substituents, these substituents may be identical or different.
  • R in the formula ( ⁇ -2) has the same definition as R in the formula (I), and preferred examples thereof are the same.
  • R 14 in the formula ( ⁇ -2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the preferred range of the R 14 is the same as the preferred range of R 7 .
  • R 14 may be further substituted, it may be substituted with any of the above-described substituents R, and when substituted with two or more substituents, these substituents may be identical or different.
  • the Ma in the formula ( ⁇ -2) represents a metal or a metal compound, which has the same definition as the metal atom or metal compound for composing the above-described specific complex, and the preferred ranges thereof are the same.
  • R 8 and R 9 , R 9 and R 10 , R 11 and R 12 , and R 12 and R 13 in the formula (II-2) may be each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring or an unsaturated ring.
  • the saturated or unsaturated ring to be formed has the same definition as the saturated or unsaturated ring formed by R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , or R 5 and R 6 , and preferable examples thereof are the same.
  • the specific complex in the invention is the compound represented by the formula (III).
  • R 2 to R 5 each independently represent a hydrogen atom or a substituent.
  • R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • Ma represents a metal atom or a metal compound
  • X 3 represents NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom
  • X 4 represents NRa (wherein Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or an or sulfur atom
  • Y 1 represents NRc (wherein Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfon
  • X 5 represents a group capable of being bonded to Ma, and a represents 0, 1, or 2. When a represents 2, the X 5 s may be identical or different groups.
  • R 2 to R 5 and R 7 in the formula (III) have the same definitions as R 2 to R 5 and R 7 in the formula (I), and preferred embodiments thereof are the same.
  • Ma in the formula (III) represents a metal or metal compound, which has the same definition as the above-described metal atom or metal compound for composing the specific complex, and the preferred ranges thereof are the same.
  • R and R each independently represent an alkyl group (a linear, branched, or cyclic alkyl group having preferably 1 to 36 , more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or a 1 -adamantyl group), an alkenyl group (an alkenyl group having preferably 2 to 24, more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group, or a 3-butene-l-yl group), an aryl group (an aryl group (an aryl group (an
  • alkoxy group an alkoxy group having preferably 1 to 36, more preferably 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxy group, a
  • 2-ethylhexylamino group an isopropylamino group, a t-butylamino group, a t-octylamino group, a cyclohexylamino group, an ⁇ , ⁇ -diethylamino group, an ⁇ , ⁇ -dipropylamino group, an ⁇ , ⁇ -dibutylamino group, or an N-methyl-N-ethylamino group), an arylamino group (an arylamino group having preferably 6 to 36, more preferably 6 to 18 carbon atoms, such as a phenylamino group, a naphthylamino group, an ⁇ , ⁇ -diphenylamino group, an N-ethyl-N-phenylamino group), or a heterocyclic amino group (a heterocyclic amino group having preferably 1 to 24, more preferably 1 to 12 carbon atoms, such as a 2-aminopyrrole group,
  • R 8 and R 9 when the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, and heterocyclic amino group represented by R 8 and R 9 may be further substituted, they may be substituted with any of the above-described substituents R, and when substituted with two or more substituents, these substituents may be identical or different.
  • X 3 represents NR, a nitrogen atom, an oxygen atom, or a sulfur atom
  • X 4 represents NRa, an oxygen atom, or a sulfur atom
  • R and Ra each independently represent a hydrogen atom, an alkyl group (a linear, branched, or cyclic alkyl group having preferably 1 to 36, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or an 1-adamantyl group), an alkenyl group (an alkenyl group having preferably 2 to 24, more
  • 1-pyridyl group a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, or a benzotriazole-l-yl group
  • an acyl group an acyl group having preferably 1 to 24, more preferably 2 to 18 carbon atoms, such as an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, or a cyclohexanoyl group
  • an alkylsulfonyl group an alkylsulfonyl group having preferably 1 to 24, more preferably 1 to 18 carbon atoms, such as a
  • arylsulfonyl group an arylsulfonyl group having preferably 6 to 24, more preferably 6 to 18 carbon atoms, such as a phenylsulfonyl group or a
  • alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group represented by R and Ra may be further substituted with any of the above-described substituents R, and when substituted with plural substituents, these substituents may be identical or different.
  • Y 1 represents NRc, a nitrogen atom, or a carbon atom
  • Y 2 represents a nitrogen atom or a carbon atom
  • Rc has the same definition as R in the above-described X .
  • R 8 and Y 1 may be bonded to each other to form a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, or benzothiophene), a 6-membered ring (for example, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, or quinazoline), or 7-membered ring (for example, cycloheptane, or hexamethyleneimine), together with R 8 , Y 1 , and a carbon atom.
  • a 5-membered ring for example, cyclopen
  • R and Y may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, together with R , Y , and a carbon atom.
  • 5-membered, 6-membered, and 7-membered ring to be formed may be the above-described ring formed by R 8 and Y 1 and a carbon atom wherein one single bond is replaced with a double bond.
  • X 5 represents a group capable of being bonded to Ma, and may be the same group as the group represented by X 1 in the formula (II- 1).
  • the a represents 0, 1, or 2.
  • the X 5 s may be identical or different groups.
  • R 2 to R 5 , R 7 and Ma each represent those listed in the preferred embodiments for the complex containing the compound represented by the formula (I) and a metal atom or metal compound
  • X 3 represents NR (wherein R represents a hydrogen atom or an alkyl group), a nitrogen atom, or an oxygen atom
  • X 4 represents NRa (wherein Ra represents a hydrogen atom, an alkyl group, or a heterocyclic group), or an oxygen atom
  • Y 1 represents NRc (wherein Rc represents a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom, Y represents a nitrogen atom or a carbon atom
  • X represents a group linking through an oxygen atom
  • R and R each independently represents an alkyl group, an
  • R and Y are bonded to each other to form a 5-membered or 6-membered ring, and R and Y are bonded to each other to form a 5-membered or 6-membered ring, and a represents 0 or 1.
  • R 2 to R 5 , R 7 and Ma each represent those listed in the preferred embodiments for the complex containing the compound represented by the formula (I) and a metal atom or metal compound
  • X 3 and X 4 represent oxygen atoms
  • Y 1 represents NH
  • Y 2 represents a nitrogen atom
  • X 5 represents a group linking through an oxygen atom
  • R 8 and R 9 each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R 8 and Y 1 are bonded to each other to form a 5-membered or 6-membered ring, and R and Y are bonded to each other to form a 5-membered or 6-membered ring, and a represents 0 or 1.
  • the molar extinction coefficient of the specific complex in the invention is preferably as high as possible, from the viewpoint of the film thickness.
  • the maximal absorption wavelength Xmax is preferably from 520 nm to 580 nm, and more preferably from 530 nm to 570 nm, thereby improving the color purity.
  • the maximal absorption wavelength and molar extinction coefficient are measured by a spectrophotometer UV-2400PC (trade name, manufactured by Shimadzu Corporation).
  • the melting point of the specific complex in the invention is preferably not so high, from the viewpoint of solubility.
  • the specific complex in the invention may be synthesized by the method described in, for example, U.S. Patent Nos. 4,774,339, 5,433,896, JP-A Nos. 2001-240761,
  • the method for synthesizing the specific complex in the invention may follow the method described in JP-A No. 2008-292970, paragraphs [0131] to [0157].
  • the specific complex in the invention preferably contains at least a carboxylate or metal carboxylate in its skeleton.
  • the compound is further described below.
  • the specific complex in the invention is preferably the complex A wherein R 1 to R 6 in the compound represented by the formula (I) are substituted with at least the
  • the substituent a represents a group having an ethylenically unsaturated bond at the terminal, and more preferably a group having an acryloyl group or a methacryloyl group at the terminal.
  • the substituent b represents a group having a -C0 2 M group at the terminal, wherein M represents a hydrogen atom, an organic base or a metal atom necessary for neutralizing the charge of -C0 2 .
  • M represents a hydrogen atom, an organic base or a metal atom necessary for neutralizing the charge of -C0 2 .
  • M is absent.
  • the specific complex in the invention is also preferably the complex B wherein R 2 to R 5 , R 8 , R 9 in the compound represented by the formula (III) are substituted with at least the substituent a (preferably the substituents a and b).
  • the dye in the invention may be a dye polymer obtained by polymerizing the complex A or B, or a dye polymer obtained by copolymerizing the complex A or B with other monomer component (for example, acrylic acid, or methacrylic acid, and the like).
  • the complex B is preferably the compound represented by the following formula (II).
  • R 2 to R 5 each independently represent a hydrogen atom or a monovalent substituent
  • R 7 represents a hydrogen atom or a monovalent substituent (such as a halogen atom, an alkyl group, an aryl group or a heterocyclic group)
  • R 10 and R 11 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, but (p+q) of R 2 to R 5 , R 10 , and R 11 are each converted to a divalent linking group
  • X 1 represents a group necessary for neutralizing a charge of Ma, and r represents 0, 1 or 2
  • X 3 and X 4 each independently represent NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom
  • Y and Y each independently represent NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom, R 10
  • the compound represented by the formula (II) has a polymerizable group and a carboxyl group in one molecule.
  • the presence of the polymerizable group in the compound represented by the formula (II) prevents color migration when the compound is used in a colored cured film, and the presence of the carboxyl group improves the pattern formation properties.
  • the compound represented by the formula (II) may be a tautomer.
  • R 2 to R 5 have the same definitions as R 2 to R 5 in the formula (I), respectively, and the preferred ranges thereof are the same.
  • R 7 has the same definition as R 7 in the formula (I), and the preferred ranges thereof are the same.
  • R 10 and R 11 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group.
  • the R 10 and R 11 are each preferably an alkyl group, an alkenyl group, an aryl group, an heterocyclic group, an alkoxy group, an aryloxy group, or a heterocyclic amino group, and more preferably an alkyl group, an alkenyl group, an alkoxy group, or an aryloxy group.
  • the site to which L 1 is bonded is more preferably at least one of R 3 , R 4 , R 10 and R 11 , and even more preferably at least one of R 10 and R 11 , from the viewpoint of synthesis suitability.
  • the site to which L 2 is bonded is more preferably at least one of R 3 , R 4 , R 10 and R n , and even more preferably at least one of R 10 and R 11 , from the viewpoint of synthesis suitability.
  • Ma, X 1 , and r have the same definitions as Ma, X 5 , and a in the formula (III), respectively, and the preferred ranges thereof are the same.
  • M represents a hydrogen atom, an organic base or a metal atom necessary for neutralizing the charge of -C0 2 " .
  • M is absent.
  • M is more preferably a hydrogen atom or a simple anion (that is, C0 2 M represents C0 2 " ).
  • L 1 represents a single bond or a linking group having a valence of (m+1).
  • L 1 is more preferably any one of the following linking groups.
  • * represents the site linked to -COOM
  • ** represents the site linked to the dipyrromethene skeleton directly or through any of R 2 to R 5 , R 10 , and R 11 .
  • m represents 1, 2, or 3, preferably 1 or 2, and more preferably 2.
  • p represents 1 or 2, and more preferably 1.
  • R 8 represents a hydrogen atom or a methyl group.
  • Q represents an oxygen atom or NR 9 (wherein R 9 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group).
  • L 2 represents single bond or a linking group having a valence of (n+1).
  • Examples of the linking group having a valence of (n+1) represented by L 2 include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkylthioether groups having 1 to 10 carbon atoms, arylthio ether groups having 6 to 12 carbon atoms, alkyl ether groups having 1 to 10 carbon atoms, aryl ether groups having 6 to 12 carbon atoms, alkyl amino groups having 1 to 10 carbon atoms, aryl amino groups having 6 to 12 carbon atoms, alkyl amide groups having 1 to 10 carbon atoms, aryl amide groups having 6 to 12 carbon atoms, alkyl carbamoyl groups having 1 to 10 carbon atoms, aryl carbamoyl groups having 6 to 12 carbon atoms , alkyl sulfonamide groups having 1 to 10 carbon atoms , aryl sulfonamide groups having 6 to 12 carbon atoms, alkyl sulfamoy
  • L 2 is more preferably any one of the following linking groups.
  • * represents the site linked to -Q
  • ** represents the site linked to the dipyrromethene skeleton directly or through any of R 2 to R 5 , R 10 , and R 1 1 .
  • n 1, 2, or 3, preferably 2or 3, and more preferably 2.
  • q represents 1 or 2, and preferably 1.
  • the plural ⁇ (L')-(C0 2 M) m ⁇ s may be identical or different.
  • the plural (C0 2 M)s may be identical or different.
  • the group represented by -(L')-(C0 2 M) m is preferably any of the following substituents.
  • ** represents the site linked to the dipyrromethene skeleton directly or through any of R 2 to R 5 , R 10 , and R 11 .
  • ** represents the site linked to the dipyrromethene skeleton directly or through any of R 2 to R 5 , R 10 , and R 11 .
  • X 3 and X 4 each independently represents NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom.
  • the X 3 and X 4 are each preferably NR (wherein R represents a hydrogen atom, an alkyl group, or an alkenyl group), a nitrogen atom, an oxygen atom, or a sulfur atom, and more preferably NR (wherein R represents a hydrogen atom), a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Y and Y each independently represent NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom.
  • the Y and Y are each preferably NR (wherein R represents a hydrogen atom, an alkyl group, or an alkenyl group) or an oxygen atom, and more preferably NR (wherein R represents a hydrogen atom) or an oxygen atom.
  • R 10 and Y 1 may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, R and Y may be bonded to each other to form a
  • 6-membered or 7-membered rings include the above-described rings.
  • the exemplary compounds a-5 to a-8, a- 13 to a-48, b-5 to b-8, b-13 to b-48, c-5 to c-8, and c-13 to c-48 are preferred, and b-5 to b-8, b-13 to b-48, c-5 to c-8, c-13 to c-48, d-1 , d-2, and d-3 are more preferred.
  • colorant compounds may be easily synthesized by the method described in, for example, JP-ANo. 2008-292970. Alternatively, they may be synthesized in the same manner as the below-described synthesis examples using appropriate starting materials.
  • the total concentration of the compound represented by the formula (II) in the blue curable composition is preferably from 0.5% to 80% by mass, more preferably from 0.5% to 70%» by mass, and particularly preferably from 1 % to 70%» by mass with respect to the total solid content of the composition, though the preferred value varies according to the molecular weight and molar extinction coefficient.
  • the dye in the invention has been described above, concentrating on the specific complexes (for example, the compounds represented by the formula (II- 1), ( ⁇ -2), (III), and (II)), but the dye in the invention will not be limited to these specific complexes.
  • the content of the dye in the blue curable composition is preferably from 5% to 40%» by mass, more preferably from 10% to 30%» by mass, and particularly preferably from 15%» to 25%» by mass with respect to the total solid content of the blue curable composition, from the viewpoint of the hue control.
  • the mass ratio between the phthalocyanine pigment and the dye [dye/phthalocyanine pigment] is preferably from 0.1 to 5.0, more preferably from 0.5 to 3.0, and particularly preferably from 0.7 to 1.5.
  • the blue curable composition of the invention may contain a dioxazine pigment.
  • the blue curable composition contains a dioxazine pigment in addition to the copper phthalocyanine pigment and dye, the blue curable film made from the composition has improved light resistance.
  • dioxazine pigment examples include C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 32, and C.I. Pigment Violet 37. Among them, C.I. Pigment Violet 23 is preferred.
  • the content of the dioxazine pigment in the blue curable composition is preferably from 0.1% to 40%» by mass, more preferably from 0.1 % to 20% by mass, and particularly preferably from 0.3% to 10% by mass with respect to the total solid content of the blue curable composition.
  • the mass ratio between the dioxazine pigment and the dye [dioxazine pigment/dye] is preferably from 0.01 to 2.00, more preferably from 0.05 to 1.50, and particularly preferably from 0.35 to 0.80.
  • the above-described copper phthalocyanine pigment, dioxazine pigment and dye may be used in combination with a colorant having another structure.
  • the colorant having another structure is not particularly limited, and may be selected from known colorants used in color filters. Examples of the colorant include those described in JP-A Nos. 2002-14220, 2002-14221, 2002-14222,
  • Examples of the chemical structure of the colorant include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azo methine, xanthene, phthalocyanine, benzopyran, and indigo dyes.
  • the total content of the copper phthalocyanine pigment, dioxazine pigment, and dye is preferably from 80% to 100% by mass, and more preferably from 90% to 100% by mass, with respect to all the coloring components (including the pigment and dye).
  • the blue curable composition of the invention contains a polymerizable compound.
  • the polymerizable compound examples include an addition polymerizable compound having at least one ethylenically unsaturated double bond.
  • the compound is selected from the compounds having at least one, preferably two or more terminal ethylenically unsaturated bond(s).
  • Such compounds are widely known in the relevant industrial fields, and may be freely used in the invention.
  • Their chemical form may be, for example, monomer, prepolymer, more specifically dimer, trimer, or oligomer, a mixture thereof, or a (co)polymer thereof.
  • the polymerizable compound in the invention may be used alone or in combination of two or more thereof.
  • Examples of the monomers and (co)polymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), and esters, amides and (co)polymers thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters, amides and (co)polymers thereof are preferred.
  • Other preferred examples include addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation products with monofunctional or polyfunctional carboxylic acids.
  • Yet other preferred examples include addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogen group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols.
  • compounds prepared from unsaturated phosphonic acid, styrene, or vinyl ether in place of the above-described unsaturated carboxylic acids may be used.
  • the polymerizable compound is preferably a compound having an ethylenically unsaturated group and a boiling point of 100°C or higher under normal pressure.
  • Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl
  • (meth)acrylate polyfunctional acrylates and methacrylates such as polyethylene glycol di(meth)acrylate, trimethylolethane tri (meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl) isocyanurate,
  • radical polymerizable monomers represented by the following formulae (MO-1) to (MO-5) are also preferred.
  • T represents an oxyalkylene group
  • the terminal at the side of the carbon atom is linked to R.
  • n 0 to 14
  • m 1 to 8.
  • the plural Rs and Ts contained in one molecule may be identical or different.
  • radical polymerizable monomers represented by the formulae (MO-1) to (MO-5) the compounds described in JP-A No. 2007-269779, paragraphs [0248] to [0251] are preferred in the invention.
  • the content of the above-described polymerizable compound in the blue curable composition is preferably from 5% to 90% by mass, more preferably from 10% to 80% by mass, and particularly preferably from 15% to 50% by mass, with respect to the solid content of the composition.
  • the content is within this range, sufficient curability and dissolution behavior of the unexposed areas are achieved, sufficient curability of the exposed areas is maintained, and marked deterioration of the dissolution behavior of the unexposed areas is prevented.
  • the blue curable composition of the invention contains a solvent.
  • the solvent is not particularly limited as long as it sufficiently dissolves the components and gives sufficient application properties to the blue curable composition. It is particularly preferred that the solvent be selected in consideration of the solubility of the binder, application properties, and safety.
  • Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxyacetic acid alkyl esters (for example, oxyacetic acid methyl ester, oxyacetic acid ethyl ester, oxyacetic acid butyl ester (specific examples include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate)), 3-oxypropionic acid alkyl esters (for example, methyl-3-oxypropionate and ethyl 3-oxypropanoate, (specific
  • 2-oxypropionnate ethyl 2-oxypropionnate
  • propyl 2-oxypropionate specific examples include methyl 2-methoxypropionate, ethyl 2-methoxypropanoate, propyl
  • ethers include diethyleneglycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone,
  • aromatic hydrocarbons include toluene and xylene.
  • the solvent is particularly preferably a mixed solution composed of two or more selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethyleneglycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the content of the solvent in the blue curable composition is preferably an amount which gives a total solid content of 10% to 80% by mass, and more preferably 15% to 60% by mass in the composition.
  • the blue curable composition of the invention preferably contains a dispersant.
  • the dispersant may be selected from known pigment dispersants and surfactants.
  • phthalocyanine derivatives (trade name: EFKA-745, manufactured by EFKA), SOLSPERSE 5000 (trade name, manufactured by The Lubrizol Corporation); cationic surfactants such as organosiloxane polymers (trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymers (trade name: POLYFLOW No. 75, No. 90, and No.
  • nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether,
  • polyoxyethylene nonyl phenyl ether polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester
  • anionic surfactants such as W004, W005, and W017 (trade names, manufactured by Yusho Co., Ltd.); polymeric dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (trade names, manufactured by Morishita & Co., Ltd.),
  • DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, and DISPERSE AID 9100 (trade names, manufactured by San Nopco Limited); various SOLSPERSE dispersants such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (trade names, manufactured by The Lubrizol Corporation); ADEKA PLURONIC L31 , F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (trade names, manufactured by ADEKA), and ISONET S-20 (trade name, manufactured by Sanyo Chemical Industries, Ltd.).
  • the content of the dispersant in the blue curable composition is preferably from 1% to 80% by mass, more preferably from 5% to 70% by mass, and most preferably from 10% to 60% by mass with respect to the content of the pigment.
  • the blue curable composition of the invention may contain a pigment derivative.
  • the pigment derivative in the invention is, as will be described later, a compound prepared by introducing an acidic group, a basic group, or an aromatic group as a substituent to the side chain of an organic pigment.
  • the pigment derivative having a site with affinity for the dispersant is adsorbed on the surface of the pigment, and used as the adsorption point for the dispersant, thereby enabling dispersing of fine particles of the pigment in the colored composition, and preventing reaggregation of the particles.
  • the pigment derivative modifies the surface of the pigment to promote the adsorption of the dispersant.
  • the use of a basic pigment derivative having a basic group as the pigment derivative further improves the dispersibility of the pigment, and allows effective dispersion of the fine particles of the pigment.
  • the use of the colored composition containing a basic pigment derivative allows the formation of a color filter with less color density unevenness and better color properties.
  • the pigment derivative in the invention is specifically a compound prepared by introducing an acidic group, a basic group, or an aromatic group as a substituent to the side chain of the organic pigment as the main skeleton.
  • the organic pigment as the main skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments.
  • Other examples of the main skeleton include pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline, which are not commonly called dye.
  • Examples of the pigment derivative in the invention include those described in JP-A Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, 11-199796, 2005-234478, 2003-240938, and 2001-356210.
  • the content of the pigment derivative with respect to the content of the pigment is preferably from 1% to 80% by mass, more preferably from 3% to 65% by mass, and particularly preferably from 5% to 50% by mass.
  • the content is within this range, the pigment is favorably dispersed with the viscosity kept low, and dispersion stability after dispersion is improved.
  • a color filter produced using the colored composition has a high transmittance, good color properties, and a high contrast.
  • the blue curable composition of the invention may contain, in addition to the above-described components, other components such as a resin and a crosslinking agent without impairing the effect of the invention.
  • Resin - Preferred examples of the resin include alkali-soluble binders.
  • the alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected in consideration of heat resistance, developability, and availability.
  • the alkali-soluble binder is preferably a linear organic high molecular weight polymer which is soluble in an organic solvent and developable with a weakly alkaline aqueous solution.
  • linear organic high molecular weight polymer include polymers having carboxylic acid in the side chains thereof, such as the methacrylic acid copolymers, acrylate copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers described in JP-A No.
  • alkali-soluble binder in the invention examples include adducts of hydroxyl group-containing polymers with acid anhydrides, polyhydroxystyrene resins, polysiloxane resins, poly(2-hydroxyethyl
  • the linear organic high molecular weight polymer may be a copolymer of hydrophilic monomers. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth)acrylate, morpholine (meth)acrylate, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl
  • hydrophilic monomers include those having a tetrahydrofurfuryl group, a phosphate group, a
  • phosphoester group a quaternary ammonium base, an ethylene-oxy chain, a propylene-oxy chain, a sulfonate group and a group derived from the salt thereof, or a morpholinoethyl group.
  • the alkali-soluble binder may have a polymerizable group in the side chain thereof, thereby improving the crosslinking efficiency.
  • Example of the alkali-soluble binder include the polymers having an allyl group, a (meth)acryl group, or an allyloxyalkyl group in the side chain thereof.
  • Examples of the polymer having a polymerizable group include commercial products such as KS RESIST- 106 (trade name, manufactured by Osaka Organic Chemical Industry Ltd.), and CYCLOMER P series (trade name, manufactured by Daicel Chemical Industries, Ltd.).
  • KS RESIST- 106 trade name, manufactured by Osaka Organic Chemical Industry Ltd.
  • CYCLOMER P series trade name, manufactured by Daicel Chemical Industries, Ltd.
  • alcohol-soluble nylon and a polyether of 2,2-bis-(4-hydroxyphenyl)-propane with epichlorohydrin are useful.
  • the alkali-soluble binder is also preferably the polymer (a) prepared by polymerizing the compound represented by the following formula (E-1) (hereinafter may be referred to as
  • R and R each independently represent a hydrogen atom, or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • the blue curable composition of the invention contains the polymer (a)
  • the cured coating film formed using the composition has improved heat resistance and transparency.
  • the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and example thereof include linear or branched alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a t-amyl group, a stearyl group, a lauryl group, and a 2-ethylhexyl group; aryl groups such as a phenyl group; alicyclic groups such as a cyclohexyl group, a
  • t-butylcyclohexyl group a dicyclopentadienylgroup, a tricyclodecanyl group, an isobornyl group, an adamantyl group, and a 2-methyl-2-adamantyl group; alkoxy-substituted alkyl groups such as a 1 -methoxyethyl group and a 1-ethoxyethyl group; and aryl-substituted alkyl groups such as benzyl group.
  • groups containing a primary or secondary carbon which is resistant to elimination by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, are particularly preferred from the viewpoint of heat resistance.
  • R and R may be identical or different substituents.
  • ether dimer examples include
  • di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propenoate di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.
  • dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate
  • dibenzyl-2,2'-[oxybis(methylene)]bis-2-propenoate are particularly preferred.
  • These ether dimers may be used alone or in combination of two or more thereof.
  • the alkali-soluble binder is also preferably a polymer having an epoxy group.
  • a monomer having an epoxy group (hereinafter may be referred to as "a monomer for introducing an epoxy group”) is polymerized as a monomer component.
  • the monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, and o- (or m- or p-) vinyl benzyl glycidyl ether.
  • the monomer for introducing an epoxy group may be used alone or in combination of two or more thereof.
  • the monomer component for obtaining an alkali-soluble binder contains the monomer for introducing an epoxy group, the content is not particularly limited, but may be from 5 to 70% by mass, and preferably from 10% to 60% by mass with respect to the total monomer component.
  • the alkali-soluble binder is also preferably a polymer having an acid group.
  • the acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more thereof.
  • a monomer having an acid group and/or a monomer which may have an acid group after polymerization (hereinafter may be referred to as "a monomer for introducing an acid group") is polymerized as a monomer component.
  • Examples of the monomer having an acid group include carboxylic monomers such as (meth)acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide, and monomers having a carboxylic anhydride group, such as maleic acid anhydride and itaconic acid anhydride.
  • carboxylic monomers such as (meth)acrylic acid and itaconic acid
  • monomers having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide
  • monomers having a carboxylic anhydride group such as maleic acid anhydride and itaconic acid anhydride.
  • (meth)acrylic acid is particularly preferred.
  • Examples of the monomer which may have an acid group after polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, monomers having an epoxy group such as glycidyl (meth)acrylate, and monomers having an isocyanate group such as 2-isocyanate ethyl (meth)acrylate. These monomers for introducing an acid group may be used alone or in combination of two or more thereof.
  • the treatment for giving an acid group after polymerization may be partial modification of the polar group of the polymer side chain by polymer reaction.
  • polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl/acrylamide copolymer resins are preferred, and from the viewpoint of control of developability, acrylic resins, acrylamide resins, and acryl/acrylamide copolymer resins are preferred.
  • acrylic resins include copolymers composed of monomers selected from benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, and (meth)acrylamide, and commercial products such as KS RESIST- 106 (trade name, manufactured by Osaka Organic Chemical Industry Ltd.), and CYCLOMER P series (trade name, manufactured by Daicel Chemical Industries, Ltd.).
  • the alkali-soluble binder is preferably a polymer having a weight average molecular weight of 1000 to 2 x 10 5 , more preferably from 2000 to 1 x 10 5 , and particularly preferably from 5000 to 5 x 10 4 (in terms of polystyrene as measured by the GPC method), from the viewpoints of developability and liquid viscosity.
  • the acid value of the alkali-soluble binder is preferably from 50 to 300 mgKOH/g, more preferably from 75 to 200 mgKOH/g, and particularly preferably from 80 to 160 mgKOH/g. When the acid value is within this range, fewer development residues are left after pattern formation, and the application of the composition is more uniformly achieved.
  • the blue curable composition of the invention may additionally contain a
  • crosslinking agent thereby more increasing the hardness of the color cured film formed by curing the blue curable composition.
  • the crosslinking agent is not particularly limited as long as it achieves film curing by crosslinking reaction, and examples thereof include (a) epoxy resins, (b) melamine
  • the blue curable composition of the invention is preferably mixed with a small amount of polymerization inhibitor, thereby preventing unnecessary thermal polymerization of the polymerizable compound during production or storage of the blue curable composition.
  • polymerization inhibitor examples include:
  • the content of the polymerization inhibitor is preferably about 0.01% to 5% by mass with respect to the total mass of the composition.
  • the blue curable composition of the invention may contain any surfactant, thereby further improving the application properties.
  • the surfactant include various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • the blue curable composition of the invention contains a fluorine surfactant, it exhibits better liquid properties (in particular, flowability) when prepared into a coating solution, whereby the uniformity of the coating thickness and liquid-saving effect are more improved.
  • the blue curable composition containing a fluorine surfactant when used as a coating liquid for film formation, the interfacial tension between the coated surface and the coating liquid is so low that the coated surface has good wettability, and coatability of the coated surface is improved. Therefore, the blue curable composition is effective at forming a uniform film with less thickness unevenness, even when a thin film having a thickness of several micrometers is formed with a small liquid amount.
  • the fluorine content in the fluorine surfactant is preferably from 3% to 40% by mass, more preferably from 5% to 30% by mass, and particularly preferably from 7% to 25% by mass.
  • the fluorine surfactant is effective at forming a film having uniform thickness and saving the usage of the liquid, and exhibits good solubility in the blue curable composition.
  • fluorine surfactants examples include MEGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (trade names, manufactured by DIC Corporation), FLUORAD FC430, FC431 , FC171 (trade names, manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101 , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (trade names, manufactured by Asahi Glass Co., Ltd.), and SOLSPERSE 20000 (trade name, manufactured by The Lubrizol Corporation).
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol
  • polyoxyethylene lauryl ether polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters (trade name: PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2,
  • cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymer POLYFLOW No. 75, No. 90, No. 95 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (trade name, manufactured by Yusho Co., Ltd.).
  • anionic surfactants include W004, W005, and W017 (trade names, manufactured by Yusho Co., Ltd.).
  • silicone surfactants examples include “TORAY SILICONE DC3PA”, “TORAY SILICONE SH7PA”, “TORAY SILICONE DC 11 PA”, “TORAY SILICONE
  • SILICONE SH30PA "TORAY SILICONE SH8400” (trade names, manufactured by Dow Corning Toray Co., Ltd.), "TSF-4440", “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-4452” (trade names, manufactured by Momentive Performance Materials Inc.), " P341", “KF6001”, “KF6002” (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), "BYK307",
  • BYK323 and “BYK330” (trade names, manufactured by BYK-Chemie).
  • surfactants may be used alone or in combination of two or more thereof.
  • the content of the surfactant is preferably from 0.001% to 2.0% by mass, and more preferably from 0.005% to 1.0% by mass, with respect to the total mass of the blue curable composition.
  • the composition preferably contain an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less.
  • organic carboxylic acid examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethyl malonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemellitic acid, and mesity
  • the blue curable composition may contain various additives such as fillers, polymer compounds other than the above-described ones, tackifiers, antioxidants, ultraviolet absorbers, and aggregation inhibitors.
  • additives include those listed in JP-A No. 2004-295116, paragraphs [0155] to [0156].
  • the blue curable composition of the invention may contain the sensitizers and light stabilizers described in JP-ANo. 2004-295116, in the paragraph [0078], and the heat polymerization inhibitors described in the paragraph [0081].
  • the blue curable composition of the invention is prepared by mixing the above-described essential components and, as necessary, any optional components.
  • the components of the blue curable composition may be mixed at once, or solutions or dispersions of the components may be prepared and mixed.
  • the order of mixing and working conditions are not particularly limited. For example, all the components may be dissolved or dispersed in a solvent at the same time to prepare a composition, or, as necessary, two or more solutions or dispersions of the components may be mixed before use (application) to prepare a composition.
  • the blue curable composition prepared as described above is preferably subjected to filtration using a filter having a pore size of preferably about 0.01 ⁇ to 3.0 ⁇ , and more preferably about 0.05 ⁇ to 0.5 ⁇ , before practical use.
  • the blue curable composition of the invention has no roughness or color unevenness, it is suitable for forming color pixels of color filters used in liquid crystal display devices (LCDs) and solid-state image pickup devices (for example, CCD and CMOS), and for producing printing inks, ink jet inks, and paints.
  • the blue curable composition is suitable for forming color pixels (color filters) for solid-state image pickup devices such as CCD and CMOS.
  • the method for producing a color filter using the blue curable composition of the invention (the method of the invention for producing a color filter) is described below.
  • the method of the invention for producing a color filter includes a process (A) of applying the blue curable composition of the invention to a support thereby forming a blue curable composition layer, and a process (B) of exposing the blue curable composition layer formed in the process (A) to light through a mask, followed by development to form a colored pattern.
  • the method of the invention for producing a color filter further include a process (C) of irradiating the colored pattern formed in the process (B) with ultraviolet light, and a process (D) of heating the colored pattern which has been irradiated with ultraviolet light in the process (C).
  • the blue curable composition of the invention is applied to a support by any coating method such as rotary coating, cast coating, roll apply, or ink jetting, thereby forming a blue curable composition layer, and then, as necessary, the blue curable composition layer is subjected to precuring (prebaking), and dried.
  • any coating method such as rotary coating, cast coating, roll apply, or ink jetting, thereby forming a blue curable composition layer, and then, as necessary, the blue curable composition layer is subjected to precuring (prebaking), and dried.
  • Examples of the support used in the method of the invention for producing a color filter include those used in liquid crystal display devices, such as non-alkali glass, soda glass, borosilicate glass (PYREX (registered trademark) glass), quartz glass, and these supports having a transparent conductive film attached thereto, and those used in solid-state image pickup devices, such as photoelectric transducer substrates (for example, silicon substrates for CCD and CMOS). These substrates may have black stripes for separating pixels. These supports may have thereon, as necessary, an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface.
  • liquid crystal display devices such as non-alkali glass, soda glass, borosilicate glass (PYREX (registered trademark) glass), quartz glass, and these supports having a transparent conductive film attached thereto
  • solid-state image pickup devices such as photoelectric transducer substrates (for example, silicon substrates for CCD and CMOS). These substrates may have black stripes for separating pixels
  • Examples of the method for applying the polymerizable composition of the invention for color filter to a support include various coating methods such as slit coating, ink jetting, rotary coating, cast coating, roll apply, screen printing, or ink jet coating.
  • any appropriate organic solvent may be dropped and rotated, thereby improving conformance of the blue curable composition to the support.
  • the prebaking may be carried out by heating at 70°C to 130°C for about 0.5 to 15 minutes using a hot plate or oven.
  • the thickness of the blue curable composition layer formed with the blue curable composition is selected according to the intended use. In normal cases, the thickness is preferably from 0.2 ⁇ to 5.0 ⁇ , more preferably from 0.3 ⁇ to 2.5 ⁇ , and most preferably from 0.3 ⁇ to 1.5 ⁇ .
  • the thickness of the blue curable composition layer is measured after prebaking.
  • the blue curable composition layer formed on the support is exposed to light through a mask.
  • the light or radiation used for the exposure is preferably g-line, h-line, i-line, KrF light, or ArF light, and particularly preferably i-line.
  • the exposure dose is preferably from 100 mJ/cm to 10000 mJ/cm .
  • exposure light sources include ultrahigh pressure, high pressure, medium pressure, and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet various laser light sources, fluorescent lamps, tungsten lamps, and sunlight.
  • the light source may be an ultraviolet laser.
  • the term laser is formed from the initial letters of Light Amplification by Stimulated Emission of Radiation (amplification of light by induced emission). Crystals, glass, liquids, dyes, and gases are used as oscillators, amplifiers, and exciting media which uses an induced emission phenomenon occurring in a substance with population inversion to produce monochromatic light having higher coherence and directivity by amplification and emission of light waves. These media are used in known lasers having an emission wavelength in the ultraviolet region, such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers. Among them, from the viewpoint of the output and emission wavelength of the laser, solid lasers and gas lasers are preferred.
  • the laser used in the exposure system using the laser light source is preferably an ultraviolet laser having a wavelength of 300 nm to 380 nm, and more preferably an ultraviolet laser having a wavelength of 300 nm to 360 nm, because the wavelength corresponds with the photosensitive wavelength of the resist (blue curable composition).
  • the third-order harmonic (355 nm) of Nd:YAG laser which is a relatively low-cost solid laser having a particularly high output, and excimer lasers such as XeCl (308 nm) and XeF (353 nm) are preferred.
  • the exposure dose for the object to be exposed may be from 1 mJ/cm 2 to 100 mJ/cm 2 , and more preferably from 1 mJ/cm 2 to 50 mJ/cm 2 .
  • the exposure dose within this range is preferred from the viewpoint of productivity of pattern formation.
  • the exposure equipment which may be used in the exposure system using a laser light source is not particularly limited, and examples of commercial products include
  • CALLISTO (trade name, manufactured by V Technology Co., Ltd.), EGIS (trade name, manufactured by V Technology Co., Ltd.), and DF2200G (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.). Other equipment is also preferred.
  • a light emitting diode (LED) and a laser diode (LD) may be used as actinic radiation sources.
  • an ultraviolet light source when an ultraviolet light source is necessary, an ultraviolet LED and an ultraviolet LD may be used.
  • a purple LED having main emission spectrum between 365 nm and 420 nm is available from Nichia Corporation.
  • U.S. Patent No. 6,084,250 discloses a LED which emits actinic radiation centered between 300 nm and 370 nm.
  • Other ultraviolet LEDs are also available, and they emit radiation in different ultraviolet regions.
  • the actinic radiation source in the invention is preferably a UV-LED, and particularly preferably an UV-LED having a peak wavelength at 340 nm to 370 nm.
  • the ultraviolet laser achieves good parallelism, so that it allows pattern exposure without using a mask. However, it is more preferred to use a mask, because pattern exposure using a mask achieves higher linearity of the pattern.
  • the exposed blue curable composition layer may be heated at 70°C to 180°C for about 0.5 minutes to 15 minutes using a hot plate or an oven.
  • the exposure may be carried out in a chamber in a nitrogen flow, thereby preventing oxidation fading of the coloring material in the blue curable composition layer.
  • the blue curable composition layer after exposure is subjected to development using a developing solution. As a result of this, a colored pattern is formed.
  • the developing solution may be any combination of various organic solvents or any aqueous alkaline solution, as long as it dissolves the uncured portion (unexposed areas) of the blue curable composition layer, and will not dissolve the cured portion (exposed areas).
  • the alkali used as the developing solution may be, for example, ammonia water or aqueous alkaline solution of an organic alkaline compound such as ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrrole, piperidine, l,8-diazabicyclo-[5, 4, 0]-7-undecene, diluted with pure water to a concentration of 0.001% to 10% by mass, preferably 0.01% to 1% by mass.
  • an organic alkaline compound such as ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrrole, piperidine, l,8-diazabicyclo-[5, 4, 0]-7-undecene, diluted with pure water to a concentration of
  • the developing solution may be an inorganic alkali solution, and preferred examples of the inorganic alkali include sodium hydrate, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate.
  • the developing solution is an aqueous alkaline solution
  • concentration is preferably adjusted to give a pH value of 11 to 13, and more preferably a pH value of 11.5 to 12.5.
  • an aqueous alkaline solution of tetraethyl ammonium hydroxide adjusted to have a concentration of 0.001% to 10% by mass, preferably from 0.01% to 5% by mass may be used as a developing solution.
  • the development time is preferably from 30 seconds to 300 seconds, and more preferably from 30 seconds to 120 seconds.
  • the development temperature is preferably from 20°C to 40°C, and more preferably 23°C.
  • the development may be carried out using a paddle system, a shower system, or a spray system.
  • the development using an aqueous alkaline solution is preferably followed by washing with water.
  • the washing method is appropriately selected according to the intended use, and may be rinse treatment carried out by showering pure water over a support such as a silicon wafer substrate, which is rotated at a rotation speed of 10 rpm to 500 rpm, from a jet nozzle positioned above the center of rotation.
  • the colored pattern (pixel) formed from the blue curable composition of the invention may be subjected to post-exposure by ultraviolet irradiation, thereby effectively preventing color migration to the adjacent pixels and the upper and lower layers.
  • the color migration is a problem which may occur when using a dye such as the specific complex as a coloring material in the blue curable composition of the invention.
  • the color migration is reduced by the below-described post-exposure by ultraviolet irradiation.
  • the colored pattern which has been developed as described above, is preferably irradiated with ultraviolet light (UV light) at an exposure dose [mJ/cm 2 ] of ten times or more the exposure dose in the exposure treatment before the development.
  • UV light ultraviolet light
  • UV light ultraviolet light
  • Examples of ultraviolet light sources include ultrahigh, high, and low-pressure mercury lamps, and DEEP UV lamps. Among them, preferred are those emits ultraviolet light containing light having wavelengths of 275 nm or less, wherein the irradiance [mW/cm ] of light having wavelengths of 275 nm or less is 5% or more of the integral irradiance of light of all wavelengths in the ultraviolet light.
  • the irradiance of light having wavelengths of 275 nm or less in the ultraviolet light is 5% or more, color migration to adjacent pixels or upper and lower layers is more effectively prevented, and light resistance is more effectively improved.
  • the post-exposure by ultraviolet irradiation is preferably carried out using a light source different from the light source such as i-line used in the exposure in the process (B), and specific examples of the light sources include high pressure and low pressure mercury lamps.
  • the irradiance [mW/cm 2 ] of light having wavelengths of 275 nm or less is preferably 7% or more of the integral irradiance of light of all wavelengths in the ultraviolet light.
  • the upper limit of the light having wavelengths of 275 nm or less is preferably 25% or less.
  • the integral irradiance is the total (area) of irradiance of light of respective wavelengths contained in the irradiation light represented by a curve drawn taking the irradiance of the respective spectroscopic wavelengths (radiant energy passing unit area in unit time; [mW/m 2 ]) as ordinate, and the light wavelength [nm] as abscissa.
  • the irradiation with ultraviolet light is preferably carried out at an irradiation dose
  • the irradiation dose in the process (C) is less than ten times the exposure dose during the exposure in the process (B), color migration to the adjacent pixels and upper and lower layers may not be prevented, and light resistance may deteriorate.
  • the irradiation dose of ultraviolet light is preferably 12 times or more and 200 times or less, and more preferably 15 times or more and 100 times or less the exposure dose during the exposure in the process (B).
  • the integral irradiance of ultraviolet light is preferably 200 mW/cm 2 or more.
  • the integral irradiance is 200 mW/cm or more, color migration to the adjacent pixels and upper and lower layers is more effectively prevented, and light resistance is more effectively improved.
  • the integral irradiance is preferably from 250 mW/cm 2 to 2000 mW/cm 2 , and more preferably from 300 mW/cm 2 to 1000 mW/cm 2 .
  • the colored pattern which has been subjected to post-exposure by ultraviolet irradiation is preferably subjected to heating treatment.
  • the colored pattern is subjected to heating (so-called postbaking), thereby further curing the colored pattern.
  • the heating treatment may be carried out using, for example, a hot plate, any heater, or an oven.
  • the temperature of the heating treatment is preferably from 100°C to 300°C, and more preferably 150°C to 250°C.
  • the heating time is preferably from 30 seconds to 30000 seconds, and more preferably from 60 seconds to 1000 seconds.
  • the above-described post-exposure by ultraviolet irradiation in the process (C) may be replaced with post-exposure using g-line, h-line, i-line, KrF, ArF, electron beams, or X ray.
  • the irradiation time is from 10 seconds to 180 seconds, preferably from 20 seconds to 120 seconds, and more preferably from 30 seconds to 60 seconds.
  • the post-exposure and post-heating may be carried out in any order. However, it is preferred that the post-exposure be carried out before the post-heating, because the
  • post-exposure promotes curing, thereby preventing the deformation of the shape caused by heat sagging (conglobation of the rectangular pattern) or tailing (reflowing of the pattern in the lower layer) of the colored pattern occurring during the post-heating.
  • the colored pattern thus obtained composes the pixels of the color filter.
  • the process (C) and/or the process (D) may be carried out every after the completion of the formation, exposure, and development of a monochrome layer of the blue curable composition (for every color). Alternatively, the process (C) and/or the process (D) may be carried out once after completion of the formation, exposure, and development of all the desired colored layers of the blue curable composition.
  • the color filter obtained by the method of the invention for producing a color filter (the color filter of the invention) is formed from the blue curable composition of the invention, and thus achieves good light resistance.
  • the color filter of the invention is suitable for liquid crystal display devices, solid-state image pickup devices such as CCD image sensors and CMOS image sensors, and camera systems using the same, and particularly suitable for solid-state image pickup devices requiring the formation of colored patterns having a very small size and a small thickness, and a good rectangular cross section, such as high resolution CCD and CMOS having more than 1000000 pixels.
  • the cleaning solution is preferably the above-described solvent contained in the blue curable composition of the invention.
  • 2007-281523 are also preferred as the cleaning solution for washing off the blue curable composition of the invention.
  • alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred. These solvents may be used alone in combination of two or more thereof. When two or more solvents are mixed, it is preferred that a solvent having a hydroxyl group and a solvent having no hydroxyl group be mixed.
  • the mass ratio between the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1 , preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20.
  • Particularly preferred is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), mixed at a ratio of 60/40. Also preferred are the mixture of PGMEA and cyclohexanone, and the mixture of PGMEA and 2-heptanone.
  • the cleaning solution may contain the above-described surfactant for the composition of the invention.
  • the solid-state image pickup device of the invention includes the color filter of the invention.
  • the color filter of the invention has no roughness or color unevenness, and the solid-state image pickup device including the color filter achieves good color reproducibility.
  • the solid-state image pickup device is not particularly limited as to its structure as long as it includes the color filter of the invention, and functions as a solid-state image pickup device.
  • Examples of the structure include the following one.
  • the structure includes a support having thereon a transfer electrode, the color filter of the invention, and a microlens in this order, the transfer electrode having plural photodiodes and polysilicons forming light-receptive areas of a CCD or CMOS image sensor (solid-state image pickup device).
  • the camera system including the color filter of the invention has a camera lens and an IR cut film provided with a dichroic-coated cover glass and a microlens.
  • the material preferably has the optical property of absorbing some or all of UV light having wavelengths of 400 ran or less.
  • the camera system is preferably configured to reduce the oxygen permeation to the color filter, thereby preventing oxidation fading of coloring materials.
  • the camera system is partially or completely sealed with nitrogen gas.
  • the color filter of the invention achieves good light resistance, and has color pixels with good hue. Therefore, the color filter is suitable for liquid crystal display devices.
  • the liquid crystal display device provided with the color filter displays high quality images.
  • the definition of the display device and explanations of the respective display devices are described in, for example "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990", and “Display Device (Sumiaki Ibuki, Sangyo-Tosho Publishing Co., Ltd., 1989)".
  • Liquid crystal display devices are described in, for example, “Next Generation Liquid Crystal Display Techniques (Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994)”.
  • the liquid crystal display device to which the invention is applicable is not specifically limited, and the invention is applicable to various liquid crystal display devices described in, for example, the above-described "Next Generation Liquid Crystal Display Techniques".
  • the color filter of the invention is effective for color TFT liquid crystal display devices. Details about color TFT Liquid crystal display devices are described in, for example, "Color TFT Liquid Crystal Display (published by Kyoritsu Shuppan Co., Ltd., 1996)". Furthermore, the invention is applicable to liquid crystal display devices having enlarged viewing angles, such as the IPS system driven by a transverse electric field and the pixel division system such as multi-domain vertical alignment (MVA), and also to STN, TN, VA, OCS, FFS, and R-OCB.
  • MVA multi-domain vertical alignment
  • the color filter of the invention is applicable to the COA (Color-filter On Array) system providing brightness and high definition.
  • COA liquid crystal display devices require the color filter layer to meet ordinary requirements, and requirements for interlayer insulating films, more specifically low dielectric constant and remover resistance.
  • the color filter of the invention may have improved ultraviolet laser permeability by using the exposure method by ultraviolet laser radiation, and selecting the color of the color pixels and film thickness. As a result of this, the color pixels have improved curability, and pixels free from chipping, peeling, or curling are formed. Therefore, the colored layer formed directly or indirectly on the TFT substrate has markedly improved remover resistance, and is suitable for COA liquid crystal display devices.
  • a resin film may be provided on the color filter layer.
  • the colored layer formed by the COA system requires the formation of a conduit such as a rectangular through hole or a U-shaped indentation having a side length of about 1 ⁇ to 15 ⁇ thereby achieving communication between the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer.
  • the size (more specifically, the side length) of the conduit is particularly preferably 5 ⁇ or less, and the use of the invention allows the formation of the conduit having a side length of 5 ⁇ or less.
  • the liquid crystal display device of the invention is composed of the color filter of the invention and other various members such as an electrode substrate, a polarizing film, a phase contrast film, a backlight, a spacer, and a viewing angle compensation film.
  • the color filter of the invention is suitable for liquid crystal display devices composed of these known members.
  • the poor solvent was adjusted to have a temperature of 5°C, and stirred at 500 rpm using a GK-0222-10 RAMOND stirrer (trade name, manufactured by Fujisawa
  • the copper phthalocyanine pigment solution was poured using a large-volume nonpulsating pump (trade name, NP-KX-500, manufactured by Nihon Seimitsu Kagaku, Co, Ltd., thereby contacting the copper phthalocyanine pigment solution with the poor solvent, and depositing the fine particles of the copper phthalocyanine pigment.
  • the copper phthalocyanine pigment solution was poured for 2 minutes at a flow rate of 100 ml/min, through a liquid sending pipe having a diameter of 0.5 mm at the channel and the feeding port, the feeding port being placed in the poor solvent.
  • the aqueous paste containing a pigment thus obtained was dried at 80°C for 12 hours, to obtain a powdery colorant substance A.
  • a mixture composed the following colorant substance A, dispersant, and solvent was dispersed using a bead mill, thereby preparing an a phthalocyanine PGMEA dispersion (colorant dispersion A).
  • the dispersion was carried out at a peripheral speed 9 m/s for 5 hours, using a motor mill (trade name: M-50, manufactured by Eigar Japan) and zirconia beads having a diameter of 0.1 mm.
  • Colorant substance A 11.0 parts by mass (pigment 10 parts by mass)
  • Disperbyk-200 (manufactured by BYK-Chemie) 10.0 parts by mass
  • the colorant dispersion A thus obtained was observed by an electron microscope, and found to contain fine pigment particles having a volume weighted average diameter of 20.0 ran (in terms of a sphere having the same volume), and a coefficient of variation of 15%. (In Table 1, indicated as "dispersion A”.)
  • a mixed liquid composed of 11.5 parts by mass of C.I. Pigment Blue 15:6 (average particle diameter: 55 nm), 3.5 parts by mass of a pigment dispersant BYK-161 (manufactured by BYK), and 85 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia bead, diameter: 0.3 mm), thereby preparing a pigment dispersion.
  • the liquid was further dispersed under pressure of 2000 kg/cm 3 at a flow rate of 500 g/min, using a high pressure disperser NANO-3000-10 having a pressure reducing mechanism (trade name, manufactured by Japan BEE).
  • the dispersion treatment was repeated 10 times, and thus obtaining a pigment dispersion.
  • the pigment dispersion was measured by MICROTRAC NANOTRAC UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.) using a dynamic light scattering method, and the pigment was found to have an average primary particle diameter of 25 nm.
  • a dispersion of P.V. 23 was obtained in the same manner as ⁇ Preparation of P.B. 15:6 dispersion>, except that P.V. 23 was used in place of P.B. 15:6.
  • a dispersion of P.B. 15 was obtained in the same manner as ⁇ Preparation of P.B. 15:6 dispersion>, except that P.B. 15 was used in place of P.B. 15:6.
  • Benzyl methacrylate/methacrylic acid copolymer 20% cyclohexanone solution (resin A) (molar ratio 70:30, weight average molecular weight: 30000) 0.1 parts
  • Fluorine surfactant (trade name: SOLSPERSE 20000, manufactured by The Lubrizol Corporation) 1% cyclohexanone solution 0.75 parts
  • P.V. 23 is the abbreviation of C.I. Pigment Violet 23.
  • P.B. 15:6 and P.B. 15 are the abbreviations of C.I. Pigment blue 15:6 and C.I.
  • X-ray diffractometry used a full automatic multipurpose X-ray diffractometer (trade name: X'Pert PRO MPD, manufactured by PANalytical). The diffracted intensity was measured for the angle of diffraction (2 ⁇ ) from 5° to 60°.
  • the transmission spectra were measured for 380 nm to 780 nm using an ultraviolet visible spectrophotometer (trade name: UV-2450, manufactured by Shimadzu Corporation)
  • the transmittance of the copper phthalocyanine in the transmission spectrum from 400 nm to 450 nm is greater than that of conventional ⁇ copper phthalocyanine over the entire wavelength from 400 nm to 450 nm.
  • This property was confirmed by the evaluation standard represented by T425/Tmax > 0.70, wherein T425 is the transmittance at 425 nm, and Tmax is the transmittance at the wavelength ⁇ max) at which the transmittance reaches a maximum in the transmission spectrum from 380 nm to 780 nm.
  • the copper phthalocyanine pigment (the colorant substance A obtained in Synthesis Example) contained in the colorant dispersion A used in Examples 1 to 11 and Comparative Example 4 had an a crystal form and a transmission maximum kmax) at a wavelength of less than 475 nm in a wavelength region of from 400 nm to 500 nm, and thus was found to be the copper phthalocyanine pigment according to the invention.
  • the pigment PB15:6 used in Comparative Examples 1 and 2 had an ⁇ crystal form
  • the PB15 pigment used in Comparative Example 3 had an a crystal form, but its max was in a longer wavelength region. Therefore, these pigments were found to be comparative pigments outside the scope of the invention.
  • compositions of Examples 1 to 11, and Comparative Examples 1 to 4 were applied, and subjected to heating treatment (prebaking) for 120 seconds using a hot plate at 100°C, such that the dry coating film has a thickness of 0.8 ⁇ .
  • the entire surface of the film was exposed to light having a wavelength of 365 nm at a dose of 1000 mJ/cm 2 , using an i line stepper (trade name: FPA-3000i5+, manufactured by Canon Inc.).
  • the glass substrate having a coating film after exposure was mounted on a horizontal rotary table of a spin shower developing machine (trade name, DW-30,
  • the glass substrate was placed between the objective lens and light source of an optical microscope, light was emitted toward the objective lens, and the transmitted light was observed by the optical microscope equipped with a digital camera with a magnification of 1000.
  • the digital camera installed on the optical microscope was equipped with a CCD having 1280000 pixels, and used to photograph the film surface through which light transmitted.
  • the photographed image was stored as digital converted data of 8-bit bitmap format (digital image).
  • the film surface was photographed in arbitrarily selected twenty regions.
  • the luminance of each of RGB colors of the photographed image was digitalized as a distribution of 256 tones from 0 to 255.
  • the digital image was divided into square cells (in the form of a grid) each having a size corresponding to 2 ⁇ square on the actual substrate, and the luminance was averaged within each cell.
  • the total number of cells within one photographed region was 39776, because the image was photographed at a magnification of 1000 by a digital camera having a CCD having 1 ,280,000 pixels, 2 mm in the image on the display corresponded to 2 ⁇ in the actual substrate, and the size of the image on the display was 452 mm ⁇ 352 mm.
  • the luminance of each cell in the region and the average luminance of all the cells adjacent to the cell were measured.
  • a cell in which the difference between the luminance of the cell and the average luminance of the adjacent cells was 5 or more was regarded as a significant difference cell.
  • the average number of significant difference cells per one region was calculated in all the regions, and the proportion of the average number of significant difference cells per one region to total number of cells in one region (39776) was calculated.
  • the proportion of significant difference cells to total number of cells was used as the index for carrying out the evaluation of roughness of the image, and evaluated according to the following evaluation criteria.
  • A The proportion of significant difference cells to total number of cells is less than
  • Comparative Examples 1 to 3 containing no a copper phthalocyanine pigment according to the invention showed roughness.

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Abstract

La présente invention se rapporte à une composition durcissable bleue qui comprend : un pigment de phthalocyanine de cuivre présentant une forme cristalline α ainsi qu'une transmission maximum à une longueur d'onde inférieure à 475 nm dans une zone de longueurs d'onde allant de 400 nm à 500 nm; un initiateur de polymérisation de type oxime; un composé polymérisable; et un solvant.
PCT/JP2011/067997 2010-08-13 2011-07-29 Composition durcissable bleue, filtre coloré et son procédé de fabrication, dispositif de capture d'images à semi-conducteur, et dispositif d'affichage à cristaux liquides WO2012020715A1 (fr)

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US10208208B2 (en) 2014-12-15 2019-02-19 M. Technique Co., Ltd. Composite phthalocyanine microparticles and method for producing same

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JP5908824B2 (ja) * 2012-10-29 2016-04-26 富士フイルム株式会社 着色組成物、カラーフィルタ、カラーフィルタの製造方法、画像表示装置、固体撮像素子、並びに、新規化合物及びその互変異性体
JP6750249B2 (ja) * 2016-02-26 2020-09-02 東洋インキＳｃホールディングス株式会社 感光性着色組成物およびカラーフィルタ

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JP2008233620A (ja) * 2007-03-22 2008-10-02 Dic Corp カラーフィルター用青色顔料分散体、その製造方法及びそれを用いたカラーフィルター
JP2009229761A (ja) * 2008-03-21 2009-10-08 Fujifilm Corp 着色硬化性組成物、カラーフィルタ及びその製造方法、固体撮像素子
WO2010035861A1 (fr) * 2008-09-29 2010-04-01 エム・テクニック株式会社 Nouveau pigment de phtalocyanine de cuivre et procédé de production de particules fines de phtalocyanine de cuivre

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JP5721992B2 (ja) * 2009-10-14 2015-05-20 富士フイルム株式会社 着色硬化性組成物、レジスト液、インクジェット用インク、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、液晶ディスプレイ、有機ｅｌディスプレイ、画像表示デバイス、及び色素化合物

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US20080076044A1 (en) * 2006-09-27 2008-03-27 Fujifilm Corporation Compound or its tautomer, metal complex compound, colored photosensitive curing composition, color filter, and production
JP2008233620A (ja) * 2007-03-22 2008-10-02 Dic Corp カラーフィルター用青色顔料分散体、その製造方法及びそれを用いたカラーフィルター
JP2009229761A (ja) * 2008-03-21 2009-10-08 Fujifilm Corp 着色硬化性組成物、カラーフィルタ及びその製造方法、固体撮像素子
WO2010035861A1 (fr) * 2008-09-29 2010-04-01 エム・テクニック株式会社 Nouveau pigment de phtalocyanine de cuivre et procédé de production de particules fines de phtalocyanine de cuivre

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Publication number Priority date Publication date Assignee Title
US10208208B2 (en) 2014-12-15 2019-02-19 M. Technique Co., Ltd. Composite phthalocyanine microparticles and method for producing same

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