WO2020045209A1 - Coloring composition, pixel forming method, color filter production method, and display device production method - Google Patents

Coloring composition, pixel forming method, color filter production method, and display device production method Download PDF

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Publication number
WO2020045209A1
WO2020045209A1 PCT/JP2019/032743 JP2019032743W WO2020045209A1 WO 2020045209 A1 WO2020045209 A1 WO 2020045209A1 JP 2019032743 W JP2019032743 W JP 2019032743W WO 2020045209 A1 WO2020045209 A1 WO 2020045209A1
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group
coloring composition
mass
compound
pixel
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PCT/JP2019/032743
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French (fr)
Japanese (ja)
Inventor
啓之 山本
大貴 瀧下
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富士フイルム株式会社
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Priority to JP2020539383A priority Critical patent/JP7273046B2/en
Publication of WO2020045209A1 publication Critical patent/WO2020045209A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a coloring composition for forming a color filter for a display device. Further, the present invention relates to a method for forming a pixel, a color filter, and a method for manufacturing a display device.
  • Patent Document 1 discloses a photosensitive composition for a color filter containing a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a colorant. It describes that an organic electroluminescent display device is manufactured by forming a color filter using an object.
  • a color filter may be formed on a member having low heat resistance (for example, an organic semiconductor element such as an organic electroluminescence display element). Since such a member has low heat resistance, it is desirable to form a pixel of the color filter by a low-temperature process of 150 ° C. or less, for example, to suppress thermal damage to the support.
  • a member having low heat resistance for example, an organic semiconductor element such as an organic electroluminescence display element. Since such a member has low heat resistance, it is desirable to form a pixel of the color filter by a low-temperature process of 150 ° C. or less, for example, to suppress thermal damage to the support.
  • the present invention provides the following. ⁇ 1> A coloring composition for forming pixels of a color filter for a display device, The coloring composition is used to form a pixel at a temperature of 150 ° C. or less throughout the entire process, The coloring composition contains a colorant, a resin, a photopolymerization initiator, and a polymerizable monomer, A colored composition, wherein the viscosity of the colored composition at 25 ° C.
  • the resin contains a resin b1 containing a repeating unit derived from a compound represented by the following formula (I);
  • X 1 represents O or NH
  • R 1 represents a hydrogen atom or a methyl group
  • L 1 represents a divalent linking group
  • R 10 represents a substituent
  • m represents an integer of 0 to 2
  • p represents an integer of 0 or more.
  • the photopolymerization initiator is A photopolymerization initiator A1 having an absorption coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm; A photopolymerization initiator A2 having an extinction coefficient of 1.0 ⁇ 10 2 mL / gcm or less in methanol at a wavelength of 365 nm and an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more at a wavelength of 254 nm;
  • ⁇ 8> The colored composition according to ⁇ 6> or ⁇ 7>, wherein the photopolymerization initiator A2 is a hydroxyalkylphenone compound.
  • the polymerizable monomer includes a polymerizable monomer having an acid group.
  • the polymerizable monomer includes a polymerizable monomer containing three or more ethylenically unsaturated groups.
  • the compound containing a furyl group is at least one selected from a compound represented by the following formula (fur-1) and a resin containing a repeating unit derived from the compound represented by the following formula (fur-1)
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 2 represents a divalent linking group.
  • the viscosity of the coloring composition at 25 ° C. after storage for 30 days at a temperature of 25 ° C. and a humidity of 50% is in the range of 90 to 110% of the viscosity at 25 ° C. of the coloring composition immediately after production.
  • ⁇ 14> a step of applying the coloring composition according to any one of ⁇ 1> to ⁇ 13> on a support to form a coloring composition layer, and a step of exposing the coloring composition layer to a pattern And a step of developing the colored composition layer after exposure, comprising: The pixel is formed at a temperature of 150 ° C. or lower throughout the entire process.
  • the step of exposing the colored composition layer in a pattern is performed by irradiating the colored composition layer with light having a wavelength of more than 350 nm and not more than 380 nm,
  • ⁇ 18> The method for forming a pixel according to ⁇ 17>, wherein the heating step is performed in an atmosphere of an inert gas.
  • a method for manufacturing a color filter including the method for forming a pixel according to any one of ⁇ 14> to ⁇ 18>.
  • a method for manufacturing a display device comprising the method for forming a pixel according to any one of ⁇ 14> to ⁇ 18>.
  • a coloring composition capable of forming a pixel having excellent flatness. Further, a method for forming a pixel, a method for manufacturing a color filter, and a method for manufacturing a display device can be provided.
  • the notation that does not indicate substituted or unsubstituted includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for the exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • the total solid content refers to a total mass of components excluding a solvent from all components of the composition.
  • (meth) acrylate represents both or either acrylate and methacrylate
  • (meth) acryl represents both or either acryl and methacryl
  • Allyl means both or allyl and methallyl
  • (meth) acryloyl means both or either acryloyl and methacryloyl.
  • step is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
  • the present invention is a coloring composition for forming a pixel of a color filter for a display device,
  • the coloring composition is used to form a pixel at a temperature of 150 ° C. or less throughout the entire process,
  • the coloring composition contains a colorant, a resin, a photopolymerization initiator, and a polymerizable monomer,
  • the color composition has a viscosity at 25 ° C. of 2.0 to 7.5 mPa ⁇ s.
  • the coloring composition of the present invention has the above-described viscosity characteristics, it has excellent flatness even when pixels are formed at a temperature of 150 ° C. or less (preferably a temperature of 120 ° C. or less) throughout the entire process. Pixels can be formed. Further, in particular, when a pixel having a thickness of 0.8 to 2.0 ⁇ m and a line width (pattern size) of 2.5 to 5.0 ⁇ m is formed by a low-temperature process, the conventional colored composition cannot provide a good result. Although the flatness of the obtained pixel is insufficient, a pixel having good flatness can be formed by using the coloring composition of the present invention. For this reason, the coloring composition of the present invention is particularly effective in forming pixels of such a size.
  • the coloring composition of the present invention is used for forming a pixel at a temperature of 150 ° C. or less throughout the process, and is used for forming a pixel at a temperature of 120 ° C. or less throughout the process. Is preferred. Note that in this specification, forming a pixel at a temperature of 150 ° C. or lower throughout the entire process means that all steps of forming a pixel using a coloring composition are performed at a temperature of 150 ° C. or lower.
  • the viscosity at 25 ° C. of the coloring composition of the present invention is 2.0 to 7.5 mPa ⁇ s.
  • the lower limit is preferably equal to or greater than 2.5 mPa ⁇ s, and more preferably equal to or greater than 3.0 mPa ⁇ s.
  • the upper limit is preferably equal to or less than 7.0 mPa ⁇ s, and more preferably equal to or less than 6.5 mPa ⁇ s.
  • a pixel having excellent flatness can be formed even when a pixel is formed at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process.
  • the coating property of the coloring composition is also good.
  • Examples of the method of adjusting the viscosity of the coloring composition to the above range include a method of adjusting the solid content concentration of the coloring composition, using a material having low viscosity, and using a material having good aging stability.
  • the solid content of the coloring composition of the present invention is preferably 5 to 25% by mass.
  • the upper limit is preferably 22.5% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less.
  • a pixel having excellent flatness can be formed even when a pixel is formed at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process. .
  • the viscosity of the coloring composition of the present invention at 25 ° C. after storage at a temperature of 25 ° C. and a humidity of 50% for 30 days is 90 to 110% of the viscosity at 25 ° C. of the coloring composition immediately after production. , Preferably 93 to 107%, and more preferably 95 to 105%.
  • the coloring composition of the present invention has such characteristics, it is easy to form a pixel having more excellent flatness. Means for achieving such characteristics include a method using a material having good stability over time.
  • the coloring composition of the present invention is a coloring composition for forming pixels of a color filter for a display device.
  • the type of the display device is not particularly limited, but is particularly effective for a display device in which a color filter is formed on a support having low heat resistance, such as a support including an organic semiconductor layer.
  • Examples of such a display device include a display device having an organic semiconductor element as a light source, such as an organic electroluminescence display device.
  • the thickness of a pixel formed by the coloring composition of the present invention is preferably 0.5 to 3.0 ⁇ m.
  • the lower limit is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, and still more preferably 1.1 ⁇ m or more.
  • the upper limit is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and still more preferably 1.8 ⁇ m or less.
  • the line width (pattern size) of a pixel formed by the coloring composition of the present invention is preferably 2.0 to 10.0 ⁇ m.
  • the upper limit is preferably 7.5 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 4.0 ⁇ m or less.
  • the lower limit is preferably 2.25 ⁇ m or more, more preferably 2.5 ⁇ m or more, and even more preferably 2.75 ⁇ m or more.
  • the coloring composition of the present invention contains a coloring agent.
  • the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
  • the colorant may be a pigment or a dye.
  • a pigment and a dye may be used in combination.
  • the pigment may be either an inorganic pigment or an organic pigment.
  • a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore can be used.
  • the colorant used in the present invention preferably contains a pigment. Further, the content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and more preferably 90% by mass or more. Is particularly preferred.
  • the colorant may be a pigment alone. Examples of the pigment include the following.
  • a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
  • a compound described in CN106909097A, a phthalocyanine compound having a phosphate as a ligand, or the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment.
  • Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247593 and paragraph 0047 of JP-A-2011-157478.
  • a yellow pigment a pigment described in JP-A-2017-201003 and a pigment described in JP-A-2017-197719 can be used.
  • a metal containing at least one anion, two or more metal ions, and a melamine compound selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof: Azo pigments can also be used.
  • R 1 and R 2 are each independently —OH or —NR 5 R 6
  • R 5 -R 7 Is each independently a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent.
  • the substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an amino group.
  • JP-A-2017-171912 paragraphs 0011 to 0062 and 0137 to 0276, JP-A-2017-171913, paragraphs 0010 to 0062, 0138 to 0295, and JP-A-2017-171914.
  • the descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the gazette and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.
  • yellow pigment a compound described in JP-A-2018-62644 can also be used. This compound can also be used as a pigment derivative.
  • red pigments diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, and diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838. Pigments and the like can also be used.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is introduced to a diketopyrrolopyrrole skeleton may be used. it can.
  • the dye is not particularly limited, and a known dye can be used.
  • a known dye can be used.
  • thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can be preferably used.
  • yellow dye quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can also be used.
  • a dye multimer may be used as a coloring agent.
  • the dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is a particle, it is usually dispersed in a solvent. Used.
  • the dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples thereof include a compound and a production method described in JP-A-2015-214682.
  • the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures in one molecule may be the same dye structure or different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably from 2,000 to 50,000.
  • the lower limit is more preferably 3000 or more, and still more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and still more preferably 20,000 or less.
  • the dye structure of the dye multimer includes a structure derived from a dye compound having an absorption in a visible region (preferably, a wavelength range of 400 to 700 nm, more preferably, 400 to 650 nm).
  • a dye compound having an absorption in a visible region preferably, a wavelength range of 400 to 700 nm, more preferably, 400 to 650 nm.
  • triarylmethane dye structure xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolotriazole dye structure, dipyrromethene dye structure , Isoindoline dye structure, thiazole dye structure, benzimidazole dye structure, perinone dye structure, diketopyrrolopyrrole dye structure, diiminium dye structure, naphthalocyanine dye structure, rylene dye
  • the dye multimer includes a dye multimer having a repeating unit represented by the formula (A), a dye multimer having a repeating unit represented by the formula (B), and a dye having a repeating unit represented by the formula (C)
  • a multimer and a dye multimer represented by the formula (D) are preferable, and a dye multimer having a repeating unit represented by the formula (A) and a dye multimer represented by the formula (D) are more preferable. preferable.
  • X 1 represents a main chain of a repeating unit
  • L 1 represents a single bond or a divalent linking group
  • D 1 represents a dye structure.
  • X 2 represents a main chain of a repeating unit
  • L 2 represents a single bond or a divalent linking group
  • D 2 represents a dye structure having a group capable of forming an ionic bond or a coordinate bond with Y 2.
  • Y 2 represents a group capable of forming an ionic or coordinate bond with D 2 .
  • L 3 represents a single bond or a divalent linking group
  • D 3 represents a dye structure
  • m represents 0 or 1.
  • L 4 represents a (n + k) -valent linking group
  • L 41 and L 42 each independently represent a single bond or a divalent linking group
  • D 4 represents a dye structure
  • 4 represents a substituent
  • n represents 2 to 15
  • k represents 0 to 13
  • n + k represents 2 to 15.
  • n is 2 or more
  • a plurality of D 4 may be different from each other or may be the same.
  • k is 2 or more
  • a plurality of P 4 may be different from each other or may be the same.
  • Examples of the (n + k) -valent linking group represented by L 4 include the linking groups described in paragraphs 0071 to 0072 of JP-A-2008-222950, and the linking group described in paragraph No.
  • Examples of the substituent represented by P 4 include an acid group and a polymerizable group.
  • Examples of the polymerizable group include an ethylenically unsaturated group (a group having an ethylenically unsaturated bond), an epoxy group, an oxazoline group, and a methylol group.
  • Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • the substituent represented by P 4 may be a monovalent polymer chain having a repeating unit.
  • the monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
  • Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO2016 / 031442, and the like. Compounds can also be used.
  • the content of the coloring agent is preferably 5 to 70% by mass based on the total solid content of the coloring composition.
  • the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more.
  • the upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.
  • the coloring composition of the present invention contains a polymerizable monomer.
  • the polymerizable monomer include a compound having an ethylenically unsaturated group.
  • the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable monomer is preferably a compound polymerizable by a radical (radical polymerizable monomer).
  • the molecular weight of the polymerizable monomer is preferably from 100 to 2,000.
  • the upper limit is preferably 1500 or less, more preferably 1000 or less.
  • the lower limit is more preferably 150 or more, and further preferably 250 or more.
  • the lower limit is preferably at least 3 mmol / g, more preferably at least 4 mmol / g, even more preferably at least 5 mmol / g.
  • the upper limit is preferably at most 12 mmol / g, more preferably at most 10 mmol / g, even more preferably at most 8 mmol / g.
  • the polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated groups, and more preferably a compound containing four or more ethylenically unsaturated groups. According to this aspect, the curability of the colored composition upon exposure is good.
  • the upper limit of the ethylenically unsaturated group is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less from the viewpoint of the stability over time of the composition.
  • the polymerizable monomer is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-10 functional (meth) acrylate compound. More preferably, it is particularly preferably a tri- to hexafunctional (meth) acrylate compound.
  • the polymerizable monomer is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group.
  • a polymerizable monomer has high flexibility and the ethylenically unsaturated group easily moves, so that the polymerizable monomers easily react with each other during exposure, and a cured film (pixel) having excellent adhesion to a support or the like. Can be formed.
  • a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable monomer and the photopolymerization initiator come close to each other to generate radicals in the vicinity of the polymerizable monomer so that the polymerizable monomer can be more effectively used. It is presumed that they can be reacted, and it is easy to form a cured film (pixel) having better adhesion and solvent resistance.
  • the number of alkyleneoxy groups contained in one molecule of the polymerizable monomer is preferably 3 or more, more preferably 4 or more.
  • the upper limit is preferably 20 or less from the viewpoint of the stability over time of the composition.
  • the SP value (Solubility @Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably from 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition.
  • the upper limit is preferably 10.75 or less, more preferably 10.5 or less.
  • the lower limit is preferably 9.25 or more, and more preferably 9.5 or more.
  • the SP value used the calculated value based on the Fedors method.
  • Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include a compound represented by the following formula (M-1).
  • M-1 In the formula, A 1 represents an ethylenically unsaturated group, L 1 represents a single bond or a divalent linking group, R 1 represents an alkylene group, m represents an integer of 1 to 30, and n represents 3 L 2 represents an n-valent linking group.
  • Examples of the ethylenically unsaturated group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
  • Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, and a group obtained by combining two or more of these. .
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.
  • the alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group, a linear or branched propylene group, and an ethylene group is preferable.
  • M represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably 1 to 5.
  • N represents an integer of 3 or more, and preferably an integer of 4 or more.
  • the upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
  • Examples of the n-valent linking group represented by L 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, and a group including a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group.
  • Examples include a group formed by combining at least one selected from a ring group and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched.
  • the carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclic group is preferably a 5- or 6-membered ring. Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
  • a compound represented by the following formula (M-2) is more preferable.
  • R 2 represents a hydrogen atom or a methyl group
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 30
  • n represents an integer of 3 or more
  • L 2 represents an n-valent linking group.
  • R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercially available product; Nippon Kayaku Co., Ltd.) Nippon Kayaku), dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available: KAYARAD DPHA; Nippon Kayaku ( NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
  • Aronix M-402 a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.
  • Aronix M-402 a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.
  • trimethylolpropane tri (meth) acrylate trimethylolpropanepropyleneoxy-modified tri (meth) acrylate, trimethylolpropaneethyleneoxy-modified tri (meth) acrylate, isocyanuric acid ethyleneoxy-modified tri (meth) acrylate
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a polymerizable monomer having an acid group As the polymerizable monomer.
  • the polymerizable monomer having an acid group By using the polymerizable monomer having an acid group, the unexposed portion of the colored composition layer is easily removed at the time of development, and generation of a development residue can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
  • the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
  • polymerizable monomers having an acid group Commercial products of polymerizable monomers having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.
  • the preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the solubility in a developer is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.
  • the polymerizable monomer is also preferably a compound having a caprolactone structure.
  • the polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD @ DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • the polymerizable monomers include compounds described in JP-A-2017-048367, JP-A-6057891, and JP-A-6031807, compounds described in JP-A-2017-194662, 8UH-1006, and 8UH. It is also preferable to use -1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.
  • the content of the polymerizable monomer is preferably 5.0 to 35% by mass based on the total solid content of the coloring composition.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
  • the coloring composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, and oxime derivatives. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, phenylglyoxylate compounds, and the like.
  • paragraphs 0265 to 0268 of JP-A-2013-029760 and JP-A-6301489 can be referred to, and the contents thereof are incorporated herein.
  • phenylglyoxylate compound phenylglyoxylic acid methyl ester and the like can be mentioned.
  • Commercially available products include DAROCUR-MBF (manufactured by BASF).
  • aminoalkylphenone compound examples include, for example, an aminoalkylphenone compound described in JP-A-10-291969. Further, as the aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.
  • acylphosphine compound examples include the acylphosphine compounds described in Japanese Patent No. 422598. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • acylphosphine compound IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.
  • hydroxyalkylphenone compound examples include a compound represented by the following formula (V). Equation (V) In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring, m represents an integer of 0 to 5.
  • Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms).
  • the alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear.
  • the alkyl group and the alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent.
  • Examples of the substituent include a hydroxy group and a group having a hydroxyalkylphenone structure. Examples of the group having a hydroxyalkyl phenone structures, groups of structures Rv 1 in the formula (V) is removing one hydrogen atom from a benzene ring or Rv 1 were bond.
  • Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent.
  • an alkyl group preferably an alkyl group having 1 to 10 carbon atoms
  • Rv 2 and Rv 3 may combine with each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).
  • the alkyl group is preferably linear or branched, and more preferably linear.
  • IRGACURE-184 As the hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can also be used.
  • Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and J.I. C. S. Compounds described in Perkin II (1979, pp. 1653-1660); C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer, Science and and Technology (1995, pp. 202-232), a compound described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
  • IRGACURE-OXE01 IRGACURE-OXE02
  • IRGACURE-OXE03 IRGACURE-OXE04
  • TR-PBG-304 manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
  • Adeka Optomer N-1919 (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP-A-2012-014052).
  • Examples of the oxime compound include compounds described in JP-T-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957 in which a heterosubstituent is introduced into a benzophenone moiety, and dyes.
  • JP-A-2009-221114 which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source, may be used.
  • paragraphs 0274 to 0306 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated in the present specification.
  • the oxime compound is preferably an oxime compound containing a fluorine atom.
  • the oxime compound containing a fluorine atom preferably has a group containing a fluorine atom.
  • a group containing a fluorine atom an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated group) are preferable.
  • fluorinated group examples include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , -NHCOOR At least one group selected from F1 , —SO 2 R F1 , —SO 2 OR F1, and —NHSO 2 R F1 is preferable.
  • R F1 represents a fluorine-containing alkyl group
  • R F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group.
  • the fluorine-containing group is preferably -OR F1 .
  • the carbon number of the alkyl group and the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched.
  • the substitution ratio of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, even more preferably from 60 to 100%.
  • the substitution rate of a fluorine atom means the ratio (%) of the number of substitution with a fluorine atom to the total number of hydrogen atoms of the alkyl group.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4.
  • the number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.
  • the group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2).
  • * In the formula represents a connecting hand. * -CHF 2 (1) * -CF 3 (2)
  • the total number of fluorine atoms in the fluorine atom-containing oxime compound is preferably 3 or more, more preferably 4 to 10.
  • the oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).
  • OX-1 In the formula (OX-1), Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 represents an aryl group having a group containing a fluorine atom. And R 2 and R 3 each independently represent an alkyl group or an aryl group.
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent.
  • the aromatic hydrocarbon ring may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the aromatic hydrocarbon ring is preferably from 6 to 20, more preferably from 6 to 15, and particularly preferably from 6 to 10.
  • a benzene ring and a naphthalene ring are preferable.
  • at least one of Ar 1 and Ar 2 is preferably a benzene ring, and more preferably Ar 1 is a benzene ring.
  • Ar 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.
  • Examples of the substituent which Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , and —COOR X1. , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 No.
  • R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. In the alkyl group, some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms).
  • the carbon number of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aryl group may be a single ring or a condensed ring.
  • part or all of the hydrogen atoms may be substituted with the above substituents.
  • the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
  • the aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted.
  • the aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent.
  • —COR X1 is preferable.
  • R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group.
  • the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
  • R 1 represents an aryl group having a group containing a fluorine atom.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • the group containing a fluorine atom an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom-containing alkyl group (fluorine-containing group) are preferable.
  • the group containing a fluorine atom has the same meaning as the above-mentioned range, and the preferred range is also the same.
  • R 2 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
  • R 3 represents an alkyl group or an aryl group, preferably an alkyl group.
  • the alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have.
  • the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
  • the aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
  • oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) examples include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471.
  • an oxime compound having a fluorene ring can be used as the oxime compound.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
  • an oxime compound having a benzofuran skeleton can be used as the oxime compound.
  • Specific examples include compounds OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used.
  • Specific examples of such oxime compounds include the compounds described in WO2013 / 083505.
  • an oxime compound having a nitro group can be used.
  • the oxime compound having a nitro group is preferably a dimer.
  • Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and 0070 to 0079; And the compounds described in Paragraph Nos. 0007 to 0025 of JP-A No. 195/1992.
  • a photopolymerization initiator A1 having an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at 365 nm in methanol, and an extinction coefficient of 1.0 nm in methanol at 365 nm. It is preferable to use a photoinitiator A2 having a light absorption coefficient of 0 ⁇ 10 2 mL / gcm or less and an absorption coefficient at a wavelength of 254 nm of 1.0 ⁇ 10 3 mL / gcm or more in combination.
  • the coloring composition is easily cured sufficiently by exposure, has good flatness in a low-temperature process (for example, a temperature of 150 ° C. or lower, preferably 120 ° C. or lower throughout the entire process), and A pixel excellent in characteristics such as solvent resistance can be formed.
  • a low-temperature process for example, a temperature of 150 ° C. or lower, preferably 120 ° C. or lower throughout the entire process
  • a pixel excellent in characteristics such as solvent resistance can be formed.
  • the photopolymerization initiator A1 and the photopolymerization initiator A2 it is preferable to use a compound having the above-mentioned extinction coefficient among the above-mentioned compounds.
  • the extinction coefficient at the above wavelength of the photopolymerization initiator is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies. The extinction coefficient (mL / gcm) at 254 nm was calculated. In the above equation, ⁇ represents the extinction coefficient (mL / gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents the optical path length (cm).
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 ⁇ 10 3 mL / gcm or more, preferably 1.0 ⁇ 10 4 mL / gcm or more, and more preferably 1.1 ⁇ 10 4 mL / gcm. It is more preferably at least 10 4 mL / gcm, even more preferably 1.2 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and 1.3 ⁇ 10 4 to 5.0 ⁇ 10 4 mL. / Gcm, more preferably 1.5 ⁇ 10 4 to 3.0 ⁇ 10 4 mL / gcm.
  • the extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm in methanol is preferably from 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, and from 1.5 ⁇ 10 4 to 1.5 ⁇ 10 4 mL / gcm. It is more preferably 9.5 ⁇ 10 4 mL / gcm, and still more preferably 3.0 ⁇ 10 4 to 8.0 ⁇ 10 4 mL / gcm.
  • the photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, further preferably an oxime compound, and has compatibility with other components contained in the composition.
  • an oxime compound containing a fluorine atom is particularly preferred.
  • a compound represented by the above formula (OX-1) is preferable.
  • photopolymerization initiator A1 examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (as commercial products, for example, IRGACURE-OXE01, BASF , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds ( C-13) and (C-14).
  • the extinction coefficient of the photopolymerization initiator A2 at 365 nm in methanol is 1.0 ⁇ 10 2 mL / gcm or less, preferably 10 to 1.0 ⁇ 10 2 mL / gcm. More preferably, it is about 1.0 ⁇ 10 2 mL / gcm.
  • the difference between the extinction coefficient of photopolymerization initiator A1 at 365 nm in methanol and the extinction coefficient of photopolymerization initiator A2 at 365 nm in methanol is 9.0 ⁇ 10 2 mL.
  • the extinction coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm in methanol is 1.0 ⁇ 10 3 mL / gcm or more, and 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6 mL / gcm. And more preferably 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 mL / gcm.
  • the photopolymerization initiator A2 is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, an acylphosphine compound, more preferably a hydroxyalkylphenone compound and a phenylglyoxylate compound, and further preferably a hydroxyalkylphenone compound.
  • a compound represented by the above formula (V) is preferable.
  • photopolymerization initiator A2 examples include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl 2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF).
  • the photopolymerization initiator A1 As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is preferably More preferably, the combination is an oxime compound, wherein the photopolymerization initiator A2 is a compound represented by the above formula (V), wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is Combinations of the compounds of formula (V) described above are particularly preferred.
  • the content of the photopolymerization initiator is preferably 0.1 to 17.5% by mass based on the total solid content of the coloring composition.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more.
  • the upper limit is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, even more preferably 10.0% by mass or less.
  • the coloring composition of the present invention preferably contains 1.0 to 50 parts by mass of a photopolymerization initiator based on 100 parts by mass of the polymerizable monomer.
  • the upper limit is preferably at most 40 parts by mass, more preferably at most 30 parts by mass.
  • the lower limit is preferably at least 2.5 parts by mass, more preferably at least 5.0 parts by mass. According to this aspect, the pattern shape after development is good.
  • the content of the photopolymerization initiator A1 is 0.1 to 17.5 in the total solid content of the coloring composition. It is preferable that the content is mass%.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more.
  • the upper limit is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and even more preferably 10.0% by mass or less.
  • the content of the photopolymerization initiator A2 is 0.1 to 10.0 in the total solid content of the coloring composition. It is preferable that the content is mass%.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more.
  • the upper limit is preferably equal to or less than 9.0% by mass, more preferably equal to or less than 8.0% by mass, and still more preferably equal to or less than 7.0% by mass.
  • the coloring composition of the present invention when the above-described photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator, the coloring composition of the present invention is added to 100 parts by mass of the photopolymerization initiator A1. On the other hand, it is preferable to contain 50 to 200 parts by mass of the photopolymerization initiator A2.
  • the upper limit is preferably at most 175 parts by mass, more preferably at most 150 parts by mass.
  • the lower limit is preferably at least 60 parts by mass, more preferably at least 70 parts by mass. According to this aspect, it is possible to form a pixel having excellent properties such as solvent resistance in a low-temperature process (for example, a temperature of 150 ° C. or lower, preferably a temperature of 120 ° C. or lower throughout the entire process).
  • the photopolymerization initiator A1 and the photopolymerization initiator A2 are used as the photopolymerization initiator, the photopolymerization initiator A1 and the photopolymerization initiator in the total solid content of the coloring composition are used.
  • the total content with the agent A2 is preferably 0.1 to 20.0% by mass.
  • the lower limit is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 2.5% by mass or more.
  • the upper limit is preferably 17.5% by mass or less, more preferably 15.0% by mass or less, and even more preferably 12.5% by mass or less.
  • the coloring composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder.
  • a resin mainly used for dispersing particles and the like in the composition is also referred to as a dispersant.
  • a use of the resin is an example, and the resin may be used for a purpose other than such a use.
  • the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
  • the resin examples include (meth) acrylic resin, (meth) acrylamide resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene
  • the resin used in the present invention may have an acid group.
  • the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group. These acid groups may be used alone or in combination of two or more.
  • the resin having an acid group can be used as an alkali-soluble resin or a dispersant.
  • the acid value of the resin having an acid group is preferably from 30 to 500 mgKOH / g.
  • the lower limit is more preferably at least 50 mgKOH / g, even more preferably at least 70 mgKOH / g.
  • the upper limit is more preferably 400 mg KOH / g or less, further preferably 200 mg KOH / g or less, particularly preferably 150 mg KOH / g or less, and most preferably 120 mg KOH / g or less.
  • a polymer having a carboxyl group in a side chain is preferable.
  • alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxy group.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable.
  • Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds.
  • alkyl (meth) acrylate and the aryl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.
  • vinyl compound examples include styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.
  • vinyl compound examples include styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.
  • monomers copolymerizable with (meth) acrylic acid may be used alone or in combination of two or more.
  • the resin having an acid group may have a repeating unit derived from a maleimide compound.
  • the maleimide compound include N-alkylmaleimide and N-arylmaleimide.
  • the repeating unit derived from the maleimide compound include a repeating unit represented by the formula (C-mi).
  • Rmi represents an alkyl group or an aryl group.
  • the alkyl group preferably has 1 to 20 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • the carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10.
  • Rmi is preferably an aryl group.
  • the resin having an acid group is derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferred that the resin contains a unit.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168538 can be referred to.
  • Examples of the resin containing a repeating unit derived from an ether dimer include a resin having the following structure.
  • Me represents a methyl group.
  • the resin used in the present invention may have a polymerizable group.
  • the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel @ CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (daicel UCB Co., Ltd.), Acrylicer RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).
  • the resin used in the present invention preferably contains a resin b1 containing a repeating unit derived from the compound represented by the formula (I) (hereinafter, also referred to as a repeating unit b1-1).
  • a resin having the repeating unit b1-1 low-temperature curability and transparency are excellent.
  • X 1 represents O or NH, and is preferably O.
  • R 1 represents a hydrogen atom or a methyl group.
  • L 1 represents a divalent linking group.
  • the divalent linking group include a hydrocarbon group, a heterocyclic group, -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and And a group obtained by combining two or more of the above.
  • the hydrocarbon group include an alkyl group and an aryl group.
  • the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclic group is preferably a 5- or 6-membered ring.
  • Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom.
  • the number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the hydrocarbon group and the heterocyclic group may have a substituent.
  • Examples of the substituent include an alkyl group, an aryl group, a hydroxy group, and a halogen atom.
  • R 10 represents a substituent.
  • Examples of the substituent represented by R 10 include the following substituents T, preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.
  • m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, still more preferably 0 or 1, and particularly preferably 1.
  • substituent T examples include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NHCORt 1 ,- CONT 1 Rt 2 , —NHCONT 1 Rt 2 , —NHCOORt 1 , —SRt 1 , —SO 2 Rt 1 , —SO 2 ORt 1 , —NHSO 2 Rt 1, or —SO 2 NRt 1 Rt 2 .
  • Rt 1 and Rt 2 each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group.
  • Rt 1 and Rt 2 may combine to form a ring.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • the carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably branched.
  • the carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms.
  • the alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 12.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed numbers.
  • the number of hetero atoms constituting the ring of the heterocyclic group is preferably from 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
  • the hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent T described above.
  • the compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).
  • X 1 represents O or NH, and is preferably O.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 , R 3 and R 11 each independently represent a hydrocarbon group.
  • the hydrocarbon group represented by R 2 and R 3 is preferably an alkylene group or an arylene group, and more preferably an alkylene group.
  • the carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3.
  • the hydrocarbon group represented by R 11 is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.
  • the carbon number of the alkyl group means the carbon number of the alkyl moiety.
  • R 12 represents a substituent. Examples of the substituent represented by R 12 include the substituent T described above.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.
  • m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
  • p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, still more preferably 0 to 1, and particularly preferably 0.
  • q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
  • the compound represented by the formula (I) is preferably a compound represented by the following formula (III).
  • R 1 represents a hydrogen atom or a methyl group
  • R 21 and R 22 each independently represent an alkylene group
  • n represents an integer of 0 to 15.
  • the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2 or 3. preferable.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.
  • Examples of the compound represented by the formula (I) include ethylene oxide or propylene oxide-modified (meth) acrylate of paracumylphenol.
  • Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • the resin b1 preferably further contains a repeating unit derived from an alkyl (meth) acrylate (hereinafter, also referred to as a repeating unit b1-2).
  • the alkyl portion of the alkyl (meth) acrylate preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms.
  • Preferred specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate.
  • the resin b1 preferably further contains a repeating unit having an acid group (hereinafter, also referred to as a repeating unit b1-3).
  • the coloring composition of the present invention can contain a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of an acid group is larger than the amount of a basic group.
  • the acidic dispersant (acidic resin) a resin in which the amount of the acid group accounts for 70% by mole or more when the total amount of the acid group and the amount of the basic group is 100% by mole is preferable. A resin consisting of only an acid group is more preferred.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant is preferably from 10 to 105 mgKOH / g.
  • the basic dispersant refers to a resin in which the amount of the basic group is larger than the amount of the acid group.
  • a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol% is preferable.
  • the basic group of the basic dispersant is preferably an amino group.
  • the dispersant examples include a polymer dispersant [eg, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine and the like.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.
  • the polymer dispersant adsorbs on the surface of particles such as pigments and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the particle surface such as a pigment can be cited as a preferable structure. Further, dispersants described in paragraphs 0028 to 0124 of JP-A-2011-070156 and dispersants described in JP-A-2007-277514 are also preferably used.
  • a graft copolymer can also be used as a dispersant.
  • the details of the graft copolymer can be referred to the description in paragraphs 0131 to 0160 of JP-A-2012-137564, the contents of which are incorporated herein.
  • an oligoimine-based copolymer containing a nitrogen atom in at least one of a main chain and a side chain can be used as the dispersant.
  • the description in paragraphs 0102 to 0174 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the dispersing agent is also available as a commercial product.
  • Specific examples of such a dispersing agent include Disperbyk series (for example, Disperbyk-111 and 2001) manufactured by Big Chemie, and Solsperse series (manufactured by Nippon Lubrizol Co., Ltd.).
  • Solsperse 20000, 76500, etc. and Azispar series manufactured by Ajinomoto Fine Techno Co., Ltd. are exemplified.
  • a product described in paragraph No. 0129 of JP-A-2012-137564 and a product described in paragraph No. 0235 of JP-A-2017-194662 can be used as a dispersant.
  • the content of the resin is preferably 5 to 50% by mass based on the total solid content of the coloring composition.
  • the upper limit is preferably at most 40% by mass, more preferably at most 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
  • the content of the resin is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • the upper limit is preferably 250 parts by mass or less, more preferably 150 parts by mass or less.
  • the lower limit is preferably at least 50 parts by mass, more preferably at least 75 parts by mass.
  • the content of the resin b1 (including the repeating unit derived from the compound represented by the formula (III)) in the total amount of the resin contained in the coloring composition of the present invention is 0.1 to 100% by mass. It is preferably present, and more preferably 5 to 100% by mass.
  • the upper limit can be 90% by mass or less, can be 80% by mass or less, and can be 70% by mass or less. Further, the content of the resin b1 is preferably 5 to 50% by mass based on the total solid content of the coloring composition.
  • the upper limit is preferably at most 40% by mass, more preferably at most 30% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 12.5% by mass or more.
  • the coloring composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). According to this aspect, low-temperature curing is excellent.
  • the structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan).
  • a furyl group a group obtained by removing one hydrogen atom from furan.
  • compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used.
  • the difuryl group-containing compound may be a monomer or a polymer.
  • the polymer is preferably used because it is easy to improve the durability of the obtained film.
  • the weight average molecular weight is preferably from 2000 to 70000.
  • the upper limit is preferably 60,000 or less, more preferably 50,000 or less.
  • the lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
  • the polymer type furyl group-containing compound is a component that also corresponds to the resin in the coloring composition of the present invention.
  • Examples of the monomer type furyl group-containing compound include a compound represented by the following formula (fur-1).
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 2 represents a divalent linking group.
  • Examples of the divalent linking group represented by Rf 2 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the furyl group-containing monomer is preferably a compound represented by the following formula (fur-1-1).
  • Rf 1 represents a hydrogen atom or a methyl group
  • Rf 11 represents —O— or —NH—
  • Rf 12 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group represented by Rf 12 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups.
  • the carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15.
  • the alkylene group may be linear, branched or cyclic.
  • the carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
  • the alkylene group and the arylene group may have a substituent. Examples of the
  • furyl group-containing monomer examples include a compound having the following structure.
  • Rf 1 represents a hydrogen atom or a methyl group.
  • the polymer type furyl group-containing compound (hereinafter also referred to as a furyl group-containing polymer) is preferably a resin containing a repeating unit containing a furyl group, and is preferably a resin derived from the compound represented by the above formula (fur-1). More preferably, the resin contains units.
  • the concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol, per 1 g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a pixel having excellent solvent resistance and the like. When the concentration of the furyl group is 6.0 mmol or less, preferably 4.0 mmol or less, the coloring composition has good temporal stability.
  • the furyl group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group in addition to the repeating unit having a furyl group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • its acid value is preferably from 10 to 200 mgKOH / g, more preferably from 40 to 130 mgKOH / g.
  • the furyl group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a pixel having more excellent solvent resistance and the like.
  • the furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
  • the content of the furyl group-containing compound is preferably from 0.1 to 70% by mass based on the total solid content of the coloring composition.
  • the lower limit is preferably at least 2.5% by mass, more preferably at least 5.0% by mass, even more preferably at least 7.5% by mass.
  • the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the furyl group-containing polymer in the resin contained in the coloring composition is preferably from 0.1 to 100% by mass.
  • the lower limit is preferably at least 10 parts by mass, more preferably at least 15 parts by mass.
  • the upper limit is preferably at most 90 parts by mass, more preferably at most 80 parts by mass. Further, when the resin used in the coloring composition of the present invention contains the resin b1 described above, and a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer is the same as that of the resin b1. It is preferably from 10 to 200 parts by mass per 100 parts by mass.
  • the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less.
  • the lower limit is preferably 25 parts by mass or more, and more preferably 150 parts by mass or more.
  • the coloring composition of the present invention may further contain a compound having an epoxy group.
  • a compound having two or more epoxy groups in one molecule is preferable.
  • the epoxy group preferably has 2 to 100 epoxy groups in one molecule.
  • the upper limit can be, for example, 10 or less, or 5 or less.
  • the compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
  • the upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
  • Examples of the compound having an epoxy group include paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408.
  • the compounds described and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
  • the content of the compound having an epoxy group is preferably 0.1 to 40% by mass based on the total solid content of the coloring composition.
  • the lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • the compound having an epoxy group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
  • the coloring composition of the present invention preferably contains a solvent.
  • the solvent include an organic solvent.
  • the solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For these details, reference can be made to paragraph No. 0223 of WO 2015/166779, the contents of which are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like.
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons or the like (for example, 50 mass ppm (parts per part based on the total amount of the organic solvent). (million) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • a solvent having a low metal content it is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent be, for example, 10 mass ppb (parts per per billion) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide.
  • the content of the solvent in the coloring composition is preferably from 60 to 95% by mass.
  • the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and even more preferably 85% by mass or less.
  • the lower limit is preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass.
  • the coloring composition of the present invention does not substantially contain an environmental control substance from the viewpoint of environmental control.
  • the term "substantially free of environmental control substances” means that the content of the environmental control substances in the coloring composition is 50 ppm by mass or less, and preferably 30 ppm by mass or less. Is more preferably 10 ppm by mass or less, particularly preferably 1 ppm by mass or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • azeotrope When a small amount of environmentally regulated substances are distilled off, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency.
  • a polymerization inhibitor or the like When a compound having a radical polymerizability is contained, a polymerization inhibitor or the like is added in order to suppress the radical polymerization reaction from proceeding and crosslinking between molecules during the distillation under reduced pressure, followed by distillation under reduced pressure. You may.
  • These distillation methods are performed at the stage of the raw material, at the stage of a product obtained by reacting the raw material (for example, a resin solution or a polyfunctional monomer solution after polymerization), or at the stage of a colored composition prepared by mixing these compounds. It is also possible at the stage.
  • the coloring composition of the present invention can contain a pigment derivative.
  • the pigment derivative include a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group.
  • the chromophores constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, and a perinone skeleton.
  • quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole-based skeleton, an azo-based skeleton, a quinophthalone-based skeleton, an isoindoline-based skeleton, and a phthalocyanine-based skeleton are preferred, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferred.
  • the acid group of the pigment derivative a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
  • the basic group of the pigment derivative an amino group is preferable, and a tertiary amino group is more preferable.
  • the content of the pigment derivative is preferably from 1 to 30 parts by mass, more preferably from 3 to 20 parts by mass, based on 100 parts by mass of the pigment.
  • One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.
  • a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable monomer or lowering the curing temperature.
  • the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in a molecule.
  • the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1). Equation (T1) (In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • the curing accelerator may be a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-034963), an amine, a phosphonium salt, an amidine salt, an amide compound (for example, JP-A-2013-41165, paragraph No. 0186, a base generator (for example, an ionic compound described in JP-A-2014-55114), and a cyanate compound (for example, JP-A-2012-150180) Japanese Patent Application Laid-Open No.
  • a methylol-based compound for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-034963
  • an amine for example, a phosphonium salt, an amidine salt, an amide compound (for example, JP-A-2013-41165, paragraph No. 0186, a base generator (for example, an ionic compound described
  • an alkoxysilane compound for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-25305
  • an onium salt compound for example, a compound described in JP-A-2015-34963.
  • Chemical compounds exemplified as an acid generator in paragraph No. 0216 Things, compounds described in JP-A-2009-180949) or the like can be used.
  • the content of the curing accelerator is preferably from 0.3 to 8.9% by mass, and preferably from 0.8 to 6.4% by mass based on the total solid content of the coloring composition. % Is more preferred.
  • the coloring composition of the present invention can contain a silane coupling agent.
  • a silane coupling agent a silane compound having at least two kinds of functional groups having different reactivities in one molecule is preferable.
  • the silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. Is preferred.
  • silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu) KBE-903 manufactured by Chemical Industry Co., Ltd., 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Manufactured by KBM-40
  • the description of paragraphs 0155 to 0158 of JP-A-2013-254407 can be referred to, and the contents thereof are incorporated herein.
  • the content of the silane coupling agent is preferably 0.001 to 20% by mass, and more preferably 0.01 to 10% by mass based on the total solid content of the coloring composition. Is more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the coloring composition of the present invention may include only one type of silane coupling agent, or may include two or more types of silane coupling agents. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts and the like) and the like.
  • the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the coloring composition.
  • the coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used.
  • UV absorbers include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • benzotriazole compound examples include MYUA series (manufactured by Chemical Industry Daily, Feb. 1, 2016) manufactured by Miyoshi Oil & Fat.
  • compounds described in paragraphs 0049 to 0059 of JP-A-6268967 can also be used as an ultraviolet absorber.
  • the coloring composition of the present invention contains an ultraviolet absorber
  • the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is particularly preferably 0.1 to 3% by mass.
  • only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the coloring composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • paragraphs 0238 to 0245 of WO2015 / 166779 can be referred to, and the contents thereof are incorporated herein.
  • the surfactant is preferably a fluorinated surfactant.
  • the coloring composition contains a fluorine-based surfactant, liquid properties (particularly, fluidity) are further improved, and liquid saving properties can be further improved. Further, a film with small thickness unevenness can be formed.
  • the fluorine content in the fluorine-based 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.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of a coating film and liquid saving properties, and has good solubility in a coloring composition.
  • fluorinated surfactant examples include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of corresponding International Publication 2014/017669), and JP-A-2011-132503.
  • the surfactants described in paragraph Nos. 0117 to 0132 of the above-mentioned publications are exemplified, and the contents thereof are incorporated herein.
  • fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox @ PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. .
  • fluorine-based surfactants have a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized. It can be suitably used.
  • fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21.
  • a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant.
  • the description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, and the contents thereof are incorporated herein.
  • the fluorine-based surfactant a block polymer can also be used.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used.
  • a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used.
  • compounds described in paragraphs [0050] to [0090] and paragraphs [0289] to [0295] of JP-A-2010-164965 for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation , RS-72-K and the like.
  • the fluorinated surfactant compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS ), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured
  • silicone-based surfactant examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).
  • the content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass.
  • the surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention may optionally contain various additives such as a filler, an adhesion promoter, an antioxidant, and an anti-agglomeration agent.
  • additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein.
  • the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound, or the like can be used.
  • antioxidants described in 0048 can also be used.
  • One type of antioxidant may be used, or two or more types may be used.
  • the coloring composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • a compound in which a protecting group is eliminated to function as an antioxidant can be mentioned.
  • Specific examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP-A-2017-008219.
  • Commercially available products include Adeka Aquel's GPA-5001 (manufactured by ADEKA Corporation).
  • the coloring composition of the present invention includes a sensitizer and a light stabilizer described in paragraph No.
  • JP-A-2004-295116 a thermal polymerization inhibitor described in paragraph 0081 of the same, and JP-A-2018-295. It can contain a storage stabilizer described in paragraph No. 0242 of JP-A-091940.
  • the content of a free metal not bound or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less. , Is particularly preferably not substantially contained.
  • stabilization of pigment dispersibility suppression of aggregation
  • improvement of spectral characteristics due to improvement of dispersibility stabilization of curable components
  • suppression of fluctuation in conductivity due to elution of metal atoms and metal ions The effects such as improvement of display characteristics can be expected.
  • the types of the above free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi and the like.
  • the curable composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. Is more preferable, and it is particularly preferable that it is not substantially contained.
  • Examples of a method for reducing free metals and halogens in the curable composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the coloring composition of the present invention does not contain a terephthalic acid ester.
  • the container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used. Further, as a storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the coloring composition, a multi-layer bottle in which the inner wall of the container is formed of six types and six layers of resin or a bottle in which six types of resin are formed in a seven-layer structure It is also preferred to use Examples of such a container include a container described in JP-A-2015-123351.
  • the coloring composition of the present invention can be produced by mixing the above-mentioned components.
  • the coloring composition may be produced by simultaneously dissolving and / or dispersing all the components in a solvent, or, if necessary, appropriately converting each component into two or more solutions or dispersions. At the time of use (at the time of application), these may be mixed to produce a colored composition.
  • the production of the coloring composition may include a process of dispersing particles such as pigments.
  • examples of mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like.
  • fine processing of particles may be performed in a salt milling step.
  • the materials, equipment, processing conditions, and the like used in the salt milling step can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PTFE polytetrafluoroethylene
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin).
  • PP polypropylene
  • nylon high-density polypropylene
  • nylon are preferred.
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
  • a fibrous filter medium examples include a polypropylene fiber, a nylon fiber, and a glass fiber.
  • Commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
  • filters for example, a first filter and a second filter
  • the filtration by each filter may be performed only once or may be performed twice or more.
  • filters having different hole diameters may be combined within the above-described range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.
  • the method for forming a pixel of the present invention includes the steps of applying the coloring composition of the present invention on a support to form a coloring composition layer, exposing the coloring composition layer in a pattern, and after the exposure. Developing the coloring composition layer.
  • the process is performed at a temperature of 150 ° C. or less throughout the entire process.
  • “performed at a temperature of 150 ° C. or lower throughout the entire process” means that all steps of forming a pixel using a coloring composition are performed at a temperature of 150 ° C. or lower.
  • this heating step is also performed at a temperature of 150 ° C. or less.
  • each step will be described in detail.
  • the colored composition of the present invention is applied on a support to form a colored composition layer.
  • the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate.
  • An organic light emitting layer may be formed on these substrates.
  • the substrate may be provided with an undercoat layer for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the surface.
  • a known method can be used as a method for applying the coloring composition.
  • a dropping method drop casting
  • a slit coating method for example, a spraying method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, JP-A-2009-145395).
  • Publications inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods a transfer method using a mold or the like; a nanoimprint method, and the like.
  • the application method in the ink jet is not particularly limited, and for example, a method shown in “Spread and usable ink jets—infinite possibilities seen in patents”, published in February 2005, Sumibe Techno Research (especially from page 115). 133 page), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261828, JP-A-2012-126830, JP-A-2006-169325, and the like.
  • No. regarding the method for applying the coloring composition the descriptions in WO2017 / 030174 and WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
  • the colored composition layer formed on the support may be dried (prebaked).
  • the prebaking temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C or lower, and particularly preferably 50 ° C or lower.
  • the lower limit can be, for example, 40 ° C. or higher.
  • the prebake time is preferably from 10 to 3600 seconds. Prebaking can be performed on a hot plate, an oven, or the like.
  • the colored composition layer is exposed in a pattern (exposure step).
  • the colored composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine or the like through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line.
  • Light with a wavelength of 300 nm or less (preferably, light with a wavelength of 180 to 300 nm) can also be used.
  • Examples of the light having a wavelength of 300 nm or less include a KrF line (wavelength 248 nm) and an ArF line (wavelength 193 nm), and a KrF line (wavelength 248 nm) is preferable.
  • a long-wavelength light source of 300 nm or more can be used.
  • the pulse exposure is an exposure method of a method in which light irradiation and pause are repeatedly performed in a short cycle (for example, millisecond level or less) cycle.
  • the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less.
  • the lower limit of the pulse width is not particularly limited, it may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more.
  • the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, even more preferably 4 kHz or more.
  • the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less.
  • Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
  • the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
  • the pulse width is a time during which light is irradiated in a pulse cycle.
  • the frequency refers to the number of pulse periods per second.
  • the maximum instantaneous illuminance is an average illuminance within a time period during which light is irradiated in a pulse cycle.
  • the pulse cycle is a cycle in which light irradiation and pause in pulse exposure are one cycle.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected.
  • a low oxygen atmosphere having an oxygen concentration of 19% by volume or less for example, 15% by volume, 5% by volume, or substantially Exposure may be performed under oxygen-free conditions, or under a high oxygen atmosphere having an oxygen concentration of more than 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). Can be. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the colored composition layer can be sufficiently cured, and a pixel having excellent properties such as solvent resistance can be manufactured.
  • the exposed colored composition layer is developed. That is, a pattern (pixel) is formed by developing and removing an unexposed portion of the coloring composition layer.
  • the development removal of the unexposed portion of the coloring composition layer can be performed using a developer.
  • the colored composition layer in the unexposed portion in the exposure step elutes into the developer, leaving only the photocured portion.
  • the developer include an organic solvent and an alkali developer, and an alkali developer is preferable.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • the alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene
  • Alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate.
  • the alkali agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • the surfactant include the surfactants described above, and a nonionic surfactant is preferable.
  • the developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage.
  • the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development.
  • the rinsing is preferably performed by supplying a rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when the nozzle is moved from the central portion to the peripheral portion of the support, the nozzle may be moved while gradually lowering the moving speed. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually lowering the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
  • the additional exposure processing and post bake are post-development curing treatments to complete the curing.
  • the heating temperature is preferably 100 to 150 ° C.
  • the upper limit of the heating temperature is preferably 120 ° C. or lower.
  • the heating time is preferably at least 1 minute, more preferably at least 5 minutes, even more preferably at least 10 minutes.
  • the upper limit is not particularly limited, but is preferably 20 minutes or less from the viewpoint of productivity.
  • Post-baking is also preferably performed in an inert gas atmosphere. According to this aspect, the thermal polymerization can proceed at a very high efficiency without being hindered by oxygen, and even when pixels are manufactured at a temperature of 120 ° C. or less throughout the entire process, the flatness can be improved. And a pixel excellent in characteristics such as solvent resistance can be manufactured.
  • the inert gas include a nitrogen gas, an argon gas, a helium gas and the like, and a nitrogen gas is preferable.
  • the oxygen concentration at the time of post baking is preferably 100 ppm or less.
  • the step of exposing the colored composition layer in a pattern includes light having a wavelength of more than 350 nm and not more than 380 nm (preferably light having a wavelength of 355 to 370 nm, Exposure is performed by irradiating with i-line), and the additional exposure treatment (exposure after development) is performed on the colored composition layer after development with light having a wavelength of 254 to 350 nm (preferably light having a wavelength of 254 nm). ) Is preferably exposed.
  • the colored composition layer can be appropriately cured by the first exposure (exposure before development), and the entire colored composition layer is almost completely cured by the next exposure (exposure after development).
  • the color composition layer can be sufficiently cured even under a low temperature condition, and a pixel having excellent properties such as solvent resistance, adhesion, and rectangularity can be formed.
  • the colored composition includes, as a photopolymerization initiator, a photopolymerization initiator A1 having an absorption coefficient of 1.0 ⁇ 10 3 mL / gcm or more at a wavelength of 365 nm in methanol.
  • a photopolymerization initiator A2 having an extinction coefficient at 365 nm in methanol of 1.0 ⁇ 10 2 mL / gcm or less and an extinction coefficient of 254 nm at 1.0 ⁇ 10 3 mL / gcm or more in methanol. It is preferable to use one.
  • Exposure after development can be performed using, for example, an ultraviolet photoresist curing device.
  • an ultraviolet photoresist curing device for example, light having a wavelength of 254 to 350 nm and other light (for example, i-line) may be irradiated.
  • Irradiation amount of exposure after development (exposure) is preferably 30 ⁇ 4000mJ / cm 2, more preferably 50 ⁇ 3500mJ / cm 2.
  • the difference between the wavelength of light used in exposure before development and the wavelength of light used in exposure after development is preferably 200 nm or less, and more preferably 100 to 150 nm.
  • the method for manufacturing a color filter according to the present invention includes the above-described method for forming a pixel according to the present invention.
  • the above-described method of forming a pixel of the present invention is performed for each pixel of each color, whereby a color filter having pixels of a plurality of colors can be formed.
  • the color filter include a filter having one or more colored pixels such as a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, and a yellow pixel.
  • the color filter include a filter having at least a red pixel, a blue pixel, and a green pixel, and a filter having at least a cyan pixel, a magenta pixel, and a yellow pixel.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition into, for example, a lattice.
  • the partition in this case preferably has a low refractive index for each colored pixel.
  • the partition wall may be formed by the configuration described in US2018 / 0040656.
  • a method for manufacturing a display device according to the present invention includes the above-described method for forming a pixel according to the present invention.
  • Examples of the display device include a liquid crystal display device and an organic electroluminescence display device.
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited.
  • the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “next-generation liquid crystal display technology”.
  • the organic electroluminescence display device may have a light source including a white organic electroluminescence element.
  • the white organic electroluminescent element preferably has a tandem structure.
  • the spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in a blue region (430 nm to 485 nm), a green region (530 nm to 580 nm), and a yellow region (580 nm to 620 nm). Those having a maximum emission peak in a red region (650 nm to 700 nm) in addition to these emission peaks are more preferable.
  • Pigment dispersion liquid PR ⁇ Preparation of pigment dispersion>
  • the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 ⁇ m.
  • Eiger mill Mini Model M-250MKII manufactured by Eiger Japan
  • a filter having a pore size of 5 ⁇ m a pigment dispersion PR was prepared.
  • C. I. Pigment Red 254 8.96 parts by mass
  • Pigment Red 177 1.42 parts by mass
  • Pigment Yellow 150 1.16 parts by mass Dispersant (manufactured by Nippon Lubrizol Co., Ltd., Solsperse 20000) ⁇ 2.29 parts by mass Alkali-soluble resin solution D2: 7.66 parts by mass Cyclohexanone: 75.82 parts by mass
  • alkali-soluble resin solution D2 one produced by the following method was used. 90.0 parts by mass of cyclohexanone is placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel. A mixture of 20.0 parts by mass, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate, and 2.5 parts by mass of 2,2′-azobisisobutyronitrile was mixed with 2 parts by mass. The polymerization reaction was performed by dropping over time.
  • the mixture was further reacted at 60 ° C. for 1 hour, and a solution prepared by dissolving 0.5 part by mass of 2,2′-azobisisobutyronitrile in 10.0 parts by mass of propylene glycol monomethyl ether acetate was added. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with cyclohexanone to obtain an alkali-soluble resin solution D2 having a solid content of 20%. The weight average molecular weight was 30,000.
  • Pigment dispersion liquid PG After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 ⁇ m. Thus, a pigment dispersion liquid PG was prepared.
  • C.I. I. Pigment Yellow 150 4.14 parts by mass Dispersant (Disperbyk-2001, manufactured by BYK Chemie, solid content concentration: 46% by mass) ... 6.09 parts by mass Alkali-soluble resin solution
  • D2 5.53 parts by mass Propylene glycol monomethyl ether acetate: 76.71 parts by mass
  • Pigment dispersion liquid PB After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 ⁇ m. Thus, a pigment dispersion liquid PB was prepared.
  • Example 1 After mixing and stirring the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a colored composition having a solid content of 17% by mass. The solid content of the coloring composition was adjusted by the amount of propylene glycol monomethyl ether acetate.
  • Examples 2 to 25, Comparative Examples 1 and 2 The types and contents of the pigment dispersion, the photopolymerization initiator, the resin, the furyl group-containing compound, the polymerizable monomer and the solvent were each changed as described in the following table, and a colored composition was prepared in the same manner as in Example 1. .
  • the solid content concentration of each coloring composition was adjusted by the amount of the solvent.
  • Initiator 1 IRGACURE-OXE02 (manufactured by BASF, a compound having the following structure, the absorption coefficient in methanol at a wavelength of 365 nm is 7749 mL / gcm)
  • Initiator 2 IRGACURE-OXE01 (manufactured by BASF, a compound having the following structure, the extinction coefficient in methanol of 365 nm at a wavelength of 6969 mL / gcm)
  • Initiator 3 a compound having the following structure (the extinction coefficient of light having a wavelength of 365 nm in methanol is 18900 mL / gcm)
  • Initiator 4 IRGACURE-2959 (manufactured by BASF, a compound having the following structure, the extinction coefficient in methanol at a wavelength of 365 nm is 48.93 mL / gcm, and the extinction
  • Resin A Resin synthesized by the following method: 70.0 parts by mass of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer, and heated to 80 ° C. After the atmosphere in the flask was replaced with nitrogen, 13.3 parts by weight of n-butyl methacrylate, 4.6 parts by weight of 2-hydroxyethyl methacrylate, 4.3 parts by weight of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (Toa) were added through a dropping tube.
  • Resin C Resin synthesized by the following method: 90.0 parts by mass of propylene glycol monomethyl ether acetate is charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction pipe, and nitrogen gas is injected into the vessel. While heating to 60 ° C., a mixture of 35.0 parts by mass of glycidyl methacrylate, 45.0 parts by mass of methyl methacrylate, and 2.5 parts by mass of 2,2′-azobisisobutyronitrile was added at the same temperature for 2 hours. Then, the polymerization reaction was carried out by dropping. After the completion of the dropwise addition, the mixture was further reacted at 60 ° C.
  • (Furyl group-containing compound) F1 Furyl group-containing compound F1 synthesized by the following method 90.0 parts by mass of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel.
  • furfuryl methacrylate 50.0 parts by mass, 2-methacryloyloxyethyl succinic acid 26.7 parts by mass, 2-hydroxyethyl methacrylate 23.3 parts by mass, 2,2′-azobis (2,4-dimethylvaleronitrile) ) 2.5 parts by mass of the mixture was dropped over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate.
  • F2 Furyl group-containing compound F2 synthesized by the following method 90.0 parts by mass of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel. At a temperature, a mixture of 50.0 parts by mass of furfuryl methacrylate, 10 parts by mass of methacrylic acid, 40.0 parts by mass of methyl methacrylate, and 5.0 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) is added for 2 hours. The polymerization reaction was carried out by dropping.
  • viscosity The viscosity (initial viscosity, unit: mPa ⁇ s) immediately after the preparation of the coloring composition was measured using a viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24, measuring range: 0.6 to 1200 mPa ⁇ s) manufactured by Toki Sangyo. The measurement was performed with the temperature adjusted to 25 ° C.
  • the storage stability of the coloring composition was determined according to the following criteria.
  • the viscosity of the coloring composition was measured using a viscometer RE85L manufactured by Toki Sangyo (rotor: 1 ° 34 ′ ⁇ R24, measurement range: 0.6 to 1200 mPa ⁇ s) with the temperature adjusted to 25 ° C.
  • AA The viscosity after storage was more than 95% and less than 105% of the initial viscosity.
  • A The viscosity after storage was more than 93% and less than 95% of the initial viscosity, or was more than 105% and less than 107% of the initial viscosity.
  • B The viscosity after storage was in the range of 90% to 93% of the initial viscosity, or in the range of 107% to 110% of the initial viscosity.
  • C The viscosity after storage is less than 90% of the initial viscosity or more than 110% of the initial viscosity.
  • the glass wafer on which the green coloring pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from a nozzle above a rotation center from a nozzle above the rotation center. And rinsed, followed by spray drying. Thereafter, the entire glass wafer on which the pattern was formed was subjected to additional exposure using an ultraviolet photoresist curing device (UMA-802-HC-552; manufactured by Ushio Electric Co., Ltd.), and a 3.0 ⁇ m Bayer pattern was formed on the glass wafer. Green pixels were formed.
  • UMA-802-HC-552 ultraviolet photoresist curing device
  • An island-colored pixel pattern was formed between the Green pixels in the same manner except that the coloring compositions of Examples and Comparative Examples were used with a mask having an island pattern of 3.0 ⁇ m.
  • the height of the island colored pixel pattern prepared above was measured along the diagonal line of the pixel using an atomic force microscope (AFM, SPA-400AFM, manufactured by Seiko Instruments Inc.). From the measured values, the difference between the highest point and the height at the center was evaluated as flatness based on the following evaluation criteria.
  • AA The difference between the height of the highest point and the center is less than 75 nm.
  • A The difference between the height of the highest point and the center is 75 nm or more and less than 100 nm.
  • C difference in height between the highest point and the central part is not less than 150 nm
  • the coloring compositions of Examples had excellent flatness evaluations. Furthermore, the storage stability and the applicability were excellent.
  • an organic electroluminescence display device having excellent luminance viewing angle characteristics can be obtained.
  • Example 1 On a glass substrate, a spin coater was used so that the film thickness of the colored composition of Example 1, Example 16, Example 17, Example 18, Comparative Example 1 or Comparative Example 2 was 1.2 ⁇ m after prebaking. Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. to form a film. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), i-line was irradiated at an exposure amount of 3000 mJ / cm 2 to form a film.
  • FPA-3000i5 + manufactured by Canon Inc.
  • NMP N-methylpyrrolidone
  • Remaining film ratio Thickness of film before and after solvent resistance test / Thickness of film before solvent resistance test AA: The remaining film ratio is 0.95 or more and 1.0 or less. A: The residual film ratio is 0.90 or more and less than 0.95. B: The residual film ratio is 0.85 or more and less than 0.90. C: The residual film ratio is less than 0.85.
  • Example 2 On a glass substrate, a spin coater was used so that the film thickness of the colored composition of Example 1, Example 16, Example 17, Example 18, Comparative Example 1 or Comparative Example 2 was 1.2 ⁇ m after prebaking. Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. to form a film. Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), i-line was irradiated at an exposure amount of 100 mJ / cm 2 . Next, heat treatment was performed on a hot plate at 120 ° C. for 900 seconds to form a film.
  • prebaking heat treatment
  • FPA-3000i5 + manufactured by Canon Inc.

Abstract

A coloring composition for forming a color filter for a display device, wherein the coloring composition is used for forming pixels at a temperature of 150°C or less throughout the entire process, the coloring composition contains a coloring agent, a resin, a photoinitiator, and polymerizable monomers, and the viscosity of the coloring composition at 25°C is 2.0 to 7.5 mPa·s. A pixel forming method, a color filter production method, and a display device production method in which the coloring composition is used.

Description

着色組成物、画素の形成方法、カラーフィルタの製造方法および表示装置の製造方法Colored composition, pixel forming method, color filter manufacturing method, and display device manufacturing method
　本発明は、表示装置用のカラーフィルタ形成用の着色組成物に関する。また、本発明は、画素の形成方法、カラーフィルタおよび表示装置の製造方法に関する。 << The present invention relates to a coloring composition for forming a color filter for a display device. Further, the present invention relates to a method for forming a pixel, a color filter, and a method for manufacturing a display device.
　各種表示装置において、表示画像のカラー化のためにカラーフィルタが一般的に用いられている。例えば、特許文献１には、フリル基を含む化合物（Ａ）、光重合性官能基を含む化合物（Ｂ）、光重合開始剤（Ｃ）、および着色剤を含有する、カラーフィルタ用感光性組成物を用いてカラーフィルタを形成し、有機エレクトロルミネッセンス表示装置を製造することが記載されている。 カ ラ ー In various display devices, a color filter is generally used for colorizing a display image. For example, Patent Document 1 discloses a photosensitive composition for a color filter containing a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a colorant. It describes that an organic electroluminescent display device is manufactured by forming a color filter using an object.
特開２０１７－１９４６６２号公報JP 2017-194662A
　カラーフィルタを備える表示装置について、近年では輝度のさらなる向上が望まれている。本発明者が表示装置の輝度を向上させる方法について鋭意検討したところ、着色組成物を用いて画素を形成してカラーフィルタを製造する際において、平坦性の良い画素を形成することで表示装置の輝度を向上できることを見出した。更には、得られる画素の平坦性を向上させることにより、表示装置の斜め方向の輝度の低下も抑制することができ、輝度の視野角特性も高めることができることを見出した。 表示 In recent years, with respect to a display device having a color filter, further improvement in luminance has been desired. The present inventors have conducted intensive studies on a method for improving the luminance of a display device, and found that when a pixel is formed using a coloring composition and a color filter is manufactured, a pixel with good flatness is formed by forming a pixel with good flatness. It has been found that brightness can be improved. Furthermore, it has been found that by improving the flatness of the obtained pixels, a decrease in the luminance of the display device in an oblique direction can be suppressed, and the viewing angle characteristics of the luminance can be increased.
　一方で、近年においては、耐熱性の低い部材（例えば、有機エレクトロルミネッセンス表示素子などの有機半導体素子）上にカラーフィルタを形成することもある。このような部材は耐熱性が低いため、例えば１５０℃以下の低温プロセスでカラーフィルタの画素を形成して、支持体への熱的ダメージを抑制することが望ましい。 On the other hand, in recent years, a color filter may be formed on a member having low heat resistance (for example, an organic semiconductor element such as an organic electroluminescence display element). Since such a member has low heat resistance, it is desirable to form a pixel of the color filter by a low-temperature process of 150 ° C. or less, for example, to suppress thermal damage to the support.
　しかしながら、本発明者の検討によれば、低温プロセスで画素を形成した場合、画素の平坦性が劣りやすいことが分かった。 However, according to the study of the present inventors, it was found that when pixels were formed by a low-temperature process, the flatness of the pixels was likely to be inferior.
　よって、本発明の目的は、平坦性に優れた画素を形成することができる着色組成物を提供することにある。また、本発明の目的は、画素の形成方法、カラーフィルタの製造方法および表示装置の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a coloring composition capable of forming a pixel having excellent flatness. Another object of the present invention is to provide a method for forming a pixel, a method for manufacturing a color filter, and a method for manufacturing a display device.
　本発明者の検討によれば、着色組成物の粘度を特定の範囲に調整することで、全工程を通じて１５０℃以下の温度で画素を形成した場合であっても平坦性に優れた画素を形成できることを見出し、本発明を完成するに至った。本発明は以下を提供する。
　＜１＞　表示装置用のカラーフィルタの画素形成用の着色組成物であって、
　着色組成物は全工程を通じて１５０℃以下の温度で画素を形成するために用いられ、
　着色組成物は着色剤と樹脂と光重合開始剤と重合性モノマーとを含み、
　着色組成物の２５℃における粘度が２．０～７．５ｍＰａ・ｓである、着色組成物。
　＜２＞　着色組成物の固形分濃度が５～２５％である、＜１＞に記載の着色組成物。
　＜３＞　樹脂は、下記式（Ｉ）で表される化合物由来の繰り返し単位を含む樹脂ｂ１を含有する、＜１＞または＜２＞に記載の着色組成物；
Figure JPOXMLDOC01-appb-C000003
 　式中、Ｘ1は、ＯまたはＮＨを表し、
　Ｒ1は水素原子またはメチル基を表し、
　Ｌ1は２価の連結基を表し、
　Ｒ10は置換基を表し、
　ｍは０～２の整数を表し、
　ｐは０以上の整数を表す。
　＜４＞　樹脂ｂ１は、更に、アルキル（メタ）アクリレート由来の繰り返し単位を含む、＜３＞に記載の着色組成物。
　＜５＞　光重合開始剤はオキシム化合物を含有する、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　光重合開始剤は、
　メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ１と、
　メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ２と、
　を含む、＜１＞～＜５＞のいずれか１つに記載の着色組成物。
　＜７＞　光重合開始剤Ａ１がフッ素原子を含むオキシム化合物である、＜６＞に記載の着色組成物。
　＜８＞　光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である、＜６＞または＜７＞に記載の着色組成物。
　＜９＞　重合性モノマーは、酸基を有する重合性モノマーを含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　重合性モノマーは、エチレン性不飽和基を３個以上含む重合性モノマーを含む、＜１＞～＜９＞のいずれか１つに記載の着色組成物。
　＜１１＞　フリル基を含む化合物を含む、＜１＞～＜１０＞のいずれか１つに記載の着色組成物。
　＜１２＞　フリル基を含む化合物は、下記式（ｆｕｒ－１）で表される化合物、および、下記式（ｆｕｒ－１）で表される化合物由来の繰り返し単位を含む樹脂から選ばれる少なくとも１種である、＜１１＞に記載の着色組成物；
Figure JPOXMLDOC01-appb-C000004
 　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ2は２価の連結基を表す。
　＜１３＞　温度２５℃、湿度５０％の条件で３０日間保存した後の着色組成物の２５℃における粘度が、製造直後の着色組成物の２５℃における粘度の９０～１１０％の範囲である、＜１＞～＜１２＞のいずれか１つに記載の着色組成物。
　＜１４＞　支持体上に＜１＞～＜１３＞のいずれか１つに記載の着色組成物を塗布して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、露光後の着色組成物層を現像する工程と、を含む画素の形成方法であって、
　画素の形成方法は、全工程を通じて１５０℃以下の温度で行う、画素の形成方法。
　＜１５＞　着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光を１Ｊ／ｃｍ2以上の露光量で照射して露光する、＜１４＞に記載の画素の形成方法。
　＜１６＞　着色組成物層をパターン状に露光する工程は、着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光を照射して露光を行い、
　更に、現像後の着色組成物層に対して、波長２５４～３５０ｎｍの光を照射して露光する工程を含む、＜１４＞または＜１５＞に記載の画素の形成方法。
　＜１７＞　現像後の着色組成物層を１００～１５０℃の温度で１０分以上加熱する工程を含む、＜１４＞～＜１６＞のいずれか１つに記載の画素の形成方法。
　＜１８＞　加熱する工程は、不活性ガスの雰囲気下で行う、＜１７＞に記載の画素の形成方法。
　＜１９＞　＜１４＞～＜１８＞のいずれか１つに記載の画素の形成方法を含むカラーフィルタの製造方法。
　＜２０＞　＜１４＞～＜１８＞のいずれか１つに記載の画素の形成方法を含む表示装置の製造方法。 According to the study of the present inventors, by adjusting the viscosity of the coloring composition to a specific range, a pixel having excellent flatness can be formed even when a pixel is formed at a temperature of 150 ° C. or less throughout the entire process. They have found that they can do this and have completed the present invention. The present invention provides the following.
<1> A coloring composition for forming pixels of a color filter for a display device,
The coloring composition is used to form a pixel at a temperature of 150 ° C. or less throughout the entire process,
The coloring composition contains a colorant, a resin, a photopolymerization initiator, and a polymerizable monomer,
A colored composition, wherein the viscosity of the colored composition at 25 ° C. is 2.0 to 7.5 mPa · s.
<2> The colored composition according to <1>, wherein the colored composition has a solid content of 5 to 25%.
<3> the colored composition according to <1> or <2>, wherein the resin contains a resin b1 containing a repeating unit derived from a compound represented by the following formula (I);
Figure JPOXMLDOC01-appb-C000003
 In the formula, X 1 represents O or NH;
R 1 represents a hydrogen atom or a methyl group,
L 1 represents a divalent linking group,
R 10 represents a substituent,
m represents an integer of 0 to 2,
p represents an integer of 0 or more.
<4> The colored composition according to <3>, wherein the resin b1 further includes a repeating unit derived from an alkyl (meth) acrylate.
<5> The colored composition according to any one of <1> to <4>, wherein the photopolymerization initiator contains an oxime compound.
<6> The photopolymerization initiator is
A photopolymerization initiator A1 having an absorption coefficient of 1.0 × 10 3 mL / gcm or more in methanol at a wavelength of 365 nm;
A photopolymerization initiator A2 having an extinction coefficient of 1.0 × 10 2 mL / gcm or less in methanol at a wavelength of 365 nm and an extinction coefficient of 1.0 × 10 3 mL / gcm or more at a wavelength of 254 nm;
The coloring composition according to any one of <1> to <5>, comprising:
<7> The colored composition according to <6>, wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom.
<8> The colored composition according to <6> or <7>, wherein the photopolymerization initiator A2 is a hydroxyalkylphenone compound.
<9> The colored composition according to any one of <1> to <8>, wherein the polymerizable monomer includes a polymerizable monomer having an acid group.
<10> The colored composition according to any one of <1> to <9>, wherein the polymerizable monomer includes a polymerizable monomer containing three or more ethylenically unsaturated groups.
<11> The colored composition according to any one of <1> to <10>, comprising a compound containing a furyl group.
<12> The compound containing a furyl group is at least one selected from a compound represented by the following formula (fur-1) and a resin containing a repeating unit derived from the compound represented by the following formula (fur-1) The colored composition according to <11>,
Figure JPOXMLDOC01-appb-C000004
 In the formula, Rf 1 represents a hydrogen atom or a methyl group, and Rf 2 represents a divalent linking group.
<13> The viscosity of the coloring composition at 25 ° C. after storage for 30 days at a temperature of 25 ° C. and a humidity of 50% is in the range of 90 to 110% of the viscosity at 25 ° C. of the coloring composition immediately after production. The coloring composition according to any one of <1> to <12>.
<14> a step of applying the coloring composition according to any one of <1> to <13> on a support to form a coloring composition layer, and a step of exposing the coloring composition layer to a pattern And a step of developing the colored composition layer after exposure, comprising:
The pixel is formed at a temperature of 150 ° C. or lower throughout the entire process.
<15> The method for forming a pixel according to <14>, wherein the colored composition layer is exposed to light having a wavelength of more than 350 nm and not more than 380 nm at an exposure amount of 1 J / cm 2 or more.
<16> The step of exposing the colored composition layer in a pattern is performed by irradiating the colored composition layer with light having a wavelength of more than 350 nm and not more than 380 nm,
The method of forming a pixel according to <14> or <15>, further comprising irradiating the colored composition layer after development with light having a wavelength of 254 to 350 nm.
<17> The method for forming a pixel according to any one of <14> to <16>, comprising a step of heating the colored composition layer after development at a temperature of 100 to 150 ° C. for 10 minutes or more.
<18> The method for forming a pixel according to <17>, wherein the heating step is performed in an atmosphere of an inert gas.
<19> A method for manufacturing a color filter, including the method for forming a pixel according to any one of <14> to <18>.
<20> A method for manufacturing a display device, comprising the method for forming a pixel according to any one of <14> to <18>.
　本発明によれば、平坦性に優れた画素を形成することができる着色組成物を提供することができる。また、画素の形成方法、カラーフィルタの製造方法および表示装置の製造方法を提供することができる。 According to the present invention, it is possible to provide a coloring composition capable of forming a pixel having excellent flatness. Further, a method for forming a pixel, a method for manufacturing a color filter, and a method for manufacturing a display device can be provided.
　以下において、本発明の内容について詳細に説明する。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の合計質量をいう。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定したポリスチレン換算値として定義される。 Hereinafter, the contents of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation that does not indicate substituted or unsubstituted includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. It is. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for the exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present specification, the total solid content refers to a total mass of components excluding a solvent from all components of the composition.
In this specification, “(meth) acrylate” represents both or either acrylate and methacrylate, “(meth) acryl” represents both or either acryl and methacryl, and “(meth) acrylate” ) "Allyl" means both or allyl and methallyl, and "(meth) acryloyl" means both or either acryloyl and methacryloyl.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
＜着色組成物＞
　本発明は、表示装置用のカラーフィルタの画素形成用の着色組成物であって、
　上記着色組成物は全工程を通じて１５０℃以下の温度で画素を形成するために用いられ、
　上記着色組成物は着色剤と樹脂と光重合開始剤と重合性モノマーとを含み、
　上記着色組成物の２５℃における粘度が２．０～７．５ｍＰａ・ｓであることを特徴とする。 <Coloring composition>
The present invention is a coloring composition for forming a pixel of a color filter for a display device,
The coloring composition is used to form a pixel at a temperature of 150 ° C. or less throughout the entire process,
The coloring composition contains a colorant, a resin, a photopolymerization initiator, and a polymerizable monomer,
The color composition has a viscosity at 25 ° C. of 2.0 to 7.5 mPa · s.
　本発明の着色組成物は、上述した粘度特性を有することにより、全工程を通じて１５０℃以下の温度（好ましくは１２０℃以下の温度）で画素を形成した場合であっても、平坦性に優れた画素を形成することができる。また、特に、厚さが０．８～２．０μｍで、かつ、線幅（パターンサイズ）が２．５～５．０μｍである画素を低温プロセスで形成した場合、従来の着色組成物では得られる画素の平坦性が不十分であったが、本発明の着色組成物を用いることで、平坦性の良い画素を形成することができる。このため、本発明の着色組成物は、このようなサイズの画素を形成する場合において特に効果的である。 Since the coloring composition of the present invention has the above-described viscosity characteristics, it has excellent flatness even when pixels are formed at a temperature of 150 ° C. or less (preferably a temperature of 120 ° C. or less) throughout the entire process. Pixels can be formed. Further, in particular, when a pixel having a thickness of 0.8 to 2.0 μm and a line width (pattern size) of 2.5 to 5.0 μm is formed by a low-temperature process, the conventional colored composition cannot provide a good result. Although the flatness of the obtained pixel is insufficient, a pixel having good flatness can be formed by using the coloring composition of the present invention. For this reason, the coloring composition of the present invention is particularly effective in forming pixels of such a size.
　本発明の着色組成物は、全工程を通じて１５０℃以下の温度で画素を形成するために用いられるものであり、全工程を通じて１２０℃以下の温度で画素を形成するために用いられるものであることが好ましい。なお、本明細書において全工程を通じて１５０℃以下の温度で画素を形成するとは、着色組成物を用いて画素を形成する工程の全てを１５０℃以下の温度で行うことを意味する。 The coloring composition of the present invention is used for forming a pixel at a temperature of 150 ° C. or less throughout the process, and is used for forming a pixel at a temperature of 120 ° C. or less throughout the process. Is preferred. Note that in this specification, forming a pixel at a temperature of 150 ° C. or lower throughout the entire process means that all steps of forming a pixel using a coloring composition are performed at a temperature of 150 ° C. or lower.
　本発明の着色組成物の２５℃における粘度は２．０～７．５ｍＰａ・ｓである。下限は、２．５ｍＰａ・ｓ以上が好ましく、３．０ｍＰａ・ｓ以上がより好ましい。上限は、７．０ｍＰａ・ｓ以下が好ましく、６．５ｍＰａ・ｓ以下がより好ましい。粘度が上記範囲であれば、全工程を通じて１５０℃以下の温度（好ましくは１２０℃以下の温度）で画素を形成した場合であっても、平坦性に優れた画素を形成することができる。さらには着色組成物の塗布性も良好である。
　着色組成物の粘度を上記範囲に調整する方法としては、着色組成物の固形分濃度を調整する、粘度の低い素材を用いる、経時安定性のよい素材を用いるなどの方法が挙げられる。 The viscosity at 25 ° C. of the coloring composition of the present invention is 2.0 to 7.5 mPa · s. The lower limit is preferably equal to or greater than 2.5 mPa · s, and more preferably equal to or greater than 3.0 mPa · s. The upper limit is preferably equal to or less than 7.0 mPa · s, and more preferably equal to or less than 6.5 mPa · s. When the viscosity is within the above range, a pixel having excellent flatness can be formed even when a pixel is formed at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process. Furthermore, the coating property of the coloring composition is also good.
Examples of the method of adjusting the viscosity of the coloring composition to the above range include a method of adjusting the solid content concentration of the coloring composition, using a material having low viscosity, and using a material having good aging stability.
　本発明の着色組成物の固形分濃度は、５～２５質量％であることが好ましい。上限は、２２．５質量％以下が好ましく、２０質量％以下がより好ましく、１８質量％以下が更に好ましい。固形分濃度が上記範囲であれば、全工程を通じて１５０℃以下の温度（好ましくは１２０℃以下の温度）で画素を形成した場合であっても、平坦性に優れた画素を形成することができる。 (4) The solid content of the coloring composition of the present invention is preferably 5 to 25% by mass. The upper limit is preferably 22.5% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less. When the solid content concentration is in the above range, a pixel having excellent flatness can be formed even when a pixel is formed at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process. .
　本発明の着色組成物は、温度２５℃、湿度５０％の条件で３０日間保存した後の着色組成物の２５℃における粘度が、製造直後の着色組成物の２５℃における粘度の９０～１１０％の範囲であることが好ましく、９３～１０７％の範囲であることがより好ましく、９５～１０５％の範囲であることが更に好ましい。本発明の着色組成物がこのような特性を有していることにより、より平坦性に優れた画素を形成しやすい。このような特性を達成するための手段としては、経時安定性のよい素材を用いる方法などが挙げられる。 The viscosity of the coloring composition of the present invention at 25 ° C. after storage at a temperature of 25 ° C. and a humidity of 50% for 30 days is 90 to 110% of the viscosity at 25 ° C. of the coloring composition immediately after production. , Preferably 93 to 107%, and more preferably 95 to 105%. When the coloring composition of the present invention has such characteristics, it is easy to form a pixel having more excellent flatness. Means for achieving such characteristics include a method using a material having good stability over time.
　本発明の着色組成物は、表示装置用のカラーフィルタの画素形成用の着色組成物である。表示装置の種類としては特に限定はないが、有機半導体層を含む支持体などの耐熱性が低い支持体上にカラーフィルタが形成される表示装置の場合特に効果的である。このような表示装置としては、有機エレクトロルミネッセンス表示装置などの有機半導体素子を光源として有する表示装置などが挙げられる。 着色 The coloring composition of the present invention is a coloring composition for forming pixels of a color filter for a display device. The type of the display device is not particularly limited, but is particularly effective for a display device in which a color filter is formed on a support having low heat resistance, such as a support including an organic semiconductor layer. Examples of such a display device include a display device having an organic semiconductor element as a light source, such as an organic electroluminescence display device.
　本発明の着色組成物によって形成される画素の厚さは、０．５～３．０μｍであることが好ましい。下限は０．８μｍ以上が好ましく、１．０μｍ以上がより好ましく、１．１μｍ以上が更に好ましい。上限は２．５μｍ以下が好ましく、２．０μｍ以下がより好ましく、１．８μｍ以下がさらに好ましい。画素の厚さが上記範囲である場合、本発明の効果がより顕著である。 画素 The thickness of a pixel formed by the coloring composition of the present invention is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and still more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less. When the thickness of the pixel is within the above range, the effect of the present invention is more remarkable.
　また、本発明の着色組成物によって形成される画素の線幅（パターンサイズ）は、２．０～１０．０μｍであることが好ましい。上限は７．５μｍ以下が好ましく、５．０μｍ以下がより好ましく、４．０μｍ以下が更に好ましい。下限は２．２５μｍ以上が好ましく、２．５μｍ以上がより好ましく、２．７５μｍ以上がさらに好ましい。画素の線幅（パターンサイズ）が上記範囲である場合、本発明の効果がより顕著である。 線 Further, the line width (pattern size) of a pixel formed by the coloring composition of the present invention is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more. When the pixel line width (pattern size) is in the above range, the effect of the present invention is more remarkable.
　以下、本発明の着色組成物について詳細に説明する。 Hereinafter, the coloring composition of the present invention will be described in detail.
＜＜着色剤＞＞
　本発明の着色組成物は着色剤を含有する。着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などの有彩色着色剤が挙げられる。本発明において、着色剤は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。また、顔料は、無機顔料、有機顔料のいずれでもよい。また、顔料には、無機顔料または有機－無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機－無機顔料の一部を有機発色団で置換することで、色相設計をしやすくできる。
　本発明で用いられる着色剤は、顔料を含むことが好ましい。また、着色剤中における顔料の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが更に好ましく、９０質量％以上であることが特に好ましい。また、着色剤は顔料のみであってもよい。顔料としては以下に示すものが挙げられる。 << Colorant >>
The coloring composition of the present invention contains a coloring agent. Examples of the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. In the present invention, the colorant may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment. In addition, as the pigment, a material in which a part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore can be used. By substituting a part of the inorganic pigment or the organic-inorganic pigment with the organic chromophore, the hue can be easily designed.
The colorant used in the present invention preferably contains a pigment. Further, the content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and more preferably 90% by mass or more. Is particularly preferred. The colorant may be a pigment alone. Examples of the pigment include the following.
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２３１，２３２等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９，２９４等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９，６２，６３等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２，６０，６１等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等（以上、青色顔料）。 Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231,232 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Or more, orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3. 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294, etc. ,Red Pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 etc. (above, purple pigment),
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87,88 etc. , Blue pigment).
　また、緑色顔料として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色顔料としてＣＮ１０６９０９０２７Ａに記載の化合物、リン酸エステルを配位子として有するフタロシアニン化合物などを用いることもできる。 Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Can also be used. Specific examples include the compounds described in WO 2015/118720. As the green pigment, a compound described in CN106909097A, a phthalocyanine compound having a phosphate as a ligand, or the like can also be used.
　また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落００２２～００３０、特開２０１１－１５７４７８号公報の段落００４７に記載の化合物が挙げられる。 ア ル ミ ニ ウ ム Also, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247593 and paragraph 0047 of JP-A-2011-157478.
　また、黄色顔料として、特開２０１７－２０１００３号公報に記載されている顔料、特開２０１７－１９７７１９号公報に記載されている顔料を用いることができる。また、黄色顔料として、下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料を用いることもできる。
Figure JPOXMLDOC01-appb-C000005
 　式中、Ｒ1およびＲ2はそれぞれ独立して、－ＯＨまたは－ＮＲ5Ｒ6であり、Ｒ3およびＲ4はそれぞれ独立して、＝Ｏまたは＝ＮＲ7であり、Ｒ5～Ｒ7はそれぞれ独立して、水素原子またはアルキル基である。Ｒ5～Ｒ7が表すアルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよく、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基は、ハロゲン原子、ヒドロキシ基、アルコキシ基、シアノ基およびアミノ基が好ましい。 Further, as a yellow pigment, a pigment described in JP-A-2017-201003 and a pigment described in JP-A-2017-197719 can be used. In addition, as a yellow pigment, a metal containing at least one anion, two or more metal ions, and a melamine compound selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof: Azo pigments can also be used.
Figure JPOXMLDOC01-appb-C000005
 Wherein R 1 and R 2 are each independently —OH or —NR 5 R 6 , R 3 and R 4 are each independently ＝ O or ＮＲNR 7 , and R 5 -R 7 Is each independently a hydrogen atom or an alkyl group. The alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and still more preferably has 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an amino group.
　上記の金属アゾ顔料については、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The metal azo pigments described above are described in JP-A-2017-171912, paragraphs 0011 to 0062 and 0137 to 0276, JP-A-2017-171913, paragraphs 0010 to 0062, 0138 to 0295, and JP-A-2017-171914. The descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the gazette and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.
　また、黄色顔料として、特開２０１８－６２６４４号公報に記載の化合物を用いることもできる。この化合物は顔料誘導体としても使用可能である。 化合物 Further, as the yellow pigment, a compound described in JP-A-2018-62644 can also be used. This compound can also be used as a pigment derivative.
　赤色顔料として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つ臭素原子が置換したジケトピロロピロール系顔料、特許第６２４８８３８号の段落番号００１６～００２２に記載のジケトピロロピロール系顔料などを用いることもできる。また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 As red pigments, diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, and diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838. Pigments and the like can also be used. Further, as the red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is introduced to a diketopyrrolopyrrole skeleton may be used. it can.
　染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。また、特開２０１２－１５８６４９号公報に記載のチアゾール化合物、特開２０１１－１８４４９３号公報に記載のアゾ化合物、特開２０１１－１４５５４０号公報に記載のアゾ化合物も好ましく用いることができる。また、黄色染料として、特開２０１３－０５４３３９号公報の段落番号００１１～００３４に記載のキノフタロン化合物、特開２０１４－０２６２２８号公報の段落番号００１３～００５８に記載のキノフタロン化合物などを用いることもできる。 The dye is not particularly limited, and a known dye can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, phenothiazine, pyrrolopyrazoleazomethine, xanthene, Dyes of phthalocyanine type, benzopyran type, indigo type, pyromethene type and the like can be mentioned. Also, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can be preferably used. In addition, as the yellow dye, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can also be used.
　本発明において、着色剤として色素多量体を用いることもできる。色素多量体は、溶剤に溶解して用いられる染料であることが好ましいが、色素多量体は、粒子を形成していてもよく、色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開２０１５－２１４６８２号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、一分子中に、色素構造を２以上有するものであり、色素構造を３以上有することが好ましい。上限は、特に限定はないが、１００以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量（Ｍｗ）は、２０００～５００００が好ましい。下限は、３０００以上がより好ましく、６０００以上がさらに好ましい。上限は、３００００以下がより好ましく、２００００以下がさらに好ましい。 に お い て In the present invention, a dye multimer may be used as a coloring agent. The dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is a particle, it is usually dispersed in a solvent. Used. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples thereof include a compound and a production method described in JP-A-2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably from 2,000 to 50,000. The lower limit is more preferably 3000 or more, and still more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and still more preferably 20,000 or less.
　色素多量体が有する色素構造は、可視領域（好ましくは、波長４００～７００ｎｍの範囲、より好ましくは４００～６５０ｎｍの範囲）に吸収を有する色素化合物に由来する構造が挙げられる。例えば、トリアリールメタン色素構造、キサンテン色素構造、アントラキノン色素構造、シアニン色素構造、スクアリリウム色素構造、キノフタロン色素構造、フタロシアニン色素構造、サブフタロシアニン色素構造、アゾ色素構造、ピラゾロトリアゾール色素構造、ジピロメテン色素構造、イソインドリン色素構造、チアゾール色素構造、ベンズイミダゾール色素構造、ぺリノン色素構造、ジケトピロロピロール色素構造、ジイミニウム色素構造、ナフタロシアニン色素構造、リレン色素構造、ジベンゾフラノン色素構造、メロシアニン色素構造、クロコニウム色素構造、オキソノール色素構造などが挙げられる。 色素 The dye structure of the dye multimer includes a structure derived from a dye compound having an absorption in a visible region (preferably, a wavelength range of 400 to 700 nm, more preferably, 400 to 650 nm). For example, triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolotriazole dye structure, dipyrromethene dye structure , Isoindoline dye structure, thiazole dye structure, benzimidazole dye structure, perinone dye structure, diketopyrrolopyrrole dye structure, diiminium dye structure, naphthalocyanine dye structure, rylene dye structure, dibenzofuranone dye structure, merocyanine dye structure, croconium And a dye structure, an oxonol dye structure, and the like.
　色素多量体は、式（Ａ）で表される繰り返し単位を有する色素多量体、式（Ｂ）で表される繰り返し単位を有する色素多量体、式（Ｃ）で表される繰り返し単位を有する色素多量体、および、式（Ｄ）で表される色素多量体が好ましく、式（Ａ）で表される繰り返し単位を有する色素多量体、および、式（Ｄ）で表される色素多量体がより好ましい。
Figure JPOXMLDOC01-appb-C000006
 The dye multimer includes a dye multimer having a repeating unit represented by the formula (A), a dye multimer having a repeating unit represented by the formula (B), and a dye having a repeating unit represented by the formula (C) A multimer and a dye multimer represented by the formula (D) are preferable, and a dye multimer having a repeating unit represented by the formula (A) and a dye multimer represented by the formula (D) are more preferable. preferable.
Figure JPOXMLDOC01-appb-C000006
　式（Ａ）中、Ｘ1は繰り返し単位の主鎖を表し、Ｌ1は単結合または２価の連結基を表し、Ｄ1は色素構造を表す。式（Ａ）についての詳細は、特開２０１３－０２９７６０号公報の段落０１３８～０１５２を参酌することができ、この内容は本明細書に組み込まれる。 In the formula (A), X 1 represents a main chain of a repeating unit, L 1 represents a single bond or a divalent linking group, and D 1 represents a dye structure. For details of the formula (A), paragraphs 0138 to 0152 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
　式（Ｂ）中、Ｘ2は繰り返し単位の主鎖を表し、Ｌ2は単結合または２価の連結基を表し、Ｄ2はＹ2とイオン結合もしくは配位結合可能な基を有する色素構造を表し、Ｙ2はＤ2とイオン結合または配位結合可能な基を表す。式（Ｂ）の詳細については、特開２０１３－０２９７６０号公報の段落０１５６～０１６１を参酌することができ、この内容は本明細書に組み込まれる。 In formula (B), X 2 represents a main chain of a repeating unit, L 2 represents a single bond or a divalent linking group, and D 2 represents a dye structure having a group capable of forming an ionic bond or a coordinate bond with Y 2. And Y 2 represents a group capable of forming an ionic or coordinate bond with D 2 . For details of the formula (B), paragraphs 0156 to 0161 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated herein.
　式（Ｃ）中、Ｌ3は単結合または２価の連結基を表し、Ｄ3は色素構造を表し、ｍは０または１を表す。式（Ｃ）の詳細については、特開２０１３－０２９７６０号公報の段落０１６５～０１６７を参酌することができ、この内容は本明細書に組み込まれる。 In the formula (C), L 3 represents a single bond or a divalent linking group, D 3 represents a dye structure, and m represents 0 or 1. For details of the formula (C), paragraphs 0165 to 0167 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated in the present specification.
　式（Ｄ）中、Ｌ4は（ｎ＋ｋ）価の連結基を表し、Ｌ41およびＬ42は、それぞれ独立に、単結合または２価の連結基を表し、Ｄ4は色素構造を表し、Ｐ4は置換基を表す；ｎは２～１５を表し、ｋは０～１３を表し、ｎ＋ｋは２～１５である。ｎが２以上の場合、複数のＤ4は互いに異なっていても良く、同一であってもよい。ｋが２以上の場合、複数のＰ4は互いに異なっていても良く、同一であってもよい。Ｌ4が表す（ｎ＋ｋ）価の連結基としては、特開２００８－２２２９５０号公報の段落番号００７１～００７２に記載された連結基、特開２０１３－０２９７６０号公報の段落番号０１７６に記載された連結基などが挙げられる。Ｐ4が表す置換基は、酸基、重合性基等が挙げられる。重合性基としては、エチレン性不飽和基（エチレン性不飽和結合を有する基）、エポキシ基、オキサゾリン基、メチロール基等が挙げられる。エチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。酸基としては、カルボキシル基、スルホン酸基、リン酸基等が挙げられる。Ｐ4が表す置換基は、繰り返し単位を有する１価のポリマー鎖であってもよい。繰り返し単位を有する１価のポリマー鎖は、ビニル化合物由来の繰り返し単位を有する１価のポリマー鎖が好ましい。 In the formula (D), L 4 represents a (n + k) -valent linking group, L 41 and L 42 each independently represent a single bond or a divalent linking group, D 4 represents a dye structure, 4 represents a substituent; n represents 2 to 15, k represents 0 to 13, and n + k represents 2 to 15. When n is 2 or more, a plurality of D 4 may be different from each other or may be the same. When k is 2 or more, a plurality of P 4 may be different from each other or may be the same. Examples of the (n + k) -valent linking group represented by L 4 include the linking groups described in paragraphs 0071 to 0072 of JP-A-2008-222950, and the linking group described in paragraph No. 0176 of JP-A-2013-029760. And the like. Examples of the substituent represented by P 4 include an acid group and a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group (a group having an ethylenically unsaturated bond), an epoxy group, an oxazoline group, and a methylol group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The substituent represented by P 4 may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
　色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報、国際公開第２０１６／０３１４４２号等に記載されている化合物を用いることもできる。 Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO2016 / 031442, and the like. Compounds can also be used.
　着色剤の含有量は、着色組成物の全固形分中５～７０質量％が好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましく、２０質量％以上が更に好ましい。上限は、６０質量％以下が好ましく、５５質量％以下が更に好ましく、５０質量％以下がより一層好ましい。 含有 The content of the coloring agent is preferably 5 to 70% by mass based on the total solid content of the coloring composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.
＜＜重合性モノマー＞＞
　本発明の着色組成物は、重合性モノマーを含有する。重合性モノマーとしては、エチレン性不飽和基を有する化合物などが挙げられる。エチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。重合性モノマーはラジカルにより重合可能な化合物（ラジカル重合性モノマー）であることが好ましい。 <<< Polymerizable monomer >>>
The coloring composition of the present invention contains a polymerizable monomer. Examples of the polymerizable monomer include a compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable monomer is preferably a compound polymerizable by a radical (radical polymerizable monomer).
　重合性モノマーの分子量は、１００～２０００が好ましい。上限は、１５００以下が好ましく、１０００以下がより好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。 分子 The molecular weight of the polymerizable monomer is preferably from 100 to 2,000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.
　重合性モノマーのエチレン性不飽和基価（以下、Ｃ＝Ｃ価という）は、組成物の経時安定性の観点から２～１４ｍｍｏｌ／ｇであることが好ましい。下限は、３ｍｍｏｌ／ｇ以上であることが好ましく、４ｍｍｏｌ／ｇ以上であることがより好ましく、５ｍｍｏｌ／ｇ以上であることが更に好ましい。上限は１２ｍｍｏｌ／ｇ以下であることが好ましく、１０ｍｍｏｌ／ｇ以下であることがより好ましく、８ｍｍｏｌ／ｇ以下であることが更に好ましい。重合性モノマーのＣ＝Ｃ価は、重合性モノマーの１分子中に含まれるエチレン性不飽和基の数を重合性モノマーの分子量で割ることで算出した。 (4) The ethylenically unsaturated group value (hereinafter referred to as C = C value) of the polymerizable monomer is preferably 2 to 14 mmol / g from the viewpoint of the stability over time of the composition. The lower limit is preferably at least 3 mmol / g, more preferably at least 4 mmol / g, even more preferably at least 5 mmol / g. The upper limit is preferably at most 12 mmol / g, more preferably at most 10 mmol / g, even more preferably at most 8 mmol / g. The C = C value of the polymerizable monomer was calculated by dividing the number of ethylenically unsaturated groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.
　重合性モノマーは、エチレン性不飽和基を３個以上含む化合物であることが好ましく、エチレン性不飽和基を４個以上含む化合物であることがより好ましい。この態様によれば、露光による着色組成物の硬化性が良好である。エチレン性不飽和基の上限は、組成物の経時安定性の観点から１５個以下であることが好ましく、１０個以下であることがより好ましく、６個以下であることが更に好ましい。また、重合性モノマーは、３官能以上の（メタ）アクリレート化合物であることが好ましく、３～１５官能の（メタ）アクリレート化合物であることがより好ましく、３～１０官能の（メタ）アクリレート化合物であることが更に好ましく、３～６官能の（メタ）アクリレート化合物であることが特に好ましい。 (4) The polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated groups, and more preferably a compound containing four or more ethylenically unsaturated groups. According to this aspect, the curability of the colored composition upon exposure is good. The upper limit of the ethylenically unsaturated group is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less from the viewpoint of the stability over time of the composition. The polymerizable monomer is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-10 functional (meth) acrylate compound. More preferably, it is particularly preferably a tri- to hexafunctional (meth) acrylate compound.
　重合性モノマーは、エチレン性不飽和基とアルキレンオキシ基とを含む化合物であることも好ましい。このような重合性モノマーは柔軟性が高く、エチレン性不飽和基が移動し易いため、露光時において重合性モノマー同士が反応し易く、支持体などとの密着性に優れた硬化膜（画素）を形成できる。また、光重合開始剤としてヒドロキシアルキルフェノン化合物を用いた場合においては、重合性モノマーと光重合開始剤とが近接して重合性モノマーの近傍でラジカルを発生させて重合性モノマーをより効果的に反応させることができると推測され、より優れた密着性や耐溶剤性を有する硬化膜（画素）を形成し易い。 The polymerizable monomer is also preferably a compound containing an ethylenically unsaturated group and an alkyleneoxy group. Such a polymerizable monomer has high flexibility and the ethylenically unsaturated group easily moves, so that the polymerizable monomers easily react with each other during exposure, and a cured film (pixel) having excellent adhesion to a support or the like. Can be formed. Further, when a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable monomer and the photopolymerization initiator come close to each other to generate radicals in the vicinity of the polymerizable monomer so that the polymerizable monomer can be more effectively used. It is presumed that they can be reacted, and it is easy to form a cured film (pixel) having better adhesion and solvent resistance.
　重合性モノマーの１分子中に含まれるアルキレンオキシ基の数は、３個以上であることが好ましく、４個以上であることがより好ましい。上限は、組成物の経時安定性の観点から２０個以下が好ましい。 数 The number of alkyleneoxy groups contained in one molecule of the polymerizable monomer is preferably 3 or more, more preferably 4 or more. The upper limit is preferably 20 or less from the viewpoint of the stability over time of the composition.
　また、エチレン性不飽和基とアルキレンオキシ基とを含む化合物のＳＰ値（Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒ）は、組成物中の他の成分との相溶性の観点から９．０～１１．０が好ましい。上限は、１０．７５以下が好ましく、１０．５以下がより好ましい。下限は、９．２５以上が好ましく、９．５以上が更に好ましい。なお、本明細書において、ＳＰ値はＦｅｄｏｒｓ法に基づく計算値を使用した。 The SP value (Solubility @Parameter) of the compound containing an ethylenically unsaturated group and an alkyleneoxy group is preferably from 9.0 to 11.0 from the viewpoint of compatibility with other components in the composition. The upper limit is preferably 10.75 or less, more preferably 10.5 or less. The lower limit is preferably 9.25 or more, and more preferably 9.5 or more. In addition, in this specification, the SP value used the calculated value based on the Fedors method.
　エチレン性不飽和基とアルキレンオキシ基とを有する化合物としては、下記式（Ｍ－１）で表される化合物が挙げられる。
式（Ｍ－１）
Figure JPOXMLDOC01-appb-C000007
 　式中Ａ1は、エチレン性不飽和基を表し、Ｌ1は単結合または２価の連結基を表し、Ｒ1は、アルキレン基を表し、ｍは１～３０の整数を表し、ｎは３以上の整数を表し、Ｌ2はｎ価の連結基を表す。 Examples of the compound having an ethylenically unsaturated group and an alkyleneoxy group include a compound represented by the following formula (M-1).
Formula (M-1)
Figure JPOXMLDOC01-appb-C000007
 In the formula, A 1 represents an ethylenically unsaturated group, L 1 represents a single bond or a divalent linking group, R 1 represents an alkylene group, m represents an integer of 1 to 30, and n represents 3 L 2 represents an n-valent linking group.
　Ａ1が表すエチレン性不飽和基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基が挙げられ、（メタ）アクリロイル基が好ましい。 Examples of the ethylenically unsaturated group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
　Ｌ1が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。 Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, and a group obtained by combining two or more of these. . The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10.
　Ｒ1が表すアルキレン基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、２または３が特に好ましく、２が最も好ましい。Ｒ1が表すアルキレン基は、直鎖、分岐が好ましく、直鎖がより好ましい。Ｒ1が表すアルキレンの具体例は、エチレン基、直鎖または分岐のプロピレン基などが挙げられ、エチレン基が好ましい。 The carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2. The alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group, a linear or branched propylene group, and an ethylene group is preferable.
　ｍは、１～３０の整数を表し、１～２０の整数が好ましく、１～１０の整数がより好ましく、１～５が更に好ましい。 M represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably 1 to 5.
　ｎは３以上の整数を表し、４以上の整数が好ましい。ｎの上限は１５以下の整数が好ましく、１０以下の整数がより好ましく、６以下の整数が更に好ましい。 N represents an integer of 3 or more, and preferably an integer of 4 or more. The upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
　Ｌ2が表すｎ価の連結基としては、脂肪族炭化水素基、芳香族炭化水素基、複素環基およびこれらの組み合わせからなる基、ならびに、脂肪族炭化水素基、芳香族炭化水素基および複素環基から選ばれる少なくとも１種と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－および－ＮＨ－から選ばれる少なくとも１種とを組み合わせてなる基が挙げられる。脂肪族炭化水素基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。芳香族炭化水素基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。複素環基は、非芳香族の複素環基であってもよく、芳香族複素環基であってもよい。複素環基は、５員環または６員環が好ましい。複素環基を構成するヘテロ原子の種類は窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基を構成するヘテロ原子の数は１～３が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。Ｌ2が表すｎ価の連結基は、多官能アルコールから誘導される基であることも好ましい。 Examples of the n-valent linking group represented by L 2 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, and a group including a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. Examples include a group formed by combining at least one selected from a ring group and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched. The carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered ring. Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
　エチレン性不飽和基とアルキレンオキシ基とを有する化合物としては、下記式（Ｍ－２）で表される化合物がより好ましい。
式（Ｍ－２）
Figure JPOXMLDOC01-appb-C000008
 　式中Ｒ2は水素原子またはメチル基を表し、Ｒ1は、アルキレン基を表し、ｍは１～３０の整数を表し、ｎは３以上の整数を表し、Ｌ2はｎ価の連結基を表す。式（Ｍ－２）のＲ1、Ｌ2、ｍ、ｎは、式（Ｍ－１）のＲ1、Ｌ2、ｍ、ｎと同義であり、好ましい範囲も同様である。 As the compound having an ethylenically unsaturated group and an alkyleneoxy group, a compound represented by the following formula (M-2) is more preferable.
Formula (M-2)
Figure JPOXMLDOC01-appb-C000008
 In the formula, R 2 represents a hydrogen atom or a methyl group, R 1 represents an alkylene group, m represents an integer of 1 to 30, n represents an integer of 3 or more, and L 2 represents an n-valent linking group. Represent. R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
　エチレン性不飽和基とアルキレンオキシ基とを有する化合物の市販品としては、ＫＡＹＡＲＡＤ　Ｔ－１４２０（Ｔ）、ＲＰ－１０４０（日本化薬（株）製）などが挙げられる。 Commercially available compounds having an ethylenically unsaturated group and an alkyleneoxy group include KAYARAD T-1420 (T) and RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
　重合性モノマーとして、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）などを用いることもできる。
　また、重合性モノマーとして、アロニックス　Ｍ－４０２（東亞合成（株）製、ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物）を用いることも好ましい。
　また、重合性モノマーとして、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることもできる。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 As polymerizable monomers, dipentaerythritol triacrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercially available product; Nippon Kayaku Co., Ltd.) Nippon Kayaku), dipentaerythritol penta (meth) acrylate (commercially available: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available: KAYARAD DPHA; Nippon Kayaku ( NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. (For example, commercially available from Sartomer , SR454, SR499) can also be used.
It is also preferable to use Aronix M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.) as the polymerizable monomer.
Further, as a polymerizable monomer, trimethylolpropane tri (meth) acrylate, trimethylolpropanepropyleneoxy-modified tri (meth) acrylate, trimethylolpropaneethyleneoxy-modified tri (meth) acrylate, isocyanuric acid ethyleneoxy-modified tri (meth) acrylate And a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And the like.
　重合性モノマーとして、酸基を有する重合性モノマーを用いることも好ましい。酸基を有する重合性モノマーを用いることで、現像時に未露光部の着色組成物層が除去されやすく、現像残渣の発生を抑制できる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性モノマーとしては、コハク酸変性ジペンタエリスリトールペンタ（メタ）アクリレートなどが挙げられる。酸基を有する重合性モノマーの市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。酸基を有する重合性モノマーの好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性モノマーの酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。 も It is also preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using the polymerizable monomer having an acid group, the unexposed portion of the colored composition layer is easily removed at the time of development, and generation of a development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Commercial products of polymerizable monomers having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like. The preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the solubility in a developer is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.
　重合性モノマーは、カプロラクトン構造を有する化合物であることも好ましい。カプロラクトン構造を有する重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 The polymerizable monomer is also preferably a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD @ DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
　重合性モノマーは、特開２０１７－０４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物、特開２０１７－１９４６６２号公報に記載されている化合物、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。 The polymerizable monomers include compounds described in JP-A-2017-048367, JP-A-6057891, and JP-A-6031807, compounds described in JP-A-2017-194662, 8UH-1006, and 8UH. It is also preferable to use -1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.
　重合性モノマーの含有量は、着色組成物の全固形分中５．０～３５質量％であることが好ましい。上限は、３０質量％以下であることが好ましく、２５質量％以下であることがより好ましい。下限は、７．５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。 (4) The content of the polymerizable monomer is preferably 5.0 to 35% by mass based on the total solid content of the coloring composition. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
＜＜光重合開始剤＞＞
　本発明の着色組成物は光重合開始剤を含有する。光重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール化合物、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル化合物、アミノアルキルフェノン化合物、ヒドロキシアルキルフェノン化合物、フェニルグリオキシレート化合物などが挙げられる。光重合開始剤の具体例としては、例えば、特開２０１３－０２９７６０号公報の段落番号０２６５～０２６８、特許第６３０１４８９号公報の記載を参酌することができ、この内容は本明細書に組み込まれる。 << Photopolymerization initiator >>
The coloring composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, and oxime derivatives. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, phenylglyoxylate compounds, and the like. As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-029760 and JP-A-6301489 can be referred to, and the contents thereof are incorporated herein.
　フェニルグリオキシレート化合物としては、フェニルグリオキシリックアシッドメチルエステルなどが挙げられる。市販品としては、ＤＡＲＯＣＵＲ－ＭＢＦ（ＢＡＳＦ社製）などが挙げられる。 As the phenylglyoxylate compound, phenylglyoxylic acid methyl ester and the like can be mentioned. Commercially available products include DAROCUR-MBF (manufactured by BASF).
　アミノアルキルフェノン化合物としては、例えば、特開平１０－２９１９６９号公報に記載のアミノアルキルフェノン化合物が挙げられる。また、アミノアルキルフェノン化合物としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９（いずれもＢＡＳＦ社製）を用いることもできる。 Examples of the aminoalkylphenone compound include, for example, an aminoalkylphenone compound described in JP-A-10-291969. Further, as the aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.
　アシルホスフィン化合物としては、特許第４２２５８９８号公報に記載のアシルホスフィン化合物が挙げられる。具体例としては、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイドなどが挙げられる。アシルホスフィン化合物としては、ＩＲＧＡＣＵＲＥ－８１９、ＤＡＲＯＣＵＲ－ＴＰＯ（いずれもＢＡＳＦ社製）を用いることもできる。 Examples of the acylphosphine compound include the acylphosphine compounds described in Japanese Patent No. 422598. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.
　ヒドロキシアルキルフェノン化合物としては、下記式（Ｖ）で表される化合物が挙げられる。
式（Ｖ）
Figure JPOXMLDOC01-appb-C000009
 　式中Ｒｖ1は、置換基を表し、Ｒｖ2およびＲｖ3は、それぞれ独立して水素原子または置換基を表し、Ｒｖ2とＲｖ3とが互いに結合して環を形成していてもよく、ｍは０～５の整数を表す。 Examples of the hydroxyalkylphenone compound include a compound represented by the following formula (V).
Equation (V)
Figure JPOXMLDOC01-appb-C000009
 In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may combine with each other to form a ring, m represents an integer of 0 to 5.
　Ｒｖ1が表す置換基としては、アルキル基（好ましくは、炭素数１～１０のアルキル基）、アルコキシ基（好ましくは、炭素数１～１０のアルコキシ基）が挙げられる。アルキル基およびアルコキシ基は、直鎖または分岐が好ましく、直鎖がより好ましい。Ｒｖ1が表すアルキル基およびアルコキシ基は、無置換であってもよく、置換基を有していてもよい。置換基としては、ヒドロキシ基や、ヒドロキシアルキルフェノン構造を有する基などが挙げられる。ヒドロキシアルキルフェノン構造を有する基としては、式（Ｖ）におけるＲｖ1が結合したベンゼン環またはＲｖ1から水素原子を１個除去した構造の基が挙げられる。 Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear. The alkyl group and the alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group and a group having a hydroxyalkylphenone structure. Examples of the group having a hydroxyalkyl phenone structures, groups of structures Rv 1 in the formula (V) is removing one hydrogen atom from a benzene ring or Rv 1 were bond.
　Ｒｖ2およびＲｖ3は、それぞれ独立して水素原子または置換基を表す。置換基としては、アルキル基（好ましくは炭素数１～１０のアルキル基）が好ましい。また、Ｒｖ2とＲｖ3は互いに結合して環（好ましくは炭素数４～８の環、より好ましくは、炭素数４～８の脂肪族環）を形成していてもよい。アルキル基は、直鎖または分岐が好ましく、直鎖がより好ましい。 Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. Rv 2 and Rv 3 may combine with each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably linear or branched, and more preferably linear.
　式（Ｖ）で表される化合物の具体例としては、下記化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000010
 Specific examples of the compound represented by the formula (V) include the following compounds.
Figure JPOXMLDOC01-appb-C000010
　ヒドロキシアルキルフェノン化合物としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（商品名：いずれもＢＡＳＦ社製）を用いることもできる。 As the hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can also be used.
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３８に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光重合開始剤２）が挙げられる。 Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, and J.I. C. S. Compounds described in Perkin II (1979, pp. 1653-1660); C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer, Science and and Technology (1995, pp. 202-232), a compound described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 No./152153, compounds described in WO2017 / 051680, compounds described in JP-A-2017-198865, and compounds described in paragraphs 0025 to 0038 of WO2017 / 164127. Such compounds, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyimiminobtan-2-one, 3-propionyloxyimiminobtan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one. Commercial products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and Adeka Optomer N-1919. (Photopolymerization initiator 2 manufactured by ADEKA Corporation and described in JP-A-2012-014052).
　またオキシム化合物としては、カルバゾール環のＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－０１５０２５号公報および米国特許公開２００９－２９２０３９号に記載の化合物、国際公開第２００９／１３１１８９号に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有し、ｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物などを用いてもよい。好ましくは、例えば、特開２０１３－０２９７６０号公報の段落番号０２７４～０３０６を参酌することができ、この内容は本明細書に組み込まれる。 Examples of the oxime compound include compounds described in JP-T-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, compounds described in US Pat. No. 7,626,957 in which a heterosubstituent is introduced into a benzophenone moiety, and dyes. Compounds described in JP-A-2010-015025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the site, the ketoxime compound described in WO2009 / 131189, and a triazine skeleton and an oxime skeleton in the same molecule And a compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-line light source, may be used. Preferably, for example, paragraphs 0274 to 0306 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated in the present specification.
　オキシム化合物は、フッ素原子を含むオキシム化合物であることが好ましい。フッ素原子を含むオキシム化合物は、フッ素原子を含む基を有することが好ましい。フッ素原子を含む基は、フッ素原子を有するアルキル基（以下、含フッ素アルキル基ともいう）、および、フッ素原子を有するアルキル基を含む基（以下、含フッ素基ともいう）が好ましい。含フッ素基としては、－ＯＲF1、－ＳＲF1、－ＣＯＲF1、－ＣＯＯＲF1、－ＯＣＯＲF1、－ＮＲF1ＲF2、－ＮＨＣＯＲF1、－ＣＯＮＲF1ＲF2、－ＮＨＣＯＮＲF1ＲF2、－ＮＨＣＯＯＲF1、－ＳＯ2ＲF1、－ＳＯ2ＯＲF1および－ＮＨＳＯ2ＲF1から選ばれる少なくとも１種の基が好ましい。ＲF1は、含フッ素アルキル基を表し、ＲF2は、水素原子、アルキル基、含フッ素アルキル基、アリール基またはヘテロ環基を表す。含フッ素基は、－ＯＲF1が好ましい。 The oxime compound is preferably an oxime compound containing a fluorine atom. The oxime compound containing a fluorine atom preferably has a group containing a fluorine atom. As the group containing a fluorine atom, an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorinated group) are preferable. Examples of the fluorinated group include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , -NHCOOR At least one group selected from F1 , —SO 2 R F1 , —SO 2 OR F1, and —NHSO 2 R F1 is preferable. R F1 represents a fluorine-containing alkyl group, and R F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group. The fluorine-containing group is preferably -OR F1 .
　アルキル基および含フッ素アルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましく、１～４が特に好ましい。アルキル基および含フッ素アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。含フッ素アルキル基において、フッ素原子の置換率は４０～１００％であることが好ましく、５０～１００％であることがより好ましく、６０～１００％であることがさらに好ましい。なお、フッ素原子の置換率とは、アルキル基が有する全水素原子の数に対してフッ素原子に置換されている数の比率（％）をいう。 The carbon number of the alkyl group and the fluorine-containing alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched. In the fluorinated alkyl group, the substitution ratio of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, even more preferably from 60 to 100%. In addition, the substitution rate of a fluorine atom means the ratio (%) of the number of substitution with a fluorine atom to the total number of hydrogen atoms of the alkyl group.
　アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
　ヘテロ環基は、５員環または６員環が好ましい。ヘテロ環基は、単環であってもよく、縮合環であってもよい。縮合数は、２～８が好ましく、２～６がより好ましく、３～５が更に好ましく、３～４が特に好ましい。ヘテロ環基を構成する炭素原子の数は３～４０が好ましく、３～３０がより好ましく、３～２０がより好ましい。ヘテロ環基を構成するヘテロ原子の数は１～３が好ましい。ヘテロ環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましく、窒素原子がより好ましい。 The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a nitrogen atom.
　フッ素原子を含む基は、式（１）または（２）で表される末端構造を有することが好ましい。式中の＊は、連結手を表す。
＊－ＣＨＦ2　　　（１）
＊－ＣＦ3　　　（２） The group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2). * In the formula represents a connecting hand.
* -CHF 2 (1)
* -CF 3 (2)
　フッ素原子を含むオキシム化合物中の全フッ素原子数は３以上が好ましく、４～１０がより好ましい。 は The total number of fluorine atoms in the fluorine atom-containing oxime compound is preferably 3 or more, more preferably 4 to 10.
　フッ素原子を含むオキシム化合物は、式（ＯＸ－１）で表される化合物が好ましい。
（ＯＸ－１）
Figure JPOXMLDOC01-appb-C000011
 　式（ＯＸ－１）において、Ａｒ1およびＡｒ2は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、Ｒ1は、フッ素原子を含む基を有するアリール基を表し、Ｒ2およびＲ3は、それぞれ独立に、アルキル基またはアリール基を表す。 The oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).
(OX-1)
Figure JPOXMLDOC01-appb-C000011
 In the formula (OX-1), Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 represents an aryl group having a group containing a fluorine atom. And R 2 and R 3 each independently represent an alkyl group or an aryl group.
　Ａｒ1およびＡｒ2は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表す。芳香族炭化水素環は、単環でもよく、縮合環であってもよい。芳香族炭化水素環の環を構成する炭素原子数は、６～２０が好ましく、６～１５がより好ましく、６～１０が特に好ましい。芳香族炭化水素環は、ベンゼン環およびナフタレン環が好ましい。なかでも、Ａｒ1およびＡｒ2の少なくとも一方がベンゼン環であることが好ましく、Ａｒ1がベンゼン環であることがより好ましい。Ａｒ2は、ベンゼン環またはナフタレン環が好ましく、ナフタレン環がより好ましい。 Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably from 6 to 20, more preferably from 6 to 15, and particularly preferably from 6 to 10. As the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable. Among them, at least one of Ar 1 and Ar 2 is preferably a benzene ring, and more preferably Ar 1 is a benzene ring. Ar 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.
　Ａｒ1およびＡｒ2が有してもよい置換基としては、アルキル基、アリール基、ヘテロ環基、ニトロ基、シアノ基、ハロゲン原子、－ＯＲX1、－ＳＲX1、－ＣＯＲX1、－ＣＯＯＲX1、－ＯＣＯＲX1、－ＮＲX1ＲX2、－ＮＨＣＯＲX1、－ＣＯＮＲX1ＲX2、－ＮＨＣＯＮＲX1ＲX2、－ＮＨＣＯＯＲX1、－ＳＯ2ＲX1、－ＳＯ2ＯＲX1、－ＮＨＳＯ2ＲX1などが挙げられる。ＲX1およびＲX2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロ環基を表す。
　ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、フッ素原子が好ましい。置換基としてのアルキル基、ならびに、ＲX1およびＲX2が表すアルキル基の炭素数は、１～３０が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アルキル基は、水素原子の一部または全部がハロゲン原子（好ましくは、フッ素原子）で置換されていてもよい。また、アルキル基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。置換基としてのアリール基、ならびに、ＲX1およびＲX2が表すアリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。アリール基は、単環であってもよく、縮合環であってもよい。また、アリール基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。置換基としてのヘテロ環基、ならびに、ＲX1およびＲX2が表すヘテロ環基は、５員環または６員環が好ましい。ヘテロ環基は、単環であってもよく、縮合環であってもよい。ヘテロ環基を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。ヘテロ環基を構成するヘテロ原子の数は１～３が好ましい。ヘテロ環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。また、ヘテロ環基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。 Examples of the substituent which Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , and —COOR X1. , -OCOR X1 , -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR X1 R X2 , -NHCOOR X1 , -SO 2 R X1 , -SO 2 OR X1 , -NHSO 2 R X1 No. R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. The alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. In the alkyl group, some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms). In the alkyl group, part or all of the hydrogen atoms may be substituted with the above substituents. The carbon number of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. Further, in the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents. The heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably a 5- or 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
　Ａｒ1が表す芳香族炭化水素環は、無置換が好ましい。Ａｒ2が表す芳香族炭化水素環は、無置換であってもよく、置換基を有していてもよい。置換基を有していることが好ましい。置換基としては、－ＣＯＲX1が好ましい。ＲX1は、アルキル基、アリール基またはヘテロ環基が好ましく、アリール基がより好ましい。アリール基は置換基を有していてもよく、無置換であってもよい。置換基としては、炭素数１～１０のアルキル基などが挙げられる。 The aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted. The aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent. As a substituent, —COR X1 is preferable. R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
　Ｒ1は、フッ素原子を含む基を有するアリール基を表す。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。フッ素原子を含む基は、フッ素原子を有するアルキル基（含フッ素アルキル基）およびフッ素原子を有するアルキル基を含む基（含フッ素基）が好ましい。フッ素原子を含む基については、上述した範囲と同義であり、好ましい範囲も同様である。 R 1 represents an aryl group having a group containing a fluorine atom. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. As the group containing a fluorine atom, an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom-containing alkyl group (fluorine-containing group) are preferable. The group containing a fluorine atom has the same meaning as the above-mentioned range, and the preferred range is also the same.
　Ｒ2は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基およびアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したＡｒ1およびＡｒ2が有してもよい置換基で説明した置換基が挙げられる。アルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましく、１～４が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 R 2 represents an alkyl group or an aryl group, and is preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have. The carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10.
　Ｒ3は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基およびアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したＡｒ1およびＡｒ2が有してもよい置換基で説明した置換基が挙げられる。Ｒ3が表すアルキル基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。Ｒ3が表すアリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。 R 3 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described for the substituents that Ar 1 and Ar 2 may have. The number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and still more preferably has 6 to 10 carbon atoms.
　フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471. Compound (C-3).
　また、オキシム化合物は、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。この内容は本明細書に組み込まれる。 オ キ シ Also, as the oxime compound, an oxime compound having a fluorene ring can be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
　また、オキシム化合物は、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載の化合物ＯＥ－０１～ＯＥ－７５が挙げられる。 オ キ シ Alternatively, as the oxime compound, an oxime compound having a benzofuran skeleton can be used. Specific examples include compounds OE-01 to OE-75 described in WO 2015/036910.
　また、オキシム化合物は、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 オ キ シ Alternatively, as the oxime compound, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can be used. Specific examples of such oxime compounds include the compounds described in WO2013 / 083505.
　また、オキシム化合物は、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載の化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載の化合物などが挙げられる。 オ キ シ As the oxime compound, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008 to 0012 of JP-A-2014-137466, and 0070 to 0079; And the compounds described in Paragraph Nos. 0007 to 0025 of JP-A No. 195/1992.
　オキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　本発明では、光重合開始剤として、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ２と、を併用することが好ましい。この態様によれば、露光によって着色組成物を十分に硬化させやすく、低温プロセス（例えば全工程を通じて１５０℃以下の温度、好ましくは１２０℃以下の温度）にて、平坦性が良好で、かつ、耐溶剤性などの特性にも優れた画素を形成することができる。光重合開始剤Ａ１および光重合開始剤Ａ２としては、上述した化合物のなかから上記の吸光係数を有する化合物を選択して用いることが好ましい。 In the present invention, as the photopolymerization initiator, a photopolymerization initiator A1 having an extinction coefficient of 1.0 × 10 3 mL / gcm or more in methanol at 365 nm in methanol, and an extinction coefficient of 1.0 nm in methanol at 365 nm. It is preferable to use a photoinitiator A2 having a light absorption coefficient of 0 × 10 2 mL / gcm or less and an absorption coefficient at a wavelength of 254 nm of 1.0 × 10 3 mL / gcm or more in combination. According to this aspect, the coloring composition is easily cured sufficiently by exposure, has good flatness in a low-temperature process (for example, a temperature of 150 ° C. or lower, preferably 120 ° C. or lower throughout the entire process), and A pixel excellent in characteristics such as solvent resistance can be formed. As the photopolymerization initiator A1 and the photopolymerization initiator A2, it is preferable to use a compound having the above-mentioned extinction coefficient among the above-mentioned compounds.
　なお、本発明において、光重合開始剤の上記波長における吸光係数は、以下のようにして測定した値である。すなわち、光重合開始剤をメタノールに溶解させて測定溶液を調製し、前述の測定溶液の吸光度を測定することで算出した。具体的には、前述の測定溶液を幅１ｃｍのガラスセルに入れ、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製ＵＶ－Ｖｉｓ－ＮＩＲスペクトルメーター（Ｃａｒｙ５０００）を用いて吸光度を測定し、下記式に当てはめて、波長３６５ｎｍおよび波長２５４ｎｍにおける吸光係数（ｍＬ／ｇｃｍ）を算出した。
Figure JPOXMLDOC01-appb-M000014
 　上記式においてεは吸光係数（ｍＬ／ｇｃｍ）、Ａは吸光度、ｃは光重合開始剤の濃度（ｇ／ｍＬ）、ｌは光路長（ｃｍ）を表す。 In the present invention, the extinction coefficient at the above wavelength of the photopolymerization initiator is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies. The extinction coefficient (mL / gcm) at 254 nm was calculated.
Figure JPOXMLDOC01-appb-M000014
 In the above equation, ε represents the extinction coefficient (mL / gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents the optical path length (cm).
　光重合開始剤Ａ１のメタノール中での波長３６５ｎｍにおける吸光係数は、１．０×１０3ｍＬ／ｇｃｍ以上であり、１．０×１０4ｍＬ／ｇｃｍ以上であることが好ましく、１．１×１０4ｍＬ／ｇｃｍ以上であることがより好ましく、１．２×１０4～１．０×１０5ｍＬ／ｇｃｍであることが更に好ましく、１．３×１０4～５．０×１０4ｍＬ／ｇｃｍであることがより一層好ましく、１．５×１０4～３．０×１０4ｍＬ／ｇｃｍであることが特に好ましい。
　また、光重合開始剤Ａ１のメタノール中での波長２５４ｎｍの光の吸光係数は、１．０×１０4～１．０×１０5ｍＬ／ｇｃｍであることが好ましく、１．５×１０4～９．５×１０4ｍＬ／ｇｃｍであることがより好ましく、３．０×１０4～８．０×１０4ｍＬ／ｇｃｍであることが更に好ましい。 The extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 × 10 3 mL / gcm or more, preferably 1.0 × 10 4 mL / gcm or more, and more preferably 1.1 × 10 4 mL / gcm. It is more preferably at least 10 4 mL / gcm, even more preferably 1.2 × 10 4 to 1.0 × 10 5 mL / gcm, and 1.3 × 10 4 to 5.0 × 10 4 mL. / Gcm, more preferably 1.5 × 10 4 to 3.0 × 10 4 mL / gcm.
The extinction coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm in methanol is preferably from 1.0 × 10 4 to 1.0 × 10 5 mL / gcm, and from 1.5 × 10 4 to 1.5 × 10 4 mL / gcm. It is more preferably 9.5 × 10 4 mL / gcm, and still more preferably 3.0 × 10 4 to 8.0 × 10 4 mL / gcm.
　光重合開始剤Ａ１としては、オキシム化合物、アミノアルキルフェノン化合物、アシルホスフィン化合物が好ましく、オキシム化合物およびアシルホスフィン化合物がより好ましく、オキシム化合物が更に好ましく、組成物に含まれる他の成分との相溶性の観点からフッ素原子を含むオキシム化合物であることが特に好ましい。フッ素原子を含むオキシム化合物としては、上述した式（ＯＸ－１）で表される化合物が好ましい。光重合開始剤Ａ１の具体例としては、１，２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＢＡＳＦ社製）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＢＡＳＦ社製）、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－８１９、ＢＡＳＦ社製）、上記のオキシム化合物の具体例で示した（Ｃ－１３）、（Ｃ－１４）などが挙げられる。 The photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, further preferably an oxime compound, and has compatibility with other components contained in the composition. From the viewpoint of, an oxime compound containing a fluorine atom is particularly preferred. As the oxime compound containing a fluorine atom, a compound represented by the above formula (OX-1) is preferable. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (as commercial products, for example, IRGACURE-OXE01, BASF , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds ( C-13) and (C-14).
　光重合開始剤Ａ２のメタノール中での波長３６５ｎｍの光の吸光係数は、１．０×１０2ｍＬ／ｇｃｍ以下であり、１０～１．０×１０2ｍＬ／ｇｃｍであることが好ましく、２０～１．０×１０2ｍＬ／ｇｃｍであることがより好ましい。また、光重合開始剤Ａ１のメタノール中での波長３６５ｎｍの光の吸光係数と、光重合開始剤Ａ２のメタノール中での波長３６５ｎｍの光の吸光係数との差は、９．０×１０2ｍＬ／ｇｃｍ以上であり、１．０×１０3ｍＬ／ｇｃｍ以上であることが好ましく、５．０×１０3～３．０×１０4ｍＬ／ｇｃｍであることがより好ましく、１．０×１０4～２．０×１０4ｍＬ／ｇｃｍであることが更に好ましい。また、光重合開始剤Ａ２のメタノール中での波長２５４ｎｍの光の吸光係数は、１．０×１０3ｍＬ／ｇｃｍ以上であり、１．０×１０3～１．０×１０6ｍＬ／ｇｃｍであることが好ましく、５．０×１０3～１．０×１０5ｍＬ／ｇｃｍであることがより好ましい。 The extinction coefficient of the photopolymerization initiator A2 at 365 nm in methanol is 1.0 × 10 2 mL / gcm or less, preferably 10 to 1.0 × 10 2 mL / gcm. More preferably, it is about 1.0 × 10 2 mL / gcm. The difference between the extinction coefficient of photopolymerization initiator A1 at 365 nm in methanol and the extinction coefficient of photopolymerization initiator A2 at 365 nm in methanol is 9.0 × 10 2 mL. / Gcm or more, preferably 1.0 × 10 3 mL / gcm or more, more preferably 5.0 × 10 3 to 3.0 × 10 4 mL / gcm, and more preferably 1.0 × 10 3 mL / gcm. More preferably, it is 4 to 2.0 × 10 4 mL / gcm. Further, the extinction coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm in methanol is 1.0 × 10 3 mL / gcm or more, and 1.0 × 10 3 to 1.0 × 10 6 mL / gcm. And more preferably 5.0 × 10 3 to 1.0 × 10 5 mL / gcm.
　光重合開始剤Ａ２としては、ヒドロキシアルキルフェノン化合物、フェニルグリオキシレート化合物、アミノアルキルフェノン化合物、アシルホスフィン化合物が好ましく、ヒドロキシアルキルフェノン化合物およびフェニルグリオキシレート化合物がより好ましく、ヒドロキシアルキルフェノン化合物が更に好ましい。また、ヒドロキシアルキルフェノン化合物としては、上述した式（Ｖ）で表される化合物が好ましい。光重合開始剤Ａ２の具体例としては、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－１８４、ＢＡＳＦ社製）、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（市販品としては、例えば、ＩＲＧＡＣＵＲＥ－２９５９、ＢＡＳＦ社製）などが挙げられる。 The photopolymerization initiator A2 is preferably a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, an acylphosphine compound, more preferably a hydroxyalkylphenone compound and a phenylglyoxylate compound, and further preferably a hydroxyalkylphenone compound. preferable. Further, as the hydroxyalkylphenone compound, a compound represented by the above formula (V) is preferable. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl 2-hydroxy-2-methyl-1-propan-1-one (commercially available, for example, IRGACURE-2959, manufactured by BASF).
　光重合開始剤Ａ１と光重合開始剤Ａ２との組み合わせとしては、光重合開始剤Ａ１がオキシム化合物であり、光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である組み合わせが好ましく、光重合開始剤Ａ１がオキシム化合物であり、光重合開始剤Ａ２が上述した式（Ｖ）で表される化合物である組み合わせがより好ましく、光重合開始剤Ａ１がフッ素原子を含むオキシム化合物であり、光重合開始剤Ａ２が上述した式（Ｖ）で表される化合物である組み合わせが特に好ましい。 As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is preferably More preferably, the combination is an oxime compound, wherein the photopolymerization initiator A2 is a compound represented by the above formula (V), wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is Combinations of the compounds of formula (V) described above are particularly preferred.
　光重合開始剤の含有量は、着色組成物の全固形分中０．１～１７．５質量％であることが好ましい。下限は、０．５質量％以上であることが好ましく、１．０質量％以上であることがより好ましく、１．５質量％以上であることが更に好ましい。上限は、１５．０質量％以下であることが好ましく、１２．５質量％以下であることがより好ましく、１０．０質量％以下であることが更に好ましい。
　また、本発明の着色組成物は、重合性モノマー１００質量部に対して光重合開始剤を１．０～５０質量部含有することが好ましい。上限は、４０質量部以下であることが好ましく、３０質量部以下であることがより好ましい。下限は、２．５質量部以上であることが好ましく、５．０質量部以上であることが更に好ましい。この態様によれば、現像後のパターン形状が良好である。 The content of the photopolymerization initiator is preferably 0.1 to 17.5% by mass based on the total solid content of the coloring composition. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, even more preferably 10.0% by mass or less.
Further, the coloring composition of the present invention preferably contains 1.0 to 50 parts by mass of a photopolymerization initiator based on 100 parts by mass of the polymerizable monomer. The upper limit is preferably at most 40 parts by mass, more preferably at most 30 parts by mass. The lower limit is preferably at least 2.5 parts by mass, more preferably at least 5.0 parts by mass. According to this aspect, the pattern shape after development is good.
　本発明の着色組成物において、光重合開始剤として上述した光重合開始剤Ａ１を用いた場合、光重合開始剤Ａ１の含有量は、着色組成物の全固形分中０．１～１７．５質量％であることが好ましい。下限は、０．５質量％以上であることが好ましく、１．０質量％以上であることがより好ましく、１．５質量％以上であることが更に好ましい。上限は、１５．０質量％以下であることが好ましく、１２．５質量％以下であることがより好ましく、１０．０質量％以下であることが更に好ましい。 When the above-mentioned photopolymerization initiator A1 is used as the photopolymerization initiator in the coloring composition of the present invention, the content of the photopolymerization initiator A1 is 0.1 to 17.5 in the total solid content of the coloring composition. It is preferable that the content is mass%. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and even more preferably 10.0% by mass or less.
　本発明の着色組成物において、光重合開始剤として上述した光重合開始剤Ａ２を用いた場合、光重合開始剤Ａ２の含有量は、着色組成物の全固形分中０．１～１０．０質量％であることが好ましい。下限は、０．５質量％以上であることが好ましく、１．０質量％以上であることがより好ましく、１．５質量％以上であることが更に好ましい。上限は、９．０質量％以下であることが好ましく、８．０質量％以下であることがより好ましく、７．０質量％以下であることが更に好ましい。 When the above-mentioned photopolymerization initiator A2 is used as the photopolymerization initiator in the coloring composition of the present invention, the content of the photopolymerization initiator A2 is 0.1 to 10.0 in the total solid content of the coloring composition. It is preferable that the content is mass%. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably equal to or less than 9.0% by mass, more preferably equal to or less than 8.0% by mass, and still more preferably equal to or less than 7.0% by mass.
　本発明の着色組成物において、光重合開始剤として上述した光重合開始剤Ａ１と光重合開始剤Ａ２とを用いた場合、本発明の着色組成物は、光重合開始剤Ａ１の１００質量部に対して、光重合開始剤Ａ２を５０～２００質量部含有することが好ましい。上限は、１７５質量部以下であることが好ましく、１５０質量部以下であることがより好ましい。下限は、６０質量部以上であることが好ましく、７０質量部以上であることが更に好ましい。この態様によれば、低温プロセス（例えば全工程を通じて１５０℃以下の温度、好ましくは１２０℃以下の温度）にて耐溶剤性などの特性に優れた画素を形成することができる。 In the coloring composition of the present invention, when the above-described photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator, the coloring composition of the present invention is added to 100 parts by mass of the photopolymerization initiator A1. On the other hand, it is preferable to contain 50 to 200 parts by mass of the photopolymerization initiator A2. The upper limit is preferably at most 175 parts by mass, more preferably at most 150 parts by mass. The lower limit is preferably at least 60 parts by mass, more preferably at least 70 parts by mass. According to this aspect, it is possible to form a pixel having excellent properties such as solvent resistance in a low-temperature process (for example, a temperature of 150 ° C. or lower, preferably a temperature of 120 ° C. or lower throughout the entire process).
　本発明の着色組成物において、光重合開始剤として上述した光重合開始剤Ａ１と光重合開始剤Ａ２とを用いた場合、着色組成物の全固形分中における光重合開始剤Ａ１と光重合開始剤Ａ２との合計の含有量は、０．１～２０．０質量％であることが好ましい。下限は、１．０質量％以上であることが好ましく、２．０質量％以上であることがより好ましく、２．５質量％以上であることが更に好ましい。上限は、１７．５質量％以下であることが好ましく、１５．０質量％以下であることがより好ましく、１２．５質量％以下であることが更に好ましい。 In the coloring composition of the present invention, when the above-described photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator, the photopolymerization initiator A1 and the photopolymerization initiator in the total solid content of the coloring composition are used. The total content with the agent A2 is preferably 0.1 to 20.0% by mass. The lower limit is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and even more preferably 2.5% by mass or more. The upper limit is preferably 17.5% by mass or less, more preferably 15.0% by mass or less, and even more preferably 12.5% by mass or less.
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含む。樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に粒子等を組成物中で分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外を目的として樹脂を使用することもできる。 << Resin >>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder. Note that a resin mainly used for dispersing particles and the like in the composition is also referred to as a dispersant. However, such a use of the resin is an example, and the resin may be used for a purpose other than such a use.
　樹脂の重量平均分子量（Ｍｗ）は、２０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、３０００以上が好ましく、４０００以上がより好ましく、５０００以上が更に好ましい。 The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more.
　樹脂としては、例えば、（メタ）アクリル樹脂、（メタ）アクリルアミド樹脂、エポキシ樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂などが挙げられる。 Examples of the resin include (meth) acrylic resin, (meth) acrylamide resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene Examples include ether phosphine oxide resins, polyimide resins, polyamide imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and the like.
　本発明で用いる樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂や、分散剤として用いることもできる。 樹脂 The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group. These acid groups may be used alone or in combination of two or more. The resin having an acid group can be used as an alkali-soluble resin or a dispersant.
　酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上がより好ましく、７０ｍｇＫＯＨ／ｇ以上が更に好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下がより好ましく、２００ｍｇＫＯＨ／ｇ以下がさらに好ましく、１５０ｍｇＫＯＨ／ｇ以下が特に好ましく、１２０ｍｇＫＯＨ／ｇ以下が最も好ましい。 The acid value of the resin having an acid group is preferably from 30 to 500 mgKOH / g. The lower limit is more preferably at least 50 mgKOH / g, even more preferably at least 70 mgKOH / g. The upper limit is more preferably 400 mg KOH / g or less, further preferably 200 mg KOH / g or less, particularly preferably 150 mg KOH / g or less, and most preferably 120 mg KOH / g or less.
　酸基を有する樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。例えば、メタクリル酸、アクリル酸、イタコン酸、クロトン酸、マレイン酸、２－カルボキシエチル（メタ）アクリル酸、ビニル安息香酸、部分エステル化マレイン酸等のモノマーに由来する繰り返し単位を有する共重合体、ノボラック型樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシ基を有するポリマーに酸無水物を付加させたポリマーが挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、グリシジルメタクリレート、テトラヒドロフルフリルメタクリレートなどが挙げられる。ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。これらの（メタ）アクリル酸と共重合可能な他のモノマーは、１種のみであってもよいし、２種以上であってもよい。 As the resin having a diacid group, a polymer having a carboxyl group in a side chain is preferable. For example, a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, and partially esterified maleic acid; Examples include alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxy group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Is mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. These other monomers copolymerizable with (meth) acrylic acid may be used alone or in combination of two or more.
　酸基を有する樹脂は、マレイミド化合物に由来する繰り返し単位を有していてもよい。マレイミド化合物としては、Ｎ－アルキルマレイミド、Ｎ－アリールマレイミドなどが挙げられる。マレイミド化合物に由来する繰り返し単位としては、式（Ｃ－ｍｉ）で表される繰り返し単位が挙げられる。
Figure JPOXMLDOC01-appb-C000015
 The resin having an acid group may have a repeating unit derived from a maleimide compound. Examples of the maleimide compound include N-alkylmaleimide and N-arylmaleimide. Examples of the repeating unit derived from the maleimide compound include a repeating unit represented by the formula (C-mi).
Figure JPOXMLDOC01-appb-C000015
　式（Ｃ－ｍｉ）において、Ｒｍｉはアルキル基またはアリール基を表す。アルキル基の炭素数は１～２０が好ましい。アルキル基は、直鎖、分岐、環状のいずれもよい。アリール基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。Ｒｍｉはアリール基であることが好ましい。 に お い て In the formula (C-mi), Rmi represents an alkyl group or an aryl group. The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may be linear, branched or cyclic. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. Rmi is preferably an aryl group.
　酸基を有する樹脂は、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）由来の繰り返し単位を含む樹脂であることも好ましい。 The resin having an acid group is derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferred that the resin contains a unit.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ＥＤ１）中、Ｒ1およびＲ2は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000017
 　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Figure JPOXMLDOC01-appb-C000017
 In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168538 can be referred to.
　エーテルダイマーの具体例については、特開２０１３－０２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。 For specific examples of the ether dimer, Paragraph No. 0317 of JP-A-2013-029760 can be referred to, and the contents thereof are incorporated herein.
　エーテルダイマー由来の繰り返し単位を含む樹脂としては、例えば下記構造の樹脂が挙げられる。以下の構造式中Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000018
 Examples of the resin containing a repeating unit derived from an ether dimer include a resin having the following structure. In the following structural formulas, Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000018
　本発明で用いられる樹脂は、重合性基を有していてもよい。重合性基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基等のエチレン性不飽和基が挙げられる。重合性基を有する樹脂の市販品としては、ダイヤナールＮＲシリーズ（三菱レイヨン（株）製）、Ｐｈｏｔｏｍｅｒ６１７３（カルボキシル基含有ポリウレタンアクリレートオリゴマー、Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．，Ｌｔｄ．製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業（株）製）、サイクロマーＰシリーズ（例えば、ＡＣＡ２３０ＡＡ）、プラクセル　ＣＦ２００シリーズ（いずれも（株）ダイセル製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー株式会社製）、アクリキュアーＲＤ－Ｆ８（（株）日本触媒製）、ＤＰ－１３０５（富士ファインケミカルズ（株）製）などが挙げられる。 樹脂 The resin used in the present invention may have a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Commercially available resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel @ CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (daicel UCB Co., Ltd.), Acrylicer RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).
　本発明で用いられる樹脂は、式（Ｉ）で表される化合物由来の繰り返し単位（以下、繰り返し単位ｂ１－１ともいう）を含む樹脂ｂ１を含有することが好ましい。繰り返し単位ｂ１－１を有する樹脂を用いることで、低温硬化性と透明性が優れる。
Figure JPOXMLDOC01-appb-C000019
 The resin used in the present invention preferably contains a resin b1 containing a repeating unit derived from the compound represented by the formula (I) (hereinafter, also referred to as a repeating unit b1-1). By using a resin having the repeating unit b1-1, low-temperature curability and transparency are excellent.
Figure JPOXMLDOC01-appb-C000019
　Ｘ1は、ＯまたはＮＨを表し、Ｏであることが好ましい。
　Ｒ1は水素原子またはメチル基を表す。
　Ｌ1は２価の連結基を表す。２価の連結基としては、炭化水素基、複素環基、－ＮＨ－、－ＳＯ－、－ＳＯ2－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。炭化水素基としては、アルキル基、アリール基などが挙げられる。複素環基は、非芳香族の複素環基であってもよく、芳香族複素環基であってもよい。複素環基は、５員環または６員環が好ましい。複素環基を構成するヘテロ原子の種類は窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基を構成するヘテロ原子の数は１～３が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。炭化水素基および複素環基は置換基を有していてもよい。置換基としては、アルキル基、アリール基、ヒドロキシ基、ハロゲン原子などが挙げられる。
　Ｒ10は置換基を表す。Ｒ10が表す置換基としては、以下に示す置換基Ｔが挙げられ、炭化水素基であることが好ましく、アリール基を置換基として有していてもよいアルキル基であることがより好ましい。
　ｍは０～２の整数を表し、０または１が好ましく、０がより好ましい。
　ｐは０以上の整数を表し、０～４が好ましく、０～３がより好ましく、０～２が更に好ましく、０または１がより一層好ましく、１が特に好ましい。 X 1 represents O or NH, and is preferably O.
R 1 represents a hydrogen atom or a methyl group.
L 1 represents a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, a heterocyclic group, -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and And a group obtained by combining two or more of the above. Examples of the hydrocarbon group include an alkyl group and an aryl group. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered ring. Examples of the type of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of hetero atoms constituting the heterocyclic group is preferably from 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxy group, and a halogen atom.
R 10 represents a substituent. Examples of the substituent represented by R 10 include the following substituents T, preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.
m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, still more preferably 0 or 1, and particularly preferably 1.
　（置換基Ｔ）
　置換基Ｔとしては、ハロゲン原子、シアノ基、ニトロ基、炭化水素基、複素環基、－ＯＲｔ1、－ＣＯＲｔ1、－ＣＯＯＲｔ1、－ＯＣＯＲｔ1、－ＮＲｔ1Ｒｔ2、－ＮＨＣＯＲｔ1、－ＣＯＮＲｔ1Ｒｔ2、－ＮＨＣＯＮＲｔ1Ｒｔ2、－ＮＨＣＯＯＲｔ1、－ＳＲｔ1、－ＳＯ2Ｒｔ1、－ＳＯ2ＯＲｔ1、－ＮＨＳＯ2Ｒｔ1または－ＳＯ2ＮＲｔ1Ｒｔ2が挙げられる。Ｒｔ1およびＲｔ2は、それぞれ独立して水素原子、炭化水素基または複素環基を表す。Ｒｔ1とＲｔ2が結合して環を形成してもよい。 (Substituent T)
Examples of the substituent T include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NHCORt 1 ,- CONT 1 Rt 2 , —NHCONT 1 Rt 2 , —NHCOORt 1 , —SRt 1 , —SO 2 Rt 1 , —SO 2 ORt 1 , —NHSO 2 Rt 1, or —SO 2 NRt 1 Rt 2 . Rt 1 and Rt 2 each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rt 1 and Rt 2 may combine to form a ring.
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　炭化水素基としては、アルキル基、アルケニル基、アルキニル基、アリール基が挙げられる。アルキル基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましく、分岐がより好ましい。
　アルケニル基の炭素数は、２～３０が好ましく、２～１２がより好ましく、２～８が特に好ましい。アルケニル基は直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
　アルキニル基の炭素数は、２～３０が好ましく、２～２５がより好ましい。アルキニル基は直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。
　複素環基は、単環であってもよく、縮合環であってもよい。複素環基は、単環または縮合数が２～４の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は１～３が好ましい。複素環基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。複素環基の環を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。
　炭化水素基および複素環基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基Ｔで説明した置換基が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably branched.
The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 12.
The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed numbers. The number of hetero atoms constituting the ring of the heterocyclic group is preferably from 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent T described above.
　式（Ｉ）で表される化合物は、下記式（Ｉ－１）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000020
 The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).
Figure JPOXMLDOC01-appb-C000020
　Ｘ1は、ＯまたはＮＨを表し、Ｏであることが好ましい。
　Ｒ1は水素原子またはメチル基を表す。
　Ｒ2、Ｒ3およびＲ11はそれぞれ独立して炭化水素基を表す。
　Ｒ2およびＲ3が表す炭化水素基は、アルキレン基またはアリーレン基であることが好ましく、アルキレン基であることがより好ましい。アルキレン基の炭素数は１～１０であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましく、２または３であることが特に好ましい。Ｒ11が表す炭化水素基は、アリール基を置換基として有していてもよいアルキル基であることが好ましく、アリール基を置換基として有するアルキル基であることがより好ましい。アルキル基の炭素数は、１～２０が好ましく、１～１０がより好ましく、１～５が更に好ましい。なお、アルキル基が置換基としてアリール基を有する場合におけるアルキル基の炭素数は、アルキル部位の炭素数のことを意味する。
　Ｒ12は置換基を表す。Ｒ12が表す置換基としては、上述した置換基Ｔが挙げられる。
　ｎは０～１５の整数を表し、０～５の整数であることが好ましく、０～４の整数であることがより好ましく、０～３の整数であることが更に好ましい。
　ｍは０～２の整数を表し、０または１であることが好ましく、０であることがより好ましい。
　ｐ１は０以上の整数を表し、０～４が好ましく、０～３がより好ましく、０～２が更に好ましく、０～１がより一層好ましく、０が特に好ましい。
　ｑ１は１以上の整数を表し、１～４が好ましく、１～３がより好ましく、１～２が更に好ましく、１が特に好ましい。 X 1 represents O or NH, and is preferably O.
R 1 represents a hydrogen atom or a methyl group.
R 2 , R 3 and R 11 each independently represent a hydrocarbon group.
The hydrocarbon group represented by R 2 and R 3 is preferably an alkylene group or an arylene group, and more preferably an alkylene group. The carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. The hydrocarbon group represented by R 11 is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5. In the case where the alkyl group has an aryl group as a substituent, the carbon number of the alkyl group means the carbon number of the alkyl moiety.
R 12 represents a substituent. Examples of the substituent represented by R 12 include the substituent T described above.
n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.
m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, still more preferably 0 to 1, and particularly preferably 0.
q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
　式（Ｉ）で表される化合物は、下記式（ＩＩＩ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000021
 　式中、Ｒ1は水素原子またはメチル基を表し、Ｒ21およびＲ22はそれぞれ独立してアルキレン基を表し、ｎは０～１５の整数を表す。Ｒ21およびＲ22が表すアルキレン基の炭素数は１～１０であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましく、２または３であることが特に好ましい。ｎは０～１５の整数を表し、０～５の整数であることが好ましく、０～４の整数であることがより好ましく、０～３の整数であることが更に好ましい。 The compound represented by the formula (I) is preferably a compound represented by the following formula (III).
Figure JPOXMLDOC01-appb-C000021
 In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.
　式（Ｉ）で表される化合物としては、パラクミルフェノールのエチレンオキサイドまたはプロピレンオキサイド変性（メタ）アクリレートなどが挙げられる。市販品としては、アロニックスＭ－１１０（東亞合成（株）製）などが挙げられる。 化合物 Examples of the compound represented by the formula (I) include ethylene oxide or propylene oxide-modified (meth) acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
　樹脂ｂ１は、更に、アルキル（メタ）アクリレート由来の繰り返し単位（以下、繰り返し単位ｂ１－２ともいう）を含むことが好ましい。アルキル（メタ）アクリレートのアルキル部位の炭素数は、３～１０であることが好ましく、３～８であることがより好ましく、３～６であることが更に好ましい。アルキル（メタ）アクリレートの好ましい具体例としては、ｎ－ブチル（メタ）アクリレートなどが挙げられる。 The resin b1 preferably further contains a repeating unit derived from an alkyl (meth) acrylate (hereinafter, also referred to as a repeating unit b1-2). The alkyl portion of the alkyl (meth) acrylate preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms. Preferred specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate.
　樹脂ｂ１は、更に、酸基を有する繰り返し単位（以下、繰り返し単位ｂ１－３ともいう）を含むことも好ましい。 The resin b1 preferably further contains a repeating unit having an acid group (hereinafter, also referred to as a repeating unit b1-3).
　本発明の着色組成物は、分散剤としての樹脂を含有することができる。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、１０～１０５ｍｇＫＯＨ／ｇが好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。 着色 The coloring composition of the present invention can contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of an acid group is larger than the amount of a basic group. As the acidic dispersant (acidic resin), a resin in which the amount of the acid group accounts for 70% by mole or more when the total amount of the acid group and the amount of the basic group is 100% by mole is preferable. A resin consisting of only an acid group is more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably from 10 to 105 mgKOH / g. The basic dispersant (basic resin) refers to a resin in which the amount of the basic group is larger than the amount of the acid group. As the basic dispersant (basic resin), a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the acid group and the amount of the basic group is 100 mol% is preferable. The basic group of the basic dispersant is preferably an amino group.
　分散剤としては、例えば、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン等が挙げられる。高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。高分子分散剤は、顔料などの粒子表面に吸着し、再凝集を防止するように作用する。そのため、顔料などの粒子表面へのアンカー部位を有する末端変性型高分子、グラフト型高分子、ブロック型高分子を好ましい構造として挙げることができる。また、特開２０１１－０７０１５６号公報の段落番号００２８～０１２４に記載の分散剤や特開２００７－２７７５１４号公報に記載の分散剤も好ましく用いられる。 Examples of the dispersant include a polymer dispersant [eg, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine and the like. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure. The polymer dispersant adsorbs on the surface of particles such as pigments and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the particle surface such as a pigment can be cited as a preferable structure. Further, dispersants described in paragraphs 0028 to 0124 of JP-A-2011-070156 and dispersants described in JP-A-2007-277514 are also preferably used.
　本発明において、分散剤にはグラフト共重合体を用いることもできる。グラフト共重合体の詳細は、特開２０１２－１３７５６４号公報の段落番号０１３１～０１６０の記載を参酌でき、この内容は本明細書に組み込まれる。また、本発明において、分散剤には主鎖及び側鎖の少なくとも一方に窒素原子を含むオリゴイミン系共重合体を用いることもできる。オリゴイミン系共重合体については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１７４の記載を参酌でき、この内容は本明細書に組み込まれる。 グ ラ フ ト In the present invention, a graft copolymer can also be used as a dispersant. The details of the graft copolymer can be referred to the description in paragraphs 0131 to 0160 of JP-A-2012-137564, the contents of which are incorporated herein. In the present invention, an oligoimine-based copolymer containing a nitrogen atom in at least one of a main chain and a side chain can be used as the dispersant. Regarding the oligoimine-based copolymer, the description in paragraphs 0102 to 0174 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ビックケミー社製のＤｉｓｐｅｒｂｙｋシリーズ（例えば、Ｄｉｓｐｅｒｂｙｋ－１１１、２００１など）、日本ルーブリゾール（株）製のソルスパースシリーズ（例えば、ソルスパース２００００、７６５００など）、味の素ファインテクノ（株）製のアジスパーシリーズ等が挙げられる。また、特開２０１２－１３７５６４号公報の段落番号０１２９に記載された製品、特開２０１７－１９４６６２号公報の段落番号０２３５に記載された製品を分散剤として用いることもできる。 The dispersing agent is also available as a commercial product. Specific examples of such a dispersing agent include Disperbyk series (for example, Disperbyk-111 and 2001) manufactured by Big Chemie, and Solsperse series (manufactured by Nippon Lubrizol Co., Ltd.). For example, Solsperse 20000, 76500, etc.) and Azispar series manufactured by Ajinomoto Fine Techno Co., Ltd. are exemplified. Further, a product described in paragraph No. 0129 of JP-A-2012-137564 and a product described in paragraph No. 0235 of JP-A-2017-194662 can be used as a dispersant.
　樹脂の含有量は、着色組成物の全固形分中５～５０質量％であることが好ましい。上限は、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。下限は、７．５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。
　また、樹脂の含有量は重合性モノマーの１００質量部に対して２５～５００質量部であることが好ましい。上限は２５０質量部以下が好ましく、１５０質量部以下がより好ましい。下限は５０質量部以上が好ましく、７５質量部以上がより好ましい。
　また、本発明の着色組成物に含まれる樹脂の全量中における上述した樹脂ｂ１（式（ＩＩＩ）で表される化合物由来の繰り返し単位を含む）の含有量は、０．１～１００質量％であることが好ましく、５～１００質量％であることがより好ましい。上限は、９０質量％以下とすることもでき、８０質量％以下とすることもでき、７０質量％以下とすることもできる。
　また、上述した樹脂ｂ１の含有量は、着色組成物の全固形分中５～５０質量％であることが好ましい。上限は、４０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。下限は、１０質量％以上であることが好ましく、１２．５質量％以上であることがより好ましい。 The content of the resin is preferably 5 to 50% by mass based on the total solid content of the coloring composition. The upper limit is preferably at most 40% by mass, more preferably at most 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
Further, the content of the resin is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The upper limit is preferably 250 parts by mass or less, more preferably 150 parts by mass or less. The lower limit is preferably at least 50 parts by mass, more preferably at least 75 parts by mass.
The content of the resin b1 (including the repeating unit derived from the compound represented by the formula (III)) in the total amount of the resin contained in the coloring composition of the present invention is 0.1 to 100% by mass. It is preferably present, and more preferably 5 to 100% by mass. The upper limit can be 90% by mass or less, can be 80% by mass or less, and can be 70% by mass or less.
Further, the content of the resin b1 is preferably 5 to 50% by mass based on the total solid content of the coloring composition. The upper limit is preferably at most 40% by mass, more preferably at most 30% by mass. The lower limit is preferably 10% by mass or more, more preferably 12.5% by mass or more.
＜＜フリル基含有化合物＞＞
　本発明の着色組成物は、フリル基を含む化合物（以下、フリル基含有化合物ともいう）を含有することが好ましい。この態様によれば、低温硬化に優れる。 << Frill group-containing compound >>
The coloring composition of the present invention preferably contains a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). According to this aspect, low-temperature curing is excellent.
　フリル基含有化合物は、フリル基（フランから１つの水素原子を除いた基）を含んでいれば特にその構造が限定されるものではない。
フリル基含有化合物については、特開２０１７－１９４６６２号公報の段落番号００４９～００８９に記載された化合物を用いることができる。また、特開２０００－２３３５８１号公報、特開１９９４－２７１５５８号公報、特開１９９４－２９３８３０号公報、特開１９９６－２３９４２１号公報、特開１９９８－５０８６５５号公報、特開２０００－００１５２９号公報、特開２００３－１８３３４８号公報、特開２００６－１９３６２８号公報、特開２００７－１８６６８４号公報、特開２０１０－２６５３７７号公報、特開２０１１－１７００６９号公報などに記載されている化合物を用いることもできる。 The structure of the furyl group-containing compound is not particularly limited as long as it contains a furyl group (a group obtained by removing one hydrogen atom from furan).
As the furyl group-containing compound, compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used. Also, JP-A-2000-233581, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, JP-A-1998-508655, JP-A-2000-001529, Compounds described in JP-A-2003-183348, JP-A-2006-193628, JP-A-2007-186684, JP-A-2010-265377, JP-A-2011-170069 may also be used. it can.
　フリル基含有化合物は、モノマーであってもよく、ポリマーであってもよい。得られる膜の耐久性を向上させやすいという理由からポリマーであることが好ましい。ポリマーの場合、重量平均分子量は、２０００～７００００が好ましい。上限は、６００００以下が好ましく、５００００以下がより好ましい。下限は、３０００以上が好ましく、４０００以上がより好ましく、５０００以上が更に好ましい。なお、ポリマータイプのフリル基含有化合物は、本発明の着色組成物における樹脂にも該当する成分である。 The difuryl group-containing compound may be a monomer or a polymer. The polymer is preferably used because it is easy to improve the durability of the obtained film. In the case of a polymer, the weight average molecular weight is preferably from 2000 to 70000. The upper limit is preferably 60,000 or less, more preferably 50,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. The polymer type furyl group-containing compound is a component that also corresponds to the resin in the coloring composition of the present invention.
　モノマータイプのフリル基含有化合物（以下、フリル基含有モノマーともいう）としては、下記式（ｆｕｒ－１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000022
 　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ2は２価の連結基を表す。 Examples of the monomer type furyl group-containing compound (hereinafter, also referred to as a furyl group-containing monomer) include a compound represented by the following formula (fur-1).
Figure JPOXMLDOC01-appb-C000022
 In the formula, Rf 1 represents a hydrogen atom or a methyl group, and Rf 2 represents a divalent linking group.
　Ｒｆ2が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。 Examples of the divalent linking group represented by Rf 2 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group.
　フリル基含有モノマーは、下記式（ｆｕｒ－１－１）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000023
 　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ11は－Ｏ－または－ＮＨ－を表し、Ｒｆ12は単結合または２価の連結基を表す。Ｒｆ12が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。 The furyl group-containing monomer is preferably a compound represented by the following formula (fur-1-1).
Figure JPOXMLDOC01-appb-C000023
 In the formula, Rf 1 represents a hydrogen atom or a methyl group, Rf 11 represents —O— or —NH—, and Rf 12 represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Rf 12 include an alkylene group, an arylene group, —O—, —CO—, —COO—, —OCO—, —NH—, —S—, and a combination of two or more of these. Groups. The carbon number of the alkylene group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 15. The alkylene group may be linear, branched or cyclic. The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 10. The alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group.
　フリル基含有モノマーの具体例としては、下記構造の化合物が挙げられる。以下の構造式中、Ｒｆ1は水素原子またはメチル基を表す。
Figure JPOXMLDOC01-appb-C000024
 Specific examples of the furyl group-containing monomer include a compound having the following structure. In the following structural formula, Rf 1 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000024
　ポリマータイプのフリル基含有化合物（以下、フリル基含有ポリマーともいう）としては、フリル基を含む繰り返し単位を含む樹脂であることが好ましく、上記式（ｆｕｒ－１）で表される化合物由来の繰り返し単位を含む樹脂であることがより好ましい。フリル基含有ポリマー中のフリル基の濃度は、フリル基含有ポリマー１ｇあたり０．５～６．０ｍｍｏｌが好ましく、１．０～４．０ｍｍｏｌがさらに好ましい。フリル基の濃度が０．５ｍｍｏｌ以上、好ましくは１．０ｍｍｏｌ以上であると耐溶剤性などに優れた画素を形成しやすい。フリル基の濃度が６．０ｍｍｏｌ以下、好ましくは４．０ｍｍｏｌ以下であれば、着色組成物の経時安定性が良好である。 The polymer type furyl group-containing compound (hereinafter also referred to as a furyl group-containing polymer) is preferably a resin containing a repeating unit containing a furyl group, and is preferably a resin derived from the compound represented by the above formula (fur-1). More preferably, the resin contains units. The concentration of the furyl group in the furyl group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol, per 1 g of the furyl group-containing polymer. When the concentration of the furyl group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a pixel having excellent solvent resistance and the like. When the concentration of the furyl group is 6.0 mmol or less, preferably 4.0 mmol or less, the coloring composition has good temporal stability.
　フリル基含有ポリマーは、フリル基を有する繰り返し単位の他に、酸基を有する繰り返し単位および／または重合性基を有する繰り返し単位を含んでいてもよい。酸基としては、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。重合性基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基等のエチレン性不飽和基が挙げられる。フリル基含有ポリマーが酸基を有する繰り返し単位を含む場合、その酸価は１０～２００ｍｇＫＯＨ／ｇが好ましく、４０～１３０ｍｇＫＯＨ／ｇがより好ましい。 The furyl group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group in addition to the repeating unit having a furyl group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. Examples of the polymerizable group include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. When the furyl group-containing polymer contains a repeating unit having an acid group, its acid value is preferably from 10 to 200 mgKOH / g, more preferably from 40 to 130 mgKOH / g.
　フリル基含有ポリマーが重合性基を有する繰り返し単位を含む場合は、より耐溶剤性などに優れた画素を形成しやすい。 When the furyl group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a pixel having more excellent solvent resistance and the like.
　フリル基含有ポリマーは、特開２０１７－１９４６６２号公報の段落番号００５２～０１０１に記載された方法で製造することができる。 The furyl group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
　フリル基含有化合物の含有量は、着色組成物の全固形分中０．１～７０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、５．０質量％以上であることがより好ましく、７．５質量％以上であることが更に好ましい。上限は、６５質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることが更に好ましい。
　また、フリル基含有化合物としてフリル基含有ポリマーを用いた場合、着色組成物に含まれる樹脂中におけるフリル基含有ポリマーの含有量は、０．１～１００質量％であることが好ましい。下限は、１０質量部以上であることが好ましく、１５質量部以上であることがより好ましい。上限は、９０質量部以下であることが好ましく、８０質量部以下であることがより好ましい。
　また、本発明の着色組成物に用いられる樹脂が上述した樹脂ｂ１を含み、かつ、フリル基含有化合物としてフリル基含有ポリマーを用いた場合には、フリル基含有ポリマーの含有量は、樹脂ｂ１の１００質量部に対して１０～２００質量部であることが好ましい。上限は、１７５質量部以下であることが好ましく、１５０質量部以下であることが好ましい。下限は、２５質量部以上であることが好ましく、１５０質量部以上であることが好ましい。樹脂ｂ１とフリル基含有ポリマーとを併用することにより、低温硬化性と透明性に優れるという効果が期待できる。更に、両者の割合が上記範囲である場合には得られる膜の耐久性をより向上できるという効果も期待できる。 The content of the furyl group-containing compound is preferably from 0.1 to 70% by mass based on the total solid content of the coloring composition. The lower limit is preferably at least 2.5% by mass, more preferably at least 5.0% by mass, even more preferably at least 7.5% by mass. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
When a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer in the resin contained in the coloring composition is preferably from 0.1 to 100% by mass. The lower limit is preferably at least 10 parts by mass, more preferably at least 15 parts by mass. The upper limit is preferably at most 90 parts by mass, more preferably at most 80 parts by mass.
Further, when the resin used in the coloring composition of the present invention contains the resin b1 described above, and a furyl group-containing polymer is used as the furyl group-containing compound, the content of the furyl group-containing polymer is the same as that of the resin b1. It is preferably from 10 to 200 parts by mass per 100 parts by mass. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 25 parts by mass or more, and more preferably 150 parts by mass or more. By using the resin b1 and the furyl group-containing polymer in combination, an effect of being excellent in low-temperature curability and transparency can be expected. Further, when the ratio of both is within the above range, the effect that the durability of the obtained film can be further improved can be expected.
＜＜エポキシ基を有する化合物＞＞
　本発明の着色組成物は、更にエポキシ基を有する化合物を含有することができる。エポキシ基を有する化合物としては、１分子内にエポキシ基を２つ以上有する化合物が好ましい。エポキシ基は、１分子内に２～１００個有することが好ましい。上限は、例えば、１０個以下とすることもでき、５個以下とすることもできる。エポキシ基を有する化合物のエポキシ当量（＝エポキシ基を有する化合物の分子量／エポキシ基の数）は、５００ｇ／ｅｑ以下であることが好ましく、１００～４００ｇ／ｅｑであることがより好ましく、１００～３００ｇ／ｅｑであることがさらに好ましい。エポキシ基を有する化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）のいずれでもよい。エポキシ基を有する化合物の分子量（ポリマーの場合は、重量平均分子量）は、２００～１０００００が好ましく、５００～５００００がより好ましい。分子量（ポリマーの場合は、重量平均分子量）の上限は、３０００以下が好ましく、２０００以下がより好ましく、１５００以下が更に好ましい。 << Compound having epoxy group >>
The coloring composition of the present invention may further contain a compound having an epoxy group. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. The epoxy group preferably has 2 to 100 epoxy groups in one molecule. The upper limit can be, for example, 10 or less, or 5 or less. The epoxy equivalent of the compound having an epoxy group (= the molecular weight of the compound having an epoxy group / the number of epoxy groups) is preferably 500 g / eq or less, more preferably 100 to 400 g / eq, and 100 to 300 g. / Eq is more preferable. The compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (a macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). . The molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.
　エポキシ基を有する化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。 Examples of the compound having an epoxy group include paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408. The compounds described and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
　本発明の着色組成物がエポキシ基を有する化合物を含有する場合、エポキシ基を有する化合物の含有量は、着色組成物の全固形分中、０．１～４０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。エポキシ基を有する化合物は、１種単独であってもよいし、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲となることが好ましい。 When the coloring composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass based on the total solid content of the coloring composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably within the above range.
＜＜溶剤＞＞
　本発明の着色組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や着色組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドなどが挙げられる。ただし溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << Solvent >>
The coloring composition of the present invention preferably contains a solvent. Examples of the solvent include an organic solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For these details, reference can be made to paragraph No. 0223 of WO 2015/166779, the contents of which are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons or the like (for example, 50 mass ppm (parts per part based on the total amount of the organic solvent). (million) or less, 10 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない溶剤を用いることが好ましく、溶剤の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。 に お い て In the present invention, it is preferable to use a solvent having a low metal content, and it is preferable that the metal content of the solvent be, for example, 10 mass ppb (parts per per billion) or less. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
　溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 方法 Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one isomer may be contained, or a plurality of isomers may be contained.
　本発明において、有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 に お い て In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide.
　着色組成物中における溶剤の含有量は、６０～９５質量％であることが好ましい。上限は９０質量％以下であることが好ましく、８７．５質量％以下であることがより好ましく、８５質量％以下であることが更に好ましい。下限は、６５質量％以上であることが好ましく、７０質量％以上であることがより好ましく、７５質量％以上であることが更に好ましい。 溶 剤 The content of the solvent in the coloring composition is preferably from 60 to 95% by mass. The upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and even more preferably 85% by mass or less. The lower limit is preferably at least 65% by mass, more preferably at least 70% by mass, even more preferably at least 75% by mass.
　また、本発明の着色組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、着色組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、本発明の着色組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として着色組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した着色組成物の段階いずれの段階でも可能である。 着色 In addition, it is preferable that the coloring composition of the present invention does not substantially contain an environmental control substance from the viewpoint of environmental control. In the present invention, the term "substantially free of environmental control substances" means that the content of the environmental control substances in the coloring composition is 50 ppm by mass or less, and preferably 30 ppm by mass or less. Is more preferably 10 ppm by mass or less, particularly preferably 1 ppm by mass or less. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are regulated by the REACH (Registration, Evaluation, Authorization, Restriction, of Chemicals) rules, PRTR (Pollutant Release, Transfer and Register), VOC (Volatile, Regulated, etc.) The method is strictly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition of the present invention, and may be mixed into the coloring composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and environmental considerations. As a method of reducing the amount of environmentally controlled substances, there is a method of heating or reducing the pressure in the system to make the temperature equal to or higher than the boiling point of the environmentally controlled substances and distilling and reducing the environmentally controlled substances from the system. When a small amount of environmentally regulated substances are distilled off, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. When a compound having a radical polymerizability is contained, a polymerization inhibitor or the like is added in order to suppress the radical polymerization reaction from proceeding and crosslinking between molecules during the distillation under reduced pressure, followed by distillation under reduced pressure. You may. These distillation methods are performed at the stage of the raw material, at the stage of a product obtained by reacting the raw material (for example, a resin solution or a polyfunctional monomer solution after polymerization), or at the stage of a colored composition prepared by mixing these compounds. It is also possible at the stage.
＜＜顔料誘導体＞＞
　本発明の着色組成物は、顔料誘導体を含有することができる。顔料誘導体としては、発色団の一部分を、酸基、塩基性基またはフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体を構成する発色団としては、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、フタロシアニン系骨格、アンスラキノン系骨格、キナクリドン系骨格、ジオキサジン系骨格、ペリノン系骨格、ペリレン系骨格、チオインジゴ系骨格、イソインドリン系骨格、イソインドリノン系骨格、キノフタロン系骨格、スレン系骨格、金属錯体系骨格等が挙げられ、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、キノフタロン系骨格、イソインドリン系骨格およびフタロシアニン系骨格が好ましく、アゾ系骨格およびベンゾイミダゾロン系骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。顔料誘導体の具体例としては、例えば、特開２０１１－２５２０６５号公報の段落番号０１６２～０１８３の記載を参酌でき、この内容は本明細書に組み込まれる。
　顔料誘導体の含有量は、顔料１００質量部に対し、１～３０質量部が好ましく、３～２０質量部がさらに好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。 << Pigment derivative >>
The coloring composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of a chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. The chromophores constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, and a perinone skeleton. Skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, sullen skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole-based skeleton, an azo-based skeleton, a quinophthalone-based skeleton, an isoindoline-based skeleton, and a phthalocyanine-based skeleton are preferred, and an azo-based skeleton and a benzimidazolone-based skeleton are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable. As specific examples of the pigment derivative, for example, the description of paragraph Nos. 0162 to 0183 of JP-A-2011-252065 can be referred to, and the contents thereof are incorporated herein.
The content of the pigment derivative is preferably from 1 to 30 parts by mass, more preferably from 3 to 20 parts by mass, based on 100 parts by mass of the pigment. One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.
＜＜硬化促進剤＞＞
　本発明の着色組成物は、重合性モノマーの反応を促進させたり、硬化温度を下げる目的で、硬化促進剤を添加してもよい。硬化促進剤としては、分子内に２個以上のメルカプト基を有する多官能チオール化合物などが挙げられる。多官能チオール化合物は安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、２級のアルカンチオール類であることが好ましく、式（Ｔ１）で表される化合物であることがより好ましい。
　式（Ｔ１）
Figure JPOXMLDOC01-appb-C000025
 （式（Ｔ１）中、ｎは２～４の整数を表し、Ｌは２～４価の連結基を表す。） << Curing accelerator >>
To the colored composition of the present invention, a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable monomer or lowering the curing temperature. Examples of the curing accelerator include a polyfunctional thiol compound having two or more mercapto groups in a molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by the formula (T1).
Equation (T1)
Figure JPOXMLDOC01-appb-C000025
 (In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
　式（Ｔ１）において、連結基Ｌは炭素数２～１２の脂肪族基であることが好ましく、ｎが２であり、Ｌが炭素数２～１２のアルキレン基であることが特に好ましい。 In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
　また、硬化促進剤は、メチロール系化合物（例えば特開２０１５－０３４９６３号公報の段落番号０２４６において、架橋剤として例示されている化合物）、アミン類、ホスホニウム塩、アミジン塩、アミド化合物（以上、例えば特開２０１３－４１１６５号公報の段落番号０１８６に記載の硬化剤）、塩基発生剤（例えば、特開２０１４－５５１１４号公報に記載のイオン性化合物）、シアネート化合物（例えば、特開２０１２－１５０１８０号公報の段落番号００７１に記載の化合物）、アルコキシシラン化合物（例えば、特開２０１１－２５３０５４号公報に記載のエポキシ基を有するアルコキシシラン化合物）、オニウム塩化合物（例えば、特開２０１５－３４９６３号公報の段落番号０２１６に酸発生剤として例示されている化合物、特開２００９－１８０９４９号公報に記載の化合物）などを用いることもできる。 The curing accelerator may be a methylol-based compound (for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-034963), an amine, a phosphonium salt, an amidine salt, an amide compound (for example, JP-A-2013-41165, paragraph No. 0186, a base generator (for example, an ionic compound described in JP-A-2014-55114), and a cyanate compound (for example, JP-A-2012-150180) Japanese Patent Application Laid-Open No. 2015-34963), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253054), and an onium salt compound (for example, a compound described in JP-A-2015-34963). Chemical compounds exemplified as an acid generator in paragraph No. 0216 Things, compounds described in JP-A-2009-180949) or the like can be used.
　本発明の着色組成物が硬化促進剤を含有する場合、硬化促進剤の含有量は、着色組成物の全固形分中０．３～８．９質量％が好ましく、０．８～６．４質量％がより好ましい。 When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably from 0.3 to 8.9% by mass, and preferably from 0.8 to 6.4% by mass based on the total solid content of the coloring composition. % Is more preferred.
＜＜シランカップリング剤＞＞
　本発明の着色組成物は、シランカップリング剤を含有することできる。シランカップリング剤としては、一分子中に少なくとも２種の反応性の異なる官能基を有するシラン化合物が好ましい。シランカップリング剤は、ビニル基、エポキシ基、スチレン基、メタクリル基、アミノ基、イソシアヌレート基、ウレイド基、メルカプト基、スルフィド基、および、イソシアネート基から選ばれる少なくとも１種の基と、アルコキシ基とを有するシラン化合物が好ましい。シランカップリング剤の具体例としては、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン（信越化学工業（株）製、ＫＢＭ－６０２）、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－６０３）、３－アミノプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－９０３）、３－アミノプロピルトリエトキシシラン（信越化学工業（株）製、ＫＢＥ－９０３）、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－５０３）、３－グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ－４０３）等が挙げられる。シランカップリング剤の詳細については、特開２０１３－２５４０４７号公報の段落番号０１５５～０１５８の記載を参酌でき、この内容は本明細書に組み込まれる。本発明の着色組成物がシランカップリング剤を含有する場合、シランカップリング剤の含有量は、着色組成物の全固形分中０．００１～２０質量％が好ましく、０．０１～１０質量％がより好ましく、０．１質量％～５質量％が特に好ましい。本発明の着色組成物は、シランカップリング剤を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 << silane coupling agent >>
The coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two kinds of functional groups having different reactivities in one molecule is preferable. The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureide group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. Is preferred. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.) and N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu) KBE-903 manufactured by Chemical Industry Co., Ltd., 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Manufactured by KBM-403). For the details of the silane coupling agent, the description of paragraphs 0155 to 0158 of JP-A-2013-254407 can be referred to, and the contents thereof are incorporated herein. When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, and more preferably 0.01 to 10% by mass based on the total solid content of the coloring composition. Is more preferable, and 0.1 to 5% by mass is particularly preferable. The coloring composition of the present invention may include only one type of silane coupling agent, or may include two or more types of silane coupling agents. When two or more kinds are contained, the total amount thereof is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明の着色組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）等が挙げられる。本発明の着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、着色組成物の全固形分中０．０００１～５質量％が好ましい。本発明の着色組成物は、重合禁止剤を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 << polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts and the like) and the like. When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the coloring composition. The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, the total amount thereof is preferably within the above range.
＜＜紫外線吸収剤＞＞
　本発明の着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－０６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。また、紫外線吸収剤として特許第６２６８９６７号公報の段落番号００４９～００５９に記載の化合物も使用できる。本発明の着色組成物が紫外線吸収剤を含有する場合、紫外線吸収剤の含有量は、着色組成物の全固形分中０．１～１０質量％が好ましく、０．１～５質量％がより好ましく、０．１～３質量％が特に好ましい。また、紫外線吸収剤は、１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 <<<< UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used. For details of these, see paragraphs 0052 to 0072 in JP-A-2012-208374, paragraphs 0317 to 0334 in JP-A-2013-068814, and paragraphs 0061 to 0080 in JP-A-2016-162946. For reference, their contents are incorporated herein. Commercially available UV absorbers include, for example, UV-503 (manufactured by Daito Chemical Co., Ltd.). Examples of the benzotriazole compound include MYUA series (manufactured by Chemical Industry Daily, Feb. 1, 2016) manufactured by Miyoshi Oil & Fat. Further, compounds described in paragraphs 0049 to 0059 of JP-A-6268967 can also be used as an ultraviolet absorber. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is particularly preferably 0.1 to 3% by mass. In addition, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.
＜＜界面活性剤＞＞
　本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開第２０１５／１６６７７９号の段落番号０２３８～０２４５を参酌でき、この内容は本明細書に組み込まれる。 << Surfactant >>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Regarding surfactants, paragraphs 0238 to 0245 of WO2015 / 166779 can be referred to, and the contents thereof are incorporated herein.
　本発明において、界面活性剤はフッ素系界面活性剤であることが好ましい。着色組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。 に お い て In the present invention, the surfactant is preferably a fluorinated surfactant. When the coloring composition contains a fluorine-based surfactant, liquid properties (particularly, fluidity) are further improved, and liquid saving properties can be further improved. Further, a film with small thickness unevenness can be formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、着色組成物中における溶解性も良好である。 フ ッ 素 The fluorine content in the fluorine-based 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. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of a coating film and liquid saving properties, and has good solubility in a coloring composition.
　フッ素系界面活性剤としては、特開２０１４－０４１３１８号公報の段落番号００６０～００６４（対応する国際公開２０１４／０１７６６９号の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 Examples of the fluorinated surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (paragraphs 0060 to 0064 of corresponding International Publication 2014/017669), and JP-A-2011-132503. The surfactants described in paragraph Nos. 0117 to 0132 of the above-mentioned publications are exemplified, and the contents thereof are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PolyFox @ PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. .
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報、２０１６年２月２２日）（日経産業新聞、２０１６年２月２３日）、例えばメガファックＤＳ－２１が挙げられる。 In addition, fluorine-based surfactants have a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized. It can be suitably used. Examples of such a fluorinated surfactant include Megafac DS series (manufactured by DIC Corporation, Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafac DS. -21.
　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Also, it is preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant. The description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, and the contents thereof are incorporated herein.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－０８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000026
 　上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 As the fluorine-based surfactant, a block polymer can also be used. For example, compounds described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000026
 The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of the repeating unit is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 Alternatively, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used. As specific examples, compounds described in paragraphs [0050] to [0090] and paragraphs [0289] to [0295] of JP-A-2010-164965, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation , RS-72-K and the like. As the fluorinated surfactant, compounds described in Paragraph Nos. 0015 to 0158 of JP-A-2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS ), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
　シリコン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越化学工業（株）製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。 Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).
　着色組成物の全固形分中における界面活性剤の含有量は、０．００１～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。界面活性剤は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。 (4) The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
＜＜その他添加剤＞＞
　本発明の着色組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加剤としては、特開２００４－２９５１１６号公報の段落番号０１５５～０１５６に記載の添加剤を挙げることができ、この内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物（例えば特開２０１１－０９０１４７号公報の段落番号００４２に記載の化合物）、チオエーテル化合物などを用いることができる。市販品としては、例えば（株）ＡＤＥＫＡ製のアデカスタブシリーズ（ＡＯ－２０、ＡＯ－３０、ＡＯ－４０、ＡＯ－５０、ＡＯ－５０Ｆ、ＡＯ－６０、ＡＯ－６０Ｇ、ＡＯ－８０、ＡＯ－３３０など）が挙げられる。また、酸化防止剤として、国際公開第２０１７／００６６００号に記載された多官能ヒンダードアミン酸化防止剤、国際公開第２０１７／１６４０２４号に記載された酸化防止剤、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された酸化防止剤を用いることもできる。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。また、本発明の着色組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤の具体例としては、国際公開第２０１４／０２１０２３号、国際公開第２０１７／０３０００５号、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。また、本発明の着色組成物は、特開２００４－２９５１１６号公報の段落番号００７８に記載の増感剤や光安定剤、同公報の段落番号００８１に記載の熱重合防止剤、特開２０１８－０９１９４０号公報の段落番号０２４２に記載の貯蔵安定化剤を含有することができる。 << Other additives >>
The coloring composition of the present invention may optionally contain various additives such as a filler, an adhesion promoter, an antioxidant, and an anti-agglomeration agent. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated herein. Further, as the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound, or the like can be used. Commercially available products include, for example, ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330 etc.). Examples of the antioxidant include a polyfunctional hindered amine antioxidant described in International Publication No. 2017/0066600, an antioxidant described in International Publication No. 2017/164024, and paragraph No. 0023- of Patent No. 6268967. The antioxidants described in 0048 can also be used. One type of antioxidant may be used, or two or more types may be used. Further, the coloring composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which a protecting group is eliminated to function as an antioxidant can be mentioned. Specific examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP-A-2017-008219. Commercially available products include Adeka Aquel's GPA-5001 (manufactured by ADEKA Corporation). Further, the coloring composition of the present invention includes a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph 0081 of the same, and JP-A-2018-295. It can contain a storage stabilizer described in paragraph No. 0242 of JP-A-091940.
　本発明の着色組成物は、顔料などと結合または配位していない遊離の金属の含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。この態様によれば、顔料分散性の安定化（凝集抑止）、分散性良化に伴う分光特性の向上、硬化性成分の安定化や、金属原子・金属イオンの溶出に伴う導電性変動の抑止、表示特性の向上などの効果が期待できる。また、特開２０１２－１５３７９６号公報、特開２０００－３４５０８５号公報、特開２００５－２００５６０号公報、特開平０８－０４３６２０号公報、特開２００４－１４５０７８号公報、特開２０１４－１１９４８７号公報、特開２０１０－０８３９９７号公報、特開２０１７－０９０９３０号公報、特開２０１８－０２５６１２号公報、特開２０１８－０２５７９７号公報、特開２０１７－１５５２２８号公報、特開２０１８－０３６５２１号公報などに記載された効果も得られる。上記の遊離の金属の種類としては、Ｎａ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｒ、Ｃｏ、Ｍｇ、Ａｌ、Ｓｎ、Ｚｒ、Ｇａ、Ｇｅ、Ａｇ、Ａｕ、Ｐｔ、Ｃｓ、Ｂｉ等が挙げられる。また、本発明の硬化性組成物は、顔料などと結合または配位していない遊離のハロゲンの含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。硬化性組成物中の遊離の金属やハロゲンの低減方法としては、イオン交換水による洗浄、ろ過、限外ろ過、イオン交換樹脂による精製等の方法が挙げられる。 In the coloring composition of the present invention, the content of a free metal not bound or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less. , Is particularly preferably not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, and suppression of fluctuation in conductivity due to elution of metal atoms and metal ions. The effects such as improvement of display characteristics can be expected. Also, JP-A-2012-153796, JP-A-2000-345085, JP-A-2005-200560, JP-A-08-043620, JP-A-2004-145078, JP-A-2014-119487, JP-A-2010-083997, JP-A-2017-090930, JP-A-2018-025612, JP-A-2018-025797, JP-A-2017-155228, JP-A-2018-036521 and the like The effect obtained is also obtained. The types of the above free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi and the like. Further, the curable composition of the present invention preferably has a content of free halogen not bound or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. Is more preferable, and it is particularly preferable that it is not substantially contained. Examples of a method for reducing free metals and halogens in the curable composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
　本発明の着色組成物は、テレフタル酸エステルを含まないことも好ましい。 着色 It is also preferable that the coloring composition of the present invention does not contain a terephthalic acid ester.
＜収容容器＞
　本発明の着色組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や着色組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 <Container>
The container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used. Further, as a storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the coloring composition, a multi-layer bottle in which the inner wall of the container is formed of six types and six layers of resin or a bottle in which six types of resin are formed in a seven-layer structure It is also preferred to use Examples of such a container include a container described in JP-A-2015-123351.
＜着色組成物の製造方法＞
　本発明の着色組成物は、前述の成分を混合して製造できる。着色組成物の製造に際しては、全成分を同時に溶剤に溶解および／または分散して着色組成物を製造してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して着色組成物を製造してもよい。 <Method for producing colored composition>
The coloring composition of the present invention can be produced by mixing the above-mentioned components. In producing the coloring composition, the coloring composition may be produced by simultaneously dissolving and / or dispersing all the components in a solvent, or, if necessary, appropriately converting each component into two or more solutions or dispersions. At the time of use (at the time of application), these may be mixed to produce a colored composition.
　また、着色組成物の製造に際して、顔料などの粒子を分散させるプロセスを含んでいてもよい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」や「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 In addition, the production of the coloring composition may include a process of dispersing particles such as pigments. In the process of dispersing the pigment, examples of mechanical force used for dispersing the pigment include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. In the pulverization of the pigment in a sand mill (bead mill), it is preferable to use beads having a small diameter or to increase the filling rate of the beads, etc., so as to increase the pulverization efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. The process and the disperser for dispersing the pigment are described in "Dispersion Technology Taizen, published by Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology mainly for suspensions (solid / liquid dispersion system) and industrial applications. The process and the disperser described in paragraph # 0022 of JP-A-2015-157893 can be suitably used. Further, in the process of dispersing the pigment, fine processing of particles may be performed in a salt milling step. The materials, equipment, processing conditions, and the like used in the salt milling step can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.
　着色組成物の製造にあたり、異物の除去や欠陥の低減などの目的で、着色組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 In producing the coloring composition, it is preferable to filter the coloring composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high-density, ultra-high molecular weight (Including polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 孔 The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. When the pore size of the filter is in the above range, fine foreign matter can be more reliably removed. As for the pore diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 It is also preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include a polypropylene fiber, a nylon fiber, and a glass fiber. Commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using a filter, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration by each filter may be performed only once or may be performed twice or more. Further, filters having different hole diameters may be combined within the above-described range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.
＜画素の形成方法＞
　本発明の画素の形成方法は、支持体上に本発明の着色組成物を塗布して着色組成物層を形成する工程と、この着色組成物層をパターン状に露光する工程と、露光後の着色組成物層を現像する工程と、を含む。そして、本発明においては、全工程を通じて１５０℃以下の温度で行うことを特徴とする。なお、本発明において、「全工程を通じて１５０℃以下の温度で行う」とは、着色組成物を用いて画素を形成する工程の全てを、１５０℃以下の温度で行うことを意味する。露光後の着色組成物層を現像した後、更に加熱する工程を設ける場合は、この加熱する工程も１５０℃以下の温度で行うことを意味する。以下、各工程について詳細を述べる。 <Method for Forming Pixel>
The method for forming a pixel of the present invention includes the steps of applying the coloring composition of the present invention on a support to form a coloring composition layer, exposing the coloring composition layer in a pattern, and after the exposure. Developing the coloring composition layer. In the present invention, the process is performed at a temperature of 150 ° C. or less throughout the entire process. In the present invention, “performed at a temperature of 150 ° C. or lower throughout the entire process” means that all steps of forming a pixel using a coloring composition are performed at a temperature of 150 ° C. or lower. In the case where a heating step is further provided after developing the colored composition layer after exposure, this heating step is also performed at a temperature of 150 ° C. or less. Hereinafter, each step will be described in detail.
　着色組成物層を形成する工程では、支持体上に本発明の着色組成物を塗布して着色組成物層を形成する。支持体としては、ガラス基板、ポリカーボネート基板、ポリエステル基板、芳香族ポリアミド基板、ポリアミドイミド基板、ポリイミド基板等が挙げられる。これらの基板上には有機発光層が形成されていてもよい。また、基板には、上部の層との密着性改良、物質の拡散防止或いは表面の平坦化のために下塗り層が設けられていてもよい。 で は In the step of forming a colored composition layer, the colored composition of the present invention is applied on a support to form a colored composition layer. Examples of the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light emitting layer may be formed on these substrates. In addition, the substrate may be provided with an undercoat layer for improving adhesion to an upper layer, preventing diffusion of a substance, or planarizing the surface.
　着色組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、着色組成物の塗布方法については、国際公開第２０１７／０３０１７４号公報、国際公開第２０１７／０１８４１９号の記載を参酌でき、これらの内容は本明細書に組み込まれる。 公 知 A known method can be used as a method for applying the coloring composition. For example, a dropping method (drop casting); a slit coating method; a spraying method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, JP-A-2009-145395). Publications); inkjet (eg, on-demand method, piezo method, thermal method), discharge printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; a transfer method using a mold or the like; a nanoimprint method, and the like. The application method in the ink jet is not particularly limited, and for example, a method shown in “Spread and usable ink jets—infinite possibilities seen in patents”, published in February 2005, Sumibe Techno Research (especially from page 115). 133 page), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261828, JP-A-2012-126830, JP-A-2006-169325, and the like. No. Regarding the method for applying the coloring composition, the descriptions in WO2017 / 030174 and WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.
　支持体上に形成した着色組成物層は、乾燥（プリベーク）してもよい。プリベークを行う場合、プリベーク温度は、８０℃以下が好ましく、７０℃以下がより好ましく、６０℃以下が更に好ましく、５０℃以下が特に好ましい。下限は、例えば、４０℃以上とすることができる。プリベーク時間は、１０～３６００秒が好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 着色 The colored composition layer formed on the support may be dried (prebaked). When performing prebaking, the prebaking temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, still more preferably 60 ° C or lower, and particularly preferably 50 ° C or lower. The lower limit can be, for example, 40 ° C. or higher. The prebake time is preferably from 10 to 3600 seconds. Prebaking can be performed on a hot plate, an oven, or the like.
　次に、着色組成物層をパターン状に露光する（露光工程）。例えば、着色組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、露光部分を硬化することができる。 Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine or the like through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 放射線 Examples of radiation (light) that can be used for exposure include g-line and i-line. Light with a wavelength of 300 nm or less (preferably, light with a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include a KrF line (wavelength 248 nm) and an ArF line (wavelength 193 nm), and a KrF line (wavelength 248 nm) is preferable. In addition, a long-wavelength light source of 300 nm or more can be used.
　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。パルス露光の場合、パルス幅は、１００ナノ秒（ｎｓ）以下であることが好ましく、５０ナノ秒以下であることがより好ましく、３０ナノ秒以下であることが更に好ましい。パルス幅の下限は、特に限定はないが、１フェムト秒（ｆｓ）以上とすることができ、１０フェムト秒以上とすることもできる。周波数は、１ｋＨｚ以上であることが好ましく、２ｋＨｚ以上であることがより好ましく、４ｋＨｚ以上であることが更に好ましい。周波数の上限は５０ｋＨｚ以下であることが好ましく、２０ｋＨｚ以下であることがより好ましく、１０ｋＨｚ以下であることが更に好ましい。最大瞬間照度は、５０００００００Ｗ／ｍ2以上であることが好ましく、１００００００００Ｗ／ｍ2以上であることがより好ましく、２００００００００Ｗ／ｍ2以上であることが更に好ましい。また、最大瞬間照度の上限は、１０００００００００Ｗ／ｍ2以下であることが好ましく、８００００００００Ｗ／ｍ2以下であることがより好ましく、５００００００００Ｗ／ｍ2以下であることが更に好ましい。なお、パルス幅とは、パルス周期における光が照射されている時間のことである。また、周波数とは、１秒あたりのパルス周期の回数のことである。また、最大瞬間照度とは、パルス周期における光が照射されている時間内での平均照度のことである。また、パルス周期とは、パルス露光における光の照射と休止を１サイクルとする周期のことである。 Further, at the time of exposure, light may be continuously irradiated to perform exposure, or pulsed irradiation may be performed (pulse exposure). Note that the pulse exposure is an exposure method of a method in which light irradiation and pause are repeatedly performed in a short cycle (for example, millisecond level or less) cycle. In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. Although the lower limit of the pulse width is not particularly limited, it may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, even more preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more. The upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less. Note that the pulse width is a time during which light is irradiated in a pulse cycle. The frequency refers to the number of pulse periods per second. In addition, the maximum instantaneous illuminance is an average illuminance within a time period during which light is irradiated in a pulse cycle. In addition, the pulse cycle is a cycle in which light irradiation and pause in pulse exposure are one cycle.
　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ2が好ましく、０．０５～１．０Ｊ／ｃｍ2がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ2～１０００００Ｗ／ｍ2（例えば、５０００Ｗ／ｍ2、１５０００Ｗ／ｍ2、または、３５０００Ｗ／ｍ2）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ2、酸素濃度３５体積％で照度２００００Ｗ／ｍ2などとすることができる。 Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2. The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing the treatment under the air, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially Exposure may be performed under oxygen-free conditions, or under a high oxygen atmosphere having an oxygen concentration of more than 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). Can be. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
　また、波長３５０ｎｍを超え３８０ｎｍ以下の光（好ましくはｉ線）を１Ｊ／ｃｍ2以上の露光量で照射して露光することも好ましい。このように露光することにより、着色組成物層を十分に硬化させることができ、耐溶剤性などの特性に優れた画素を製造することができる。 Further, it is also preferable to irradiate light having a wavelength of more than 350 nm and 380 nm or less (preferably i-line) at an exposure amount of 1 J / cm 2 or more. By performing such exposure, the colored composition layer can be sufficiently cured, and a pixel having excellent properties such as solvent resistance can be manufactured.
　次に、露光後の着色組成物層を現像する。すなわち、着色組成物層の未露光部を現像除去してパターン（画素）を形成する。着色組成物層の未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液としては、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液であることが好ましい。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the exposed colored composition layer is developed. That is, a pattern (pixel) is formed by developing and removing an unexposed portion of the coloring composition layer. The development removal of the unexposed portion of the coloring composition layer can be performed using a developer. As a result, the colored composition layer in the unexposed portion in the exposure step elutes into the developer, leaving only the photocured portion. Examples of the developer include an organic solvent and an alkali developer, and an alkali developer is preferable. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably from 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
　アルカリ現像液は、アルカリ剤を純水で希釈したアルカリ性水溶液であることが好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の着色組成物層が形成された支持体を回転させつつ、現像後の着色組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkali agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. Further, the developer may further contain a surfactant. Examples of the surfactant include the surfactants described above, and a nonionic surfactant is preferable. The developer may be once produced as a concentrated solution and diluted to a necessary concentration at the time of use, from the viewpoint of convenience of transportation and storage. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. The rinsing is preferably performed by supplying a rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when the nozzle is moved from the central portion to the peripheral portion of the support, the nozzle may be moved while gradually lowering the moving speed. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually lowering the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.
　現像後、乾燥を施した後に追加露光処理や加熱処理（ポストベーク）を行うことも好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。 追加 It is also preferable to perform additional exposure treatment and heat treatment (post-bake) after drying after development. The additional exposure processing and post bake are post-development curing treatments to complete the curing.
　ポストベークを行う場合、加熱温度は、１００～１５０℃が好ましい。加熱温度の上限は１２０℃以下が好ましい。加熱時間は１分以上が好ましく、５分以上がより好ましく、１０分以上が更に好ましい。上限は特に限定はないが、生産性の観点から２０分以下が好ましい。ポストベークは、不活性ガスの雰囲気下で行うことも好ましい。この態様によれば、熱重合を、酸素に阻害されることなく、非常に高い効率で進行させることができ、全工程を通じて１２０℃以下の温度で画素を製造した場合であっても、平坦性が良好で、耐溶剤性などの特性に優れた画素を製造することができる。不活性ガスとしては、窒素ガス、アルゴンガス、ヘリウムガス等が挙げられ、窒素ガスであることが好ましい。ポストベーク時の酸素濃度は、１００ｐｐｍ以下であることが好ましい。 When performing post-baking, the heating temperature is preferably 100 to 150 ° C. The upper limit of the heating temperature is preferably 120 ° C. or lower. The heating time is preferably at least 1 minute, more preferably at least 5 minutes, even more preferably at least 10 minutes. The upper limit is not particularly limited, but is preferably 20 minutes or less from the viewpoint of productivity. Post-baking is also preferably performed in an inert gas atmosphere. According to this aspect, the thermal polymerization can proceed at a very high efficiency without being hindered by oxygen, and even when pixels are manufactured at a temperature of 120 ° C. or less throughout the entire process, the flatness can be improved. And a pixel excellent in characteristics such as solvent resistance can be manufactured. Examples of the inert gas include a nitrogen gas, an argon gas, a helium gas and the like, and a nitrogen gas is preferable. The oxygen concentration at the time of post baking is preferably 100 ppm or less.
　追加露光処理を行う場合、波長２５４～３５０ｎｍの光を照射して露光することが好ましい。より好ましい態様としては、着色組成物層をパターン状に露光する工程（現像前の露光）は、着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光（好ましくは波長３５５～３７０ｎｍの光、より好ましくはｉ線）を照射して露光して行い、追加露光処理（現像後の露光）は、現像後の着色組成物層に対して、波長２５４～３５０ｎｍの光（好ましくは波長２５４ｎｍの光）を照射して露光することが好ましい。この態様によれば、最初の露光（現像前の露光）で着色組成物層を適度に硬化させることができ、次の露光（現像後の露光）で着色組成物層全体をほぼ完全に硬化させることができるので、結果として、低温条件でも、着色組成物層を十分に硬化させて、耐溶剤性、密着性および矩形性などの特性に優れた画素を形成することができる。このように２段階で露光を行う場合、着色組成物には、光重合開始剤として、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ１と、メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ２とを含むものを用いることが好ましい。 When performing the additional exposure process, it is preferable to perform exposure by irradiating light having a wavelength of 254 to 350 nm. As a more preferred embodiment, the step of exposing the colored composition layer in a pattern (exposure before development) includes light having a wavelength of more than 350 nm and not more than 380 nm (preferably light having a wavelength of 355 to 370 nm, Exposure is performed by irradiating with i-line), and the additional exposure treatment (exposure after development) is performed on the colored composition layer after development with light having a wavelength of 254 to 350 nm (preferably light having a wavelength of 254 nm). ) Is preferably exposed. According to this aspect, the colored composition layer can be appropriately cured by the first exposure (exposure before development), and the entire colored composition layer is almost completely cured by the next exposure (exposure after development). As a result, the color composition layer can be sufficiently cured even under a low temperature condition, and a pixel having excellent properties such as solvent resistance, adhesion, and rectangularity can be formed. When the exposure is performed in two stages as described above, the colored composition includes, as a photopolymerization initiator, a photopolymerization initiator A1 having an absorption coefficient of 1.0 × 10 3 mL / gcm or more at a wavelength of 365 nm in methanol. And a photopolymerization initiator A2 having an extinction coefficient at 365 nm in methanol of 1.0 × 10 2 mL / gcm or less and an extinction coefficient of 254 nm at 1.0 × 10 3 mL / gcm or more in methanol. It is preferable to use one.
　現像後の露光は、例えば紫外線フォトレジスト硬化装置を用いて行うことができる。紫外線フォトレジスト硬化装置からは、例えば波長２５４～３５０ｎｍの光とともに、これ以外の光（例えばｉ線）が照射されてもよい。 露 光 Exposure after development can be performed using, for example, an ultraviolet photoresist curing device. From the ultraviolet photoresist curing device, for example, light having a wavelength of 254 to 350 nm and other light (for example, i-line) may be irradiated.
　現像前の露光での照射量（露光量）としては、例えば、３０～１５００ｍＪ／ｃｍ2が好ましく、５０～１０００ｍＪ／ｃｍ2がより好ましい。現像後の露光での照射量（露光量）は、３０～４０００ｍＪ／ｃｍ2が好ましく、５０～３５００ｍＪ／ｃｍ2がより好ましい。現像前の露光で用いられる光の波長と、現像後の露光で用いられる光の波長の差は、２００ｎｍ以下であることが好ましく、１００～１５０ｎｍであることがより好ましい。 The irradiation amount of exposure before development (exposure), for example, preferably 30 ~ 1500mJ / cm 2, more preferably 50 ~ 1000mJ / cm 2. Irradiation amount of exposure after development (exposure) is preferably 30 ~ 4000mJ / cm 2, more preferably 50 ~ 3500mJ / cm 2. The difference between the wavelength of light used in exposure before development and the wavelength of light used in exposure after development is preferably 200 nm or less, and more preferably 100 to 150 nm.
＜カラーフィルタの製造方法＞
　本発明のカラーフィルタの製造方法は、上述した本発明の画素の形成方法を含む。
　カラーフィルタが複数色の画素を有する場合には、上述した本発明の画素の形成方法を各色の画素ごとに行うことで、複数色の画素を有するカラーフィルタを形成することができる。カラーフィルタは、赤色画素、青色画素、緑色画素、シアン色画素、マゼンタ色画素、イエロー画素などの着色画素を１色以上有するフィルタが挙げられる。カラーフィルタの具体例としては、赤色画素、青色画素および緑色画素を少なくとも有するフィルタや、シアン色画素、マゼンタ色画素およびイエロー画素を少なくとも有するフィルタなどが挙げられる。カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各着色画素が埋め込まれた構造を有していてもよい。この場合の隔壁は各着色画素に対して低屈折率であることが好ましい。また、ＵＳ２０１８／００４０６５６号公報に記載の構成で隔壁を形成しても良い。 <Production method of color filter>
The method for manufacturing a color filter according to the present invention includes the above-described method for forming a pixel according to the present invention.
When the color filter has pixels of a plurality of colors, the above-described method of forming a pixel of the present invention is performed for each pixel of each color, whereby a color filter having pixels of a plurality of colors can be formed. Examples of the color filter include a filter having one or more colored pixels such as a red pixel, a blue pixel, a green pixel, a cyan pixel, a magenta pixel, and a yellow pixel. Specific examples of the color filter include a filter having at least a red pixel, a blue pixel, and a green pixel, and a filter having at least a cyan pixel, a magenta pixel, and a yellow pixel. The color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition into, for example, a lattice. The partition in this case preferably has a low refractive index for each colored pixel. Further, the partition wall may be formed by the configuration described in US2018 / 0040656.
＜表示装置の製造方法＞
　本発明の表示装置の製造方法は、上述した本発明の画素の形成方法を含む。
　表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Method of manufacturing display device>
A method for manufacturing a display device according to the present invention includes the above-described method for forming a pixel according to the present invention.
Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of image display devices and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, Inc., 1990)", "Display Device (by Junsho Ibuki, Industrial Books ( Co., Ltd.). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by the Industrial Research Institute, Inc., 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “next-generation liquid crystal display technology”.
　有機エレクトロルミネッセンス表示装置は、白色有機エレクトロルミネッセンス素子からなる光源を有するものであってもよい。白色有機エレクトロルミネッセンス素子としては、タンデム構造であることが好ましい。有機エレクトロルミネッセンス素子のタンデム構造については、特開２００３－０４５６７６号公報、三上明義監修、「有機ＥＬ技術開発の最前線－高輝度・高精度・長寿命化・ノウハウ集－」、技術情報協会、３２６－３２８ページ、２００８年などに記載されている。有機ＥＬ素子が発光する白色光のスペクトルは、青色領域（４３０ｎｍ－４８５ｎｍ）、緑色領域（５３０ｎｍ－５８０ｎｍ）及び黄色領域（５８０ｎｍ－６２０ｎｍ）に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域（６５０ｎｍ－７００ｎｍ）に極大発光ピークを有するものがより好ましい。 The organic electroluminescence display device may have a light source including a white organic electroluminescence element. The white organic electroluminescent element preferably has a tandem structure. For a tandem structure of an organic electroluminescence device, see JP-A-2003-045676, supervised by Akiyoshi Mikami, "The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection", Technical Information Association 326-328, 2008. The spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in a blue region (430 nm to 485 nm), a green region (530 nm to 580 nm), and a yellow region (580 nm to 620 nm). Those having a maximum emission peak in a red region (650 nm to 700 nm) in addition to these emission peaks are more preferable.
　以下に実施例を挙げて本発明を具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 (4) The present invention will be specifically described below with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.
＜顔料分散液の調製＞
（顔料分散液Ｐ－Ｒ）
　下記の組成の混合物を均一に撹拌混合した後、直径１ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ－２５０ＭＫＩＩ」）で５時間分散した後、孔径５μｍのフィルタで濾過して顔料分散液Ｐ－Ｒを作製した。
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４　　・・・８．９６質量部
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７　　・・・１．４２質量部
　Ｃ．Ｉ．　Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０　　・・・１．１６質量部
　分散剤（日本ルーブリゾール社製、ソルスパース２００００）　　・・・２．２９質量部
　顔料誘導体（下記構造の化合物）　　・・・２．６９質量部
Figure JPOXMLDOC01-appb-C000027
 　アルカリ可溶性樹脂溶液Ｄ２　　・・・７．６６質量部
　シクロヘキサノン　　・・・７５．８２質量部 <Preparation of pigment dispersion>
(Pigment dispersion liquid PR)
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 μm. Thus, a pigment dispersion PR was prepared.
C. I. Pigment Red 254: 8.96 parts by mass C.I. I. Pigment Red 177: 1.42 parts by mass C.I. I. Pigment Yellow 150 ··· 1.16 parts by mass Dispersant (manufactured by Nippon Lubrizol Co., Ltd., Solsperse 20000) ··· 2.29 parts by mass
Figure JPOXMLDOC01-appb-C000027
 Alkali-soluble resin solution D2: 7.66 parts by mass Cyclohexanone: 75.82 parts by mass
　アルカリ可溶性樹脂溶液Ｄ２は、以下の方法で製造したものを用いた。
　攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にシクロヘキサノン９０．０質量部を入れ、容器に窒素ガスを注入しながら６０℃に加熱して、同温度でメタクリル酸２０．０質量部、メチルメタクリレート１０．０質量部、ｎ－ブチルメタクリレート５５．０質量部、ベンジルメタクリレート１５質量部、２，２’－アゾビスイソブチロニトリル２．５質量部の混合物を２時間かけて滴下して重合反応を行った。滴下終了後、さらに６０℃で１時間反応させた後、２，２’－アゾビスイソブチロニトリル０．５質量部をプロピレングリコールモノメチルエーテルアセテート１０．０質量部に溶解させたものを添加し、その後３時間、同じ温度で攪拌を続け共重合体を得た。室温に冷却後、シクロヘキサノンで希釈することにより、固形分濃度２０％のアルカリ可溶性樹脂溶液Ｄ２を得た。重量平均分子量は３００００であった。 As the alkali-soluble resin solution D2, one produced by the following method was used.
90.0 parts by mass of cyclohexanone is placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel. A mixture of 20.0 parts by mass, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate, and 2.5 parts by mass of 2,2′-azobisisobutyronitrile was mixed with 2 parts by mass. The polymerization reaction was performed by dropping over time. After the completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and a solution prepared by dissolving 0.5 part by mass of 2,2′-azobisisobutyronitrile in 10.0 parts by mass of propylene glycol monomethyl ether acetate was added. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with cyclohexanone to obtain an alkali-soluble resin solution D2 having a solid content of 20%. The weight average molecular weight was 30,000.
（顔料分散液Ｐ－Ｇ）
　下記の組成の混合物を均一に撹拌混合した後、直径１ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ－２５０ＭＫＩＩ」）で５時間分散した後、孔径５μｍのフィルタで濾過して顔料分散液Ｐ－Ｇを作製した。
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　５８　　・・・７．５３質量部
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０　　・・・４．１４質量部
　分散剤（ビックケミー社製、Ｄｉｓｐｅｒｂｙｋ－２００１、固形分濃度４６質量％）　　・・・６．０９質量部
　アルカリ可溶性樹脂溶液Ｄ２　　・・・５．５３質量部
　プロピレングリコールモノメチルエーテルアセテート　　・・・７６．７１質量部 (Pigment dispersion liquid PG)
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 μm. Thus, a pigment dispersion liquid PG was prepared.
C. I. Pigment Green 58 ... 7.53 parts by mass C.I. I. Pigment Yellow 150: 4.14 parts by mass Dispersant (Disperbyk-2001, manufactured by BYK Chemie, solid content concentration: 46% by mass) ... 6.09 parts by mass Alkali-soluble resin solution D2: 5.53 parts by mass Propylene glycol monomethyl ether acetate: 76.71 parts by mass
（顔料分散液Ｐ－Ｂ）
　下記の組成の混合物を均一に撹拌混合した後、直径１ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ－２５０ＭＫＩＩ」）で５時間分散した後、孔径５μｍのフィルタで濾過して顔料分散液Ｐ－Ｂを作製した。
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６　　・・・１２．８８質量部
　分散剤（日本ルーブリゾール社製、ソルスパース２００００）　　・・・５．６２質量部
　アルカリ可溶性樹脂溶液Ｄ２　　・・・１．５０質量部
　シクロヘキサノン　　・・・８０．００質量部 (Pigment dispersion liquid PB)
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a filter having a pore size of 5 μm. Thus, a pigment dispersion liquid PB was prepared.
C. I. Pigment Blue 15: 6 ... 12.88 parts by mass Dispersant (Solsperse 20000, manufactured by Lubrizol Japan Ltd.) ... 5.62 parts by mass Alkali-soluble resin solution D2 ... 1.50 parts by mass cyclohexanone ... 80.00 parts by mass
＜着色組成物の調製＞
　（実施例１）
　以下に示す原料を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して固形分濃度１７質量％の着色組成物を調製した。なお、着色組成物の固形分濃度はプロピレングリコールモノメチルエーテルアセテートの配合量で調整した。
　・顔料分散液Ｐ－Ｒ・・・６５質量部
　・光重合開始剤Ａ１（開始剤１）・・・０．１質量部
　・樹脂（樹脂Ａ）・・・４．３３質量部
　・フリル基含有化合物（Ｆ１）・・・６．５質量部
　・重合性モノマー（Ｍ１）・・・２．６質量部
　・プロピレングリコールモノメチルエーテルアセテート・・・残部 <Preparation of coloring composition>
(Example 1)
After mixing and stirring the following raw materials, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a colored composition having a solid content of 17% by mass. The solid content of the coloring composition was adjusted by the amount of propylene glycol monomethyl ether acetate.
-Pigment dispersion liquid PR-65 parts by mass-Photopolymerization initiator A1 (Initiator 1)-0.1 parts by mass-Resin (resin A)-4.33 parts by mass-Contains a furyl group Compound (F1): 6.5 parts by mass Polymerizable monomer (M1): 2.6 parts by mass Propylene glycol monomethyl ether acetate: balance
　（実施例２～２５、比較例１～２）
　顔料分散液、光重合開始剤、樹脂、フリル基含有化合物、重合性モノマーおよび溶剤の種類および含有量をそれぞれ下記表に記載の通り変更し、実施例１と同様にして着色組成物を調製した。各着色組成物の固形分濃度は溶剤の配合量で調整した。 (Examples 2 to 25, Comparative Examples 1 and 2)
The types and contents of the pigment dispersion, the photopolymerization initiator, the resin, the furyl group-containing compound, the polymerizable monomer and the solvent were each changed as described in the following table, and a colored composition was prepared in the same manner as in Example 1. . The solid content concentration of each coloring composition was adjusted by the amount of the solvent.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　上記表に記載の原料は以下の通りである。
（重合性モノマー）
　Ｍ１：アロニックス　Ｍ－４０２（東亞合成（株）製、ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合物）
　Ｍ２：下記構造の化合物（ａ＋ｂ＋ｃ＝３）
　Ｍ３：下記構造の化合物（ａ＋ｂ＋ｃ＝４）
　Ｍ４：下記構造の化合物の混合物（ａ＋ｂ＋ｃ＝５の化合物：ａ＋ｂ＋ｃ＝６の化合物＝３：１（モル比））
Figure JPOXMLDOC01-appb-C000029
 　Ｍ５：下記構造の化合物
Figure JPOXMLDOC01-appb-C000030
 　Ｍ６：アロニックスＭ―３０９（東亞合成（株）製、トリメチロールプロパントリアクリレート） The raw materials described in the above table are as follows.
(Polymerizable monomer)
M1: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
M2: Compound having the following structure (a + b + c = 3)
M3: Compound having the following structure (a + b + c = 4)
M4: mixture of compounds having the following structure (compound of a + b + c = 5: compound of a + b + c = 6 = 3: 1 (molar ratio))
Figure JPOXMLDOC01-appb-C000029
 M5: Compound having the following structure
Figure JPOXMLDOC01-appb-C000030
 M6: ARONIX M-309 (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd.)
（光重合開始剤）
　・開始剤１：ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製、下記構造の化合物、メタノール中での波長３６５ｎｍにおける吸光係数が７７４９ｍＬ／ｇｃｍである。）
　・開始剤２：ＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製、下記構造の化合物、メタノール中での波長３６５ｎｍにおける吸光係数が６９６９ｍＬ／ｇｃｍである。）
　開始剤３：下記構造の化合物（メタノール中での波長３６５ｎｍの光の吸光係数が１８９００ｍＬ／ｇｃｍである。）
　・開始剤４：ＩＲＧＡＣＵＲＥ－２９５９（ＢＡＳＦ社製、下記構造の化合物、メタノール中での波長３６５ｎｍにおける吸光係数が４８．９３ｍＬ／ｇｃｍであり、波長２５４ｎｍにおける吸光係数が３．０×１０4ｍＬ／ｇｃｍである。）
　・開始剤５：ＩＲＧＡＣＵＲＥ－１８４（ＢＡＳＦ社製、下記構造の化合物、メタノール中での波長３６５ｎｍにおける吸光係数が８８．６４ｍＬ／ｇｃｍであり、波長２５４ｎｍにおける吸光係数が３．３×１０4ｍＬ／ｇｃｍである。）
　開始剤６：下記構造の化合物（メタノール中での波長３６５ｎｍの光の吸光係数が１３２００ｍＬ／ｇｃｍである。）
Figure JPOXMLDOC01-appb-C000031
 (Photopolymerization initiator)
Initiator 1: IRGACURE-OXE02 (manufactured by BASF, a compound having the following structure, the absorption coefficient in methanol at a wavelength of 365 nm is 7749 mL / gcm)
-Initiator 2: IRGACURE-OXE01 (manufactured by BASF, a compound having the following structure, the extinction coefficient in methanol of 365 nm at a wavelength of 6969 mL / gcm)
Initiator 3: a compound having the following structure (the extinction coefficient of light having a wavelength of 365 nm in methanol is 18900 mL / gcm)
Initiator 4: IRGACURE-2959 (manufactured by BASF, a compound having the following structure, the extinction coefficient in methanol at a wavelength of 365 nm is 48.93 mL / gcm, and the extinction coefficient at a wavelength of 254 nm is 3.0 × 10 4 mL / gcm.)
Initiator 5: IRGACURE-184 (manufactured by BASF, a compound having the following structure, the absorption coefficient in methanol at a wavelength of 365 nm is 88.64 mL / gcm, and the absorption coefficient at a wavelength of 254 nm is 3.3 × 10 4 mL / gcm.)
Initiator 6: a compound having the following structure (the extinction coefficient of light having a wavelength of 365 nm in methanol is 13,200 mL / gcm)
Figure JPOXMLDOC01-appb-C000031
（樹脂）
　樹脂Ａ：以下の方法で合成した樹脂
　温度計、冷却管、窒素ガス導入管、滴下管および撹拌装置を備えたセパラブル４口フラスコにシクロヘキサノン７０．０質量部を仕込み、８０℃に昇温し、フラスコ内を窒素置換した後、滴下管より、ｎ－ブチルメタクリレート１３．３質量部、２－ヒドロキシエチルメタクリレート４．６質量部、メタクリル酸４．３質量部、パラクミルフェノールエチレンオキサイド変性アクリレート（東亞合成（株）製、アロニックスＭ１１０）７．４質量部および２，２’－アゾビスイソブチロニトリル０．４質量部の混合物を２時間かけて滴下した。滴下終了後、さらに３時間反応を継続して樹脂Ａ（Ｍｗ＝２６０００）の３０質量％溶液を得た。 (resin)
Resin A: Resin synthesized by the following method: 70.0 parts by mass of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer, and heated to 80 ° C. After the atmosphere in the flask was replaced with nitrogen, 13.3 parts by weight of n-butyl methacrylate, 4.6 parts by weight of 2-hydroxyethyl methacrylate, 4.3 parts by weight of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (Toa) were added through a dropping tube. A mixture of 7.4 parts by mass of Aronix M110 (manufactured by Gosei Co., Ltd.) and 0.4 parts by mass of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a 30% by mass solution of resin A (Mw = 26000).
　樹脂Ｂ：下記構造の樹脂（Ｍｗ＝３００００、主鎖に付記した数値はモル比である。）
Figure JPOXMLDOC01-appb-C000032
 Resin B: a resin having the following structure (Mw = 30000, the numerical value added to the main chain is a molar ratio)
Figure JPOXMLDOC01-appb-C000032
　樹脂Ｃ：以下の方法で合成した樹脂
　攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にプロピレングリコールモノメチルエーテルアセテート９０．０質量部を入れ、容器に窒素ガスを注入しながら６０℃に加熱して、同温度でグリシジルメタクリレート３５．０質量部、メチルメタクリレート４５．０質量部、２，２’－アゾビスイソブチロニトリル２．５質量部の混合物を２時間かけて滴下して重合反応を行った。滴下終了後、さらに６０℃で１時間反応させた後、２，２’－アゾビスイソブチロニトリル０．５質量部をプロピレングリコールモノメチルエーテルアセテート１０．０質量部に溶解させたものを添加し、その後３時間、同じ温度で攪拌を続け共重合体を得た。続いて、反応容器に乾燥空気を注入し、アクリル酸１０．０質量部、プロピレングリコールモノメチルエーテルアセテート３０．２質量部、ジメチルベンジルアミン１．３０質量部、メトキノン０．２６質量部を入れ、１００℃に加熱して、２０時間撹拌を続け、酸価測定を行って目的物が生成していることを確認した。さらに続けて反応容器にテトラヒドロ無水フタル酸１０．０質量部、プロピレングリコールモノメチルエーテルアセテート２７．７質量部を入れ、６０℃で３時間撹拌したのち室温に冷却後、プロピレングリコールモノメチルエーテルアセテートで希釈することにより、樹脂Ｃ（Ｍｗ＝１２０００）の２０質量％溶液を得た。 Resin C: Resin synthesized by the following method: 90.0 parts by mass of propylene glycol monomethyl ether acetate is charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction pipe, and nitrogen gas is injected into the vessel. While heating to 60 ° C., a mixture of 35.0 parts by mass of glycidyl methacrylate, 45.0 parts by mass of methyl methacrylate, and 2.5 parts by mass of 2,2′-azobisisobutyronitrile was added at the same temperature for 2 hours. Then, the polymerization reaction was carried out by dropping. After the completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and a solution prepared by dissolving 0.5 part by mass of 2,2′-azobisisobutyronitrile in 10.0 parts by mass of propylene glycol monomethyl ether acetate was added. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. Subsequently, dry air was injected into the reaction vessel, and 10.0 parts by mass of acrylic acid, 30.2 parts by mass of propylene glycol monomethyl ether acetate, 1.30 parts by mass of dimethylbenzylamine, and 0.26 parts by mass of methoquinone were added, and 100 parts by mass were added. It heated to ° C and continued stirring for 20 hours, and measured the acid value and confirmed that the target product was formed. Subsequently, 10.0 parts by mass of tetrahydrophthalic anhydride and 27.7 parts by mass of propylene glycol monomethyl ether acetate are put in a reaction vessel, stirred at 60 ° C. for 3 hours, cooled to room temperature, and diluted with propylene glycol monomethyl ether acetate. As a result, a 20% by mass solution of the resin C (Mw = 12000) was obtained.
（フリル基含有化合物）
　Ｆ１：以下の方法で合成したフリル基含有化合物Ｆ１
　攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にプロピレングリコールモノメチルエーテルアセテート９０．０質量部を入れ、容器に窒素ガスを注入しながら６０℃に加熱して、同温度でフルフリルメタクリレート５０．０質量部、２－メタクリロイロキシエチルコハク酸２６．７質量部、２－ヒドロキシエチルメタクリレート２３．３質量部、２，２’－アゾビス（２，４－ジメチルバレロニトリル）２．５質量部の混合物を２時間かけて滴下して重合反応を行った。滴下終了後、さらに６０℃で１時間反応させた後、２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．５質量部をプロピレングリコールモノメチルエーテルアセテート１０．０質量部に溶解させたものを添加し、その後３時間、同じ温度で攪拌を続け共重合体を得た。室温に冷却後、プロピレングリコールモノメチルエーテルアセテートで希釈することにより、フリル基含有化合物Ｆ１（Ｍｗ＝５２０００）の２０質量％溶液を得た。 (Furyl group-containing compound)
F1: Furyl group-containing compound F1 synthesized by the following method
90.0 parts by mass of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel. At temperature, furfuryl methacrylate 50.0 parts by mass, 2-methacryloyloxyethyl succinic acid 26.7 parts by mass, 2-hydroxyethyl methacrylate 23.3 parts by mass, 2,2′-azobis (2,4-dimethylvaleronitrile) ) 2.5 parts by mass of the mixture was dropped over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain a 20% by mass solution of a furyl group-containing compound F1 (Mw = 52000).
　Ｆ２：以下の方法で合成したフリル基含有化合物Ｆ２
　攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にプロピレングリコールモノメチルエーテルアセテート９０．０質量部を入れ、容器に窒素ガスを注入しながら６０℃に加熱して、同温度でフルフリルメタクリレート５０．０質量部、メタクリル酸１０質量部、メチルメタクリレート４０．０質量部、２，２’－アゾビス（２，４－ジメチルバレロニトリル）５．０質量部の混合物を２時間かけて滴下して重合反応を行った。滴下終了後、さらに６０℃で１時間反応させた後、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１．０質量部をプロピレングリコールモノメチルエーテルアセテート１０．０質量部に溶解させたものを添加し、その後３時間、同じ温度で攪拌を続け共重合体を得た。室温に冷却後、プロピレングリコールモノメチルエーテルアセテートで希釈することにより、フリル基含有化合物Ｆ２（Ｍｗ＝２６０００）の２０質量％溶液を得た。 F2: Furyl group-containing compound F2 synthesized by the following method
90.0 parts by mass of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated to 60 ° C. while injecting nitrogen gas into the vessel. At a temperature, a mixture of 50.0 parts by mass of furfuryl methacrylate, 10 parts by mass of methacrylic acid, 40.0 parts by mass of methyl methacrylate, and 5.0 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) is added for 2 hours. The polymerization reaction was carried out by dropping. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour, and then 1.0 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain a 20% by mass solution of a furyl group-containing compound F2 (Mw = 26000).
（溶剤）
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
　ＰＧＭＥ：プロピレングリコールメチルエーテル (solvent)
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol methyl ether
＜評価＞
（粘度）
　着色組成物の調製直後の粘度（初期粘度、単位：ｍＰａ・ｓ）を、東機産業製　粘度計　ＲＥ８５Ｌ（ローター：１°３４’×Ｒ２４測定範囲０．６～１２００ｍＰａ・ｓ）を使用し、２５℃に温度調整を施した状態で測定した。 <Evaluation>
(viscosity)
The viscosity (initial viscosity, unit: mPa · s) immediately after the preparation of the coloring composition was measured using a viscometer RE85L (rotor: 1 ° 34 ′ × R24, measuring range: 0.6 to 1200 mPa · s) manufactured by Toki Sangyo. The measurement was performed with the temperature adjusted to 25 ° C.
（保存安定性）
　着色組成物の調製後の粘度（初期粘度、単位：ｍＰａ・ｓ）を測定した。この着色組成物を２５℃湿度５０％の恒温槽で３０日保管した後の粘度（保管後の粘度、単位：ｍＰａ・ｓ）を測定した。着色組成物の保存安定性は以下の基準で判断した。着色組成物の粘度は、東機産業製　粘度計　ＲＥ８５Ｌ（ローター：１°３４’×Ｒ２４測定範囲０．６～１２００ｍＰａ・ｓ）を使用し、２５℃に温度調整を施した状態で測定した。
　ＡＡ：保管後の粘度が、初期粘度の９５％を超え１０５％未満の範囲であった。
　Ａ：保管後の粘度が、初期粘度の９３％を超え９５％以下の範囲であるか、あるいは、初期粘度の１０５％以上１０７％未満の範囲であった。
　Ｂ：保管後の粘度が、初期粘度の９０％以上９３％以下の範囲であるか、あるいは、初期粘度の１０７％以上１１０％以下の範囲であった。
　Ｃ：保管後の粘度が、初期粘度の９０％未満であるか、あるいは、初期粘度の１１０％を超える。 (Storage stability)
The viscosity (initial viscosity, unit: mPa · s) after the preparation of the coloring composition was measured. The viscosity (viscosity after storage, unit: mPa · s) after storing the coloring composition in a thermostat at 25 ° C. and 50% humidity for 30 days was measured. The storage stability of the coloring composition was determined according to the following criteria. The viscosity of the coloring composition was measured using a viscometer RE85L manufactured by Toki Sangyo (rotor: 1 ° 34 ′ × R24, measurement range: 0.6 to 1200 mPa · s) with the temperature adjusted to 25 ° C.
AA: The viscosity after storage was more than 95% and less than 105% of the initial viscosity.
A: The viscosity after storage was more than 93% and less than 95% of the initial viscosity, or was more than 105% and less than 107% of the initial viscosity.
B: The viscosity after storage was in the range of 90% to 93% of the initial viscosity, or in the range of 107% to 110% of the initial viscosity.
C: The viscosity after storage is less than 90% of the initial viscosity or more than 110% of the initial viscosity.
（塗布性）
　８インチ（２０．３２ｃｍ）のシリコン基板上に、各着色組成物をプリベーク後の膜厚が１．２μｍになるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行い膜を形成した。得られた膜を光学顕微鏡で観察して以下の基準で塗布性を評価した。
　ＡＡ：膜全体に、塗布ムラや気泡がない
　Ａ：膜周辺部に極僅かに塗布ムラや気泡がある
　Ｂ：膜周辺部に僅かに塗布ムラや気泡があるが、実用可能なレベルである
　Ｃ：膜全体に塗布ムラや気泡があり、実用不可能なレベルである (Applicability)
Each coloring composition is applied on an 8-inch (20.32 cm) silicon substrate using a spin coater so that the film thickness after prebaking becomes 1.2 μm, and heated using a hot plate at 100 ° C. for 120 seconds. Processing (pre-bake) was performed to form a film. The obtained film was observed with an optical microscope, and the applicability was evaluated based on the following criteria.
AA: There is no coating unevenness or bubbles in the whole film. A: There is very slight coating unevenness or bubbles in the peripheral portion of the film. B: There is slight coating unevenness or bubbles in the peripheral portion of the film, but it is a practical level. : Unusable level due to coating unevenness and bubbles throughout the film
（平坦性）
（Ｇｒｅｅｎ画素の形成）
　特開２０１５－０４１０５８号公報の表８中のＲＧ－１組成物を、予めヘキサメチルジシラザンを噴霧した８インチ（２０．３２ｃｍ）のガラスウエハの上に塗布し、光硬化性の塗布膜を形成した。そして、この塗布膜の乾燥膜厚が１．２μｍになるように、１００℃のホットプレートを用いて１８０秒間加熱処理（プリベーク）を行った。
　次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を使用し、３．０μｍ四方のベイヤーパターンマスクを通して波長３６５ｎｍの光を２００ｍＪ／ｃｍ2の露光量にて照射した。その後、照射された塗布膜が形成されているシリコンウエハをスピン・シャワー現像機（ＤＷ－３０型；（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ（株）製）の４０％希釈液を用いて２３℃で１８０秒間パドル現像を行ない、ガラスウエハに緑色着色パターンを形成した。
　緑色着色パターンが形成されたガラスウエハを真空チャック方式で水平回転テーブルに固定し、回転装置によって該ガラスウエハを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スプレー乾燥した。
　その後、パターンが形成されたガラスウエハ全体に、紫外線フォトレジスト硬化装置（ＵＭＡ－８０２－ＨＣ－５５２；ウシオ電気株式会社製）を用いて追加露光を行い、ガラスウエハ上に３．０μｍベイヤーパターンのＧｒｅｅｎ画素を形成した。 (Flatness)
(Formation of Green pixel)
The RG-1 composition shown in Table 8 of JP-A-2015-041058 was applied on an 8-inch (20.32 cm) glass wafer sprayed with hexamethyldisilazane in advance to form a photocurable coating film. Formed. Then, a heat treatment (pre-bake) was performed using a hot plate at 100 ° C. for 180 seconds so that the dry film thickness of the coating film was 1.2 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm was irradiated at an exposure dose of 200 mJ / cm 2 through a 3.0 μm square Bayer pattern mask. Thereafter, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30; manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fujifilm Electronics) Paddle development was performed at 23 ° C. for 180 seconds using a 40% diluent from Materials Co., Ltd. to form a green colored pattern on the glass wafer.
The glass wafer on which the green coloring pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from a nozzle above a rotation center from a nozzle above the rotation center. And rinsed, followed by spray drying.
Thereafter, the entire glass wafer on which the pattern was formed was subjected to additional exposure using an ultraviolet photoresist curing device (UMA-802-HC-552; manufactured by Ushio Electric Co., Ltd.), and a 3.0 μm Bayer pattern was formed on the glass wafer. Green pixels were formed.
　実施例および比較例の着色組成物を３．０μｍアイランドパターンのマスクを用いる以外は同様にしてＧｒｅｅｎ画素間にアイランド着色画素パターンを形成した。
　上記で作製したアイランド着色画素パターンの高さを原子間力顕微鏡（ＡＦＭ、セイコーインスツルメンツ株式会社製、ＳＰＡ－４００ＡＦＭ）を用いて、画素の対角線に沿って測定した。測定された値から、最高点と中央部の高さの差を、下記評価基準に基づき、平坦性として評価した。
　ＡＡ：最高点と中央部の高さの差が７５ｎｍ未満である
　Ａ：最高点と中央部の高さの差が７５ｎｍ以上１００ｎｍ未満である
　Ｂ：最高点と中央部の高さの差が１００ｎｍ以上１５０ｎｍ未満である
　Ｃ：最高点と中央部の高さの差が１５０ｎｍ以上である An island-colored pixel pattern was formed between the Green pixels in the same manner except that the coloring compositions of Examples and Comparative Examples were used with a mask having an island pattern of 3.0 μm.
The height of the island colored pixel pattern prepared above was measured along the diagonal line of the pixel using an atomic force microscope (AFM, SPA-400AFM, manufactured by Seiko Instruments Inc.). From the measured values, the difference between the highest point and the height at the center was evaluated as flatness based on the following evaluation criteria.
AA: The difference between the height of the highest point and the center is less than 75 nm. A: The difference between the height of the highest point and the center is 75 nm or more and less than 100 nm. B: The difference between the height of the highest point and the height of the center is 100 nm. Not less than 150 nm C: difference in height between the highest point and the central part is not less than 150 nm
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　上記表に示すとおり、実施例の着色組成物は、平坦性の評価が優れていた。更には、保存安定性および塗布性も優れていた。
　実施例１～２５の着色組成物を用いて形成したカラーフィルタを有機エレクトロルミネッセンス表示装置に組み込むことで、輝度の視野角特性に優れた有機エレクトロルミネッセンス表示装置を得ることができる。 As shown in the above table, the coloring compositions of Examples had excellent flatness evaluations. Furthermore, the storage stability and the applicability were excellent.
By incorporating the color filters formed using the coloring compositions of Examples 1 to 25 into an organic electroluminescence display device, an organic electroluminescence display device having excellent luminance viewing angle characteristics can be obtained.
（試験例１）
　ガラス基板上に、実施例１、実施例１６、実施例１７、実施例１８、比較例１または比較例２の着色組成物をプリベーク後の膜厚が１．２μｍになるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行い膜を形成した。次にｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、ｉ線を３０００ｍＪ／ｃｍ2の露光量で照射して膜を作製した。得られた膜について、Ｎ－メチルピロリドン（ＮＭＰ）を滴下後、２００秒放置し、流水にて１０秒リンスして耐溶剤性試験を行った。耐溶剤性試験前後の膜の厚みを測定し、残膜率を測定して耐溶剤性を評価した。残膜率が１に近いほど耐溶剤性に優れる。
　実施例１、実施例１６、実施例１７、実施例１８の着色組成物を用いた場合は、いずれも耐溶剤性はＡＡの評価であった。
　一方、比較例１の着色組成物を用いた場合の耐溶剤性はＣであり、比較例２の着色組成物を用いた場合の耐溶剤性はＣであった。
　残膜率＝耐溶剤性試験前後の膜の厚さ／耐溶剤性試験前の膜の厚さ
　ＡＡ：残膜率が０．９５以上１．０以下。
　Ａ：残膜率が０．９０以上０．９５未満。
　Ｂ：残膜率が０．８５以上０．９０未満。
　Ｃ：残膜率が０．８５未満。 (Test Example 1)
On a glass substrate, a spin coater was used so that the film thickness of the colored composition of Example 1, Example 16, Example 17, Example 18, Comparative Example 1 or Comparative Example 2 was 1.2 μm after prebaking. Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. to form a film. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), i-line was irradiated at an exposure amount of 3000 mJ / cm 2 to form a film. After N-methylpyrrolidone (NMP) was added dropwise to the obtained film, it was left for 200 seconds, rinsed with running water for 10 seconds, and subjected to a solvent resistance test. The thickness of the film before and after the solvent resistance test was measured, and the residual film ratio was measured to evaluate the solvent resistance. The closer the residual film ratio is to 1, the better the solvent resistance.
When the coloring compositions of Examples 1, 16, 17, and 18 were used, the solvent resistance was evaluated as AA in all cases.
On the other hand, the solvent resistance when the colored composition of Comparative Example 1 was used was C, and the solvent resistance when the colored composition of Comparative Example 2 was used was C.
Remaining film ratio = Thickness of film before and after solvent resistance test / Thickness of film before solvent resistance test AA: The remaining film ratio is 0.95 or more and 1.0 or less.
A: The residual film ratio is 0.90 or more and less than 0.95.
B: The residual film ratio is 0.85 or more and less than 0.90.
C: The residual film ratio is less than 0.85.
（試験例２）
　ガラス基板上に、実施例１、実施例１６、実施例１７、実施例１８、比較例１または比較例２の着色組成物をプリベーク後の膜厚が１．２μｍになるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行い膜を形成した。次にｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、ｉ線を１００ｍＪ／ｃｍ2の露光量で照射した。次に１２０℃のホットプレートで９００秒間加熱処理を行い膜を作製した。得られた膜について試験例１と同様の方法で耐溶剤性を評価したところ、実施例１、実施例１６、実施例１７、実施例１８の着色組成物を用いた場合は、いずれも耐溶剤性はＡＡの評価であった。
　一方、比較例１の着色組成物を用いた場合の耐溶剤性はＣであり、比較例２の着色組成物を用いた場合の耐溶剤性はＣであった。 (Test Example 2)
On a glass substrate, a spin coater was used so that the film thickness of the colored composition of Example 1, Example 16, Example 17, Example 18, Comparative Example 1 or Comparative Example 2 was 1.2 μm after prebaking. Then, heat treatment (prebaking) was performed for 120 seconds using a hot plate at 100 ° C. to form a film. Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), i-line was irradiated at an exposure amount of 100 mJ / cm 2 . Next, heat treatment was performed on a hot plate at 120 ° C. for 900 seconds to form a film. When the solvent resistance of the obtained film was evaluated by the same method as in Test Example 1, when the coloring compositions of Examples 1, 16, 16, and 18 were used, all of the solvent resistance was evaluated. The sex was evaluated by AA.
On the other hand, the solvent resistance when the colored composition of Comparative Example 1 was used was C, and the solvent resistance when the colored composition of Comparative Example 2 was used was C.

Claims (20)

  1. 　表示装置用のカラーフィルタの画素形成用の着色組成物であって、
    　前記着色組成物は全工程を通じて１５０℃以下の温度で画素を形成するために用いられ、
    　前記着色組成物は着色剤と樹脂と光重合開始剤と重合性モノマーとを含み、
    　前記着色組成物の２５℃における粘度が２．０～７．５ｍＰａ・ｓである、着色組成物。     A coloring composition for forming a pixel of a color filter for a display device,
    The coloring composition is used to form a pixel at a temperature of 150 ° C. or less throughout the entire process,
    The coloring composition includes a colorant, a resin, a photopolymerization initiator, and a polymerizable monomer,
    A coloring composition, wherein the viscosity of the coloring composition at 25 ° C. is 2.0 to 7.5 mPa · s.
  2. 　前記着色組成物の固形分濃度が５～２５％である、請求項１に記載の着色組成物。 着色 The coloring composition according to claim 1, wherein the solid content of the coloring composition is 5 to 25%.
  3. 　前記樹脂は、下記式（Ｉ）で表される化合物由来の繰り返し単位を含む樹脂ｂ１を含有する、請求項１または２に記載の着色組成物；
    Figure JPOXMLDOC01-appb-C000001
     　式中、Ｘ1は、ＯまたはＮＨを表し、
    　Ｒ1は水素原子またはメチル基を表し、
    　Ｌ1は２価の連結基を表し、
    　Ｒ10は置換基を表し、
    　ｍは０～２の整数を表し、
    　ｐは０以上の整数を表す。     The coloring composition according to claim 1, wherein the resin comprises a resin b1 containing a repeating unit derived from a compound represented by the following formula (I);
    Figure JPOXMLDOC01-appb-C000001
     In the formula, X 1 represents O or NH;
    R 1 represents a hydrogen atom or a methyl group,
    L 1 represents a divalent linking group,
    R 10 represents a substituent,
    m represents an integer of 0 to 2,
    p represents an integer of 0 or more.
  4. 　前記樹脂ｂ１は、更に、アルキル（メタ）アクリレート由来の繰り返し単位を含む、請求項３に記載の着色組成物。 The colored composition according to claim 3, wherein the resin b1 further includes a repeating unit derived from an alkyl (meth) acrylate.
  5. 　前記光重合開始剤はオキシム化合物を含有する、請求項１～４のいずれか１項に記載の着色組成物。 着色 The colored composition according to any one of claims 1 to 4, wherein the photopolymerization initiator contains an oxime compound.
  6. 　前記光重合開始剤は、
    　メタノール中での波長３６５ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ１と、
    　メタノール中での波長３６５ｎｍの吸光係数が１．０×１０2ｍＬ／ｇｃｍ以下で、かつ、波長２５４ｎｍの吸光係数が１．０×１０3ｍＬ／ｇｃｍ以上の光重合開始剤Ａ２と、
    　を含む、請求項１～５のいずれか１項に記載の着色組成物。     The photopolymerization initiator,
    A photopolymerization initiator A1 having an absorption coefficient of 1.0 × 10 3 mL / gcm or more in methanol at a wavelength of 365 nm;
    A photopolymerization initiator A2 having an extinction coefficient of 1.0 × 10 2 mL / gcm or less in methanol at a wavelength of 365 nm and an extinction coefficient of 1.0 × 10 3 mL / gcm or more at a wavelength of 254 nm;
    The colored composition according to any one of claims 1 to 5, comprising:
  7. 　前記光重合開始剤Ａ１がフッ素原子を含むオキシム化合物である、請求項６に記載の着色組成物。 The colored composition according to claim 6, wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom.
  8. 　前記光重合開始剤Ａ２がヒドロキシアルキルフェノン化合物である、請求項６または７に記載の着色組成物。 The colored composition according to claim 6, wherein the photopolymerization initiator A2 is a hydroxyalkylphenone compound.
  9. 　前記重合性モノマーは、酸基を有する重合性モノマーを含む、請求項１～８のいずれか１項に記載の着色組成物。 The colored composition according to any one of claims 1 to 8, wherein the polymerizable monomer includes a polymerizable monomer having an acid group.
  10. 　前記重合性モノマーは、エチレン性不飽和基を３個以上含む重合性モノマーを含む、請求項１～９のいずれか１項に記載の着色組成物。 10. The colored composition according to claim 1, wherein the polymerizable monomer includes a polymerizable monomer having three or more ethylenically unsaturated groups.
  11. 　フリル基を含む化合物を含む、請求項１～１０のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 10, comprising a compound containing a furyl group.
  12. 　前記フリル基を含む化合物は、下記式（ｆｕｒ－１）で表される化合物、および、下記式（ｆｕｒ－１）で表される化合物由来の繰り返し単位を含む樹脂から選ばれる少なくとも１種である、請求項１１に記載の着色組成物；
    Figure JPOXMLDOC01-appb-C000002
     　式中、Ｒｆ1は水素原子またはメチル基を表し、Ｒｆ2は２価の連結基を表す。     The compound containing a furyl group is at least one selected from a compound represented by the following formula (fur-1) and a resin containing a repeating unit derived from the compound represented by the following formula (fur-1). A coloring composition according to claim 11;
    Figure JPOXMLDOC01-appb-C000002
     In the formula, Rf 1 represents a hydrogen atom or a methyl group, and Rf 2 represents a divalent linking group.
  13. 　温度２５℃、湿度５０％の条件で３０日間保存した後の前記着色組成物の２５℃における粘度が、製造直後の前記着色組成物の２５℃における粘度の９０～１１０％の範囲である、請求項１～１２のいずれか１項に記載の着色組成物。 The viscosity of the coloring composition at 25 ° C. after storage at a temperature of 25 ° C. and a humidity of 50% for 30 days is in the range of 90 to 110% of the viscosity at 25 ° C. of the coloring composition immediately after production. Item 13. The coloring composition according to any one of Items 1 to 12.
  14. 　支持体上に請求項１～１３のいずれか１項に記載の着色組成物を塗布して着色組成物層を形成する工程と、前記着色組成物層をパターン状に露光する工程と、露光後の前記着色組成物層を現像する工程と、を含む画素の形成方法であって、
    　前記画素の形成方法は、全工程を通じて１５０℃以下の温度で行う、画素の形成方法。     14. A step of applying the coloring composition according to claim 1 on a support to form a coloring composition layer, a step of exposing the coloring composition layer in a pattern, and And a step of developing the colored composition layer of the above, comprising:
    The method of forming a pixel is performed at a temperature of 150 ° C. or less throughout the entire process.
  15. 　前記着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光を１Ｊ／ｃｍ2以上の露光量で照射して露光する、請求項１４に記載の画素の形成方法。 15. The pixel forming method according to claim 14, wherein the colored composition layer is exposed by irradiating light having a wavelength of more than 350 nm and not more than 380 nm with an exposure amount of 1 J / cm < 2 > or more.
  16. 　前記着色組成物層をパターン状に露光する工程は、前記着色組成物層に対して波長３５０ｎｍを超え３８０ｎｍ以下の光を照射して露光を行い、
    　更に、前記現像後の着色組成物層に対して、波長２５４～３５０ｎｍの光を照射して露光する工程を含む、請求項１４または１５に記載の画素の形成方法。     The step of exposing the colored composition layer to a pattern is performed by irradiating the colored composition layer with light having a wavelength of more than 350 nm and not more than 380 nm,
    16. The pixel forming method according to claim 14, further comprising a step of irradiating the colored composition layer after development with light having a wavelength of 254 to 350 nm to expose the colored composition layer.
  17. 　前記現像後の着色組成物層を１００～１５０℃の温度で１０分以上加熱する工程を含む、請求項１４～１６のいずれか１項に記載の画素の形成方法。 17. The method of forming a pixel according to claim 14, further comprising a step of heating the colored composition layer after the development at a temperature of 100 to 150 ° C. for 10 minutes or more.
  18. 　前記加熱する工程は、不活性ガスの雰囲気下で行う、請求項１７に記載の画素の形成方法。 18. The method according to claim 17, wherein the heating is performed in an inert gas atmosphere.
  19. 　請求項１４～１８のいずれか１項に記載の画素の形成方法を含むカラーフィルタの製造方法。 A method for manufacturing a color filter, including the method for forming a pixel according to any one of claims 14 to 18.
  20. 　請求項１４～１８のいずれか１項に記載の画素の形成方法を含む表示装置の製造方法。 A method for manufacturing a display device, comprising the method for forming a pixel according to any one of claims 14 to 18.
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