WO2022080046A1 - Coloring composition, film, color filter, optical sensor, and display device - Google Patents

Coloring composition, film, color filter, optical sensor, and display device Download PDF

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Publication number
WO2022080046A1
WO2022080046A1 PCT/JP2021/033195 JP2021033195W WO2022080046A1 WO 2022080046 A1 WO2022080046 A1 WO 2022080046A1 JP 2021033195 W JP2021033195 W JP 2021033195W WO 2022080046 A1 WO2022080046 A1 WO 2022080046A1
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WO
WIPO (PCT)
Prior art keywords
group
mass
coloring composition
pigment
yellow
Prior art date
Application number
PCT/JP2021/033195
Other languages
French (fr)
Japanese (ja)
Inventor
貴洋 大谷
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2022557273A priority Critical patent/JPWO2022080046A1/ja
Priority to KR1020237012557A priority patent/KR20230067652A/en
Publication of WO2022080046A1 publication Critical patent/WO2022080046A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/22—Monoazo compounds containing other metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a coloring composition. More specifically, the present invention relates to a coloring composition used for forming yellow pixels of a color filter and the like. The present invention also relates to a film, a color filter, an optical sensor and a display device using a coloring composition.
  • color filters are generally used for colorizing displayed images. Further, in a color filter, an attempt is made to adjust the spectroscopy by using a plurality of pigments in combination.
  • Patent Document 1 describes a coloring composition for a solid-state imaging device containing a green pigment and a yellow pigment, wherein the green pigment contains a phthalocyanine-based green pigment and the yellow pigment is C.I. I. Pigment Yellow 185 and C.I. I. Inventions relating to a coloring composition for a solid-state image sensor containing Pigment Yellow 150 are described.
  • the pigment tends to aggregate during storage of the coloring composition and the viscosity tends to increase with time.
  • the viscosity tends to increase with time.
  • the present invention provides: ⁇ 1> A coloring composition containing a coloring agent, a resin, a polymerizable compound, and a photopolymerization initiator.
  • the colorant contains a yellow pigment and contains The yellow pigment includes a color index pigment yellow 185, an isoindrin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment.
  • ⁇ 3> The coloring composition according to ⁇ 1> or ⁇ 2>, wherein the content of Color Index Pigment Yellow 185 in the colorant is 40% by mass or more.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, which contains 10 to 60 parts by mass of the azomethine-based yellow pigment with respect to 100 parts by mass of the total of the color index pigment yellow 185 and the isoindoline-based yellow pigment.
  • the coloring composition according to one. ⁇ 5> The coloring composition according to any one of ⁇ 1> to ⁇ 4>, which contains 10 to 70 parts by mass of the above-mentioned isoindoline-based yellow pigment with respect to 100 parts by mass of Color Index Pigment Yellow 185.
  • the isoindoline-based yellow pigment is Color Index Pigment Yellow 139.
  • the azomethine-based yellow pigment is Color Index Pigment Yellow 150.
  • ⁇ 7> The content of Color Index Pigment Yellow 185 in the colorant is 40 to 70% by mass, the content of Color Index Pigment Yellow 139 is 10 to 30% by mass, and the content of Color Index Pigment Yellow 150 is.
  • ⁇ 8> The coloring composition according to any one of ⁇ 1> to ⁇ 7>, wherein the photopolymerization initiator contains an oxime compound.
  • the above-mentioned polymerizable compound contains at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and modified products thereof.
  • ⁇ 12> When a film having a film thickness of 0.6 ⁇ m is formed using the coloring composition, the average value of the transmittance of the film in the wavelength range of 400 to 475 nm is less than 4%, and the wavelength is 550 to 700 nm.
  • ⁇ 14> A film obtained by using the coloring composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A color filter containing the film according to ⁇ 14>.
  • ⁇ 16> An optical sensor including the film according to ⁇ 14>.
  • ⁇ 17> A display device including the film according to ⁇ 14>.
  • the present invention it is possible to provide a colored composition having good storage stability and capable of forming a film having excellent light resistance and spectral characteristics.
  • the present invention can also provide a film, a color filter, an optical sensor and a display device using the coloring composition.
  • the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • 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).
  • the term "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 exposure generally includes an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • “(meth) acrylate” represents both acrylate and methacrylate, or either
  • “(meth) acrylic” represents both acrylic and methacrylic, or either.
  • Allyl represents both allyl and / or methacrylic
  • “ (meth) acryloyl ” represents both / or either acryloyl and methacrylic acid.
  • the term "process” is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • 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 coloring composition of the present invention is a coloring composition containing a coloring agent, a resin, a polymerizable compound, and a photopolymerization initiator.
  • the colorant contains a yellow pigment and contains The yellow pigment includes a color index pigment yellow 185, an isoindrin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment.
  • the content of Color Index Pigment Yellow 185 in the colorant is 10% by mass or more.
  • the coloring composition of the present invention uses a color index pigment yellow 185, an isoindolin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment as the yellow pigment, and the color index pigment in the colorant. Since the content of yellow 185 is 10% by mass or more, the storage stability is good even though it contains three or more kinds of pigments, the increase in viscosity with time can be suppressed, and further, the present invention By using the coloring composition, a film having excellent light resistance and spectral characteristics can be formed.
  • the coloring composition of the present invention is preferably a yellow coloring composition. Specifically, it can be preferably used as a coloring composition for a yellow color filter.
  • the average value of the transmittance of the above-mentioned film in the wavelength range of 400 to 475 nm was less than 4%, and the wavelength was 550 to 700 nm. It is preferable that the average value of the transmittance in the range is 90% or more.
  • a film satisfying such spectral characteristics is preferably used as a yellow color filter.
  • the average value of the transmittance of the film in the wavelength range of 400 to 475 nm is preferably less than 3%, more preferably less than 2%. Further, the average value of the transmittance in the wavelength range of 550 to 700 nm of the film is preferably 93% or more, and more preferably 95% or more.
  • the wavelength at which the transmittance of the film exhibits 50% is preferably in the wavelength range of 485 to 515 nm, more preferably in the wavelength range of 490 to 510 nm, and in the wavelength range of 495 to 505 nm. It is more preferred to be present.
  • the coloring composition of the present invention contains a coloring agent containing a yellow pigment.
  • the yellow pigment is C.I. I. (Color Index) Pigment Yellow 185 and C.I. I. It contains an isoindoline-based yellow pigment other than Pigment Yellow 185 and an azomethine-based yellow pigment.
  • Pigment Yellow 185 and C.I. I. A combination of an isoindoline-based yellow pigment other than Pigment Yellow 185 and an azomethine-based yellow pigment is also referred to as a specific yellow pigment.
  • the average primary particle size of the yellow pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less.
  • the primary particle size of the pigment can be obtained from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle diameter in the present specification is an arithmetic average value of the primary particle diameter for the primary particles of 400 pigments.
  • the primary particles of the pigment refer to independent particles without aggregation.
  • C. used as a yellow pigment C. used as a yellow pigment.
  • isoindoline-based yellow pigment other than Pigment Yellow 185 include C.I. I. Pigment Yellow 139 is preferred.
  • Examples of the azomethine-based yellow pigment used as the yellow pigment include C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 153 and the like, and C.I. I. Pigment Yellow 150 is preferred. Further, as the azomethine-based yellow pigment, a nickel azobarbiturate complex having the following structure can also be used.
  • yellow pigment a yellow pigment other than the above-mentioned specific yellow pigment can be further used.
  • Other yellow pigments include C.I. 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, 98,100,101,104,106,108,113,114,115,116,118,119,120,123,125,126,127,128,137,138,147,148,151,152,154 155,156,161,162,164,166,167,168,169,170,171,172,174,175,176,177,179,180,181,182,187,188,193,194,199, 213,214,215,228,231,232, 233,234,235,236
  • JP-A-2018-155881 The quinophthalone compound described in JP-A-2018-11757, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2017-197640, JP-A-2016
  • a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.
  • X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph No. 0016 of Japanese Patent No. 6443711.
  • Y1 to Y3 independently represent halogen atoms.
  • n and m represent integers of 0 to 6, and p represents an integer of 0 to 5.
  • (N + m) is 1 or more.
  • Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
  • the coloring agent may contain a coloring agent other than the yellow pigment (hereinafter, also referred to as another coloring agent).
  • a coloring agent other than the yellow pigment hereinafter, also referred to as another coloring agent.
  • other colorants include red colorants, green colorants, blue colorants, purple colorants, orange colorants and the like.
  • the other colorant may be either a pigment or a dye.
  • red colorant C.I. 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, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291
  • red pigments such as 294, 295, 296, and 297.
  • red colorant a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolop according to paragraph Nos. 0016 to 0022 of Patent No. 6248838.
  • Pyrol compound, diketopyrrolopyrrole compound described in International Publication No. 2012/102399, diketopyrrolopyrrole compound described in International Publication No. 2012/117956, naphtholazo compound described in JP-A-2012-229344 patent.
  • C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like green pigments can be mentioned.
  • halogenated zinc phthalocyanine has an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green colorant, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphate ester as a ligand according to International Publication No.
  • JP-A-2018-180023 the compound described in JP-A-2019-038958, and the like can also be used.
  • the core-shell type dye described in JP-A-2020-07695 can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A. Further, as the green colorant or the blue colorant, the compounds described in JP-A-2020-504758 can be used.
  • C.I. I. Pigment Violet 1,19,23,27,32,37,42,60,61 and other purple pigments can be mentioned.
  • the content of the colorant in the total solid content of the coloring composition is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less, still more preferably 65% by mass or less.
  • the content of Pigment Yellow 185 is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.
  • the upper limit is preferably 70% by mass or less.
  • the content of the isoindoline-based yellow pigment other than Pigment Yellow 185 is preferably 10 to 30% by mass.
  • the lower limit is preferably 15% by mass or more.
  • the upper limit is preferably 28% by mass or less.
  • the content of the azomethine-based yellow pigment (preferably the content of CI Pigment Yellow 150) in the colorant is preferably 10 to 30% by mass.
  • the lower limit is preferably 15% by mass or more.
  • the upper limit is preferably 28% by mass or less.
  • the content of the yellow pigment in the colorant is preferably 60 to 100% by mass, more preferably 75 to 100% by mass, further preferably 90 to 100% by mass, and substantially yellow pigment. It is particularly preferable that it is only.
  • the case where the colorant is substantially only a yellow pigment means that the content of the yellow pigment in the colorant is 99% by mass or more, and is 99.9% by mass or more. It is more preferably present, and even more preferably 100% by mass.
  • the content of the above-mentioned specific yellow pigment in the colorant is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and substantially. It is particularly preferable that only the specific yellow pigment is used.
  • the case where the colorant is substantially only the specific yellow pigment means that the content of the specific yellow pigment in the colorant is 99% by mass or more, and is 99.9% by mass. The above is more preferable, and 100% by mass is further preferable.
  • the coloring composition of the present invention is C.I. I. Pigment Yellow 185 and C.I. I. It is preferable to contain 10 to 60 parts by mass of the azomethine-based yellow pigment with respect to a total of 100 parts by mass of the isoindoline-based yellow pigment other than Pigment Yellow 185. According to this aspect, the light resistance can be further improved.
  • the upper limit is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.
  • the lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more.
  • the coloring composition of the present invention is C.I. I.
  • C.I. I. For 100 parts by mass of Pigment Yellow 185, C.I. I. It is preferable to contain 10 to 70 parts by mass of an isoindoline-based yellow pigment other than Pigment Yellow 185.
  • a film having a suitable spectroscopy can be formed.
  • the upper limit is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less.
  • the lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more.
  • the colorant used in the colorant of the present invention is C.I. I.
  • the content of Pigment Yellow 185 is 40 to 70% by mass, and C.I. I.
  • the content of Pigment Yellow 139 is 10 to 30% by mass, and C.I. I.
  • the content of Pigment Yellow 150 is preferably 10 to 30% by mass.
  • the total content of Pigment Yellow 150 is preferably 75 to 100% by mass, more preferably 85 to 100% by mass, and even more preferably 95 to 100% by mass.
  • the coloring composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing the pigment in the coloring composition or for the purpose of a binder.
  • the resin mainly used to disperse the pigment in the coloring composition is also referred to as a dispersant.
  • a dispersant such an application of the resin is an example, and the resin can be used for purposes other than such an application.
  • the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • the resin examples include (meth) acrylic resin, epoxy resin, (meth) acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, and polyarylene.
  • examples thereof include ether phosphin oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
  • the resin described in paragraphs 0041 to 0060 of JP-A-2017-206689, the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856, the resin described in JP-A-2017-057256, Use the resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, the resin described in JP-A-2017-066240, and the resin described in JP-A-2017-173787. You can also.
  • the resin it is preferable to use a resin having an acid group.
  • the acid group include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like.
  • the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
  • the lower limit is more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more.
  • the upper limit is more preferably 400 mgKOH / g or less, further preferably 300 mgKOH / g or less, and particularly preferably 200 mgKOH / g or less.
  • the weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100,000, more preferably 5000 to 50000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.
  • the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the resin is derived from a monomer component containing 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 preferable to use a resin containing a repeating unit.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • 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 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
  • Examples of the compound represented by the formula (X) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate.
  • Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • the resin it is also preferable to use a resin having a crosslinkable group.
  • the crosslinkable group include an ethylenically unsaturated bond-containing group and a cyclic ether group.
  • the resin it is preferable to use a resin having a cyclic ether group.
  • Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth) allyl group, and a (meth) acryloyl group.
  • Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.
  • the epoxy group may be an alicyclic epoxy group.
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the cyclic ether group is preferably at least one selected from the group represented by the formula (e-1) and the group represented by the formula (e-2), and forms a film having excellent moisture resistance.
  • the group is represented by the formula (e-2) because it is easy to use.
  • the group represented by the formula (e-1) is an epoxy group, and when n is 1, it is represented by the formula (e-1).
  • the group is an oxetanyl group.
  • the group represented by the formula (e-2) is an alicyclic epoxy group.
  • RE1 represents a hydrogen atom or an alkyl group, n represents 0 or 1, * represents a bond;
  • ring A E1 represents an aliphatic hydrocarbon. It represents a ring, and * represents a bond.
  • the number of carbon atoms of the alkyl group represented by RE1 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group represented by RE1 is preferably linear or branched, and more preferably linear.
  • RE1 is a hydrogen atom.
  • RE1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the formula (e-1) is a group represented by the following formula (e-1a).
  • the aliphatic hydrocarbon ring represented by the ring AE1 of the formula (e-2) may be a monocyclic aliphatic hydrocarbon ring or an aliphatic hydrocarbon ring of a fused ring. Further, the aliphatic hydrocarbon ring represented by the ring A E1 may have a crosslinked structure. Among them, the aliphatic hydrocarbon ring of the condensed ring is preferable because it is easy to form a film having excellent moisture resistance, and the aliphatic hydrocarbon ring of the condensed ring having a crosslinked structure is preferable.
  • aliphatic hydrocarbon ring represented by the ring AE1 include the groups shown below, which are represented by the group represented by the formula (e-2-3) and the formula (e-2-4). Groups are preferred. In the following formula, * represents a bond.
  • the resin having a cyclic ether group it is preferable to use a resin containing a repeating unit having a cyclic ether group.
  • the repeating unit having a cyclic ether group include a repeating unit represented by the formula (A1).
  • X a1 represents a trivalent linking group
  • La 1 represents a single bond or a divalent linking group
  • Z a1 represents a cyclic ether group.
  • the trivalent linking group represented by Xa1 of the formula (A1) includes a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, and a polyamide-based linking group.
  • Examples include a linking group, a polyether-based linking group, a polystyrene-based linking group, a bisphenol-based linking group, a novolak-based linking group, and a poly (meth) acrylic-based linking group, a polyether-based linking group, a polyester-based linking group, and a bisphenol-based linking group.
  • the linking group and the novolak-based linking group are preferable, the polyether-based linking group, the novolak-based linking group and the poly (meth) acrylic-based linking group are more preferable, and the poly (meth) acrylic-based linking group is further preferable.
  • the divalent linking group represented by La1 of the formula ( A1 ) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and -NH-. , -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned.
  • the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • Examples of the cyclic ether group represented by Z a1 of the formula (A1) include an epoxy group and an oxetanyl group, and an epoxy group is preferable. Further, the cyclic ether group represented by Z a1 is preferably a group represented by the formula (e-1) or a group represented by the formula (e-2), and is represented by the formula (e-2). It is more preferable that it is a group to be used.
  • the content of the repeating unit having a cyclic ether group in the resin having a cyclic ether group is preferably 1 to 100 mol% in all the repeating units of the resin having a cyclic ether group.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the resin having a cyclic ether group may have another repeating unit in addition to the repeating unit having a cyclic ether group.
  • Other repeating units include a repeating unit having an acid group (hereinafter, also referred to as a repeating unit B-1) and a repeating unit having a group in which the acid group is protected by a protective group (hereinafter, also referred to as a repeating unit B-2). , Repeating unit having an ethylenically unsaturated bond-containing group (hereinafter, repeating unit B-3) and the like.
  • Examples of the acid group contained in the repeating unit B-1 and the acid group protected by the protecting group in the repeating unit B-2 include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group.
  • a phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.
  • Examples of the protecting group that protects the acid group in the repeating unit B-2 include a group that decomposes and is eliminated by the action of an acid or a base.
  • the protecting group is preferably a group represented by any of the formulas (Y1) to (Y5), and is a group represented by the formula (Y3) or the formula (Y5) because it is easy to deprotect. Is more preferable.
  • RY1 to RY3 each independently represent an alkyl group, and two of RY1 to RY3 may be bonded to form a ring;
  • RY4 to RY6 each independently represent an alkyl group, and two of RY4 to RY6 may be bonded to form a ring;
  • RY7 and RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of RY7 and RY8 is an alkyl group or an aryl group, and RY9 is an alkyl.
  • Representing a group or aryl group, RY7 or RY8 and RY9 may be combined to form a ring;
  • Ar Y1 represents an aryl group and RY10 represents an alkyl or aryl group;
  • RY11 represents an alkyl or aryl group.
  • the number of carbon atoms of the alkyl group represented by RY1 to RY3 in the formula ( Y1 ) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. In the formula ( Y1 ), two of RY1 to RY3 may be combined to form a ring.
  • the ring formed by combining the two of RY1 to RY3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl.
  • a monocyclic cycloalkyl group such as a group
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
  • one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
  • the number of carbon atoms of the alkyl group represented by RY4 to RY6 in the formula (Y2) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. It is preferable that at least two of RY4 to RY6 of the formula (Y2) are methyl groups. In the formula (Y2), two of RY4 to RY6 may be combined to form a ring. Examples of the ring formed include the ring described by the formula (Y1).
  • RY7 and RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of RY7 and RY8 is an alkyl group or an aryl group, and RY9 is an alkyl. It represents a group or an aryl group, and RY7 or RY8 may be bonded to RY9 to form a ring.
  • the alkyl group may be linear, branched or cyclic.
  • the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Examples of the ring formed by binding RY7 or RY8 and RY9 include a tetrahydrofuranyl group and a tetrahydropyranyl group.
  • RY7 or RY8 and RY9 are combined to form a ring.
  • one of RY7 and RY8 is a hydrogen atom.
  • Ar Y1 represents an aryl group
  • RY10 represents an alkyl group or an aryl group
  • Ar Y1 and RY10 may be bonded to each other to form a ring.
  • the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • RY10 is preferably an alkyl group.
  • RY11 represents an alkyl group or an aryl group, and is preferably an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the molecular weight of the protecting group is preferably 40 to 200, more preferably 40 to 150, and even more preferably 40 to 120.
  • a coloring composition having excellent storage stability and excellent curability at a low temperature can be obtained.
  • protective group examples include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group and 1-cyclopentyloxyethyl group.
  • Examples of the ethylenically unsaturated bond-containing group of the repeating unit B-3 include a vinyl group, a styrene group, a (meth) allyl group, a (meth) acryloyl group, and the like.
  • repeating unit B-1 examples include a repeating unit represented by the following formula (B1). Further, as the repeating unit B-2, a repeating unit represented by the following formula (B2) can be mentioned. Further, as the repeating unit B-3, a repeating unit represented by the following formula (B3) can be mentioned.
  • X b1 represents a trivalent linking group
  • L b1 represents a single bond or a divalent linking group
  • Z b1 represents an acid group.
  • X b2 represents a trivalent linking group
  • L b2 represents a single bond or a divalent linking group
  • Z b2 represents a group in which the acid group is protected by a protecting group.
  • X b3 represents a trivalent linking group
  • L b3 represents a single bond or a divalent linking group
  • Z b3 represents an ethylenically unsaturated bond-containing group.
  • the trivalent linking group represented by X b1 of the formula (B1), the trivalent linking group represented by X b2 of the formula (B2), and the trivalent linking group represented by X b3 of the formula (B3) are not particularly limited. not.
  • Examples thereof include a system-based linking group and a novolak-based linking group, and poly (meth) acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups and novolac-based linking groups are preferable, and poly (meth) acrylic is preferable.
  • System linking groups are more preferred.
  • the divalent linking group represented by L b1 of the formula (B1), the divalent linking group represented by L b2 of the formula (B2), and the divalent linking group represented by L b3 of the formula (B3) include an alkylene group (as a divalent linking group).
  • the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • Examples of the acid group represented by Z b1 of the formula (B1) include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and the acid group is a carboxy group. Is more preferable.
  • Examples of the group in which the acid group represented by Z b2 of the formula (B2) is protected by a protecting group include a group in which the acid group is protected by a group represented by any of the above-mentioned formulas (Y1) to (Y5). It is preferable that the acid group is a group protected by a group represented by the formula (Y3) or the formula (Y5).
  • Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.
  • Examples of the ethylenically unsaturated bond-containing group represented by Z b3 of the formula (B3) include a vinyl group, a styrene group, a (meth) allyl group, a (meth) acryloyl group and the like.
  • the content of the unit B-1 in the resin having a cyclic ether group is 5 to 85 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have.
  • the upper limit is preferably 60 mol% or less, more preferably 40 mol% or less.
  • the lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.
  • the content of the unit B-2 in the resin having a cyclic ether group is 1 to 65 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have.
  • the upper limit is preferably 45 mol% or less, more preferably 30 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the resin having a cyclic ether group contains the repeating unit B-1 and the repeating unit B-2, respectively, the resin having the cyclic ether group has the repeating unit B-2 for 1 mol of the repeating unit B-1. It preferably contains 0.4 to 3.2 mol, more preferably 0.8 to 2.8 mol, and even more preferably 1.2 to 2.4 mol.
  • the content of the unit B-3 in the resin having a cyclic ether group is 1 to 65 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have.
  • the upper limit is preferably 45 mol% or less, more preferably 30 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the resin having a cyclic ether group preferably further contains a repeating unit having an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring.
  • the aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group and the like.
  • the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 1 in all the repeating units of the resin having a cyclic ether group. It is preferably 65 mol%.
  • the upper limit is preferably 45 mol% or less, more preferably 30 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the repeating unit having an aromatic hydrocarbon ring include a repeating unit derived from a monofunctional polymerizable compound having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth) acrylate.
  • Examples of commercially available resins having a cyclic ether group include naphthalene-modified epoxy resins such as EPICLON HP5000 and EPICLON HP4032D (all manufactured by DIC Corporation).
  • Examples of the alkyldiphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation).
  • jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EP (Made by Co., Ltd.) and the like.
  • Bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by DIC Corporation). As mentioned above, Nippon Kayaku Co., Ltd.) and the like can be mentioned.
  • Phenolic novolak type epoxy resins include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Can be mentioned.
  • cresol novolak type epoxy resin EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation).
  • EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), celoxide 2021P, celoxide 2081, celoxside 2083, celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPO Examples include PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation) and the like.
  • Examples of the resin having a cyclic ether group include the resins described in paragraphs 0034 to 0036 of JP2013-011869, and the resins described in paragraphs 0147 to 0156 of JP2014-043556.
  • Resins, the resins described in paragraphs 0117 to 0120 of JP-A-2020-515680, and the resins described in paragraph number 0084 of International Publication No. 2020/175011 can also be used.
  • the coloring composition of the present invention preferably contains a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol% or more is preferable when the total amount of the acid group and the basic group is 100 mol%.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g.
  • the basic dispersant represents a resin in which the amount of basic groups is larger than the amount of acid groups.
  • a resin in which the amount of basic groups exceeds 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
  • the basic group contained in the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is a graft resin.
  • the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.
  • the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
  • the resin to have is preferable.
  • the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
  • the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
  • the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.
  • the resin described in JP-A-2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and the like Polyethylenimine having a polyester side chain described in WO2016 / 104803, a block copolymer described in WO2019 / 125940, and a block polymer having an acrylamide structural unit described in JP-A-2020-06667.
  • Block polymers having an acrylamide structural unit described in JP-A-2020-066688, dispersants described in International Publication No. 2016/10403, and the like can also be used.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 161 and 2001) and Solspers manufactured by Japan Lubrizol Co., Ltd. Examples include a series (for example, Solspers 20000, 76500, etc.), an Ajinomoto Fine Techno Co., Ltd. Ajispar series, and the like. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 can also be used as a dispersant.
  • the resin content is preferably 5 to 50% by mass in the total solid content of the coloring composition.
  • the upper limit is preferably 40% by mass or less, and more preferably 30% 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 may contain only one kind of resin, or may contain two or more kinds of resins. When two or more kinds of resins are contained, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is preferably 2000 or less, and more preferably 1500 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more.
  • the upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the ethylenically unsaturated bond-containing group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less, from the viewpoint of stability over time of the coloring composition.
  • the polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and a 3 to 10 functional (meth) acrylate compound. It is more preferably present, and it is particularly preferable that it is a (meth) acrylate compound having 3 to 6 functions.
  • Examples of the polymerizable compound include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and modified products of these compounds. Can be mentioned.
  • Examples of the modified product include compounds having a structure in which the (meth) acryloyl group of the above compound is bonded via an alkyleneoxy group. Specific examples include a compound represented by the formula (Z-4), a compound represented by the formula (Z-5), and the like.
  • E is independently ⁇ ((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-.
  • Y each independently represents an integer of 0 to 10
  • X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each of m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth) acryloyl groups is 5 or 6, where n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • -((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-in the formula (Z-4) or the formula (Z-5) is on the oxygen atom side. The form in which the end of is bound to X is preferable.
  • polypentaerythritol poly (meth) acrylate as shown in the following formula (Z-6) can also be used.
  • X 1 to X 6 independently represent a hydrogen atom or a (meth) acryloyl group, and n represents an integer of 1 to 10. However, at least one of X 1 to X 6 is a (meth) acryloyl group.
  • the polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polypentaerythritol poly (meth) acrylate and modified products thereof. It is preferably a seed.
  • Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (all manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, and TPOA-50 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Can be mentioned.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetra (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • NK Ester A-TMMT 1,6-hexanediol diacrylate
  • RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Aronix TO-2349 Toagosei Co., Ltd.
  • NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • 8UH-1006, 8UH-1012 manufactured by Taisei Fine Chemical Co., Ltd.
  • Light Acrylate POB-A0 manufactured by Kyoeisha
  • Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth). It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or 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, M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group such as a carboxy group, a sulfo group, and a phosphoric acid group can also be used.
  • examples of commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.
  • a compound having a caprolactone structure can also be used.
  • the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification.
  • Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • examples of commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene.
  • an environmentally regulatory substance such as toluene.
  • commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
  • urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A No. 01-105238.
  • the polymerizable compounds are UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the content of the polymerizable compound is preferably 5 to 35% by mass in the total solid content of the coloring composition.
  • the upper limit is preferably 30% by mass or less, and 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 may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more kinds of polymerizable compounds are contained, it is preferable that the total amount thereof is in the above range.
  • the coloring composition preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible light region is preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
  • It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an ⁇ -hydroxyketone compound.
  • ⁇ -Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable.
  • the photopolymerization initiator the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864.
  • Examples thereof include the above-mentioned aminoacetophenone-based initiators having an oxazolidine group, the oxime-based photopolymerization initiators described in JP-A-2013-190459, and the contents thereof are incorporated in the present specification.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on.
  • acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
  • Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
  • oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Patent Publication No. 10-2016-0109444. Will be.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) and the like can be mentioned.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).
  • an oxime compound having a benzofuran skeleton can also be used.
  • Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
  • the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
  • the benzoyl group may have a substituent.
  • the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
  • an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
  • RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
  • RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
  • RX3 to RX14 independently represent hydrogen atoms or substituents; However, at least one of RX10 to RX14 is an electron-withdrawing group.
  • RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 , and RX14 are hydrogen atoms.
  • oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photopolymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in an organic solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the coloring composition with time is improved.
  • Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • only one kind of photopolymerization initiator may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention preferably contains a solvent.
  • the solvent include organic solvents.
  • the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition.
  • the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. For these details, paragraph 0223 of International Publication No. 2015/166779 can be referred to, 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, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-di
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) 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 the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts per tension) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical 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 diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • the content of the solvent in the coloring composition is preferably 60 to 95% by mass.
  • the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and further preferably 85% by mass or less.
  • the lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
  • the solvent may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
  • substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evolution Analysis and Restriction of Chemicals
  • PRTR Policy Release and Transfer Register
  • VOC Volatile and Transfer Registor
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • a method for reducing the environmentally regulated substance there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency.
  • a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be.
  • distillation methods are either a raw material step, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a colored composition step prepared by mixing these compounds. It is also possible at the stage of.
  • the coloring composition of the present invention can contain a pigment derivative.
  • Pigment derivatives are used, for example, as dispersion aids.
  • examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • the pigment skeletons constituting the pigment derivatives include squarylium pigment skeleton, pyrolopyrrolop pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzoisoindole pigment skeleton, and thiazine indigo pigment skeleton.
  • Azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzoimidazolone pigment skeleton, benzothiazole pigment skeleton, benzoimidazole pigment skeleton and benzoxazole pigment skeleton The squarylium pigment skeleton, the pyrolopyrrolop pigment skeleton, the diketopyrrolopyrrole pigment skeleton, the phthalocyanine pigment skeleton, the quinacridone pigment skeleton and the benzoimidazolone pigment skeleton are preferable, and the squarylium pigment skeleton and the pyrolopyrrolop pigment skeleton are more preferable.
  • Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imic acid group and salts thereof.
  • alkali metal ions Li + , Na + , K + , etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+ , etc.
  • ammonium ions imidazolium ions, pyridinium ions, etc.
  • Examples include phosphonium ions.
  • the carboxylic acid amide group a group represented by -NHCOR X1 is preferable.
  • sulfonamide group a group represented by -NHSO 2 RX2 is preferable.
  • imidic acid group a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable, and -SO 2 NHSO 2 R X3 is more preferable.
  • RX1 to RX6 independently represent an alkyl group or an aryl group, respectively.
  • the alkyl group and aryl group represented by RX1 to RX6 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
  • Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • the pigment derivative examples include JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-09961 and JP-A-03-026767.
  • Examples thereof include the compounds described in Japanese Patent Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, paragraph numbers 0086 to 0998 of International Publication No. 2011/024896, and paragraph numbers 0063 to 0094 of International Publication No. 2012/102399. The contents of are incorporated herein by reference.
  • the content of the pigment derivative is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit of this range is more preferably 0.25 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable to have.
  • the upper limit of this range is more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.
  • the content of the pigment derivative is within the above range, the storage stability of the coloring composition can be further improved.
  • the pigment derivative only one kind may be used, or two or more kinds may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.
  • a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature.
  • the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the 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 compound, 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 linking group of 2 to 4 valences.)
  • 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 is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example.
  • an alkoxysilane compound for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504
  • an onium salt compound eg, JP-A-2015-034963
  • Compounds exemplified as acid generators in paragraph No. 0216, compounds described in JP-A-2009-180949), polyvalent carboxylic acids and the like can also be used.
  • the polyvalent carboxylic acid include succinic acid, trimellitic acid, pyromellitic acid, N, N-dimethyl-4-aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate) and the like.
  • the compounds described in paragraphs 0072 to 0078 of JP-A-2016-07520 and the compounds described in JP-A-2017-036379 can also be used.
  • the content of the curing accelerator is preferably 0.3 to 8.9% by mass, preferably 0.8 to 6.4% by mass in the total solid content of the coloring composition. More preferably by mass.
  • 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 reactivity 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 methacrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group.
  • silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2- (aminoethyl) -3.
  • the description in paragraphs 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.
  • the content of the silane coupling agent is preferably 0.001 to 20% by mass, preferably 0.01 to 10% by mass, based on the total solid content of the coloring composition. Is more preferable, and 0.1% by mass to 5% by mass is particularly preferable.
  • the coloring composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention can contain an antioxidant.
  • the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • the antioxidant a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • a phosphorus-based antioxidant can also be preferably used.
  • the compound described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass.
  • the coloring composition of the present invention may contain only one kind of antioxidant, or may contain two or more kinds of antioxidants. When two or more kinds are contained, it is preferable that the total amount thereof is 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), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.).
  • 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 of the polymerization inhibitor. When two or more kinds are contained, it is preferable that the total amount thereof is 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 and the like can be used.
  • paragraph numbers 0052 to 0072 of JP2012-208374A paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. It can be taken into consideration and these contents are incorporated in the present specification.
  • Examples of commercially available products of ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
  • Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
  • the coloring composition of the present invention contains an ultraviolet absorber
  • the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is preferable, and 0.1 to 3% by mass is particularly preferable.
  • the ultraviolet absorber only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is 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 silicone-based surfactant can be used.
  • the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
  • the surfactant is preferably a fluorine-based surfactant.
  • the liquid characteristics particularly, fluidity
  • the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in a coloring composition.
  • fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
  • the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
  • fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
  • the fluorine-based surfactant has 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 and the fluorine atom volatilizes when heat is applied.
  • a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • fluorine-based surfactant it is also 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.
  • a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
  • 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 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000.
  • % indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by the formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • ⁇ represents 1 or 2
  • X ⁇ + represents an ⁇ -valent metal ion, a primary ammonium ion, and a first.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • silicone-based surfactant examples include DOWNSIL SH 8400 FLUID, DOWNSIL SF 8419 OIL, FZ-2122 (all manufactured by Dow Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460. , TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK- 323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by Big Chemie) and the like can be mentioned.
  • a compound having the following structure can also be used as the silicone-based surfactant.
  • the content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, 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 types, it is preferable that the total amount is within the above range.
  • the coloring composition of the present invention may be used as a sensitizer, a curing accelerator, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant), if necessary. , Leveling agent, peeling accelerator, fragrance, surface tension adjusting agent, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos.
  • the coloring composition may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
  • Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
  • the coloring composition of the present invention may contain a light resistance improving agent.
  • the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774.
  • the coloring composition of the present invention does not substantially contain terephthalic acid ester.
  • substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
  • perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt may be restricted.
  • perfluoroalkyl sulfonic acid particularly, perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • a salt thereof, and a perfluoroalkyl carboxylic acid are used.
  • the content of the acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is in the range of 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb.
  • the coloring composition may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof.
  • a coloring composition that is substantially free of salts thereof may be selected.
  • compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group.
  • the coloring composition may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
  • the container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used.
  • a storage container for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the composition, and suppressing the deterioration of the components.
  • the coloring composition of the present invention can be produced by mixing the above-mentioned components.
  • all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to produce a colored composition.
  • a process of dispersing particles such as pigments may be included.
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • 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.
  • the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial”. Practical application The process and disperser described in Paragraph No.
  • JP-A-2015-157893 "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used.
  • the particles may be miniaturized in the salt milling step.
  • the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP).
  • filters using materials such as (including high-density, ultra-high molecular weight polyethylene resin).
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore diameter 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. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.
  • Advantech Toyo Co., Ltd. Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc.
  • KITZ Microfilter Co., Ltd. etc.
  • a fiber-like filter medium As the filter.
  • the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
  • filters different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
  • the film of the present invention is a film obtained by using the coloring composition of the present invention described above.
  • the film of the present invention can be used as a color filter or the like. Specifically, it can be preferably used as a yellow color filter. For example, it can be used as a yellow pixel of a color filter.
  • the film thickness of the film of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the film of the present invention preferably has an average transmittance of less than 4%, more preferably less than 3%, and even more preferably less than 2% in the wavelength range of 400 to 475 nm. Further, in the film of the present invention, the average value of the transmittance in the wavelength range of 550 to 700 nm is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more.
  • the wavelength at which the transmittance of the film of the present invention is 50% is preferably in the wavelength range of 485 to 515 nm, more preferably in the wavelength range of 490 to 510 nm, and in the wavelength range of 495 to 505 nm. It is more preferable to be present in.
  • the color filter of the present invention has the above-mentioned film of the present invention.
  • the film of the present invention is provided as the yellow pixel of the color filter.
  • the color filter of the present invention can be used for an optical sensor or a display device.
  • the color filter of the present invention has colored pixels of other hues in addition to the pixels of the film of the present invention.
  • the colored pixels of other hues include blue pixels, red pixels, magenta pixels, cyan pixels, and the like.
  • a preferred embodiment of the color filter is an embodiment having a magenta color pixel, a cyan color pixel, and a yellow pixel composed of the film of the present invention. Further, as another preferred embodiment of the color filter of the present invention, there is an embodiment having a red pixel, a blue pixel, and a yellow pixel composed of the film of the present invention, a red pixel, a cyan pixel, and the present invention. An embodiment having a yellow pixel composed of a film can be mentioned.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each colored pixel.
  • the partition wall may be formed by the configuration described in US Patent Application Publication No. 2018/0040656.
  • the film of the present invention can be produced through a step of applying the coloring composition of the present invention.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel).
  • the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
  • the pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and a step of exposing the colored composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
  • the coloring composition layer of the present invention is used to form the coloring composition layer on the support.
  • the support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.
  • the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • a known method can be used as a method for applying the coloring composition.
  • a drop method drop cast
  • a slit coat method for example, a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
  • Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned.
  • the method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
  • the colored composition layer formed on the support may be dried (prebaked).
  • prebaking may not be performed.
  • the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.
  • the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking 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 exposing the colored composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
  • pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).
  • the irradiation amount is, for example, preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 .
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% 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 , 15,000 W / m 2 , or 35,000 W / m 2 ). Can be done.
  • the oxygen concentration and the exposure illuminance may be appropriately combined with each other.
  • the illuminance may be 10,000 W / m 2 at an oxygen concentration of 10% by volume, an illuminance of 20,000 W / m 2 at an oxygen concentration of 35% by volume, and the like.
  • the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel).
  • the development and removal of the unexposed portion of the coloring composition layer can be performed using a developing solution.
  • the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
  • the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
  • 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, etc.
  • examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • the alkaline 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 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed.
  • the nozzle for discharging the rinse liquid from the central portion of the support it is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support.
  • the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.
  • Additional exposure processing and post-baking are post-development curing treatments to complete the curing.
  • the heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. ..
  • the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • the pattern formation by the dry etching method includes a step of forming a colored composition layer on a support using the colored composition of the present invention and curing the entire colored composition layer to form a cured product layer.
  • the optical sensor of the present invention has the above-mentioned film of the present invention.
  • the optical sensor include devices that perform various sensing and imaging using light such as visible light, ultraviolet rays, and infrared rays.
  • Examples of the optical sensor include an image sensor such as a solid-state image sensor.
  • Examples of the solid-state image pickup device include the following configurations.
  • a transfer electrode formed of a plurality of photodiodes constituting a light receiving area of a solid-state image pickup device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and polycarbonate on a substrate. It has a light-shielding film having only the light-receiving part of the photodiode open on the photodiode and the transfer electrode, and is formed of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a device protective film and a color filter on the device protective film.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • a configuration having a condensing means for example, a microlens or the like; the same applies hereinafter
  • a configuration having a condensing means on the color filter and the like.
  • the pixels of the color filter may be embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the refractive index of the partition wall is preferably lower than that of the pixel. Examples of the image pickup apparatus having such a structure are described in JP-A-2012-227478, JP-A-2014-179757, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. Equipment is mentioned.
  • Devices equipped with optical sensors can be used for digital cameras, electronic devices with imaging functions (mobile phones, etc.), in-vehicle cameras, surveillance cameras, and the like.
  • the display device of the present invention has the above-mentioned film of the present invention.
  • Examples of the display device include a liquid crystal display device and an organic electroluminescence display device.
  • Examples of each display device see, for example, “Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", “Display Devices (Junaki Ibuki, Sangyo Tosho Co., Ltd.)” (Published in 1989) ”and so on.
  • liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)".
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, 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 composed of a white organic electroluminescence element.
  • the white organic electroluminescence device preferably has a tandem structure.
  • Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association It is described on pages 326-328, 2008 and the like.
  • the spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.
  • the organic electroluminescence display device may have a lens on the color filter.
  • the shape of the lens various shapes derived by the optical system design can be taken, and examples thereof include a convex shape and a concave shape. For example, it is easy to improve the light condensing property by making it a concave shape (concave lens).
  • the lens may be in direct contact with the color filter, or another layer such as an adhesion layer or a flattening layer may be provided between the lens and the color filter.
  • the lens can also be arranged and used in the manner described in International Publication No. 2018/135189.
  • Dispersion 1 ⁇ Preparation of dispersion> (Dispersion 1)
  • C. After mixing 12.0 parts by mass of Pigment Yellow 139, 4.0 parts by mass of Dispersant 1, and 83.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), zirconia beads having a diameter of 1 mm are used.
  • PMEA propylene glycol monomethyl ether acetate
  • Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a filter having a pore size of 5 ⁇ m to prepare a dispersion liquid 1.
  • Dispersion 2 C. I. Pigment Yellow 150 (azomethine-based yellow pigment) 11.6 parts by mass, dispersant 2 6.9 parts by mass, PGMEA 78.0 parts by mass, and propylene glycol monomethyl ether (PGME) 3.5 parts by mass.
  • Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, the mixture was dispersed for 5 hours and then filtered through a filter having a pore size of 5 ⁇ m to prepare a dispersion liquid 2. ..
  • Dispersion liquid 3 (Dispersion liquid 3) C. I. After mixing 13.0 parts by mass of Pigment Yellow 185, 5.0 parts by mass of Dispersant 1, 74.0 parts by mass of PGMEA, and 8.0 parts by mass of PGME, zirconia beads having a diameter of 1 mm are obtained. After dispersing for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.), the dispersion liquid 3 was prepared by filtering with a filter having a pore size of 5 ⁇ m.
  • Dispersion liquid 4 C. I. Pigment Yellow 129 (azomethine-based yellow pigment) 11.6 parts by mass, dispersant 2 6.9 parts by mass, PGMEA 78.0 parts by mass, and propylene glycol monomethyl ether (PGME) 3.5 parts by mass.
  • Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, the mixture was dispersed for 5 hours and then filtered through a filter having a pore size of 5 ⁇ m to prepare a dispersion liquid 2. ..
  • Dispersant 1 Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 52.5 mgKOH / g)
  • Dispersant 2 Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 21000, acid value 36 mgKOH / g)
  • (resin) B-1 40% by mass PGMEA solution of the resin (resin having an epoxy group) synthesized by the following method PGMEA is replaced with a nitrogen atmosphere by flowing an appropriate amount of nitrogen into a flask equipped with a reflux condenser, a dropping funnel and a stirrer. 371 parts by mass of the above was added and heated to 85 ° C. with stirring. Then 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8 and / and 9-ylacrylate, vinyl toluene (isomer).
  • a mixed solution of 81 parts by mass of the mixture) and 80 parts by mass of PGMEA was added dropwise over 4 hours.
  • a solution prepared by dissolving 30 parts by mass of the polymerization initiator (2,2-azobis (2,4-dimethylvaleronitrile)) in 160 parts by mass of PGMEA was added dropwise over 5 hours. After the addition of the initiator solution was completed, the solution was added dropwise. After keeping at the same temperature for 4 hours, the resin was cooled to room temperature to obtain a resin.
  • the acid value of the obtained resin was 43 mgKOH / g, the weight average molecular weight was 10600, and the dispersibility was 2.01. Was added to adjust the solid content concentration to 40% by mass to prepare B-1.
  • B-4 40% by mass PGMEA solution of the resin (resin having an epoxy group) synthesized by the following method A suitable amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere. 340 parts by mass of PGMEA was added and heated to 80 ° C. with stirring. Next, 57 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0].
  • C-1 Irgure OXE02 (Oxime compound manufactured by BASF)
  • C-2 Irgure OXE01 (Oxime compound manufactured by BASF)
  • C-3 Irgacure 369 (acetophenone compound manufactured by BASF)
  • C-4 TR-PBG-327 (Oxime compound manufactured by Tronley, 1- [4- (phenylthio) phenyl] -3-cyclohexyl-propane-1,2-dione-2- (O-acetyloxime))
  • D-1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
  • D-2 NK Ester A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd., a mixture of ethoxylated dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol pentaacrylate)
  • D-3 Dipentaerythritol polyacrylate
  • F-1 Compound with the following structure
  • F-2 A compound having the following structure (weight average molecular weight 14000,% value indicating the ratio of repeating units is mol%, fluorine-based surfactant)
  • F-3 Megafuck F-554 (DIC Corporation, fluorine-based surfactant)
  • F-4 PolyFox PF6320 (OMNOVA, fluorine-based surfactant)
  • F-5 Futergent 208G (NEOS, fluorine-based surfactant)
  • F-6 DOWNSIL SH 8400 FLUID (Silicone-based surfactant manufactured by Dow Toray Co., Ltd.)
  • F-7 DOWNSIL SF 8419 OIL (made by Dow Toray Co., Ltd., silicone-based surfactant)
  • ⁇ Evaluation> Evaluation of spectral characteristics
  • the coloring composition is applied onto a glass substrate by a spin coating method, then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate, and then i-rays are irradiated with an exposure amount of 1000 mj / cm 2 .
  • the film was exposed and then heated at 200 ° C. for 5 minutes to prepare a film having a thickness of 0.6 ⁇ m.
  • the light transmittance (transmittance) in the range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the average value of the transmittance in the wavelength range of 400 to 475 nm (T1). )
  • the average value of the transmittance (T2) in the wavelength range of 550 to 700 nm, and the wavelength ( ⁇ 50) showing the transmittance of 50% were obtained, and the spectral characteristics were evaluated according to the following criteria.
  • T1 is less than 2%
  • B T1 is 2% or more and less than 3%
  • C T1 is 3% or more and less than 4%
  • D T1 is 4% or more
  • T2 is 95% or more
  • B T2 is 93% or more and less than 95%
  • C T2 is 90% or more and less than 93%
  • D T2 is less than 90%
  • ⁇ 50 is in the range of 495 nm or more and 505 nm or less
  • B ⁇ 50 is in the range of 490 nm or more and less than 495 nm
  • C ⁇ 50 is in the range of more than 505 nm and less than 510 nm
  • C ⁇ 50 is in the range of 485 nm or more and less than 490 nm
  • D ⁇ 50 is in the range of 480 nm or more and less than 485 nm, or is in the range of more than 515 nm and 520 nm or less.
  • the viscosity (mPa ⁇ s) of the coloring composition was measured with "RE-85L” manufactured by Toki Sangyo Co., Ltd. After the above measurement, the colored composition was allowed to stand at 45 ° C. under the conditions of light shielding for 3 days, and the viscosity (mPa ⁇ s) was measured again.
  • the storage stability was evaluated according to the following evaluation criteria from the viscosity difference ( ⁇ Vis) before and after standing. In each of the above viscosity measurements, the temperature and humidity were controlled to 22 ⁇ 5 ° C. and 60 ⁇ 20% in a laboratory, and the temperature of the coloring composition was adjusted to 25 ° C.
  • ⁇ Vis is 0.5 mPa ⁇ s or less
  • the coloring composition was applied onto a glass substrate by a spin coating method, then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate, and then i-rays were exposed to an exposure amount of 1000 mj / cm 2 . Then, it was heated at 200 ° C. for 5 minutes to prepare a film having a thickness of 0.6 ⁇ m. With respect to the obtained film, the light transmittance (transmittance) in the wavelength range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
  • the film prepared above was irradiated with light of 100,000 Lux over 1000 hours using a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.) (total irradiation amount 100 million Lux ⁇ hr). ).
  • the transmittance of the film after light irradiation was measured, and the light resistance was evaluated according to the following criteria.
  • B The film after light irradiation.
  • the integrated value of the transmittance of the film having a wavelength of 400 to 700 nm is 95% or more and less than 97% of the integrated value of the transmittance of the film having a wavelength of 400 to 700 nm before light irradiation.
  • C The wavelength of the film after light irradiation is 400 to 700 nm.
  • the integrated value of the transmittance of the film before light irradiation is 90% or more and less than 95% of the integrated value of the integrated value of the transmittance of the film having a wavelength of 400 to 700 nm before light irradiation.
  • the value is less than 90% of the integrated value of the transmittance of the film before light irradiation at a wavelength of 400 to 700 nm.
  • the colored composition was applied onto a silicon wafer by a spin coating method, and then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate to form a composition layer having a thickness of 0.6 ⁇ m.
  • an i-line stepper exposure apparatus FPA-3000i5 +, Canon Inc.
  • the i-line was irradiated with an exposure amount of 500 mj / cm 2 and exposed.
  • the silicon wafer on which the composition layer after exposure is formed is placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and a developer (CD-) is placed. 2000, paddle developed at 23 ° C. for 60 seconds using Fujifilm Electronics Materials Co., Ltd. Next, while rotating the silicon wafer at a rotation speed of 50 rpm, pure water was supplied from above the center of rotation in a shower shape from the ejection nozzle to perform rinsing treatment, and then spray-dried to form a substrate with a pattern (pixels). ..
  • the obtained patterned substrate was placed in a constant temperature and humidity machine (EHS-221M, manufactured by Yamato Kagaku Co., Ltd.) and allowed to stand in an atmosphere at a temperature of 85 ° C. and a relative humidity of 85% for 500 hours, 750 hours, 1000 hours, and 1500 hours. Then, a moisture resistance test was conducted. After the test, the moisture resistance was evaluated by observing with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) and observing the presence or absence of peeling of the pixels. When the pixel is completely peeled off from the silicon wafer, or when the interface of the pixel with the silicon wafer is cracked, it is determined that the pixel is peeled off.
  • SEM scanning electron microscope
  • the evaluation criteria for moisture resistance are as follows. A: No peeling is observed even in the moisture resistance test 1500 hours B: No peeling is observed in the moisture resistance test 1000 hours, but peeling is observed in 1500 hours C: No peeling is observed in the moisture resistance test 500 hours, but peeling is observed in 1000 hours. D: Peeling was observed after 500 hours of moisture resistance test.
  • the examples it was possible to form a film having good storage stability and excellent spectral characteristics and light resistance. Further, the film obtained by using the coloring composition of the example had preferable spectral characteristics as a yellow color filter.
  • Example 1001 The yellow coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 0.6 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 1 ⁇ m square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water.
  • TMAH tetramethylammonium hydroxide
  • the yellow colored composition was then patterned using a hot plate and heated at 200 ° C. for 5 minutes to form yellow pixels.
  • the red coloring composition and the blue coloring composition were patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having yellow pixels, red pixels and blue pixels.
  • the coloring composition of Example 1 was used as the yellow coloring composition.
  • the red coloring composition and the blue coloring composition will be described later.
  • yellow pixels are formed by a Bayer pattern, and red pixels and blue pixels are formed by an island pattern in an adjacent region thereof.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • Red coloring composition The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a red colored composition.
  • Red pigment dispersion 51.7 parts by mass
  • Resin 101 0.6 parts by mass Polymerizable compound (NK ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 0.6% by mass Part Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ⁇ ⁇ ⁇ 0.4 parts by mass
  • Blue coloring composition The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a blue coloring composition.
  • the materials used for the red coloring composition and the blue coloring composition are as follows.
  • a high-pressure disperser with a decompression mechanism NANO-3000-10 manufactured by Nippon BEE Co., Ltd. was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion liquid.
  • a high-pressure disperser with a decompression mechanism NANO-3000-10 manufactured by Nippon BEE Co., Ltd. was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid.
  • Surfactant 101 A 1% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000). In the following formula,% indicating the ratio of the repeating unit is mol%. (Example 1002) The blue coloring composition of Example 1001 was changed to the following cyan coloring composition 1, and a color filter was formed by the same method as in Example 1001 except that cyan colored pixels were created. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • Cyan color pigment dispersion 1 C A mixed solution consisting of 12.1 parts by mass of Pigment Blue 15: 4, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0. 3 mm diameter) was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a cyan pigment dispersion liquid 1.
  • Example 1003 The blue coloring composition of Example 1001 was changed to the cyan coloring composition 2 below, and a color filter was formed by the same method as in Example 1001 except that cyan colored pixels were created.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • Cyan color pigment dispersion 2 44.9 parts by mass Resin 101 ⁇ ⁇ ⁇ 2.1 parts by mass Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ⁇ ⁇ ⁇ 1.5 parts by mass Polymerizable compound (NK ester) A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ⁇ ⁇ ⁇ 0.7 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ⁇ ⁇ ⁇ 0.8 parts by mass Surface active agent 101 ⁇ ⁇ ⁇ 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ⁇ ⁇ ⁇ 0.3 parts by mass PGMEA ⁇ ⁇ ⁇ 45.8 parts by mass
  • Cyan color pigment dispersion liquid 2 C. I. Pigment Blue 15: 4, 1.9 parts by mass, C.I. I. 7.3 parts by mass of Pigment Green 7, C.I. I. A mixed solution consisting of 2.9 parts by mass of Pigment Green 36, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) was mixed and dispersed for 3 hours to prepare a pigment dispersion.
  • a high-pressure disperser with a decompression mechanism NANO-3000-10 manufactured by Nippon BEE Co., Ltd. was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a cyan pigment dispersion liquid 2.
  • Example 1004 A color filter was formed by the same method as in Example 1001 except that the blue coloring composition of Example 1001 was changed to the coloring curable composition of Example 1 of Paragraph No. 0121 of International Publication No. 2020/174991.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.

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Abstract

Provided are: a coloring composition that can form a film that is excellent in light resistance and spectral characteristic while also having favorable preservation stability; and a corresponding film, color filter, optical sensor, and display device. This coloring composition includes coloring agents, a resin, a polymerizable compound, and a photopolymerization initiator, the coloring agents containing yellow pigments, the yellow pigments containing color index pigment yellow 185, an isoindoline yellow pigment other than the color index pigment yellow 185, and an azomethine yellow pigment, and the content of the color index pigment yellow 185 in the coloring agents being not less than 10% by mass.

Description

着色組成物、膜、カラーフィルタ、光センサおよび表示装置Coloring compositions, films, color filters, optical sensors and display devices
　本発明は、着色組成物に関する。より詳しくは、カラーフィルタの黄色画素形成などに用いられる着色組成物に関する。また、本発明は、着色組成物を用いた膜、カラーフィルタ、光センサおよび表示装置に関する。 The present invention relates to a coloring composition. More specifically, the present invention relates to a coloring composition used for forming yellow pixels of a color filter and the like. The present invention also relates to a film, a color filter, an optical sensor and a display device using a coloring composition.
　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。また、カラーフィルタにおいては、複数の顔料を併用して分光を調整する試みが行われている。 In various display devices, color filters are generally used for colorizing displayed images. Further, in a color filter, an attempt is made to adjust the spectroscopy by using a plurality of pigments in combination.
　特許文献１には、緑色顔料と、黄色顔料とを含む固体撮像素子用着色組成物であって、緑色顔料がフタロシアニン系緑色顔料を含み、黄色顔料がＣ．Ｉ．ピグメントイエロー１８５およびＣ．Ｉ．ピグメントイエロー１５０を含む固体撮像素子用着色組成物に関する発明が記載されている。 Patent Document 1 describes a coloring composition for a solid-state imaging device containing a green pigment and a yellow pigment, wherein the green pigment contains a phthalocyanine-based green pigment and the yellow pigment is C.I. I. Pigment Yellow 185 and C.I. I. Inventions relating to a coloring composition for a solid-state image sensor containing Pigment Yellow 150 are described.
特開２０１５－０９６９１３号公報JP-A-2015-09613
　一般的に、着色剤として顔料を用いた着色組成物は、着色組成物の保管時に顔料が凝集して粘度が経時的に増加しやすい傾向にあった。特に複数の顔料を併用した着色組成物においては、粘度が経時的に増加しやすい傾向にあった。 In general, in a coloring composition using a pigment as a coloring agent, the pigment tends to aggregate during storage of the coloring composition and the viscosity tends to increase with time. In particular, in a coloring composition in which a plurality of pigments are used in combination, the viscosity tends to increase with time.
　また、本発明者の検討によれば、黄色顔料としてＣ．Ｉ．ピグメントイエロー１８５を用いることで、分光特性の良い膜が得られやすいものの、得られる膜の耐光性について改善の余地があることが分かった。 Further, according to the study of the present inventor, C.I. I. It was found that by using Pigment Yellow 185, although it is easy to obtain a film having good spectral characteristics, there is room for improvement in the light resistance of the obtained film.
　よって、本発明の目的は、保存安定性が良好で、耐光性および分光特性に優れた膜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、前述の着色組成物を用いた膜、カラーフィルタ、光センサおよび表示装置を提供することにある。 Therefore, an object of the present invention is to provide a colored composition capable of forming a film having good storage stability and excellent light resistance and spectral characteristics. Another object of the present invention is to provide a film, a color filter, an optical sensor and a display device using the above-mentioned coloring composition.
　本発明者の検討によれば、後述する着色組成物を用いることで上記目的を達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＞　着色剤と、樹脂と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
　上記着色剤は、黄色顔料を含み、
　上記黄色顔料は、カラーインデックスピグメントイエロー１８５と、カラーインデックスピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを含み、
　上記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が１０質量％以上である、着色組成物。
　＜２＞　上記着色剤中における上記黄色顔料の含有量が６０～１００質量％である、＜１＞に記載の着色組成物。
　＜３＞　上記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が４０質量％以上である、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　カラーインデックスピグメントイエロー１８５と上記イソインドリン系黄色顔料との合計の１００質量部に対して、上記アゾメチン系黄色顔料を１０～６０質量部含む、＜１＞～＜３＞のいずれか１つに記載の着色組成物。
　＜５＞　カラーインデックスピグメントイエロー１８５の１００質量部に対して、上記イソインドリン系黄色顔料を１０～７０質量部含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　上記イソインドリン系黄色顔料がカラーインデックスピグメントイエロー１３９であり、
　上記アゾメチン系黄色顔料がカラーインデックスピグメントイエロー１５０である、
　＜１＞～＜５＞のいずれか１つに記載の着色組成物。
　＜７＞　上記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が４０～７０質量％であり、カラーインデックスピグメントイエロー１３９の含有量が１０～３０質量％であり、カラーインデックスピグメントイエロー１５０の含有量が１０～３０質量％である、＜６＞に記載の着色組成物。
　＜８＞　上記光重合開始剤はオキシム化合物を含む、＜１＞～＜７＞のいずれか１つに記載の着色組成物。
　＜９＞　上記樹脂は、架橋性基を有する樹脂を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　上記樹脂は、環状エーテル基を有する樹脂を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１１＞　上記重合性化合物は、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートおよびこれらの変性体からなる群より選択される少なくとも１種を含む．＜１＞～＜１０＞のいずれか１つに記載の着色組成物。
　＜１２＞　上記着色組成物を用いて膜厚０．６μｍの膜を形成した際に、上記膜の波長４００～４７５ｎｍの範囲における透過率の平均値が４％未満であり、波長５５０～７００ｎｍの範囲における透過率の平均値が９０％以上である、＜１＞～＜１１＞のいずれか１つに記載の着色組成物。
　＜１３＞　黄色着色組成物である、＜１＞～＜１２＞のいずれか１つに記載の着色組成物。
　＜１４＞　＜１＞～＜１３＞のいずれか１つに記載の着色組成物を用いて得られる膜。
　＜１５＞　＜１４＞に記載の膜を含むカラーフィルタ。
　＜１６＞　＜１４＞に記載の膜を含む光センサ。
　＜１７＞　＜１４＞に記載の膜を含む表示装置。 According to the study of the present inventor, it has been found that the above object can be achieved by using the coloring composition described later, and the present invention has been completed. The present invention provides:
<1> A coloring composition containing a coloring agent, a resin, a polymerizable compound, and a photopolymerization initiator.
The colorant contains a yellow pigment and contains
The yellow pigment includes a color index pigment yellow 185, an isoindrin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment.
A coloring composition in which the content of Color Index Pigment Yellow 185 in the colorant is 10% by mass or more.
<2> The coloring composition according to <1>, wherein the content of the yellow pigment in the coloring agent is 60 to 100% by mass.
<3> The coloring composition according to <1> or <2>, wherein the content of Color Index Pigment Yellow 185 in the colorant is 40% by mass or more.
<4> Any one of <1> to <3>, which contains 10 to 60 parts by mass of the azomethine-based yellow pigment with respect to 100 parts by mass of the total of the color index pigment yellow 185 and the isoindoline-based yellow pigment. The coloring composition according to one.
<5> The coloring composition according to any one of <1> to <4>, which contains 10 to 70 parts by mass of the above-mentioned isoindoline-based yellow pigment with respect to 100 parts by mass of Color Index Pigment Yellow 185.
<6> The isoindoline-based yellow pigment is Color Index Pigment Yellow 139.
The azomethine-based yellow pigment is Color Index Pigment Yellow 150.
The coloring composition according to any one of <1> to <5>.
<7> The content of Color Index Pigment Yellow 185 in the colorant is 40 to 70% by mass, the content of Color Index Pigment Yellow 139 is 10 to 30% by mass, and the content of Color Index Pigment Yellow 150 is. The coloring composition according to <6>, wherein is 10 to 30% by mass.
<8> The coloring composition according to any one of <1> to <7>, wherein the photopolymerization initiator contains an oxime compound.
<9> The coloring composition according to any one of <1> to <8>, wherein the resin contains a resin having a crosslinkable group.
<10> The coloring composition according to any one of <1> to <8>, wherein the resin contains a resin having a cyclic ether group.
<11> The above-mentioned polymerizable compound contains at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and modified products thereof. The coloring composition according to any one of <1> to <10>.
<12> When a film having a film thickness of 0.6 μm is formed using the coloring composition, the average value of the transmittance of the film in the wavelength range of 400 to 475 nm is less than 4%, and the wavelength is 550 to 700 nm. The coloring composition according to any one of <1> to <11>, wherein the average value of the transmittance in the range is 90% or more.
<13> The coloring composition according to any one of <1> to <12>, which is a yellow coloring composition.
<14> A film obtained by using the coloring composition according to any one of <1> to <13>.
<15> A color filter containing the film according to <14>.
<16> An optical sensor including the film according to <14>.
<17> A display device including the film according to <14>.
　本発明によれば、保存安定性が良好で、耐光性および分光特性に優れた膜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、本発明は、着色組成物を用いた膜、カラーフィルタ、光センサおよび表示装置を提供することができる。 According to the present invention, it is possible to provide a colored composition having good storage stability and capable of forming a film having excellent light resistance and spectral characteristics. The present invention can also provide a film, a color filter, an optical sensor and a display device using the coloring composition.
　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 notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). 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).
As used herein, the term "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 exposure generally includes an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Allyl ”represents both allyl and / or methacrylic, and“ (meth) acryloyl ”represents both / or either acryloyl and methacrylic acid.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present 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＞
　本発明の着色組成物は、着色剤と、樹脂と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
　上記着色剤は、黄色顔料を含み、
　上記黄色顔料は、カラーインデックスピグメントイエロー１８５と、カラーインデックスピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを含み、
　上記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が１０質量％以上であることを特徴とする。 <Coloring composition>
The coloring composition of the present invention is a coloring composition containing a coloring agent, a resin, a polymerizable compound, and a photopolymerization initiator.
The colorant contains a yellow pigment and contains
The yellow pigment includes a color index pigment yellow 185, an isoindrin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment.
The content of Color Index Pigment Yellow 185 in the colorant is 10% by mass or more.
　本発明の着色組成物は、黄色顔料として、カラーインデックスピグメントイエロー１８５と、カラーインデックスピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを用い、かつ、着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が１０質量％以上あることにより、３種以上顔料を含んでいるにもかかわらず保存安定性が良好で、粘度の経時的な増加などを抑制でき、更には、本発明の着色組成物を用いることにより耐光性および分光特性に優れた膜を形成することができる。 The coloring composition of the present invention uses a color index pigment yellow 185, an isoindolin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment as the yellow pigment, and the color index pigment in the colorant. Since the content of yellow 185 is 10% by mass or more, the storage stability is good even though it contains three or more kinds of pigments, the increase in viscosity with time can be suppressed, and further, the present invention By using the coloring composition, a film having excellent light resistance and spectral characteristics can be formed.
　本発明の着色組成物は、黄色着色組成物であることが好ましい。具体的には、黄色カラーフィルタ用の着色組成物として好ましく用いることができる。 The coloring composition of the present invention is preferably a yellow coloring composition. Specifically, it can be preferably used as a coloring composition for a yellow color filter.
　本発明の着色組成物を用いて膜厚０．６μｍの膜を形成した際に、前述の膜の波長４００～４７５ｎｍの範囲における透過率の平均値が４％未満であり、波長５５０～７００ｎｍの範囲における透過率の平均値が９０％以上であることが好ましい。このような、分光特性を満たす膜は、黄色カラーフィルタとして好ましく用いられる。 When a film having a film thickness of 0.6 μm was formed using the coloring composition of the present invention, the average value of the transmittance of the above-mentioned film in the wavelength range of 400 to 475 nm was less than 4%, and the wavelength was 550 to 700 nm. It is preferable that the average value of the transmittance in the range is 90% or more. A film satisfying such spectral characteristics is preferably used as a yellow color filter.
　上記膜の波長４００～４７５ｎｍの範囲における透過率の平均値は３％未満であることが好ましく、２％未満であることがより好ましい。また、上記膜の波長５５０～７００ｎｍの範囲における透過率の平均値は９３％以上であることが好ましく、９５％以上であることがより好ましい。 The average value of the transmittance of the film in the wavelength range of 400 to 475 nm is preferably less than 3%, more preferably less than 2%. Further, the average value of the transmittance in the wavelength range of 550 to 700 nm of the film is preferably 93% or more, and more preferably 95% or more.
　また、上記の膜の透過率が５０％を示す波長は、波長４８５～５１５ｎｍの範囲に存在することが好ましく、波長４９０～５１０ｎｍの範囲に存在することがより好ましく、波長４９５～５０５ｎｍの範囲に存在することが更に好ましい。 Further, the wavelength at which the transmittance of the film exhibits 50% is preferably in the wavelength range of 485 to 515 nm, more preferably in the wavelength range of 490 to 510 nm, and in the wavelength range of 495 to 505 nm. It is more preferred to be present.
　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黄色顔料を含む着色剤を含有する。上記黄色顔料は、Ｃ．Ｉ．（カラーインデックス）ピグメントイエロー１８５と、Ｃ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを含む。以下、ピグメントイエロー１８５と、Ｃ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを合わせて特定黄色顔料ともいう。 << Colorant >>
The coloring composition of the present invention contains a coloring agent containing a yellow pigment. The yellow pigment is C.I. I. (Color Index) Pigment Yellow 185 and C.I. I. It contains an isoindoline-based yellow pigment other than Pigment Yellow 185 and an azomethine-based yellow pigment. Hereinafter, Pigment Yellow 185 and C.I. I. A combination of an isoindoline-based yellow pigment other than Pigment Yellow 185 and an azomethine-based yellow pigment is also referred to as a specific yellow pigment.
　黄色顔料の平均一次粒子径は、１～２００ｎｍが好ましい。下限は５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。上限は、１８０ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましく、１００ｎｍ以下が更に好ましい。黄色顔料の平均一次粒子径が上記範囲であれば、着色組成物の保存安定性をより良好なものとすることができる。なお、本明細書において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた画像写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本明細書における平均一次粒子径は、４００個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The average primary particle size of the yellow pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less. When the average primary particle size of the yellow pigment is in the above range, the storage stability of the coloring composition can be improved. In the present specification, the primary particle size of the pigment can be obtained from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present specification is an arithmetic average value of the primary particle diameter for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without aggregation.
　黄色顔料として用いられるＣ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１３９であることが好ましい。 C. used as a yellow pigment. I. Examples of the isoindoline-based yellow pigment other than Pigment Yellow 185 include C.I. I. Pigment Yellow 139 is preferred.
　黄色顔料として用いられるアゾメチン系黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１５０、Ｃ．Ｉ．ピグメントイエロー１１７、Ｃ．Ｉ．ピグメントイエロー１２９、Ｃ．Ｉ．ピグメントイエロー１５３などが挙げられ、Ｃ．Ｉ．ピグメントイエロー１５０であることが好ましい。また、アゾメチン系黄色顔料としては、下記構造のアゾバルビツール酸ニッケル錯体を用いることもできる。
Figure JPOXMLDOC01-appb-C000001
 Examples of the azomethine-based yellow pigment used as the yellow pigment include C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 153 and the like, and C.I. I. Pigment Yellow 150 is preferred. Further, as the azomethine-based yellow pigment, a nickel azobarbiturate complex having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000001
　また、黄色顔料には、上述した特定黄色顔料以外の他の黄色顔料を更に用いることもできる。他の黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１１３，１１４，１１５，１１６，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１３７，１３８，１４７，１４８，１５１，１５２，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２１５，２２８，２３１，２３２，２３３，２３４，２３５，２３６等が挙げられる。 Further, as the yellow pigment, a yellow pigment other than the above-mentioned specific yellow pigment can be further used. Other yellow pigments include C.I. 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, 98,100,101,104,106,108,113,114,115,116,118,119,120,123,125,126,127,128,137,138,147,148,151,152,154 155,156,161,162,164,166,167,168,169,170,171,172,174,175,176,177,179,180,181,182,187,188,193,194,199, 213,214,215,228,231,232, 233,234,235,236 and the like can be mentioned.
　また、他の黄色顔料として、特開２０１７－２０１００３号公報に記載の化合物、特開２０１７－１９７７１９号公報に記載の化合物、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６に記載の化合物、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５に記載の化合物、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０に記載の化合物、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２に記載の化合物、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、特開２０１８－２０３７９８号公報に記載のキノフタロン化合物、特開２０１８－０６２５７８号公報に記載のキノフタロン化合物、特許第６４３２０７６号公報に記載のキノフタロン化合物、特開２０１８－１５５８８１号公報に記載のキノフタロン化合物、特開２０１８－１１１７５７号公報に記載のキノフタロン化合物、特開２０１８－０４０８３５号公報に記載のキノフタロン化合物、特開２０１７－１９７６４０号公報に記載のキノフタロン化合物、特開２０１６－１４５２８２号公報に記載のキノフタロン化合物、特開２０１４－０８５５６５号公報に記載のキノフタロン化合物、特開２０１４－０２１１３９号公報に記載のキノフタロン化合物、特開２０１３－２０９６１４号公報に記載のキノフタロン化合物、特開２０１３－２０９４３５号公報に記載のキノフタロン化合物、特開２０１３－１８１０１５号公報に記載のキノフタロン化合物、特開２０１３－０６１６２２号公報に記載のキノフタロン化合物、特開２０１３－０３２４８６号公報に記載のキノフタロン化合物、特開２０１２－２２６１１０号公報に記載のキノフタロン化合物、特開２００８－０７４９８７号公報に記載のキノフタロン化合物、特開２００８－０８１５６５号公報に記載のキノフタロン化合物、特開２００８－０７４９８６号公報に記載のキノフタロン化合物、特開２００８－０７４９８５号公報に記載のキノフタロン化合物、特開２００８－０５０４２０号公報に記載のキノフタロン化合物、特開２００８－０３１２８１号公報に記載のキノフタロン化合物、特公昭４８－０３２７６５号公報に記載のキノフタロン化合物、特開２０１９－００８０１４号公報に記載のキノフタロン化合物、特許第６６０７４２７号公報に記載のキノフタロン化合物、韓国公開特許第１０－２０１４－００３４９６３号公報に記載の化合物、特開２０１７－０９５７０６号公報に記載の化合物、台湾特許出願公開第２０１９２０４９５号公報に記載の化合物、特許第６６０７４２７号公報に記載の化合物、特開２０２０－０３３５２１号公報に記載のキノフタロン二量体を用いることもできる。また、これらの化合物を多量体化したものも、色価向上の観点から好ましく用いられる。黄色顔料として、下記式（ＱＰ１）で表される化合物、下記式（ＱＰ２）で表される化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000002
 Further, as other yellow pigments, the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912. The compound described, the compound described in paragraphs 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, the compound described in paragraph numbers 0011 to 0062, 0139-0190 of JP-A-2017-171914, JP-A. The compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915, the quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-054339A, paragraph numbers 0013 of JP-A-2014-026228. The quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, the quinophthalone compound described in Patent No. 6432076, JP-A-2018-155881 The quinophthalone compound described in JP-A-2018-11757, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2017-197640, JP-A-2016 The quinophthalone compound described in JP-A-145282, the quinophthalone compound described in JP-A-2014-0855565, the quinophthalone compound described in JP-A-2014-0211139, the quinophthalone compound described in JP-A-2013-209614, and the present invention. The quinophthalone compound described in JP2013-209435, the quinophthalone compound described in JP2013-181015, the quinophthalone compound described in JP2013-061622, and the quinophthalone compound described in JP2013-032486. , A quinophthalone compound described in JP-A-2012-226110, a quinophthalone compound described in JP-A-2008-074987, a quinophthalone compound described in JP-A-2008-081565, and a quinophthalone compound described in JP-A-2008-074986. Kinophthalone compound, quinophthalone compound described in JP-A-2008-074985, quinophthalone compound described in JP-A-2008-054020, quinophthalone compound described in JP-A-2008-031281, Japanese Patent Application Laid-Open No. 2008-031281 The quinophthalone compound described in Japanese Patent Application Laid-Open No. 48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in Japanese Patent No. 6607427, and the quinophthalone compound described in Japanese Patent No. 10-2014-0034963. Compounds, compounds described in JP-A-2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, and quinophthalone dimer described in JP-A-2020-033521. You can also use the body. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value. As the yellow pigment, a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.
Figure JPOXMLDOC01-appb-C000002
　式（ＱＰ１）中、Ｘ１～Ｘ１６は各々独立に水素原子又はハロゲン原子を表し、Ｚ１は炭素数１～３のアルキレン基を表す。式（ＱＰ１）で表される化合物の具体例としては、特許第６４４３７１１号公報の段落番号００１６に記載されている化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000003
 In the formula (QP1), X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph No. 0016 of Japanese Patent No. 6443711.
Figure JPOXMLDOC01-appb-C000003
　式（ＱＰ２）中、Ｙ１～Ｙ３は、それぞれ独立にハロゲン原子を示す。ｎ、ｍは０～６の整数、ｐは０～５の整数を表す。（ｎ＋ｍ）は１以上である。式（ＱＰ２）で表される化合物の具体例としては、特許６４３２０７７号公報の段落番号００４７～００４８に記載されている化合物が挙げられる。 In the formula (QP2), Y1 to Y3 independently represent halogen atoms. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (N + m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
　本発明の着色組成物において、着色剤には、黄色顔料以外の着色剤（以下、他の着色剤ともいう）が含まれていてもよい。他の着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、紫色着色剤、オレンジ色着色剤などが挙げられる。他の着色剤は、顔料および染料のいずれでもよい。 In the coloring composition of the present invention, the coloring agent may contain a coloring agent other than the yellow pigment (hereinafter, also referred to as another coloring agent). Examples of other colorants include red colorants, green colorants, blue colorants, purple colorants, orange colorants and the like. The other colorant may be either a pigment or a dye.
　赤色着色剤としては、Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２６９，２７０，２７２，２７９，２９１，２９４，２９５，２９６，２９７等の赤色顔料が挙げられる。 As a red colorant, C.I. 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, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 Examples thereof include red pigments such as 294, 295, 296, and 297.
　また、赤色着色剤として、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化合物、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化合物、国際公開第２０１２／１０２３９９号に記載のジケトピロロピロール化合物、国際公開第２０１２／１１７９６５号に記載のジケトピロロピロール化合物、特開２０１２－２２９３４４号公報に記載のナフトールアゾ化合物、特許第６５１６１１９号公報に記載の赤色着色剤、特許第６５２５１０１号公報に記載の赤色着色剤、特開２０２０－０９０６３２号公報の段落番号０２２９に記載の臭素化ジケトピロロピロール化合物、韓国公開特許第１０－２０１９－０１４０７４１号公報に記載のアントラキノン化合物、韓国公開特許第１０－２０１９－０１４０７４４号公報に記載のアントラキノン化合物、特開２０２０－０７９３９６号公報に記載のペリレン化合物などを用いることもできる。また、赤色着色剤として、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。 Further, as a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolop according to paragraph Nos. 0016 to 0022 of Patent No. 6248838. Pyrol compound, diketopyrrolopyrrole compound described in International Publication No. 2012/102399, diketopyrrolopyrrole compound described in International Publication No. 2012/117956, naphtholazo compound described in JP-A-2012-229344, patent. The red colorant described in Japanese Patent No. 6516119, the red colorant described in Japanese Patent No. 6525101, the brominated diketopyrrolopyrrole compound described in paragraph No. 0229 of JP-A-2020-090632, Korean Publication No. 10 It is also possible to use the anthraquinone compound described in JP-A-2019-0140741, the anthraquinone compound described in Korean Publication No. 10-2019-0140744, the perylene compound described in JP-A-2020-07396, and the like. Further, as the red colorant, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.
　緑色着色剤としては、Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等の緑色顔料が挙げられる。また、緑色着色剤として、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、緑色着色剤として中国特許出願第１０６９０９０２７号明細書に記載の化合物、国際公開第２０１２／１０２３９５号に記載の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、特開２０１９－００８０１４号公報に記載のフタロシアニン化合物、特開２０１８－１８００２３号公報に記載のフタロシアニン化合物、特開２０１９－０３８９５８号公報に記載の化合物などを用いることもできる。また、緑色着色剤として、特開２０２０－０７６９９５号公報に記載のコアシェル型色素も使用することができる。 As a green colorant, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like green pigments can be mentioned. Further, as a green colorant, halogenated zinc phthalocyanine has an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green colorant, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphate ester as a ligand according to International Publication No. 2012/102395, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used. Further, as the green colorant, the core-shell type dye described in JP-A-2020-07695 can also be used.
　青色着色剤としては、Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等の青色顔料が挙げられる。 As a blue colorant, C.I. 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. Pigments can be mentioned.
　また、青色着色剤として、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号公報の段落番号００２２～００３０、特開２０１１－１５７４７８号公報の段落番号００４７に記載の化合物が挙げられる。また、緑色着色剤または青色着色剤とて、特表２０２０－５０４７５８号公報に記載の化合物を使用することができる。 Further, as the blue colorant, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A. Further, as the green colorant or the blue colorant, the compounds described in JP-A-2020-504758 can be used.
　紫色着色剤としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等の紫色顔料が挙げられる。 As a purple colorant, C.I. I. Pigment Violet 1,19,23,27,32,37,42,60,61 and other purple pigments can be mentioned.
　オレンジ色着色剤としては、Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等のオレンジ色顔料が挙げられる。 As an orange colorant, C.I. 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. The orange pigment of.
　着色組成物の全固形分中における着色剤の含有量は３０質量％以上であることが好ましく、３５質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。上限は、７５質量％以下が好ましく、７０質量％以下がより好ましく、６５質量％以下が更に好ましい。 The content of the colorant in the total solid content of the coloring composition is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less, still more preferably 65% by mass or less.
　着色剤中におけるＣ．Ｉ．ピグメントイエロー１８５の含有量は、１０質量％以上であり、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。上限は、７０質量%以下であることが好ましい。 C. in the colorant. I. The content of Pigment Yellow 185 is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. The upper limit is preferably 70% by mass or less.
　着色剤中におけるＣ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料の含有量（好ましくはＣ．Ｉ．ピグメントイエロー１３９の含有量）は、１０～３０質量％であることが好ましい。下限は１５質量％以上であることが好ましい。上限は、２８質量%以下であることが好ましい。 C. in the colorant. I. The content of the isoindoline-based yellow pigment other than Pigment Yellow 185 (preferably the content of CI Pigment Yellow 139) is preferably 10 to 30% by mass. The lower limit is preferably 15% by mass or more. The upper limit is preferably 28% by mass or less.
　着色剤中におけるアゾメチン系黄色顔料の含有量（好ましくはＣ．Ｉ．ピグメントイエロー１５０の含有量）は、１０～３０質量％であることが好ましい。下限は１５質量％以上であることが好ましい。上限は、２８質量%以下であることが好ましい。 The content of the azomethine-based yellow pigment (preferably the content of CI Pigment Yellow 150) in the colorant is preferably 10 to 30% by mass. The lower limit is preferably 15% by mass or more. The upper limit is preferably 28% by mass or less.
　着色剤中における黄色顔料の含有量は６０～１００質量％であることが好ましく、７５～１００質量％であることがより好ましく、９０～１００質量％であることが更に好ましく、実質的に黄色顔料のみであることが特に好ましい。なお、本明細書において、着色剤が実質的に黄色顔料のみである場合とは、着色剤中における黄色顔料の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることがより好ましく、１００質量％であることが更に好ましい。 The content of the yellow pigment in the colorant is preferably 60 to 100% by mass, more preferably 75 to 100% by mass, further preferably 90 to 100% by mass, and substantially yellow pigment. It is particularly preferable that it is only. In the present specification, the case where the colorant is substantially only a yellow pigment means that the content of the yellow pigment in the colorant is 99% by mass or more, and is 99.9% by mass or more. It is more preferably present, and even more preferably 100% by mass.
　着色剤中における上述した特定黄色顔料の含有量は７０～１００質量％であることが好ましく、８０～１００質量％であることがより好ましく、９０～１００質量％であることが更に好ましく、実質的に特定黄色顔料のみであることが特に好ましい。なお、本明細書において、着色剤が実質的に特定黄色顔料のみである場合とは、着色剤中における特定黄色顔料の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることがより好ましく、１００質量％であることが更に好ましい。 The content of the above-mentioned specific yellow pigment in the colorant is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and substantially. It is particularly preferable that only the specific yellow pigment is used. In the present specification, the case where the colorant is substantially only the specific yellow pigment means that the content of the specific yellow pigment in the colorant is 99% by mass or more, and is 99.9% by mass. The above is more preferable, and 100% by mass is further preferable.
　本発明の着色組成物は、Ｃ．Ｉ．ピグメントイエロー１８５と、Ｃ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料との合計１００質量部に対して、アゾメチン系黄色顔料を１０～６０質量部含むことが好ましい。この態様によれば耐光性をより向上できる。上限は、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましい。下限は、２０質量部以上であることが好ましく、３０質量部以上であることがより好ましい。 The coloring composition of the present invention is C.I. I. Pigment Yellow 185 and C.I. I. It is preferable to contain 10 to 60 parts by mass of the azomethine-based yellow pigment with respect to a total of 100 parts by mass of the isoindoline-based yellow pigment other than Pigment Yellow 185. According to this aspect, the light resistance can be further improved. The upper limit is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more.
　本発明の着色組成物は、Ｃ．Ｉ．ピグメントイエロー１８５の１００質量部に対して、Ｃ．Ｉ．ピグメントイエロー１８５以外のイソインドリン系黄色顔料を１０～７０質量部含むことが好ましい。この態様によれば、好適な分光を有する膜を形成することができる。上限は、６０質量部以下であることが好ましく、４０質量部以下であることがより好ましい。下限は、２０質量部以上であることが好ましく、３０質量部以上であることがより好ましい。 The coloring composition of the present invention is C.I. I. For 100 parts by mass of Pigment Yellow 185, C.I. I. It is preferable to contain 10 to 70 parts by mass of an isoindoline-based yellow pigment other than Pigment Yellow 185. According to this aspect, a film having a suitable spectroscopy can be formed. The upper limit is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more.
　本発明の着色組成物に用いられる着色剤は、着色剤中におけるＣ．Ｉ．ピグメントイエロー１８５の含有量が４０～７０質量％であり、Ｃ．Ｉ．ピグメントイエロー１３９の含有量が１０～３０質量％であり、Ｃ．Ｉ．ピグメントイエロー１５０の含有量が１０～３０質量％であることが好ましい。また、着色剤中におけるＣ．Ｉ．ピグメントイエロー１８５とＣ．Ｉ．ピグメントイエロー１３９とＣ．Ｉ．ピグメントイエロー１５０の合計の含有量は７５～１００質量％であることが好ましく、８５～１００質量％であることがより好ましく、９５～１００質量％であることが更に好ましい。このような着色剤を用いることで、上述した本発明の効果がより顕著に得られる。 The colorant used in the colorant of the present invention is C.I. I. The content of Pigment Yellow 185 is 40 to 70% by mass, and C.I. I. The content of Pigment Yellow 139 is 10 to 30% by mass, and C.I. I. The content of Pigment Yellow 150 is preferably 10 to 30% by mass. In addition, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 139 and C.I. I. The total content of Pigment Yellow 150 is preferably 75 to 100% by mass, more preferably 85 to 100% by mass, and even more preferably 95 to 100% by mass. By using such a colorant, the above-mentioned effect of the present invention can be obtained more remarkably.
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含む。樹脂は、例えば、顔料を着色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、主に顔料を着色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 the pigment in the coloring composition or for the purpose of a binder. The resin mainly used to disperse the pigment in the coloring composition is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than such an application.
　樹脂の重量平均分子量（Ｍｗ）は、３０００～２００００００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、４０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.
　樹脂としては、例えば、（メタ）アクリル樹脂、エポキシ樹脂、（メタ）アクリルアミド樹脂、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。また、特開２０１７－２０６６８９号公報の段落番号００４１～００６０に記載の樹脂、特開２０１８－０１０８５６号公報の段落番号００２２～００７１に記載の樹脂、特開２０１７－０５７２６５号公報に記載の樹脂、特開２０１７－０３２６８５号公報に記載の樹脂、特開２０１７－０７５２４８号公報に記載の樹脂、特開２０１７－０６６２４０号公報に記載の樹脂、特開２０１７－１７３７８７号公報に記載の樹脂を用いることもできる。 Examples of the resin include (meth) acrylic resin, epoxy resin, (meth) acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, and polyarylene. Examples thereof include ether phosphin oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. Further, the resin described in paragraphs 0041 to 0060 of JP-A-2017-206689, the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856, the resin described in JP-A-2017-057256, Use the resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, the resin described in JP-A-2017-066240, and the resin described in JP-A-2017-173787. You can also.
　樹脂としては、酸基を有する樹脂を用いることが好ましい。酸基としては、例えば、カルボキシ基、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。 As the resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like.
　酸基を有する樹脂の酸価は、３０～５００ｍｇＫＯＨ／ｇが好ましい。下限は、４０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上が特に好ましい。上限は、４００ｍｇＫＯＨ／ｇ以下がより好ましく、３００ｍｇＫＯＨ／ｇ以下が更に好ましく、２００ｍｇＫＯＨ／ｇ以下が特に好ましい。酸基を有する樹脂の重量平均分子量（Ｍｗ）は、５０００～１０００００が好ましく、５０００～５００００がより好ましい。また、酸基を有する樹脂の数平均分子量（Ｍｎ）は、１０００～２００００が好ましい。 The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 300 mgKOH / g or less, and particularly preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100,000, more preferably 5000 to 50000. The number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.
　酸基を有する樹脂は、酸基を側鎖に有する繰り返し単位を含むことが好ましく、酸基を側鎖に有する繰り返し単位を樹脂の全繰り返し単位中５～７０モル％含むことがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の上限は、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の下限は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましい。 The resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９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。また、酸基を有する樹脂は市販品を用いることもできる。また、樹脂への酸基の導入方法としては、特に制限はないが、例えば、特許第６３４９６２９号公報に記載の方法が挙げられる。更に、樹脂への酸基の導入方法としては、エポキシ基の開環反応で生じたヒドロキシ基に酸無水物を反応させて酸基を導入する方法も挙げられる。 Regarding the resin having an acid group, the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 0999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can also be used. The method for introducing an acid group into the resin is not particularly limited, and examples thereof include the method described in Japanese Patent No. 6349629. Further, as a method for introducing an acid group into a resin, there is also a method for introducing an acid group by reacting an acid anhydride with a hydroxy group generated by a ring opening reaction of an epoxy group.
　樹脂としては、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。）を含むモノマー成分に由来する繰り返し単位を含む樹脂を用いることも好ましい。 The resin is derived from a monomer component containing 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 preferable to use a resin containing a repeating unit.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　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-C000005
 　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）の詳細については、特開２０１０－１６８５３９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。 In the formula (ED1), R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
Figure JPOXMLDOC01-appb-C000005
 In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For the details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, and the contents thereof are incorporated in the present specification.
　エーテルダイマーの具体例としては、例えば、特開２０１３－０２９７６０号公報の段落番号０３１７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。 As a specific example of the ether dimer, for example, the description in paragraph No. 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.
　樹脂としては、式（Ｘ）で表される化合物由来の繰り返し単位を含む樹脂を用いることも好ましい。
Figure JPOXMLDOC01-appb-C000006
 　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。 As the resin, it is also preferable to use a resin containing a repeating unit derived from the compound represented by the formula (X).
Figure JPOXMLDOC01-appb-C000006
 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 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. 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 even more preferably an integer of 0 to 3.
　式（Ｘ）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。 Examples of the compound represented by the formula (X) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate. Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
　樹脂としては、架橋性基を有する樹脂を用いることも好ましい。架橋性基としては、エチレン性不飽和結合含有基および環状エーテル基が挙げられる。樹脂としては、環状エーテル基を有する樹脂を用いることが好ましい。 As the resin, it is also preferable to use a resin having a crosslinkable group. Examples of the crosslinkable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. As the resin, it is preferable to use a resin having a cyclic ether group.
　エチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられ、エポキシ基が好ましい。エポキシ基は、脂環式エポキシ基であってもよい。なお、脂環式エポキシ基とは、エポキシ環と飽和炭化水素環とが縮合した環状構造を有する１価の官能基のことを意味する。環状エーテル基は、式（ｅ－１）で表される基、および、式（ｅ－２）で表される基から選ばれる少なくとも１種であることが好ましく、耐湿性に優れた膜を形成しやすい理由から式（ｅ－２）で表される基であることがより好ましい。式（ｅ－１）のｎが０である場合は、式（ｅ－１）で表される基はエポキシ基であり、ｎが１である場合は、式（ｅ－１）で表される基はオキセタニル基である。また、式（ｅ－２）で表される基は脂環式エポキシ基である。
Figure JPOXMLDOC01-appb-C000007
 　式（ｅ－１）中、ＲＥ１は水素原子またはアルキル基を表し、ｎは０または１を表し、＊は結合手を表す；式（ｅ－２）中、環ＡＥ１は脂肪族炭化水素環を表し、＊は結合手を表す。 Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. The cyclic ether group is preferably at least one selected from the group represented by the formula (e-1) and the group represented by the formula (e-2), and forms a film having excellent moisture resistance. It is more preferable that the group is represented by the formula (e-2) because it is easy to use. When n in the formula (e-1) is 0, the group represented by the formula (e-1) is an epoxy group, and when n is 1, it is represented by the formula (e-1). The group is an oxetanyl group. The group represented by the formula (e-2) is an alicyclic epoxy group.
Figure JPOXMLDOC01-appb-C000007
 In formula (e-1), RE1 represents a hydrogen atom or an alkyl group, n represents 0 or 1, * represents a bond; in formula (e-2), ring A E1 represents an aliphatic hydrocarbon. It represents a ring, and * represents a bond.
　ＲＥ１が表す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が更に好ましく、１～３が特に好ましい。ＲＥ１が表すアルキル基は、直鎖または分岐であることが好ましく、直鎖であることがより好ましい。 The number of carbon atoms of the alkyl group represented by RE1 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group represented by RE1 is preferably linear or branched, and more preferably linear.
　ｎが０のとき、ＲＥ１は水素原子であることが好ましい。ｎが１のとき、ＲＥ１は水素原子または炭素数１～３のアルキル基であることが好ましい。 When n is 0, it is preferable that RE1 is a hydrogen atom. When n is 1, RE1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
　ここで、式（ｅ－１）のｎが０のとき、式（ｅ－１）は以下の式（ｅ－１ａ）で表される基である。
Figure JPOXMLDOC01-appb-C000008
 Here, when n in the formula (e-1) is 0, the formula (e-1) is a group represented by the following formula (e-1a).
Figure JPOXMLDOC01-appb-C000008
　式（ｅ－２）の環ＡＥ１が表す脂肪族炭化水素環は、単環の脂肪族炭化水素環であってもよく、縮合環の脂肪族炭化水素環であってもよい。また、環ＡＥ１が表す脂肪族炭化水素環は、架橋構造を有していてもよい。なかでも、耐湿性に優れた膜を形成しやすい理由から縮合環の脂肪族炭化水素環であることが好ましく、架橋構造を有する縮合環の脂肪族炭化水素環であることが好ましい。環ＡＥ１が表す脂肪族炭化水素環の具体例としては、以下に示す基が挙げられ、式（ｅ－２－３）で表される基および式（ｅ－２－４）で表される基が好ましい。以下の式中、＊は結合手を表す。
Figure JPOXMLDOC01-appb-C000009
 The aliphatic hydrocarbon ring represented by the ring AE1 of the formula (e-2) may be a monocyclic aliphatic hydrocarbon ring or an aliphatic hydrocarbon ring of a fused ring. Further, the aliphatic hydrocarbon ring represented by the ring A E1 may have a crosslinked structure. Among them, the aliphatic hydrocarbon ring of the condensed ring is preferable because it is easy to form a film having excellent moisture resistance, and the aliphatic hydrocarbon ring of the condensed ring having a crosslinked structure is preferable. Specific examples of the aliphatic hydrocarbon ring represented by the ring AE1 include the groups shown below, which are represented by the group represented by the formula (e-2-3) and the formula (e-2-4). Groups are preferred. In the following formula, * represents a bond.
Figure JPOXMLDOC01-appb-C000009
　環状エーテル基を有する樹脂としては、環状エーテル基を有する繰り返し単位を含む樹脂を用いることが好ましい。環状エーテル基を有する繰り返し単位としては、式（Ａ１）で表される繰り返し単位が挙げられる。
Figure JPOXMLDOC01-appb-C000010
 As the resin having a cyclic ether group, it is preferable to use a resin containing a repeating unit having a cyclic ether group. Examples of the repeating unit having a cyclic ether group include a repeating unit represented by the formula (A1).
Figure JPOXMLDOC01-appb-C000010
　式（Ａ１）において、Ｘａ１は３価の連結基を表し、Ｌａ１は単結合または２価の連結基を表し、Ｚａ１は環状エーテル基を表す。 In formula (A1), X a1 represents a trivalent linking group, La 1 represents a single bond or a divalent linking group, and Z a1 represents a cyclic ether group.
　式（Ａ１）のＸａ１が表す３価の連結基としては、ポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基、ポリエステル系連結基、ポリウレタン系連結基、ポリウレア系連結基、ポリアミド系連結基、ポリエーテル系連結基、ポリスチレン系連結基、ビスフェノール系連結基、ノボラック系連結基などが挙げられ、ポリ（メタ）アクリル系連結基、ポリエーテル系連結基、ポリエステル系連結基、ビスフェノール系連結基およびノボラック系連結基が好ましく、ポリエーテル系連結基、ノボラック系連結基およびポリ（メタ）アクリル系連結基がより好ましく、ポリ（メタ）アクリル系連結基が更に好ましい。 The trivalent linking group represented by Xa1 of the formula (A1) includes a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, and a polyamide-based linking group. Examples include a linking group, a polyether-based linking group, a polystyrene-based linking group, a bisphenol-based linking group, a novolak-based linking group, and a poly (meth) acrylic-based linking group, a polyether-based linking group, a polyester-based linking group, and a bisphenol-based linking group. The linking group and the novolak-based linking group are preferable, the polyether-based linking group, the novolak-based linking group and the poly (meth) acrylic-based linking group are more preferable, and the poly (meth) acrylic-based linking group is further preferable.
　式（Ａ１）のＬａ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－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。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、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、ヒドロキシ基、アルコキシ基などが挙げられる。 The divalent linking group represented by La1 of the formula ( A1 ) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and -NH-. , -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
　式（Ａ１）のＺａ１が表す環状エーテル基としては、エポキシ基およびオキセタニル基が挙げられ、エポキシ基であることが好ましい。また、Ｚａ１が表す環状エーテル基は、式（ｅ－１）で表される基、または、式（ｅ－２）で表される基であることが好ましく、式（ｅ－２）で表される基であることがより好ましい。 Examples of the cyclic ether group represented by Z a1 of the formula (A1) include an epoxy group and an oxetanyl group, and an epoxy group is preferable. Further, the cyclic ether group represented by Z a1 is preferably a group represented by the formula (e-1) or a group represented by the formula (e-2), and is represented by the formula (e-2). It is more preferable that it is a group to be used.
　環状エーテル基を有する樹脂中における環状エーテル基を有する繰り返し単位の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～１００モル％であることが好ましい。上限は９０モル％以下であることが好ましく、８０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 The content of the repeating unit having a cyclic ether group in the resin having a cyclic ether group is preferably 1 to 100 mol% in all the repeating units of the resin having a cyclic ether group. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
　環状エーテル基を有する樹脂は、環状エーテル基を有する繰り返し単位の他に他の繰り返し単位を有していてもよい。他の繰り返し単位としては、酸基を有する繰り返し単位（以下、繰り返し単位Ｂ－１ともいう）、酸基が保護基で保護された基を有する繰り返し単位（以下、繰り返し単位Ｂ－２ともいう）、エチレン性不飽和結合含有基を有する繰り返し単位（以下、繰り返し単位Ｂ－３）などが挙げられる。 The resin having a cyclic ether group may have another repeating unit in addition to the repeating unit having a cyclic ether group. Other repeating units include a repeating unit having an acid group (hereinafter, also referred to as a repeating unit B-1) and a repeating unit having a group in which the acid group is protected by a protective group (hereinafter, also referred to as a repeating unit B-2). , Repeating unit having an ethylenically unsaturated bond-containing group (hereinafter, repeating unit B-3) and the like.
　上記繰り返し単位Ｂ－１が有する酸基、および、上記繰り返し単位Ｂ－２における上記保護基で保護されている酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 Examples of the acid group contained in the repeating unit B-1 and the acid group protected by the protecting group in the repeating unit B-2 include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group. , A phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.
　上記繰り返し単位Ｂ－２における上記酸基を保護する保護基としては、酸または塩基の作用により分解して脱離する基が挙げられる。保護基は、式（Ｙ１）～（Ｙ５）のいずれかで表される基であることが好ましく、脱保護しやすいという理由から式（Ｙ３）または式（Ｙ５）で表される基であることがより好ましい。 Examples of the protecting group that protects the acid group in the repeating unit B-2 include a group that decomposes and is eliminated by the action of an acid or a base. The protecting group is preferably a group represented by any of the formulas (Y1) to (Y5), and is a group represented by the formula (Y3) or the formula (Y5) because it is easy to deprotect. Is more preferable.
　式（Ｙ１）：－Ｃ（ＲＹ１）（ＲＹ２）（ＲＹ３）
　式（Ｙ２）：－Ｃ（＝Ｏ）ＯＣ（ＲＹ４）（ＲＹ５）（ＲＹ６）
　式（Ｙ３）：－Ｃ（ＲＹ７）（ＲＹ８）（ＯＲＹ９）
　式（Ｙ４）：－Ｃ（ＲＹ１０）（Ｈ）（ＡｒＹ１）
　式（Ｙ５）：－Ｃ（＝Ｏ）（ＲＹ１１） Equation ( Y1 ): -C (RY1) ( RY2 ) ( RY3 )
Equation (Y2): -C (= O) OC ( RY4 ) ( RY5 ) ( RY6 )
Equation (Y3): -C ( RY7 ) ( RY8 ) (OR Y9 )
Equation (Y4): -C ( RY10 ) (H) (Ar Y1 )
Equation (Y5): -C (= O) ( RY11 )
　式（Ｙ１）中、ＲＹ１～ＲＹ３は、各々独立にアルキル基を表し、ＲＹ１～ＲＹ３のうちの２つが結合して環を形成していてもよい；
　式（Ｙ２）中、ＲＹ４～ＲＹ６は、各々独立にアルキル基を表し、ＲＹ４～ＲＹ６のうちの２つが結合して環を形成していてもよい；
　式（Ｙ３）中、ＲＹ７およびＲＹ８は、各々独立に、水素原子、アルキル基またはアリール基を表し、ＲＹ７およびＲＹ８の少なくとも一方がアルキル基またはアリール基であり、ＲＹ９は、アルキル基またはアリール基を表し、ＲＹ７またはＲＹ８と、ＲＹ９とが結合して環を形成していてもよい；
　式（Ｙ４）中、ＡｒＹ１は、アリール基を表し、ＲＹ１０は、アルキル基またはアリール基を表す；
　式（Ｙ５）中、ＲＹ１１は、アルキル基またはアリール基を表す。 In formula ( Y1 ), RY1 to RY3 each independently represent an alkyl group, and two of RY1 to RY3 may be bonded to form a ring;
In formula (Y2), RY4 to RY6 each independently represent an alkyl group, and two of RY4 to RY6 may be bonded to form a ring;
In formula (Y3), RY7 and RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of RY7 and RY8 is an alkyl group or an aryl group, and RY9 is an alkyl. Representing a group or aryl group, RY7 or RY8 and RY9 may be combined to form a ring;
In formula (Y4), Ar Y1 represents an aryl group and RY10 represents an alkyl or aryl group;
In formula (Y5), RY11 represents an alkyl or aryl group.
　式（Ｙ１）のＲＹ１～ＲＹ３が表すアルキル基の炭素数は、１～１２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、直鎖状、分岐状、環状のいずれでもよいが、直鎖状または分岐状であることが好ましい。式（Ｙ１）において、ＲＹ１～ＲＹ３の２つが結合して、環を形成してもよい。ＲＹ１～ＲＹ３の２つが結合して形成される環としては、シクロペンチル基やシクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基などの多環のシクロアルキル基が挙げられ、炭素数５～６の単環のシクロアルキル基であることが好ましい。また、上記のシクロアルキル基においては、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。 The number of carbon atoms of the alkyl group represented by RY1 to RY3 in the formula ( Y1 ) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. In the formula ( Y1 ), two of RY1 to RY3 may be combined to form a ring. The ring formed by combining the two of RY1 to RY3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl. Examples thereof include a polycyclic cycloalkyl group such as a group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. Further, in the above cycloalkyl group, one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
　式（Ｙ２）のＲＹ４～ＲＹ６が表すアルキル基の炭素数は、１～１２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、直鎖状、分岐状、環状のいずれでもよいが、直鎖状または分岐状であることが好ましい。式（Ｙ２）のＲＹ４～ＲＹ６のうち少なくとも２つはメチル基であることが好ましい。式（Ｙ２）において、ＲＹ４～ＲＹ６の２つが結合して、環を形成していてもよい。形成される環としては、式（Ｙ１）で説明した環が挙げられる。 The number of carbon atoms of the alkyl group represented by RY4 to RY6 in the formula (Y2) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. It is preferable that at least two of RY4 to RY6 of the formula (Y2) are methyl groups. In the formula (Y2), two of RY4 to RY6 may be combined to form a ring. Examples of the ring formed include the ring described by the formula (Y1).
　式（Ｙ３）中、ＲＹ７およびＲＹ８は、各々独立に、水素原子、アルキル基またはアリール基を表し、ＲＹ７およびＲＹ８の少なくとも一方がアルキル基またはアリール基であり、ＲＹ９は、アルキル基またはアリール基を表し、ＲＹ７またはＲＹ８と、ＲＹ９とが結合して環を形成してもよい。
アルキル基は、直鎖状、分岐状、環状のいずれでもよい。アルキル基の炭素数は１～１２であることが好ましく、１～６であることがより好ましく、１～４であることがさらに好ましい。アリール基の炭素数は６～２０が好ましく、６～１２がより好ましい。ＲＹ７またはＲＹ８と、ＲＹ９とが結合して形成される環としては、テトラヒドロフラニル基、テトラヒドロピラニル基等が挙げられる。式（Ｙ３）において、ＲＹ７またはＲＹ８と、ＲＹ９とが結合して環を形成していることが好ましい。また、ＲＹ７およびＲＹ８の一方は水素原子であることが好ましい。 In formula (Y3), RY7 and RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of RY7 and RY8 is an alkyl group or an aryl group, and RY9 is an alkyl. It represents a group or an aryl group, and RY7 or RY8 may be bonded to RY9 to form a ring.
The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the ring formed by binding RY7 or RY8 and RY9 include a tetrahydrofuranyl group and a tetrahydropyranyl group. In the formula (Y3), it is preferable that RY7 or RY8 and RY9 are combined to form a ring. Further, it is preferable that one of RY7 and RY8 is a hydrogen atom.
　式（Ｙ４）中、ＡｒＹ１は、アリール基を表し、ＲＹ１０は、アルキル基またはアリール基を表し、ＡｒＹ１とＲＹ１０とは互いに結合して環を形成してもよい。アルキル基の炭素数は１～１２であることが好ましく、１～６であることがより好ましく、１～４であることがさらに好ましい。アリール基の炭素数は６～２０が好ましく、６～１２がより好ましい。式（Ｙ４）においてＲＹ１０は、アルキル基であることが好ましい。 In the formula (Y4), Ar Y1 represents an aryl group, RY10 represents an alkyl group or an aryl group, and Ar Y1 and RY10 may be bonded to each other to form a ring. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. In formula (Y4), RY10 is preferably an alkyl group.
　式（Ｙ５）中、ＲＹ１１は、アルキル基またはアリール基を表し、アルキル基であることが好ましい。アルキル基の炭素数は１～１２であることが好ましく、１～６であることがより好ましく、１～４であることがさらに好ましい。アリール基の炭素数は６～２０が好ましく、６～１２がより好ましい。 In the formula (Y5), RY11 represents an alkyl group or an aryl group, and is preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
　保護基の分子量は４０～２００であることが好ましく、４０～１５０であることがより好ましく、４０～１２０であることが更に好ましい。保護基の分子量が上記範囲であれば保存安定性に優れ、かつ、低温での硬化性に優れた着色組成物とすることができる。 The molecular weight of the protecting group is preferably 40 to 200, more preferably 40 to 150, and even more preferably 40 to 120. When the molecular weight of the protecting group is within the above range, a coloring composition having excellent storage stability and excellent curability at a low temperature can be obtained.
　保護基の具体例としては、１－メトキシエチル基、１－エトキシエチル基、１－ｎ－プロポキシエチル基、１－ｎ－ブトキシエチル基、１－ｔ－ブトキシエチル基、１－シクロペンチルオキシエチル基、１－シクロヘキシルオキシエチル基、シクロヘキシル（メトキシ）メチル基、α－メトキシベンジル基、α－エトキシベンジル基、α－ｎ－プロポキシベンジル基、２－フェニル－１－メトキシエチル基、２－フェニル－１－エトキシエチル基、２－フェニル－１－ｉ－プロポキシエチル基、２－テトラヒドロフラニル基、２－テトラヒドロピラニル基が挙げられ、１－エトキシエチル基、１－シクロヘキシルオキシエチル基、２－テトラヒドロフラニル基、２－テトラヒドロピラニル基が好ましく、１－エトキシエチル基、１－シクロヘキシルオキシエチル基がより好ましい。 Specific examples of the protective group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group and 1-cyclopentyloxyethyl group. , 1-cyclohexyloxyethyl group, cyclohexyl (methoxy) methyl group, α-methoxybenzyl group, α-ethoxybenzyl group, α-n-propoxybenzyl group, 2-phenyl-1-methoxyethyl group, 2-phenyl-1 -Ethyl group, 2-phenyl-1-i-propoxyethyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 2-tetrahydrofuranyl A group and a 2-tetrahydropyranyl group are preferable, and a 1-ethoxyethyl group and a 1-cyclohexyloxyethyl group are more preferable.
　繰り返し単位Ｂ－３が有するエチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。 Examples of the ethylenically unsaturated bond-containing group of the repeating unit B-3 include a vinyl group, a styrene group, a (meth) allyl group, a (meth) acryloyl group, and the like.
　繰り返し単位Ｂ－１としては、下記式（Ｂ１）で表される繰り返し単位が挙げられる。また、繰り返し単位Ｂ－２としては、下記式（Ｂ２）で表される繰り返し単位が挙げられる。また、繰り返し単位Ｂ－３としては、下記式（Ｂ３）で表される繰り返し単位が挙げられる。
Figure JPOXMLDOC01-appb-C000011
 Examples of the repeating unit B-1 include a repeating unit represented by the following formula (B1). Further, as the repeating unit B-2, a repeating unit represented by the following formula (B2) can be mentioned. Further, as the repeating unit B-3, a repeating unit represented by the following formula (B3) can be mentioned.
Figure JPOXMLDOC01-appb-C000011
　式（Ｂ１）において、Ｘｂ１は３価の連結基を表し、Ｌｂ１は単結合または２価の連結基を表し、Ｚｂ１は酸基を表す。
　式（Ｂ２）において、Ｘｂ２は３価の連結基を表し、Ｌｂ２は単結合または２価の連結基を表し、Ｚｂ２は酸基が保護基で保護された基を表す。
　式（Ｂ３）において、Ｘｂ３は３価の連結基を表し、Ｌｂ３は単結合または２価の連結基を表し、Ｚｂ３はエチレン性不飽和結合含有基を表す。 In formula (B1), X b1 represents a trivalent linking group, L b1 represents a single bond or a divalent linking group, and Z b1 represents an acid group.
In formula (B2), X b2 represents a trivalent linking group, L b2 represents a single bond or a divalent linking group, and Z b2 represents a group in which the acid group is protected by a protecting group.
In formula (B3), X b3 represents a trivalent linking group, L b3 represents a single bond or a divalent linking group, and Z b3 represents an ethylenically unsaturated bond-containing group.
　式（Ｂ１）のＸｂ１が表す３価の連結基、式（Ｂ２）のＸｂ２が表す３価の連結基および式（Ｂ３）のＸｂ３が表す３価の連結基としては、特に限定はない。例えば、ポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基、ポリエステル系連結基、ポリウレタン系連結基、ポリウレア系連結基、ポリアミド系連結基、ポリエーテル系連結基、ポリスチレン系連結基、ビスフェノール系連結基、ノボラック系連結基などが挙げられ、ポリ（メタ）アクリル系連結基、ポリエーテル系連結基、ポリエステル系連結基、ビスフェノール系連結基およびノボラック系連結基が好ましく、ポリ（メタ）アクリル系連結基がより好ましい。 The trivalent linking group represented by X b1 of the formula (B1), the trivalent linking group represented by X b2 of the formula (B2), and the trivalent linking group represented by X b3 of the formula (B3) are not particularly limited. not. For example, poly (meth) acrylic linking group, polyalkyleneimine-based linking group, polyester-based linking group, polyurethane-based linking group, polyurea-based linking group, polyamide-based linking group, polyether-based linking group, polystyrene-based linking group, bisphenol. Examples thereof include a system-based linking group and a novolak-based linking group, and poly (meth) acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups and novolac-based linking groups are preferable, and poly (meth) acrylic is preferable. System linking groups are more preferred.
　式（Ｂ１）のＬｂ１が表す２価の連結基、式（Ｂ２）のＬｂ２が表す２価の連結基および式（Ｂ３）のＬｂ３が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－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。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、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、ヒドロキシ基、アルコキシ基などが挙げられる。 The divalent linking group represented by L b1 of the formula (B1), the divalent linking group represented by L b2 of the formula (B2), and the divalent linking group represented by L b3 of the formula (B3) include an alkylene group (as a divalent linking group). An alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- , -CO-, -O-, -COO. -, -OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
　式（Ｂ１）のＺｂ１が表す酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 Examples of the acid group represented by Z b1 of the formula (B1) include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and the acid group is a carboxy group. Is more preferable.
　式（Ｂ２）のＺｂ２が表す酸基が保護基で保護された基としては、酸基が上述した式（Ｙ１）～（Ｙ５）のいずれかで表される基で保護された基が挙げられる、酸基が式（Ｙ３）または式（Ｙ５）で表される基で保護された基であることが好ましい。上記酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 Examples of the group in which the acid group represented by Z b2 of the formula (B2) is protected by a protecting group include a group in which the acid group is protected by a group represented by any of the above-mentioned formulas (Y1) to (Y5). It is preferable that the acid group is a group protected by a group represented by the formula (Y3) or the formula (Y5). Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.
　式（Ｂ３）のＺｂ３が表すエチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。 Examples of the ethylenically unsaturated bond-containing group represented by Z b3 of the formula (B3) include a vinyl group, a styrene group, a (meth) allyl group, a (meth) acryloyl group and the like.
　環状エーテル基を有する樹脂が繰り返し単位Ｂ－１を含む場合、環状エーテル基を有する樹脂中における単位Ｂ－１の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中５～８５モル％であることが好ましい。上限は６０モル％以下であることが好ましく、４０モル％以下であることがより好ましい。下限は、８モル％以上が好ましく、１０モル％以上がより好ましい。 When the resin having a cyclic ether group contains the repeating unit B-1, the content of the unit B-1 in the resin having a cyclic ether group is 5 to 85 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have. The upper limit is preferably 60 mol% or less, more preferably 40 mol% or less. The lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.
　環状エーテル基を有する樹脂が繰り返し単位Ｂ－２を含む場合、環状エーテル基を有する樹脂中における単位Ｂ－２の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 When the resin having a cyclic ether group contains the repeating unit B-2, the content of the unit B-2 in the resin having a cyclic ether group is 1 to 65 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have. The upper limit is preferably 45 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
　環状エーテル基を有する樹脂が繰り返し単位Ｂ－１と繰り返し単位Ｂ－２とをそれぞれを含む場合、環状エーテル基を有する樹脂は、繰り返し単位Ｂ－１の１モルに対して繰り返し単位Ｂ－２を０．４～３．２モル含むことが好ましく、０．８～２．８モル含むことがより好ましく、１．２～２．４モル含むことが更に好ましい。 When the resin having a cyclic ether group contains the repeating unit B-1 and the repeating unit B-2, respectively, the resin having the cyclic ether group has the repeating unit B-2 for 1 mol of the repeating unit B-1. It preferably contains 0.4 to 3.2 mol, more preferably 0.8 to 2.8 mol, and even more preferably 1.2 to 2.4 mol.
　環状エーテル基を有する樹脂が繰り返し単位Ｂ－３を含む場合、環状エーテル基を有する樹脂中における単位Ｂ－３の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 When the resin having a cyclic ether group contains the repeating unit B-3, the content of the unit B-3 in the resin having a cyclic ether group is 1 to 65 mol% in all the repeating units of the resin having a cyclic ether group. It is preferable to have. The upper limit is preferably 45 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
　環状エーテル基を有する樹脂は、更に芳香族炭化水素環を有す繰り返し単位を含むことが好ましい。芳香族炭化水素環としては、ベンゼン環またはナフタレン環であることが好ましく、ベンゼン環であることが好ましい。芳香族炭化水素環は置換基を有していてもよい。置換基としては、アルキル基などが挙げられる。環状エーテル基を有する樹脂が、芳香族炭化水素環を有す繰り返し単位を含む場合、芳香族炭化水素環を有す繰り返し単位の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。芳香族炭化水素環を有す繰り返し単位としては、ビニルトルエン、ベンジル（メタ）アクリレートなどの芳香族炭化水素環を有する単官能の重合性化合物由来の繰り返し単位が挙げられる。 The resin having a cyclic ether group preferably further contains a repeating unit having an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group and the like. When the resin having a cyclic ether group contains a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 1 in all the repeating units of the resin having a cyclic ether group. It is preferably 65 mol%. The upper limit is preferably 45 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more. Examples of the repeating unit having an aromatic hydrocarbon ring include a repeating unit derived from a monofunctional polymerizable compound having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth) acrylate.
　環状エーテル基を有する樹脂の市販品としては、例えば、ナフタレン変性エポキシ樹脂として、ＥＰＩＣＬＯＮ　ＨＰ５０００、ＥＰＩＣＬＯＮ　ＨＰ４０３２Ｄ（以上、ＤＩＣ（株）製）などが挙げられる。アルキルジフェノール型エポキシ樹脂として、ＥＰＩＣＬＯＮ　８２０（ＤＩＣ（株）製）などが挙げられる。ビスフェノールＡ型エポキシ樹脂として、ｊＥＲ８２５、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１０５５、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０（以上、三菱ケミカル（株）製）、ＥＰＩＣＬＯＮ８６０、ＥＰＩＣＬＯＮ１０５０、ＥＰＩＣＬＯＮ１０５１、ＥＰＩＣＬＯＮ１０５５（以上、ＤＩＣ（株）製）等が挙げられる。ビスフェノールＦ型エポキシ樹脂として、ｊＥＲ８０６、ｊＥＲ８０７、ｊＥＲ４００４、ｊＥＲ４００５、ｊＥＲ４００７、ｊＥＲ４０１０（以上、三菱ケミカル（株）製）、ＥＰＩＣＬＯＮ８３０、ＥＰＩＣＬＯＮ８３５（以上、ＤＩＣ（株）製）、ＬＣＥ－２１、ＲＥ－６０２Ｓ（以上、日本化薬（株）製）等が挙げられる。フェノールノボラック型エポキシ樹脂として、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ１５７Ｓ６５（以上、三菱ケミカル（株）製）、ＥＰＩＣＬＯＮ　Ｎ－７４０、ＥＰＩＣＬＯＮ　Ｎ－７７０、ＥＰＩＣＬＯＮ　Ｎ－７７５（以上、ＤＩＣ（株）製）等が挙げられる。クレゾールノボラック型エポキシ樹脂として、ＥＰＩＣＬＯＮ　Ｎ－６６０、ＥＰＩＣＬＯＮ　Ｎ－６６５、ＥＰＩＣＬＯＮ　Ｎ－６７０、ＥＰＩＣＬＯＮ　Ｎ－６７３、ＥＰＩＣＬＯＮ　Ｎ－６８０、ＥＰＩＣＬＯＮ　Ｎ－６９０、ＥＰＩＣＬＯＮ　Ｎ－６９５（以上、ＤＩＣ（株）製）、ＥＯＣＮ－１０２０（日本化薬（株）製）等が挙げられる。脂肪族エポキシ樹脂として、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０８０Ｓ、同ＥＰ－４０８５Ｓ、同ＥＰ－４０８８Ｓ（以上、（株）ＡＤＥＫＡ製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、ＥＨＰＥ３１５０、ＥＰＯＬＥＡＤ　ＰＢ　３６００、ＥＰＯＬＥＡＤ　ＰＢ　４７００（以上、（株）ダイセル製）、デナコール　ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ（以上、ナガセケムテックス（株）製）等が挙げられる。また、環状エーテル基を有する樹脂としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６に記載された樹脂、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６に記載された樹脂、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された樹脂、特開２０１７－１７９１７２号公報に記載された樹脂、特開２０１８－１８００８１号公報の段落番号００２７～００５５、００９６に記載された樹脂、特表２０２０－５１５６８０号公報の段落番号０１１７～０１２０に記載された樹脂、国際公開第２０２０／１７５０１１号の段落番号００８４に記載された樹脂を用いることもできる。 Examples of commercially available resins having a cyclic ether group include naphthalene-modified epoxy resins such as EPICLON HP5000 and EPICLON HP4032D (all manufactured by DIC Corporation). Examples of the alkyldiphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation). As bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EP (Made by Co., Ltd.) and the like. Bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by DIC Corporation). As mentioned above, Nippon Kayaku Co., Ltd.) and the like can be mentioned. Phenolic novolak type epoxy resins include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Can be mentioned. As cresol novolak type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation). , EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), celoxide 2021P, celoxide 2081, celoxside 2083, celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPO Examples include PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation) and the like. Examples of the resin having a cyclic ether group include the resins described in paragraphs 0034 to 0036 of JP2013-011869, and the resins described in paragraphs 0147 to 0156 of JP2014-043556. The resin described in paragraph numbers 805 to 0092 of Japanese Patent Application Laid-Open No. 2014-089408, the resin described in Japanese Patent Application Laid-Open No. 2017-179172, and paragraph numbers 0027 to 0055,096 of Japanese Patent Application Laid-Open No. 2018-18801. Resins, the resins described in paragraphs 0117 to 0120 of JP-A-2020-515680, and the resins described in paragraph number 0084 of International Publication No. 2020/175011 can also be used.
　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好ましい。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％以上である樹脂が好ましい。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。 The coloring composition of the present invention preferably contains 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) represents a resin in which the amount of acid groups is larger than the amount of basic groups. As the acidic dispersant (acidic resin), a resin having an acid group content of 70 mol% or more is preferable when the total amount of the acid group and the basic group is 100 mol%. The acid group of the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、グラフト樹脂であることも好ましい。グラフト樹脂の詳細については、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as the dispersant is a graft resin. For details of the graft resin, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.
　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むポリイミン系分散剤であることも好ましい。ポリイミン系分散剤としては、ｐＫａ１４以下の官能基を有する部分構造を有する主鎖と、原子数４０～１００００の側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子は、塩基性を呈する窒素原子であれば特に制限はない。ポリイミン系分散剤については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. The resin to have is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えば、デンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１などが挙げられる。 It is also preferable that the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
　分散剤として用いる樹脂は、エチレン性不飽和結合含有基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合含有基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。 The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.
　また、分散剤として、特開２０１８－０８７９３９号公報に記載された樹脂、特許第６４３２０７７号公報の段落番号０２１９～０２２１に記載されたブロック共重合体（ＥＢ－１）～（ＥＢ－９）、国際公開第２０１６／１０４８０３号に記載のポリエステル側鎖を有するポリエチレンイミン、国際公開第２０１９／１２５９４０号に記載のブロック共重合体、特開２０２０－０６６６８７号公報に記載のアクリルアミド構造単位を有するブロックポリマー、特開２０２０－０６６６８８号公報に記載のアクリルアミド構造単位を有するブロックポリマー、国際公開第２０１６／１０４８０３号に記載の分散剤などを用いることもできる。 Further, as the dispersant, the resin described in JP-A-2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and the like. Polyethylenimine having a polyester side chain described in WO2016 / 104803, a block copolymer described in WO2019 / 125940, and a block polymer having an acrylamide structural unit described in JP-A-2020-06667. , Block polymers having an acrylamide structural unit described in JP-A-2020-066688, dispersants described in International Publication No. 2016/10403, and the like can also be used.
　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、１６１、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。 Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 161 and 2001) and Solspers manufactured by Japan Lubrizol Co., Ltd. Examples include a series (for example, Solspers 20000, 76500, etc.), an Ajinomoto Fine Techno Co., Ltd. Ajispar series, and the like. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 can also 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。本発明の着色組成物は、樹脂を、１種のみ含んでいてもよいし、２種以上含んでいてもよい。樹脂を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。 The resin content is preferably 5 to 50% by mass in the total solid content of the coloring composition. The upper limit is preferably 40% by mass or less, and more preferably 30% 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 may contain only one kind of resin, or may contain two or more kinds of resins. When two or more kinds of resins are contained, it is preferable that the total amount thereof is within the above range.
＜＜重合性化合物＞＞
　本発明の着色組成物は、重合性化合物を含有する。重合性化合物としては、エチレン性不飽和結合含有基を有する化合物などが挙げられる。エチレン性不飽和結合含有基としては、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。本発明で用いられる重合性化合物は、ラジカル重合性化合物であることが好ましい。 << Polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.
　重合性化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～３０００が好ましい。上限は、２０００以下が好ましく、１５００以下がより好ましい。下限は、１５０以上が好ましく、２５０以上がより好ましい。 The polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.
　重合性化合物のエチレン性不飽和結合含有基価（以下、Ｃ＝Ｃ価という）は、着色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。重合性化合物のＣ＝Ｃ価は、重合性化合物の１分子中に含まれるエチレン性不飽和結合含有基の数を重合性化合物の分子量で割ることで算出した値である。 The ethylenically unsaturated bond-containing base value (hereinafter referred to as C = C value) of the polymerizable compound is preferably 2 to 14 mmol / g from the viewpoint of the stability over time of the coloring composition. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less. The C = C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.
　重合性化合物は、エチレン性不飽和結合含有基を３個以上含む化合物であることが好ましく、エチレン性不飽和結合含有基を４個以上含む化合物であることがより好ましい。エチレン性不飽和結合含有基の上限は、着色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、重合性化合物は、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。 The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups. The upper limit of the ethylenically unsaturated bond-containing group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less, from the viewpoint of stability over time of the coloring composition. The polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and a 3 to 10 functional (meth) acrylate compound. It is more preferably present, and it is particularly preferable that it is a (meth) acrylate compound having 3 to 6 functions.
　重合性化合物としては、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートおよびこれらの化合物の変性体などが挙げられる。変性体としては、上記の化合物の（メタ）アクリロイル基がアルキレンオキシ基を介して結合している構造の化合物などが挙げられる。具体例としては、式（Ｚ－４）で表される化合物、式（Ｚ－５）で表される化合物などが挙げられる。 Examples of the polymerizable compound include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and modified products of these compounds. Can be mentioned. Examples of the modified product include compounds having a structure in which the (meth) acryloyl group of the above compound is bonded via an alkyleneoxy group. Specific examples include a compound represented by the formula (Z-4), a compound represented by the formula (Z-5), and the like.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ２）ｙＣＨ２Ｏ）－、又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、又はカルボキシ基を表す。式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In formulas (Z-4) and (Z-5), E is independently − ((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-. , Y each independently represents an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group. In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each of m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, where n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ２）ｙＣＨ２Ｏ）－又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
Further,-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-in the formula (Z-4) or the formula (Z-5) is on the oxygen atom side. The form in which the end of is bound to X is preferable.
　また、重合性化合物としては下記式（Ｚ－６）に示すようなポリペンタエリスリトールポリ（メタ）アクリレートを使用することもできる。
Figure JPOXMLDOC01-appb-C000013
 　式（Ｚ－６）中、Ｘ１～Ｘ６はそれぞれ独立して水素原子または（メタ）アクリロイル基を表し、ｎは１～１０の整数を表す。ただし、Ｘ１～Ｘ６の少なくとも一つは（メタ）アクリロイル基である。 Further, as the polymerizable compound, polypentaerythritol poly (meth) acrylate as shown in the following formula (Z-6) can also be used.
Figure JPOXMLDOC01-appb-C000013
 In formula (Z-6), X 1 to X 6 independently represent a hydrogen atom or a (meth) acryloyl group, and n represents an integer of 1 to 10. However, at least one of X 1 to X 6 is a (meth) acryloyl group.
　本発明で用いられる重合性化合物は、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ポリペンタエリスリトールポリ（メタ）アクリレートおよびこれらの変性体からなる群より選択される少なくとも１種であることが好ましい。市販品としては、ＫＡＹＡＲＡＤ　Ｄ－３１０、ＤＰＨＡ、ＤＰＥＡ－１２（以上、日本化薬（株）製）、ＮＫエステルＡ－ＤＰＨ－１２Ｅ、ＴＰＯＡ－５０（新中村化学工業（株）製）などが挙げられる。 The polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polypentaerythritol poly (meth) acrylate and modified products thereof. It is preferably a seed. Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (all manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, and TPOA-50 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Can be mentioned.
　また、重合性化合物としては、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としてはＭ－４６０；東亞合成製）、ペンタエリスリトールテトラ（メタ）アクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（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できる。 As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toagosei), pentaerythritol tetra (meth) acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. Can also be used.
　また、重合性化合物としては、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好ましい。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。 Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth). It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or 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, 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 Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
　また、重合性化合物としては、カルボキシ基、スルホ基、リン酸基等の酸基を有する化合物を用いることもできる。このような化合物の市販品としては、アロニックスＭ－３０５、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。 Further, as the polymerizable compound, a compound having an acid group such as a carboxy group, a sulfo group, and a phosphoric acid group can also be used. Examples of commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.
　また、重合性化合物としては、カプロラクトン構造を有する化合物を用いることもできる。カプロラクトン構造を有する化合物については、特開２０１３－２５３２２４号公報の段落００４２～００４５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。カプロラクトン構造を有する化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されている、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 Further, as the polymerizable compound, a compound having a caprolactone structure can also be used. For the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification. Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
　また、重合性化合物としては、フルオレン骨格を有する重合性化合物を用いることもできる。市販品としては、オグソールＥＡ－０２００、ＥＡ－０３００（大阪ガスケミカル（株）製、フルオレン骨格を有する（メタ）アクリレートモノマー）などが挙げられる。 Further, as the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. Examples of commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton).
　また、重合性化合物としては、トルエンなどの環境規制物質を実質的に含まない化合物を用いることも好ましい。このような化合物の市販品としては、ＫＡＹＡＲＡＤ　ＤＰＨＡ　ＬＴ、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２　ＬＴ（日本化薬（株）製）などが挙げられる。 Further, as the polymerizable compound, it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene. Examples of commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
　また、重合性化合物としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８号公報に記載されたエチレンオキサイド系骨格を有するウレタン化合物も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平０１－１０５２３８号公報に記載された分子内にアミノ構造やスルフィド構造を有する重合性化合物を用いることも好ましい。また、重合性化合物は、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００、ＬＩＮＣ－２０２ＵＡ（共栄社化学（株）製）などの市販品を用いることもできる。 Further, as the polymerizable compound, urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. Further, urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A No. 01-105238. The polymerizable compounds are UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
　重合性化合物の含有量は、着色組成物の全固形分中５～３５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。本発明の着色組成物は、重合性化合物を、１種のみ含んでいてもよいし、２種以上含んでいてもよい。重合性化合物を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。 The content of the polymerizable compound is preferably 5 to 35% by mass in the total solid content of the coloring composition. The upper limit is preferably 30% by mass or less, and 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 may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more kinds of polymerizable compounds are contained, it is preferable that the total amount thereof is in the above range.
＜＜光重合開始剤＞＞
　着色組成物は光重合開始剤を含むことが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視光領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 << Photopolymerization Initiator >>
The coloring composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible light region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.
　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）、アシルホスフィン化合物、ヘキサアリールビイミダゾール、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、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～０１１１、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤、特開２０２０－０５５９９２号公報に記載のオキサゾリジン基を有するアミノアセトフェノン系開始剤、特開２０１３－１９０４５９号公報に記載のオキシム系光重合開始剤などが挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an α-hydroxyketone compound. , Α-Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable. Further, as the photopolymerization initiator, the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864. The photopolymerization initiator described in JP-A-2019-044030, the peroxide-based initiator described in JP-A-2019-167313, JP-A-2020-055992. Examples thereof include the above-mentioned aminoacetophenone-based initiators having an oxazolidine group, the oxime-based photopolymerization initiators described in JP-A-2013-190459, and the contents thereof are incorporated in the present specification.
　α－ヒドロキシケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　１８４、Ｏｍｎｉｒａｄ　１１７３、Ｏｍｎｉｒａｄ　２９５９、Ｏｍｎｉｒａｄ　１２７（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　１８４、Ｉｒｇａｃｕｒｅ　１１７３、Ｉｒｇａｃｕｒｅ　２９５９、Ｉｒｇａｃｕｒｅ　１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　９０７、Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３６９Ｅ、Ｏｍｎｉｒａｄ　３７９ＥＧ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　９０７、Ｉｒｇａｃｕｒｅ　３６９、Ｉｒｇａｃｕｒｅ　３６９Ｅ、Ｉｒｇａｃｕｒｅ　３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、Ｏｍｎｉｒａｄ　８１９、Ｏｍｎｉｒａｄ　ＴＰＯ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　８１９、Ｉｒｇａｃｕｒｅ　ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
　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、国際公開第２０１３／１６７５１５号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、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、１－［４－（フェニルチオ）フェニル］－３－シクロヘキシル－プロパン－１，２－ジオン－２－（Ｏ－アセチルオキシム）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、ＴＲ－ＰＢＧ－３２７（トロンリー社製）、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。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017. The compound described in / 051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515, etc. Can be mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxyimine Examples thereof include -1-phenylpropane-1-one and 1- [4- (phenylthio) phenyl] -3-cyclohexyl-propane-1,2-dione-2- (O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronley), ADEKA PTOMER N-1919 (Co., Ltd.). ) A photopolymerization initiator 2) manufactured by ADEKA and described in JP2012-014552A. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and difficult to discolor. Examples of commercially available products include ADEKA ARCLUS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
　光重合開始剤としては、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、特許６６３６０８１号公報に記載の化合物、韓国公開特許第１０－２０１６－０１０９４４４号公報に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Patent Publication No. 10-2016-0109444. Will be.
　光重合開始剤としては、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。 As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
　光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。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。 As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like can be mentioned.
　光重合開始剤としては、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に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).
　光重合開始剤としては、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号に記載されているＯＥ－０１～ＯＥ－７５が挙げられる。 As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
　光重合開始剤としては、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。このような光重合開始剤としては国際公開第２０１９／０８８０５５号に記載された化合物などが挙げられる。 As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
　光重合開始剤としては、芳香族環に電子求引性基が導入された芳香族環基ＡｒＯＸ１を有するオキシム化合物（以下、オキシム化合物ＯＸともいう）を用いることもできる。上記芳香族環基ＡｒＯＸ１が有する電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。ベンゾイル基は、置換基を有していてもよい。置換基としては、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルケニル基、アルキルスルファニル基、アリールスルファニル基、アシル基またはアミノ基であることが好ましく、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基またはアミノ基であることがより好ましく、アルコキシ基、アルキルスルファニル基またはアミノ基であることが更に好ましい。 As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. Examples of the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group. An acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzoyl group is further preferable, because it is easy to form a film having excellent light resistance. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group. It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
　オキシム化合物ＯＸは、式（ＯＸ１）で表される化合物および式（ＯＸ２）で表される化合物から選ばれる少なくとも１種であることが好ましく、式（ＯＸ２）で表される化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000014
 　式中、ＲＸ１は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
　ＲＸ２は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
　ＲＸ３～ＲＸ１４は、それぞれ独立して水素原子または置換基を表す；
　ただし、ＲＸ１０～ＲＸ１４のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
Figure JPOXMLDOC01-appb-C000014
 In the formula, RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. Represents a group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group.
RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
RX3 to RX14 independently represent hydrogen atoms or substituents;
However, at least one of RX10 to RX14 is an electron-withdrawing group.
　上記式において、ＲＸ１２が電子求引性基であり、ＲＸ１０、ＲＸ１１、ＲＸ１３、ＲＸ１４は水素原子であることが好ましい。 In the above formula, it is preferable that RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 , and RX14 are hydrogen atoms.
　オキシム化合物ＯＸの具体例としては、特許第４６００６００号公報の段落番号００８３～０１０５に記載の化合物が挙げられる。 Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
　本発明において好ましく使用される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 preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１０００～３０００００であることがより好ましく、２０００～３０００００であることが更に好ましく、５０００～２０００００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
　光重合開始剤としては、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して有機溶剤などへの溶解性が向上して、経時で析出しにくくなり、着色組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開第２０１７／０３３６８０号の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）、特許第６４６９６６９号公報に記載されているオキシムエステル光開始剤などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in an organic solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the coloring composition with time is improved. can. Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Dimerics of oxime compounds described in paragraphs 0407 to 0412, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP-A-2013-522445. G), Cmpd1-7 described in International Publication No. 2016/034943, Oxime Esters Photoinitiator described in paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, is described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators.
　着色組成物の全固形分中における光重合開始剤の含有量は０．１～３０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、２０質量％以下が好ましく、１５質量％以下がより好ましい。着色組成物において、光重合開始剤は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、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. In the coloring composition, only one kind of photopolymerization initiator may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is 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、３－ペンタノン、４－ヘプタノン、シクロヘキサノン、２－メチルシクロヘキサノン、３－メチルシクロヘキサノン、４－メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、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、プロピレングリコールジアセテート、３－メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、１，４－ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン－１，３－ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール（ダイアセトンアルコール、４－ヒドロキシ－４－メチル－２－ペンタノン）などが挙げられる。ただし有機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 organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. For these details, paragraph 0223 of International Publication No. 2015/166779 can be referred to, 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, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methylethylketone, Gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane diacetate-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol (diacetone alcohol, 4- Hydroxy-4-methyl-2-pentanone) and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) 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）。 In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts per tension) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical 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、ポリテトラフルオロエチレン、ポリエチレンまたはナイロンが好ましい。 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 diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material 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 kind of isomer may be contained, or a plurality of kinds 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。 In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of 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、それらの合計量が上記範囲となることが好ましい。 The content of the solvent in the coloring composition is preferably 60 to 95% by mass. The upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and further preferably 85% by mass or less. The lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more. The solvent may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.
　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剤として用いられることがあり、残留溶剤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剤と同等の沸点を有する溶剤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。 Further, it is preferable that the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations. In the present invention, substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evolution Analysis and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) method, VOC (Volatile and Transfer Registor) method, VOC (Volatile Organic Compounds), and VOC (Volatile Organic Compounds). The method is strictly regulated. These compounds may be used as a solvent in producing each component used in the coloring composition of the present invention, and may be mixed in the coloring composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally regulated substance, there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency. When a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be. These distillation methods are either a raw material step, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a colored composition step prepared by mixing these compounds. It is also possible at the stage of.
＜＜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。顔料誘導体は例えば分散助剤として用いられる。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。 << Pigment derivative >>
The coloring composition of the present invention can contain a pigment derivative. Pigment derivatives are used, for example, as dispersion aids. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
　顔料誘導体を構成する色素骨格としては、スクアリリウム色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、キナクリドン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、ベンゾイソインドール色素骨格、チアジンインジゴ色素骨格、アゾ色素骨格、キノフタロン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、ジオキサジン色素骨格、ペリレン色素骨格、ペリノン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾチアゾール色素骨格、ベンゾイミダゾール色素骨格およびベンゾオキサゾール色素骨格が挙げられ、スクアリリウム色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、フタロシアニン色素骨格、キナクリドン色素骨格およびベンゾイミダゾロン色素骨格が好ましく、スクアリリウム色素骨格およびピロロピロール色素骨格がより好ましい。 The pigment skeletons constituting the pigment derivatives include squarylium pigment skeleton, pyrolopyrrolop pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzoisoindole pigment skeleton, and thiazine indigo pigment skeleton. , Azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzoimidazolone pigment skeleton, benzothiazole pigment skeleton, benzoimidazole pigment skeleton and benzoxazole pigment skeleton The squarylium pigment skeleton, the pyrolopyrrolop pigment skeleton, the diketopyrrolopyrrole pigment skeleton, the phthalocyanine pigment skeleton, the quinacridone pigment skeleton and the benzoimidazolone pigment skeleton are preferable, and the squarylium pigment skeleton and the pyrolopyrrolop pigment skeleton are more preferable.
　酸基としては、カルボキシ基、スルホ基、リン酸基、ボロン酸基、カルボン酸アミド基、スルホンアミド基、イミド酸基及びこれらの塩等が挙げられる。塩を構成する原子または原子団としては、アルカリ金属イオン（Ｌｉ＋、Ｎａ＋、Ｋ＋など）、アルカリ土類金属イオン（Ｃａ２＋、Ｍｇ２＋など）、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。カルボン酸アミド基としては、－ＮＨＣＯＲＸ１で表される基が好ましい。スルホンアミド基としては、－ＮＨＳＯ２ＲＸ２で表される基が好ましい。イミド酸基としては、－ＳＯ２ＮＨＳＯ２ＲＸ３、－ＣＯＮＨＳＯ２ＲＸ４、－ＣＯＮＨＣＯＲＸ５または－ＳＯ２ＮＨＣＯＲＸ６で表される基が好ましく、－ＳＯ２ＮＨＳＯ２ＲＸ３がより好ましい。ＲＸ１～ＲＸ６は、それぞれ独立に、アルキル基またはアリール基を表す。ＲＸ１～ＲＸ６が表すアルキル基及びアリール基は、置換基を有してもよい。置換基としてはハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。 Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imic acid group and salts thereof. As the atoms or atomic groups constituting the salt, alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, etc. Examples include phosphonium ions. As the carboxylic acid amide group, a group represented by -NHCOR X1 is preferable. As the sulfonamide group, a group represented by -NHSO 2 RX2 is preferable. As the imidic acid group, a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable, and -SO 2 NHSO 2 R X3 is more preferable. RX1 to RX6 independently represent an alkyl group or an aryl group, respectively. The alkyl group and aryl group represented by RX1 to RX6 may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.
　塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。 Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group. Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
　顔料誘導体の具体例としては、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平０１－２１７０７７号公報、特開平０３－００９９６１号公報、特開平０３－０２６７６７号公報、特開平０３－１５３７８０号公報、特開平０３－０４５６６２号公報、特開平０４－２８５６６９号公報、特開平０６－１４５５４６号公報、特開平０６－２１２０８８号公報、特開平０６－２４０１５８号公報、特開平１０－０３００６３号公報、特開平１０－１９５３２６号公報、国際公開第２０１１／０２４８９６号の段落番号００８６～００９８、国際公開第２０１２／１０２３９９号の段落番号００６３～００９４に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 Specific examples of the pigment derivative include JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-09961 and JP-A-03-026767. Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-405662, Japanese Patent Application Laid-Open No. 04-285646, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, JP-A. Examples thereof include the compounds described in Japanese Patent Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, paragraph numbers 0086 to 0998 of International Publication No. 2011/024896, and paragraph numbers 0063 to 0094 of International Publication No. 2012/102399. The contents of are incorporated herein by reference.
　顔料誘導体の含有量は、顔料１００質量部に対し、０．１～３０質量部が好ましい。この範囲の下限は、０．２５質量部以上であることがより好ましく、０．５質量部以上であることがさらに好ましく、０．７５質量部以上であることが特に好ましく、１質量部以上であることが一層好ましい。また、この範囲の上限は、２５質量部以下であることがより好ましく、２０質量部以下であることがさらに好ましく、１５質量部以下であることが特に好ましい。顔料誘導体の含有量が上記範囲内であることにより、着色組成物の保存安定性をより向上させることができる。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。２種以上を併用する場合は、それらの合計量が上記範囲となることが好ましい。 The content of the pigment derivative is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment. The lower limit of this range is more preferably 0.25 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable to have. Further, the upper limit of this range is more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content of the pigment derivative is within the above range, the storage stability of the coloring composition can be further improved. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination. When two or more kinds are used in combination, it is preferable that the total amount thereof is within the above range.
＜＜硬化促進剤＞＞
　本発明の着色組成物は、重合性化合物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-C000017
 （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 >>
In the coloring composition of the present invention, a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the 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 compound, and more preferably a compound represented by the formula (T1).
Equation (T1)
Figure JPOXMLDOC01-appb-C000017
 (In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valences.)
　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２０１３－０４１１６５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２０１４－０５５１１４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２０１５－０３４９６３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）、多価カルボン酸などを用いることもできる。多価カルボン酸としては、コハク酸、トリメリット酸、ピロメリット酸、Ｎ，Ｎ－ジメチル－４－アミノピリジン、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）などが挙げられる。また、硬化促進剤には、特開２０１６－０７５７２０号公報の段落番号００７２～００７８に記載の化合物、特開２０１７－０３６３７９号公報に記載の化合物を用いることもできる。 Further, the curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example. A curing agent described in paragraph No. 0186 of JP2013-041165A, a base generator (eg, an ionic compound described in JP2014-0551114), a cyanate compound (eg, JP2012-150180). A compound described in paragraph No. 0071 of JP-A), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504), and an onium salt compound (eg, JP-A-2015-034963). Compounds exemplified as acid generators in paragraph No. 0216, compounds described in JP-A-2009-180949), polyvalent carboxylic acids and the like can also be used. Examples of the polyvalent carboxylic acid include succinic acid, trimellitic acid, pyromellitic acid, N, N-dimethyl-4-aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate) and the like. Further, as the curing accelerator, the compounds described in paragraphs 0072 to 0078 of JP-A-2016-07520 and the compounds described in JP-A-2017-036379 can also 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 0.3 to 8.9% by mass, preferably 0.8 to 6.4% by mass in the total solid content of the coloring composition. More preferably by mass.
＜＜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 reactivity 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 methacrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having and is preferable. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N-2- (aminoethyl) -3. -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBE-903) manufactured by Kagaku Kogyo Co., Ltd., 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) , KBM-403) and the like. For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification. 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, preferably 0.01 to 10% by mass, based on the total solid content of the coloring composition. Is more preferable, and 0.1% by mass to 5% by mass is particularly preferable. The coloring composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
＜＜酸化防止剤＞＞
　本発明の着色組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位（オルト位）に置換基を有する化合物が好ましい。前述の置換基としては炭素数１～２２の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。また、酸化防止剤は、韓国公開特許第１０－２０１９－００５９３７１号公報に記載の化合物を用いることもできる。着色組成物の全固形分中における酸化防止剤の含有量は、０．０１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましい。本発明の着色組成物は、酸化防止剤を、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。 << Antioxidant >>
The coloring composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Further, as the antioxidant, the compound described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. The coloring composition of the present invention may contain only one kind of antioxidant, or may contain two or more kinds of antioxidants. When two or more kinds are contained, it is preferable that the total amount thereof is 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), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.). 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 of the polymerization inhibitor. When two or more kinds are contained, it is preferable that the total amount thereof is 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 and the like can be used. For details thereof, refer to paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. It can be taken into consideration and these contents are incorporated in the present specification. Examples of commercially available products of ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is preferable, and 0.1 to 3% by mass is particularly preferable. Further, as the ultraviolet absorber, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is 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、シリコー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に記載された界面活性剤が挙げられ、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 silicone-based surfactant can be used. As for the surfactant, the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
　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。 In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the coloring composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
　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。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, 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（対応する国際公開第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、特開２０２０－００８６３４号公報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Ｆ－１７１、Ｆ－１７２、Ｆ－１７３、Ｆ－１７６、Ｆ－１７７、Ｆ－１４１、Ｆ－１４２、Ｆ－１４３、Ｆ－１４４、Ｆ－４３７、Ｆ－４７５、Ｆ－４７７、Ｆ－４７９、Ｆ－４８２、Ｆ－５５４、Ｆ－５５５－Ａ、Ｆ－５５６、Ｆ－５５７、Ｆ－５５８、Ｆ－５５９、Ｆ－５６０、Ｆ－５６１、Ｆ－５６５、Ｆ－５６３、Ｆ－５６８、Ｆ－５７５、Ｆ－７８０、ＥＸＰ、ＭＦＳ－３３０、Ｒ－０１、Ｒ－４０、Ｒ－４０－ＬＭ、Ｒ－４１、Ｒ－４１－ＬＭ、ＲＳ－４３、ＴＦ－１９５６、ＲＳ－９０、Ｒ－９４、ＲＳ－７２－Ｋ、ＤＳ－２１（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、ＡＧＣ（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）、フタージェント２０８Ｇ、２１５Ｍ、２４５Ｆ、６０１ＡＤ、６０１ＡＤＨ２、６０２Ａ、６１０ＦＭ、７１０ＦＬ、７１０ＦＭ、７１０ＦＳ、ＦＴＸ－２１８、（以上、株）ＮＥＯＳ製）等が挙げられる。 Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560. , F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -141-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo) 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Surfactant 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710F , (Above, manufactured by NEOS Co., Ltd.) 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。 Further, the fluorine-based surfactant has 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 and the fluorine atom volatilizes when heat is applied. Can be suitably used. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
　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号公報に記載されたフッ素系界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 Further, as the fluorine-based surfactant, it is also 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. Examples of such a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
　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。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。また、特開２０１０－０３２６９８号公報の段落番号００１６～００３７に記載されたフッ素含有界面活性剤や、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-C000018
 　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. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
Figure JPOXMLDOC01-appb-C000018
 The weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和結合含有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、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。また、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。 Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
　また、国際公開第２０２０／０８４８５４号に記載の界面活性剤を、炭素数６以上のパーフルオロアルキル基を有する界面活性剤の代替として用いることも、環境規制の観点から好ましい。 It is also preferable from the viewpoint of environmental regulation to use the surfactant described in International Publication No. 2020/088454 as a substitute for the surfactant having a perfluoroalkyl group having 6 or more carbon atoms.
　また、式（ｆｉ－１）で表される含フッ素イミド塩化合物を界面活性剤として用いることも好ましい。
Figure JPOXMLDOC01-appb-C000019
 　式（ｆｉ－１）において、ｍは１または２を表し、ｎは１～４の整数を表し、αは１または２を表し、Ｘα＋はα価の金属イオン、第１級アンモニウムイオン、第２級アンモニウムイオン、第３級アンモニウムイオン、第４級アンモニウムイオンまたはＮＨ４ ＋を表す。 It is also preferable to use a fluorine-containing imide salt compound represented by the formula (fi-1) as a surfactant.
Figure JPOXMLDOC01-appb-C000019
 In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, α represents 1 or 2, and X α + represents an α-valent metal ion, a primary ammonium ion, and a first. Represents a secondary ammonium ion, a tertiary ammonium ion , a quaternary ammonium ion or NH 4+ .
　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。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.
　シリコーン系界面活性剤としては、例えば、ＤＯＷＳＩＬ　ＳＨ　８４００　ＦＬＵＩＤ、ＤＯＷＳＩＬ　ＳＦ　８４１９　ＯＩＬ、ＦＺ－２１２２（以上、ダウ・東レ（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）、ＢＹＫ－３０７、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３３０、ＢＹＫ－３７６０、ＢＹＫ－ＵＶ３５１０（以上、ビックケミー社製）等が挙げられる。 Examples of the silicone-based surfactant include DOWNSIL SH 8400 FLUID, DOWNSIL SF 8419 OIL, FZ-2122 (all manufactured by Dow Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460. , TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK- 323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by Big Chemie) and the like can be mentioned.
　また、シリコーン系界面活性剤には下記構造の化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000020
 Further, a compound having the following structure can also be used as the silicone-based surfactant.
Figure JPOXMLDOC01-appb-C000020
　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質量％～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、合計量が上記範囲となることが好ましい。 The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, 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 types, it is preferable that the total amount is within the above range.
＜＜その他成分＞＞
　本発明の着色組成物は、必要に応じて、増感剤、硬化促進剤、熱硬化促進剤、可塑剤及びその他の助剤類（例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、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。潜在酸化防止剤の市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。 << Other ingredients >>
The coloring composition of the present invention may be used as a sensitizer, a curing accelerator, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a flame retardant), if necessary. , Leveling agent, peeling accelerator, fragrance, surface tension adjusting agent, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. In addition, the coloring composition may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
　本発明の着色組成物は、耐光性改良剤を含んでもよい。耐光性改良剤としては、特開２０１７－１９８７８７号公報の段落番号００３６～００３７に記載の化合物、特開２０１７－１４６３５０号公報の段落番号００２９～００３４に記載の化合物、特開２０１７－１２９７７４号公報の段落番号００３６～００３７、００４９～００５２に記載の化合物、特開２０１７－１２９６７４号公報の段落番号００３１～００３４、００５８～００５９に記載の化合物、特開２０１７－１２２８０３号公報の段落番号００３６～００３７、００５１～００５４に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３９に記載の化合物、特開２０１７－１８６５４６号公報の段落番号００３４～００４７に記載の化合物、特開２０１５－０２５１１６号公報の段落番号００１９～００４１に記載の化合物、特開２０１２－１４５６０４号公報の段落番号０１０１～０１２５に記載の化合物、特開２０１２－１０３４７５号公報の段落番号００１８～００２１に記載の化合物、特開２０１１－２５７５９１号公報の段落番号００１５～００１８に記載の化合物、特開２０１１－１９１４８３号公報の段落番号００１７～００２１に記載の化合物、特開２０１１－１４５６６８号公報の段落番号０１０８～０１１６に記載の化合物、特開２０１１－２５３１７４号公報の段落番号０１０３～０１５３に記載の化合物などが挙げられる。 The coloring composition of the present invention may contain a light resistance improving agent. Examples of the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774. The compounds described in paragraphs 0036 to 0037 and 0049 to 0052, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, paragraph numbers 0036 to 0037 of JP-A-2017-122803. , 0051 to 0054, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017/164127, the compounds described in paragraphs 0034 to 0047 of JP-A-2017-186546, the compounds of JP-A-2015-025116. The compounds described in paragraph numbers 0019 to 0041 of JP-A, the compounds described in paragraph numbers 0101 to 0125 of JP2012-145604, the compounds described in paragraph numbers 0018 to 0021 of JP-A-2012-103475, the present invention. The compounds described in paragraphs 0015 to 0018 of JP-A-2011-257591, the compounds described in paragraph numbers 0017 to 0021 of JP-A-2011-191483, and paragraph numbers 0108 to 0116 of JP-A-2011-145668. , And the compounds described in paragraphs 0103 to 0153 of JP-A-2011-253174.
　本発明の着色組成物は、テレフタル酸エステルを実質的に含まないことも好ましい。ここで、「実質的に含まない」とは、テレフタル酸エステルの含有量が、着色組成物の全量中、１０００質量ｐｐｂ以下であることを意味し、１００質量ｐｐｂ以下であることがより好ましく、ゼロであることが特に好ましい。 It is also preferable that the coloring composition of the present invention does not substantially contain terephthalic acid ester. Here, "substantially free" means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
　環境規制の観点から、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用が規制されることがある。着色組成物において、上記した化合物の含有率を小さくする場合、パーフルオロアルキルスルホン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルスルホン酸）及びその塩、並びにパーフルオロアルキルカルボン酸（特にパーフルオロアルキル基の炭素数が６～８のパーフルオロアルキルカルボン酸）及びその塩の含有率は、着色組成物の全固形分に対して、０．０１ｐｐｂ～１，０００ｐｐｂの範囲であることが好ましく、０．０５ｐｐｂ～５００ｐｐｂの範囲であることがより好ましく、０．１ｐｐｂ～３００ｐｐｂの範囲であることが更に好ましい。着色組成物は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まなくてもよい。例えば、パーフルオロアルキルスルホン酸及びその塩の代替となりうる化合物、並びにパーフルオロアルキルカルボン酸及びその塩の代替となりうる化合物を用いることで、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を実質的に含まない着色組成物を選択してもよい。規制化合物の代替となりうる化合物としては、例えば、パーフルオロアルキル基の炭素数の違いによって規制対象から除外された化合物が挙げられる。ただし、上記した内容は、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用を妨げるものではない。着色組成物は、許容される最大の範囲内で、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩を含んでもよい。 From the viewpoint of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be restricted. When reducing the content of the above-mentioned compounds in the coloring composition, perfluoroalkyl sulfonic acid (particularly, perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group), a salt thereof, and a perfluoroalkyl carboxylic acid are used. The content of the acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is in the range of 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof. For example, by using a compound that can substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid can be used. And a coloring composition that is substantially free of salts thereof may be selected. Examples of compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The coloring composition may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
＜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。また、容器内壁は、容器内壁からの金属溶出を防ぎ、組成物の保存安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。 <Accommodation container>
The container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the composition, and suppressing the deterioration of the components.
＜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。 <Manufacturing method of coloring composition>
The coloring composition of the present invention can be produced by mixing the above-mentioned components. In the production of the coloring composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) 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、「分散技術大全集、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。 Further, in the production of the coloring composition, a process of dispersing particles such as pigments may be included. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. 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. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial". Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
　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）、ポリフッ化ビニリデン（ＰＶＤＦ）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）等のポリアミド系樹脂、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 the production of 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, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Examples thereof include filters using materials such as (including high-density, ultra-high molecular weight polyethylene resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
　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、ＤＦＡ４２０１ＮＡＥＹ、ＤＦＡ４２０１Ｊ００６Ｐ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。 The pore diameter 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. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the hole 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, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter 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。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。 It is also preferable to use a fiber-like filter medium as the filter. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd. When using filters, different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
＜膜＞
　本発明の膜は、上述した本発明の着色組成物を用いて得られる膜である。本発明の膜は、カラーフィルタなどに用いることができる。具体的には、黄色カラーフィルタとして好ましく用いることができる。例えば、カラーフィルタの黄色画素として用いることができる。本発明の膜の膜厚は、目的に応じて適宜調整できるが、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 <Membrane>
The film of the present invention is a film obtained by using the coloring composition of the present invention described above. The film of the present invention can be used as a color filter or the like. Specifically, it can be preferably used as a yellow color filter. For example, it can be used as a yellow pixel of a color filter. The film thickness of the film of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.
　本発明の膜は、波長４００～４７５ｎｍの範囲における透過率の平均値が４％未満であることが好ましく、３％未満であることがより好ましく、２％未満であることが更に好ましい。
　また、本発明の膜は、波長５５０～７００ｎｍの範囲における透過率の平均値が９０％以上であることが好ましく、９３％以上であることがより好ましく、９５％以上であることが更に好ましい。
　また、本発明の膜の透過率が５０％を示す波長は、波長４８５～５１５ｎｍの範囲に存在することが好ましく、波長４９０～５１０ｎｍの範囲に存在することがより好ましく、波長４９５～５０５ｎｍの範囲に存在することが更に好ましい。 The film of the present invention preferably has an average transmittance of less than 4%, more preferably less than 3%, and even more preferably less than 2% in the wavelength range of 400 to 475 nm.
Further, in the film of the present invention, the average value of the transmittance in the wavelength range of 550 to 700 nm is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more.
The wavelength at which the transmittance of the film of the present invention is 50% is preferably in the wavelength range of 485 to 515 nm, more preferably in the wavelength range of 490 to 510 nm, and in the wavelength range of 495 to 505 nm. It is more preferable to be present in.
＜カラーフィルタ＞
　次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の膜を有する。好ましくは、カラーフィルタの黄色画素として本発明の膜を有する。本発明のカラーフィルタは、光センサや表示装置に用いることができる。 <Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. Preferably, the film of the present invention is provided as the yellow pixel of the color filter. The color filter of the present invention can be used for an optical sensor or a display device.
　本発明のカラーフィルタは、本発明の膜の画素の他に、他の色相の着色画素を有していることが好ましい。他の色相の着色画素としては、青色画素、赤色画素、マゼンタ色画素、シアン色画素などが挙げられる。 It is preferable that the color filter of the present invention has colored pixels of other hues in addition to the pixels of the film of the present invention. Examples of the colored pixels of other hues include blue pixels, red pixels, magenta pixels, cyan pixels, and the like.
　カラーフィルタの好ましい態様としては、マゼンタ色画素と、シアン色画素と、本発明の膜で構成された黄色画素とを有する態様が挙げられる。また、本発明のカラーフィルタの別の好ましい態様として、赤色画素と、青色画素と、本発明の膜で構成された黄色画素とを有する態様や、赤色画素と、シアン色画素と、本発明の膜で構成された黄色画素とを有する態様が挙げられる。 A preferred embodiment of the color filter is an embodiment having a magenta color pixel, a cyan color pixel, and a yellow pixel composed of the film of the present invention. Further, as another preferred embodiment of the color filter of the present invention, there is an embodiment having a red pixel, a blue pixel, and a yellow pixel composed of the film of the present invention, a red pixel, a cyan pixel, and the present invention. An embodiment having a yellow pixel composed of a film can be mentioned.
　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よりも低屈折率であることが好ましい。また、米国特許出願公開第２０１８／００４０６５６号明細書に記載の構成で隔壁を形成しても良い。 The color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Further, the partition wall may be formed by the configuration described in US Patent Application Publication No. 2018/0040656.
＜膜の製造方法＞
　次に、膜の製造方法について説明する。本発明の膜は、本発明の着色組成物を塗布する工程を経て製造できる。膜の製造方法においては、更にパターン（画素）を形成する工程を含むことが好ましい。パターン（画素）の形成方法としては、フォトリソグラフィ法、ドライエッチング法が挙げられ、フォトリソグラフィ法が好ましい。 <Membrane manufacturing method>
Next, a method for manufacturing the film will be described. The film of the present invention can be produced through a step of applying the coloring composition of the present invention. The film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
　フォトリソグラフィ法によるパターン形成は、本発明の着色組成物を用いて支持体上に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、着色組成物層の未露光部を現像除去してパターン（画素）を形成する工程と、を含むことが好ましい。必要に応じて、着色組成物層をベークする工程（プリベーク工程）、および、現像されたパターン（画素）をベークする工程（ポストベーク工程）を設けてもよい。 The pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and a step of exposing the colored composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
　着色組成物層を形成する工程では、本発明の着色組成物を用いて、支持体上に着色組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下地層が設けられていてもよい。下地層の表面接触角は、ジヨードメタンで測定した際に２０～７０°であることが好ましい。また、水で測定した際に３０～８０°であることが好ましい。下地層の表面接触角が上記範囲であれば、着色組成物の塗れ性が良好である。下地層の表面接触角の調整は、例えば、界面活性剤の添加などの方法で行うことができる。 In the step of forming the coloring composition layer, the coloring composition layer of the present invention is used to form the coloring composition layer on the support. The support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
　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（例えば、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、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。 As a method for applying the coloring composition, a known method can be used. For example, a drop method (drop cast); a slit coat method; a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned. The method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents 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。低温プロセスにより膜を製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０～３００秒が好ましく、４０～２５０秒がより好ましく、８０～２２０秒がさらに好ましい。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。 The colored composition layer formed on the support may be dried (prebaked). When the membrane is manufactured by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking 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 exposing the colored composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, 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。 Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also 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。 Further, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be performed for exposure (pulse exposure). The pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).
　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。 The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm 2 , more preferably 0.05 to 1.0 J / cm 2 . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% 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 , 15,000 W / m 2 , or 35,000 W / m 2 ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other. For example, the illuminance may be 10,000 W / m 2 at an oxygen concentration of 10% by volume, an illuminance of 20,000 W / m 2 at an oxygen concentration of 35% by volume, and the like.
　次に、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 unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed portion of the coloring composition layer can be performed using a developing solution. As a result, the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
　現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液（アルカリ現像液）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。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。 Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. 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, etc. Examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline 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 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the 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 rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion 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）を行うことが好ましい。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。ポストベークにおける加熱温度は、例えば、１００～２４０℃が好ましく、２００～２４０℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長４００ｎｍ以下の光であることが好ましい。また、追加露光処理は、韓国公開特許第１０－２０１７－０１２２１３０号公報に記載された方法で行ってもよい。 It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure processing and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
　ドライエッチング法でのパターン形成は、本発明の着色組成物を用いて支持体上に着色組成物層を形成し、この着色組成物層の全体を硬化させて硬化物層を形成する工程と、この硬化物層上にフォトレジスト層を形成する工程と、フォトレジスト層をパターン状に露光したのち、現像してレジストパターンを形成する工程と、このレジストパターンをマスクとして硬化物層に対してエッチングガスを用いてドライエッチングする工程と、を含むことが好ましい。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジスト層の形成プロセスとしては、露光後の加熱処理、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 The pattern formation by the dry etching method includes a step of forming a colored composition layer on a support using the colored composition of the present invention and curing the entire colored composition layer to form a cured product layer. A step of forming a photoresist layer on the cured product layer, a step of exposing the photoresist layer in a pattern and then developing to form a resist pattern, and a step of etching the cured product layer using this resist pattern as a mask. It is preferable to include a step of dry etching with a gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as a process for forming the photoresist layer, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993 can be referred to, and this content is incorporated in the present specification.
＜光センサ＞
　本発明の光センサは、上述した本発明の膜を有する。光センサとしては、可視光、紫外線、赤外線などの光を用いて各種センシングやイメージングなどを行う装置が挙げられる。光センサとしては、例えば、固体撮像素子などのイメージセンサなどが挙げられる。固体撮像素子としては、以下のような構成などが挙げられる。 <Optical sensor>
The optical sensor of the present invention has the above-mentioned film of the present invention. Examples of the optical sensor include devices that perform various sensing and imaging using light such as visible light, ultraviolet rays, and infrared rays. Examples of the optical sensor include an image sensor such as a solid-state image sensor. Examples of the solid-state image pickup device include the following configurations.
　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等で形成される転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口した遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等で形成されるデバイス保護膜を有し、デバイス保護膜上に、カラーフィルタを有する構成である。更に、デバイス保護膜上であってカラーフィルタの下（基板に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。また、カラーフィルタの画素は、隔壁により例えば格子状に仕切られた空間に埋め込まれていてもよい。この場合の隔壁の屈折率は、画素の屈折よりも低いことが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報、国際公開第２０１８／０４３６５４号、米国特許出願公開第２０１８／００４０６５６号明細書に記載の装置が挙げられる。 A transfer electrode formed of a plurality of photodiodes constituting a light receiving area of a solid-state image pickup device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and polycarbonate on a substrate. It has a light-shielding film having only the light-receiving part of the photodiode open on the photodiode and the transfer electrode, and is formed of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a device protective film and a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There may be. Further, the pixels of the color filter may be embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the refractive index of the partition wall is preferably lower than that of the pixel. Examples of the image pickup apparatus having such a structure are described in JP-A-2012-227478, JP-A-2014-179757, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. Equipment is mentioned.
　光センサを備えた装置は、デジタルカメラや、撮像機能を有する電子機器（携帯電話等）の他、車載カメラや監視カメラなどに用いることができる。 Devices equipped with optical sensors can be used for digital cameras, electronic devices with imaging functions (mobile phones, etc.), in-vehicle cameras, surveillance cameras, and the like.
＜表示装置＞
　本発明の表示装置は、上述した本発明の膜を有する。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。表示装置の定義や各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。 <Display device>
The display device of the present invention has the above-mentioned film of the present invention. Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of display devices and the details of each display device, see, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Published in 1989) ”and so on. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, 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 composed of a white organic electroluminescence element. The white organic electroluminescence device preferably has a tandem structure. Regarding the tandem structure of organic electroluminescence elements, Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.
　また、有機エレクトロルミネッセンス表示装置は、カラーフィルタ上にレンズを有していてもよい。レンズの形状としては、光学系設計により導出された様々な形状をとることができ、例えば、凸形状、凹形状などが挙げられる。例えば凹形状（凹型レンズ）とすることで光の集光性を向上させやすい。また、レンズは、カラーフィルタと直接接していてもよく、レンズとカラーフィルタとの間に、密着層や平坦化層などの他の層を設けてもよい。また、レンズは、国際公開第２０１８／１３５１８９号に記載の態様にて配置して用いることもできる。 Further, the organic electroluminescence display device may have a lens on the color filter. As the shape of the lens, various shapes derived by the optical system design can be taken, and examples thereof include a convex shape and a concave shape. For example, it is easy to improve the light condensing property by making it a concave shape (concave lens). Further, the lens may be in direct contact with the color filter, or another layer such as an adhesion layer or a flattening layer may be provided between the lens and the color filter. The lens can also be arranged and used in the manner described in International Publication No. 2018/135189.
　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。 The present invention will be specifically described below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜分散液の調製＞
（分散液１）
　Ｃ．Ｉ．ピグメントイエロー１３９の１２．０質量部と、分散剤１の４．０質量部と、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）の８３．０質量部とを混合した後、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分散液１を調製した。 <Preparation of dispersion>
(Dispersion 1)
C. I. After mixing 12.0 parts by mass of Pigment Yellow 139, 4.0 parts by mass of Dispersant 1, and 83.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), zirconia beads having a diameter of 1 mm are used. , Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a filter having a pore size of 5 μm to prepare a dispersion liquid 1.
（分散液２）
　Ｃ．Ｉ．ピグメントイエロー１５０（アゾメチン系黄色顔料）の１１．６質量部と、分散剤２の６．９質量部と、ＰＧＭＥＡの７８．０質量部と、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）の３．５質量部とを混合した後、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分散液２を調製した。 (Dispersion 2)
C. I. Pigment Yellow 150 (azomethine-based yellow pigment) 11.6 parts by mass, dispersant 2 6.9 parts by mass, PGMEA 78.0 parts by mass, and propylene glycol monomethyl ether (PGME) 3.5 parts by mass. After mixing with Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, the mixture was dispersed for 5 hours and then filtered through a filter having a pore size of 5 μm to prepare a dispersion liquid 2. ..
（分散液３）
　Ｃ．Ｉ．ピグメントイエロー１８５の１３．０質量部と、分散剤１の５．０質量部と、ＰＧＭＥＡの７４．０質量部と、ＰＧＭＥの８．０質量部とを混合した後、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分散液３を調製した。 (Dispersion liquid 3)
C. I. After mixing 13.0 parts by mass of Pigment Yellow 185, 5.0 parts by mass of Dispersant 1, 74.0 parts by mass of PGMEA, and 8.0 parts by mass of PGME, zirconia beads having a diameter of 1 mm are obtained. After dispersing for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.), the dispersion liquid 3 was prepared by filtering with a filter having a pore size of 5 μm.
（分散液４）
　Ｃ．Ｉ．ピグメントイエロー１２９（アゾメチン系黄色顔料）の１１．６質量部と、分散剤２の６．９質量部と、ＰＧＭＥＡの７８．０質量部と、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）の３．５質量部とを混合した後、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分散液２を調製した。 (Dispersion liquid 4)
C. I. Pigment Yellow 129 (azomethine-based yellow pigment) 11.6 parts by mass, dispersant 2 6.9 parts by mass, PGMEA 78.0 parts by mass, and propylene glycol monomethyl ether (PGME) 3.5 parts by mass. After mixing with Eiger Mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, the mixture was dispersed for 5 hours and then filtered through a filter having a pore size of 5 μm to prepare a dispersion liquid 2. ..
　分散剤１：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量２４０００、酸価５２．５ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000021
 　分散剤２：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量２１０００、酸価３６ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000022
 Dispersant 1: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 52.5 mgKOH / g)
Figure JPOXMLDOC01-appb-C000021
 Dispersant 2: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 21000, acid value 36 mgKOH / g)
Figure JPOXMLDOC01-appb-C000022
＜着色組成物の調製＞
　下記表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）を用いてろ過して着色組成物を調製した。下記表のＰＹ１３９比率の欄に着色組成物に含まれる着色剤中におけるＣ．Ｉ．ピグメントイエロー１３９の含有量を記載する。また、下記表のアゾメチン系黄色顔料比率の欄に着色組成物に含まれる着色剤中におけるＣ．Ｉ．ピグメントイエロー１５０とＣ．Ｉ．ピグメントイエロー１２９の合計の含有量を記載する。また、下記表のＰＹ１８５比率の欄に着色組成物に含まれる着色剤中におけるＣ．Ｉ．ピグメントイエロー１８５の含有量を記載する。  <Preparation of coloring composition>
The raw materials shown in the table below were mixed, stirred, and then filtered using a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a colored composition. In the column of PY139 ratio in the table below, C.I. I. The content of Pigment Yellow 139 is described. Further, in the column of the azomethine-based yellow pigment ratio in the table below, C.I. I. Pigment Yellow 150 and C.I. I. The total content of Pigment Yellow 129 is described. Further, in the column of PY185 ratio in the table below, C.I. I. The content of Pigment Yellow 185 is described.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　上記表中、略語で記載した原料は以下の通りである。
（分散液）
　分散液１～４：上述の分散液１～４ In the above table, the raw materials described by abbreviations are as follows.
(Dispersion)
Dispersions 1 to 4: Dispersions 1 to 4 described above
（樹脂）
　Ｂ－１：以下の方法で合成した樹脂（エポキシ基を有する樹脂）の４０質量％ＰＧＭＥＡ溶液
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流して窒素雰囲気に置換し、ＰＧＭＥＡの３７１質量部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸の５４質量部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８又は／及び９－イルアクリレートの混合物の２２５質量部、ビニルトルエン（異性体混合物）の８１質量部、ＰＧＭＥＡの８０質量部の混合溶液を４時間かけて滴下した。一方、重合開始剤（２，２－アゾビス（２，４－ジメチルバレロニトリル）の３０質量部をＰＧＭＥＡの１６０質量部に溶解した溶液を５時間かけて滴下した。開始剤溶液の滴下終了後、４時間同温度で保持した後、室温まで冷却して樹脂を得た。得られた樹脂の酸価は４３ｍｇＫＯＨ／ｇで、重量平均分子量は１０６００で、分散度は２．０１であった。ＰＧＭＥＡを加えて固形分濃度を４０質量％に調製してＢ－１を調製した。 (resin)
B-1: 40% by mass PGMEA solution of the resin (resin having an epoxy group) synthesized by the following method PGMEA is replaced with a nitrogen atmosphere by flowing an appropriate amount of nitrogen into a flask equipped with a reflux condenser, a dropping funnel and a stirrer. 371 parts by mass of the above was added and heated to 85 ° C. with stirring. Then 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8 and / and 9-ylacrylate, vinyl toluene (isomer). A mixed solution of 81 parts by mass of the mixture) and 80 parts by mass of PGMEA was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of the polymerization initiator (2,2-azobis (2,4-dimethylvaleronitrile)) in 160 parts by mass of PGMEA was added dropwise over 5 hours. After the addition of the initiator solution was completed, the solution was added dropwise. After keeping at the same temperature for 4 hours, the resin was cooled to room temperature to obtain a resin. The acid value of the obtained resin was 43 mgKOH / g, the weight average molecular weight was 10600, and the dispersibility was 2.01. Was added to adjust the solid content concentration to 40% by mass to prepare B-1.
　Ｂ－２：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１１０００）の４０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000028
 B-2: 40% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000)
Figure JPOXMLDOC01-appb-C000028
　Ｂ－３：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１２０００、）の４０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000029
 B-3: 40% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 12000,)
Figure JPOXMLDOC01-appb-C000029
　Ｂ－４：以下の方法で合成した樹脂（エポキシ基を有する樹脂）の４０質量％ＰＧＭＥＡ溶液
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流し、窒素雰囲気に置換し、ＰＧＭＥＡの３４０質量部を入れ、撹拌しながら８０℃まで加熱した。次いで、アクリル酸の５７質量部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）の５４質量部、ベンジルメタクリレートの２３９質量部、ＰＧＭＥＡの７３質量部の混合溶液を５時間かけて滴下した。次いで、重合開始剤（２，２－アゾビス（２，４－ジメチルバレロニトリル））の４０質量部をＰＧＭＥＡの１９７質量部に溶解した溶液を６時間かけて滴下した。重合開始剤溶液の滴下終了後、８０℃で３時間保持した後、室温まで冷却して下記構造の樹脂を得た。得られた樹脂の重量平均分子量は９４００、分散度は１．８９、酸価は１１４ｍｇＫＯＨ／ｇであった。ＰＧＭＥＡを加えて固形分濃度を４０質量％に調製してＢ－４を調製した。
Figure JPOXMLDOC01-appb-C000030
 B-4: 40% by mass PGMEA solution of the resin (resin having an epoxy group) synthesized by the following method A suitable amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere. 340 parts by mass of PGMEA was added and heated to 80 ° C. with stirring. Next, 57 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0]. 2,6 ] A mixed solution of 54 parts by mass of a mixture of decane-9-ylacrylate (content ratio 1: 1 in molar ratio), 239 parts by mass of benzyl methacrylate and 73 parts by mass of PGMEA was added dropwise over 5 hours. .. Then, a solution prepared by dissolving 40 parts by mass of the polymerization initiator (2,2-azobis (2,4-dimethylvaleronitrile)) in 197 parts by mass of PGMEA was added dropwise over 6 hours. After the completion of dropping the polymerization initiator solution, the mixture was kept at 80 ° C. for 3 hours and then cooled to room temperature to obtain a resin having the following structure. The weight average molecular weight of the obtained resin was 9,400, the dispersity was 1.89, and the acid value was 114 mgKOH / g. PGMEA was added to adjust the solid content concentration to 40% by mass to prepare B-4.
Figure JPOXMLDOC01-appb-C000030
（光重合開始剤）
　Ｃ－１：Ｉｒｇａｃｕｒｅ　ＯＸＥ０２（ＢＡＳＦ社製、オキシム化合物）
　Ｃ－２：Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（ＢＡＳＦ社製、オキシム化合物）
　Ｃ－３：Ｉｒｇａｃｕｒｅ　３６９（ＢＡＳＦ社製、アセトフェノン化合物）
　Ｃ－４：ＴＲ－ＰＢＧ－３２７（トロンリー社製、オキシム化合物、１－［４－（フェニルチオ）フェニル］－３－シクロヘキシル－プロパン－１，２－ジオン－２－（Ｏ－アセチルオキシム）） (Photopolymerization initiator)
C-1: Irgure OXE02 (Oxime compound manufactured by BASF)
C-2: Irgure OXE01 (Oxime compound manufactured by BASF)
C-3: Irgacure 369 (acetophenone compound manufactured by BASF)
C-4: TR-PBG-327 (Oxime compound manufactured by Tronley, 1- [4- (phenylthio) phenyl] -3-cyclohexyl-propane-1,2-dione-2- (O-acetyloxime))
（重合性化合物）
　Ｄ－１：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（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）
　Ｄ－２：ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ（新中村化学工業（株）製、エトキシ化ジペンタエリスリトールヘキサアクリレートとエトキシ化ジペンタエリスリトールペンタアクリレートの混合物）
　Ｄ－３：ジペンタエリスリトールポリアクリレート (Polymerizable compound)
D-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
D-2: NK Ester A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd., a mixture of ethoxylated dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol pentaacrylate)
D-3: Dipentaerythritol polyacrylate
（添加剤）
　Ｅ－１：下記構造の化合物（紫外線吸収剤）
Figure JPOXMLDOC01-appb-C000031
 (Additive)
E-1: Compound with the following structure (ultraviolet absorber)
Figure JPOXMLDOC01-appb-C000031
（界面活性剤）
　Ｆ－１：下記構造の化合物
Figure JPOXMLDOC01-appb-I000032
　Ｆ－２：下記構造の化合物（重量平均分子量１４０００、繰り返し単位の割合を示す％の数値はモル％である、フッ素系界面活性剤）
Figure JPOXMLDOC01-appb-C000033
 　Ｆ－３：メガファック　Ｆ－５５４（ＤＩＣ社製、フッ素系界面活性剤）
　Ｆ－４：ＰｏｌｙＦｏｘ　ＰＦ６３２０（ＯＭＮＯＶＡ社製、フッ素系界面活性剤）
　Ｆ－５：フタージェント２０８Ｇ（ＮＥＯＳ社製、フッ素系界面活性剤）  
　Ｆ－６：ＤＯＷＳＩＬ　ＳＨ　８４００　ＦＬＵＩＤ（ダウ・東レ（株）製、シリコーン系界面活性剤）
　Ｆ－７：ＤＯＷＳＩＬ　ＳＦ　８４１９　ＯＩＬ（ダウ・東レ（株）製、シリコーン系界面活性剤） (Surfactant)
F-1: Compound with the following structure
Figure JPOXMLDOC01-appb-I000032
F-2: A compound having the following structure (weight average molecular weight 14000,% value indicating the ratio of repeating units is mol%, fluorine-based surfactant)
Figure JPOXMLDOC01-appb-C000033
 F-3: Megafuck F-554 (DIC Corporation, fluorine-based surfactant)
F-4: PolyFox PF6320 (OMNOVA, fluorine-based surfactant)
F-5: Futergent 208G (NEOS, fluorine-based surfactant)
F-6: DOWNSIL SH 8400 FLUID (Silicone-based surfactant manufactured by Dow Toray Co., Ltd.)
F-7: DOWNSIL SF 8419 OIL (made by Dow Toray Co., Ltd., silicone-based surfactant)
（重合禁止剤）
　Ｇ－１：ｐ－メトキシフェノール (Polymerization inhibitor)
G-1: p-methoxyphenol
（溶剤）
　Ｈ－１：ＰＧＭＥＡ
　Ｈ－２：アニソール
　Ｈ－３：ジアセトンアルコール (solvent)
H-1: PGMEA
H-2: Anisole H-3: Diacetone alcohol
＜評価＞
（分光特性の評価）
　ガラス基板上に、着色組成物をスピンコート法で塗布し、次いで、ホットプレートを使用して１００℃１２０秒加熱処理（プリベーク）し、次いでｉ線を１０００ｍｊ／ｃｍ２の露光量で照射して露光し、次いで、２００℃で５分間加熱を行い、厚さ０．６μｍの膜を作製した。得られた膜について、大塚電子（株）製のＭＣＰＤ－３０００を用い、４００～７００ｎｍの範囲の光透過率（透過率）を測定して波長４００～４７５ｎｍの範囲における透過率の平均値（Ｔ１）、波長５５０～７００ｎｍの範囲における透過率の平均値（Ｔ２）、透過率が５０％を示す波長（λ５０）のそれぞれを求め、以下の基準で分光特性を評価した。 <Evaluation>
(Evaluation of spectral characteristics)
The coloring composition is applied onto a glass substrate by a spin coating method, then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate, and then i-rays are irradiated with an exposure amount of 1000 mj / cm 2 . The film was exposed and then heated at 200 ° C. for 5 minutes to prepare a film having a thickness of 0.6 μm. For the obtained film, the light transmittance (transmittance) in the range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the average value of the transmittance in the wavelength range of 400 to 475 nm (T1). ), The average value of the transmittance (T2) in the wavelength range of 550 to 700 nm, and the wavelength (λ50) showing the transmittance of 50% were obtained, and the spectral characteristics were evaluated according to the following criteria.
　－波長４００～４７５ｎｍの範囲における透過率の平均値（Ｔ１）について－
　Ａ：Ｔ１が２％未満である
　Ｂ：Ｔ１が２％以上、３％未満である
　Ｃ：Ｔ１が３％以上、４％未満である
　Ｄ：Ｔ１が４％以上である -About the average value (T1) of transmittance in the wavelength range of 400 to 475 nm-
A: T1 is less than 2% B: T1 is 2% or more and less than 3% C: T1 is 3% or more and less than 4% D: T1 is 4% or more
　－波長５５０～７００ｎｍの範囲における透過率の平均値（Ｔ２）について－
　Ａ：Ｔ２が９５％以上である
　Ｂ：Ｔ２が９３％以上９５％未満である
　Ｃ：Ｔ２が９０％以上９３％未満である
　Ｄ：Ｔ２が９０％未満である -About the average value (T2) of transmittance in the wavelength range of 550 to 700 nm-
A: T2 is 95% or more B: T2 is 93% or more and less than 95% C: T2 is 90% or more and less than 93% D: T2 is less than 90%
　－透過率が５０％を示す波長（λ５０）について－
　Ａ：λ５０が４９５ｎｍ以上５０５ｎｍ以下の範囲内である
　Ｂ：λ５０が４９０ｎｍ以上４９５ｎｍ未満の範囲内であるか、または、５０５ｎｍを超え５１０ｎｍ以下の範囲内である
　Ｃ：λ５０が４８５ｎｍ以上４９０ｎｍ未満の範囲内であるか、または、５１０ｎｍを超え５１５ｎｍ以下の範囲内である
　Ｄ：λ５０が４８０ｎｍ以上４８５ｎｍ未満の範囲内であるか、または、５１５ｎｍを超え５２０ｎｍ以下の範囲内である -About the wavelength (λ50) where the transmittance shows 50%-
A: λ50 is in the range of 495 nm or more and 505 nm or less B: λ50 is in the range of 490 nm or more and less than 495 nm, or C: λ50 is in the range of more than 505 nm and less than 510 nm C: λ50 is in the range of 485 nm or more and less than 490 nm D: λ50 is in the range of 480 nm or more and less than 485 nm, or is in the range of more than 515 nm and 520 nm or less.
（保存安定性の評価）
　着色組成物の粘度（ｍＰａ・ｓ）を、東機産業（株）製「ＲＥ－８５Ｌ」にて測定した。上記測定後、着色組成物を４５℃、遮光、３日間の条件にて静置し、再度粘度（ｍＰａ・ｓ）を測定した。上記静置前後での粘度差（ΔＶｉｓ）から下記評価基準に従って保存安定性を評価した。なお、上記粘度測定は、いずれも、温湿度を２２±５℃、６０±２０％に管理した実験室で、着色組成物の温度を２５℃に調整した状態で測定した。
　Ａ：ΔＶｉｓが０．５ｍＰａ・ｓ以下である
　Ｂ：ΔＶｉｓが０．５ｍＰａ・ｓを超え、１．０ｍＰａ・ｓ以下である
　Ｃ：ΔＶｉｓが１．０ｍＰａ・ｓを超える (Evaluation of storage stability)
The viscosity (mPa · s) of the coloring composition was measured with "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the colored composition was allowed to stand at 45 ° C. under the conditions of light shielding for 3 days, and the viscosity (mPa · s) was measured again. The storage stability was evaluated according to the following evaluation criteria from the viscosity difference (ΔVis) before and after standing. In each of the above viscosity measurements, the temperature and humidity were controlled to 22 ± 5 ° C. and 60 ± 20% in a laboratory, and the temperature of the coloring composition was adjusted to 25 ° C.
A: ΔVis is 0.5 mPa · s or less B: ΔVis exceeds 0.5 mPa · s and 1.0 mPa · s or less C: ΔVis exceeds 1.0 mPa · s
（耐光性の評価）
　ガラス基板上に、着色組成物をスピンコート法で塗布し、次いで、ホットプレートを使用して１００℃１２０秒加熱処理（プリベーク）し、次いでｉ線を１０００ｍｊ／ｃｍ２の露光量で露光し、次いで、２００℃で５分間加熱を行い、厚さ０．６μｍの膜を作製した。得られた膜について、大塚電子（株）製のＭＣＰＤ－３０００を用い、波長４００～７００ｎｍの範囲の光透過率（透過率）を測定した。次に、上記で作製した膜に対し、耐光試験機（スーパーキセノンウェザーメーターＳＸ７５、スガ試験機株式会社製）を用いて１０００００Ｌｕｘの光を１０００時間かけて照射した（総照射量１億Ｌｕｘ・ｈｒ）。光照射後の膜の透過率を測定し、以下の基準にて耐光性を評価した。
　Ａ：光照射後の膜の波長４００～７００ｎｍの透過率の積算値が、光照射前の硬化膜の波長４００～７００ｎｍの透過率の積算値の９７％以上である
　Ｂ：光照射後の膜の波長４００～７００ｎｍの透過率の積算値が、光照射前の膜の波長４００～７００ｎｍの透過率の積算値の９５％以上９７％未満である
　Ｃ：光照射後の膜の波長４００～７００ｎｍの透過率の積算値が、光照射前の膜の波長４００～７００ｎｍの透過率の積算値の９０％以上９５％未満である
　Ｄ：光照射後の膜の波長４００～７００ｎｍの透過率の積算値が、光照射前の膜の波長４００～７００ｎｍの透過率の積算値の９０％未満である (Evaluation of light resistance)
The coloring composition was applied onto a glass substrate by a spin coating method, then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate, and then i-rays were exposed to an exposure amount of 1000 mj / cm 2 . Then, it was heated at 200 ° C. for 5 minutes to prepare a film having a thickness of 0.6 μm. With respect to the obtained film, the light transmittance (transmittance) in the wavelength range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. Next, the film prepared above was irradiated with light of 100,000 Lux over 1000 hours using a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.) (total irradiation amount 100 million Lux · hr). ). The transmittance of the film after light irradiation was measured, and the light resistance was evaluated according to the following criteria.
A: The integrated value of the transmittance of the film after light irradiation at a wavelength of 400 to 700 nm is 97% or more of the integrated value of the transmittance of the cured film before light irradiation at a wavelength of 400 to 700 nm. B: The film after light irradiation. The integrated value of the transmittance of the film having a wavelength of 400 to 700 nm is 95% or more and less than 97% of the integrated value of the transmittance of the film having a wavelength of 400 to 700 nm before light irradiation. C: The wavelength of the film after light irradiation is 400 to 700 nm. The integrated value of the transmittance of the film before light irradiation is 90% or more and less than 95% of the integrated value of the integrated value of the transmittance of the film having a wavelength of 400 to 700 nm before light irradiation. The value is less than 90% of the integrated value of the transmittance of the film before light irradiation at a wavelength of 400 to 700 nm.
（耐湿性の評価）
　シリコンウエハ上に着色組成物をスピンコート法で塗布し，次いで，ホットプレートを使用して１００℃１２０秒加熱処理（プリベーク）し、厚さ０．６μｍの組成物層を形成した。
　次いで、この組成物層に対して一辺１．０μｍの正方形状の非マスク部が４ｍｍ×３ｍｍの領域に配列されたマスクパターンを介して、ｉ線ステッパー露光装置（ＦＰＡ－３０００ｉ５＋、Ｃａｎｏｎ（株）製）を使用してｉ線を５００ｍｊ／ｃｍ２の露光量で照射して露光した。
　次いで、露光後の組成物層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、現像液（ＣＤ－２０００、富士フイルムエレクトロニクスマテリアルズ（株）製）を用いて２３℃で６０秒間パドル現像した。次いで、シリコンウエハを回転数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てパターン（画素）付き基板を形成した。
　得られたパターン付き基板を、恒温恒湿機（ＥＨＳ－２２１Ｍ、ヤマト科学社製）に入れ、温度８５℃、相対湿度８５％の雰囲気中、５００時間、７５０時間、１０００時間、１５００時間静置して耐湿試験を行った。試験後、走査型電子顕微鏡（ＳＥＭ）（Ｓ－４８００Ｈ、（株）日立ハイテクノロジーズ製）にて観測して画素の剥がれの有無を観察して耐湿性を評価した。なお、画素がシリコンウエハから完全に剥がれている場合、または、画素のシリコンウエハとの界面に亀裂が入っている場合は剥がれがあると判断した。
耐湿性の評価基準は以下の通りである。
　Ａ：耐湿試験１５００時間でも剥がれが観測されない
　Ｂ：耐湿試験１０００時間では剥がれは観測されないが１５００時間では剥がれが観測された
　Ｃ：耐湿試験５００時間では剥がれは観測されないが１０００時間では剥がれが観測された
　Ｄ：耐湿試験５００時間で剥がれが観測された (Evaluation of moisture resistance)
The colored composition was applied onto a silicon wafer by a spin coating method, and then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate to form a composition layer having a thickness of 0.6 μm.
Next, an i-line stepper exposure apparatus (FPA-3000i5 +, Canon Inc.) was provided via a mask pattern in which square non-masked portions having a side of 1.0 μm were arranged in a region of 4 mm × 3 mm with respect to this composition layer. The i-line was irradiated with an exposure amount of 500 mj / cm 2 and exposed.
Next, the silicon wafer on which the composition layer after exposure is formed is placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and a developer (CD-) is placed. 2000, paddle developed at 23 ° C. for 60 seconds using Fujifilm Electronics Materials Co., Ltd. Next, while rotating the silicon wafer at a rotation speed of 50 rpm, pure water was supplied from above the center of rotation in a shower shape from the ejection nozzle to perform rinsing treatment, and then spray-dried to form a substrate with a pattern (pixels). ..
The obtained patterned substrate was placed in a constant temperature and humidity machine (EHS-221M, manufactured by Yamato Kagaku Co., Ltd.) and allowed to stand in an atmosphere at a temperature of 85 ° C. and a relative humidity of 85% for 500 hours, 750 hours, 1000 hours, and 1500 hours. Then, a moisture resistance test was conducted. After the test, the moisture resistance was evaluated by observing with a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation) and observing the presence or absence of peeling of the pixels. When the pixel is completely peeled off from the silicon wafer, or when the interface of the pixel with the silicon wafer is cracked, it is determined that the pixel is peeled off.
The evaluation criteria for moisture resistance are as follows.
A: No peeling is observed even in the moisture resistance test 1500 hours B: No peeling is observed in the moisture resistance test 1000 hours, but peeling is observed in 1500 hours C: No peeling is observed in the moisture resistance test 500 hours, but peeling is observed in 1000 hours. D: Peeling was observed after 500 hours of moisture resistance test.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
　上記表に示すように、実施例は保存安定性が良好で、分光特性および耐光性に優れた膜を形成することができた。また、実施例の着色組成物を用いて得られる膜は、黄色カラーフィルタとして好ましい分光特性を有していた。 As shown in the above table, in the examples, it was possible to form a film having good storage stability and excellent spectral characteristics and light resistance. Further, the film obtained by using the coloring composition of the example had preferable spectral characteristics as a yellow color filter.
（実施例１００１）
　シリコンウエハ上に、黄色着色組成物を製膜後の膜厚が０．６μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量で１μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、黄色着色組成物をパターニングして黄色画素を形成した。同様に赤色着色組成物、青色着色組成物を同様のプロセスでパターニングして、赤色画素、青色画素を順次形成して、黄色色画素、赤色画素および青色画素を有するカラーフィルタを形成した。なお、黄色着色組成物は実施例１の着色組成物を用いた。赤色着色組成物、青色着色組成物については後述する。このカラーフィルタにおいては、黄色画素がベイヤーパターンで形成されており、その隣接する領域に、赤色画素、青色画素がアイランドパターンで形成されている。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。 (Example 1001)
The yellow coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 0.6 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 1 μm square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. The yellow colored composition was then patterned using a hot plate and heated at 200 ° C. for 5 minutes to form yellow pixels. Similarly, the red coloring composition and the blue coloring composition were patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having yellow pixels, red pixels and blue pixels. As the yellow coloring composition, the coloring composition of Example 1 was used. The red coloring composition and the blue coloring composition will be described later. In this color filter, yellow pixels are formed by a Bayer pattern, and red pixels and blue pixels are formed by an island pattern in an adjacent region thereof. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
（赤色着色組成物）
　下記成分を混合し、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、赤色着色組成物を調製した。
　赤色顔料分散液　　・・・５１．７質量部
　樹脂１０１　　・・・０．６質量部
　重合性化合物（ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ、新中村化学工業（株）製）　　・・・０．６質量部
　光重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦ社製）　　・・・０．４質量部
　界面活性剤１０１　　・・・４．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４２．６質量部 (Red coloring composition)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a red colored composition.
Red pigment dispersion: 51.7 parts by mass Resin 101: 0.6 parts by mass Polymerizable compound (NK ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 0.6% by mass Part Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ・ ・ ・ 0.4 parts by mass Surface active agent 101 ・ ・ ・ 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・・ 0.3 parts by mass PGMEA ・ ・ ・ 42.6 parts by mass
（青色着色組成物）
　下記成分を混合し、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、青色着色組成物を調製した。
　青色顔料分散液　　・・・４４．９質量部
　樹脂１０１　　・・・２．１質量部
　重合性化合物（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）製）　　・・・１．５質量部
　重合性化合物（ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ、新中村化学工業（株）製）　　・・・０．７質量部
　光重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦ社製）　　・・・０．８質量部
　界面活性剤１０１　　・・・４．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４５．８質量部 (Blue coloring composition)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a blue coloring composition.
Blue pigment dispersion ・ ・ ・ 44.9 parts by mass Resin 101 ・ ・ ・ 2.1 parts by mass Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ・ ・ ・ 1.5 parts by mass Polymerizable compound (NK) Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・ ・ ・ 0.7 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ・ ・ ・ 0.8 parts by mass Surface active agent 101 ・ ・・ 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.3 parts by mass PGMEA ・ ・ ・ 45.8 parts by mass
　赤色着色組成物および青色着色組成物に使用した素材は以下の通りである。 The materials used for the red coloring composition and the blue coloring composition are as follows.
　・赤色顔料分散液
　Ｃ．Ｉ．ピグメントレッド２５４の９．６質量部、Ｃ．Ｉ．ピグメントイエロー１３９の４．３質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ビックケミー社製）の６．８質量部、ＰＧＭＥＡの７９．３質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、赤色顔料分散液を得た。 -Red pigment dispersion C. I. 9.6 parts by mass of Pigment Red 254, C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion liquid.
　・青色顔料分散液
　Ｃ．Ｉ．ピグメントブルー１５：６の９．７質量部、Ｃ．Ｉ．ピグメントバイオレット２３の２．４質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ビックケミー社製）の５．５質量部、ＰＧＭＥＡの８２．４質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、青色顔料分散液を得た。 ・ Blue pigment dispersion liquid C. I. Pigment Blue 15: 6, 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion liquid.
　・樹脂１０１：下記構造の樹脂（酸価：７０ｍｇＫＯＨ／ｇ、Ｍｗ＝１１０００、構造単位における比はモル比である）
Figure JPOXMLDOC01-appb-C000039
 Resin 101: Resin having the following structure (acid value: 70 mgKOH / g, Mw = 11000, ratio in structural unit is molar ratio)
Figure JPOXMLDOC01-appb-C000039
　・界面活性剤１０１：下記構造の化合物（重量平均分子量１４０００）の１質量％ＰＧＭＥＡ溶液。下記の式中、繰り返し単位の割合を示す％はモル％である。
Figure JPOXMLDOC01-appb-C000040
 （実施例１００２）
　実施例１００１の青色着色組成物を下記シアン色着色組成物１に変更し、シアン色画素を作成した以外は実施例１００１と同様の方法によりカラーフィルタを形成した。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。 Surfactant 101: A 1% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000). In the following formula,% indicating the ratio of the repeating unit is mol%.
Figure JPOXMLDOC01-appb-C000040
 (Example 1002)
The blue coloring composition of Example 1001 was changed to the following cyan coloring composition 1, and a color filter was formed by the same method as in Example 1001 except that cyan colored pixels were created. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
（シアン色着色組成物１）
　下記成分を混合し、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、シアン色着色組成物１を調製した。
　シアン色顔料分散液１　　・・・４４．９質量部
　樹脂１０１　　・・・２．１質量部
　重合性化合物（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）製）　　・・・１．５質量部
　重合性化合物（ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ、新中村化学工業（株）製）　　・・・０．７質量部
　光重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦ社製）　　・・・０．８質量部
　界面活性剤１０１　　・・・４．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４５．８質量部 (Cyan Coloring Composition 1)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a cyan colored composition 1.
Cyan color pigment dispersion 1 ・ ・ ・ 44.9 parts by mass Resin 101 ・ ・ ・ 2.1 parts by mass Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ・ ・ ・ 1.5 parts by mass Polymerizable compound (NK ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・ ・ ・ 0.7 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ・ ・ ・ 0.8 parts by mass Surface active agent 101・ ・ ・ 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.3 parts by mass PGMEA ・ ・ ・ 45.8 parts by mass
・シアン色顔料分散液１
　Ｃ．Ｉ．ピグメントブルー１５：４の１２．１質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ビックケミー社製）の５．５質量部、ＰＧＭＥＡの８２．４質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、シアン色顔料分散液１を得た。 ・ Cyan color pigment dispersion 1
C. I. A mixed solution consisting of 12.1 parts by mass of Pigment Blue 15: 4, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0. 3 mm diameter) was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a cyan pigment dispersion liquid 1.
（実施例１００３）
　実施例１００１の青色着色組成物を下記シアン色着色組成物２に変更し、シアン色画素を作成した以外は実施例１００１と同様の方法によりカラーフィルタを形成した。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。 (Example 1003)
The blue coloring composition of Example 1001 was changed to the cyan coloring composition 2 below, and a color filter was formed by the same method as in Example 1001 except that cyan colored pixels were created. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
（シアン色着色組成物２）
　下記成分を混合し、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、シアン色着色組成物２を調製した。
　シアン色顔料分散液２　　４４．９質量部
　樹脂１０１　　・・・２．１質量部
　重合性化合物（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）製）　　・・・１．５質量部
　重合性化合物（ＮＫエステル　Ａ－ＤＰＨ－１２Ｅ、新中村化学工業（株）製）　　・・・０．７質量部
　光重合開始剤（Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、ＢＡＳＦ社製）　　・・・０．８質量部
　界面活性剤１０１　　・・・４．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４５．８質量部 (Cyan Coloring Composition 2)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a cyan colored composition 2.
Cyan color pigment dispersion 2 44.9 parts by mass Resin 101 ・ ・ ・ 2.1 parts by mass Polymerizable compound (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ・ ・ ・ 1.5 parts by mass Polymerizable compound (NK ester) A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) ・ ・ ・ 0.7 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ・ ・ ・ 0.8 parts by mass Surface active agent 101 ・ ・ ・4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.3 parts by mass PGMEA ・ ・ ・ 45.8 parts by mass
・シアン色顔料分散液２
　Ｃ．Ｉ．ピグメントブルー１５：４の１．９質量部、Ｃ．Ｉ．ピグメントグリーン７の７．３質量部、Ｃ．Ｉ．ピグメントグリーン３６の２．９質量部、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ビックケミー社製）の５．５質量部、ＰＧＭＥＡの８２．４質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散して、顔料分散液を調製した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、シアン色顔料分散液２を得た。 ・ Cyan color pigment dispersion liquid 2
C. I. Pigment Blue 15: 4, 1.9 parts by mass, C.I. I. 7.3 parts by mass of Pigment Green 7, C.I. I. A mixed solution consisting of 2.9 parts by mass of Pigment Green 36, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by Big Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm 3 at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a cyan pigment dispersion liquid 2.
（実施例１００４）
　実施例１００１の青色着色組成物を国際公開第２０２０／１７４９９１号の段落番号０１２１の実施例１の着色硬化性組成物に変更した以外は実施例１００１と同様の方法によりカラーフィルタを形成した。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。 (Example 1004)
A color filter was formed by the same method as in Example 1001 except that the blue coloring composition of Example 1001 was changed to the coloring curable composition of Example 1 of Paragraph No. 0121 of International Publication No. 2020/174991. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.

Claims (17)

  1. 　着色剤と、樹脂と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
    　前記着色剤は、黄色顔料を含み、
    　前記黄色顔料は、カラーインデックスピグメントイエロー１８５と、カラーインデックスピグメントイエロー１８５以外のイソインドリン系黄色顔料と、アゾメチン系黄色顔料とを含み、
    　前記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が１０質量％以上である、着色組成物。     A coloring composition containing a colorant, a resin, a polymerizable compound, and a photopolymerization initiator.
    The colorant contains a yellow pigment and contains
    The yellow pigment contains a color index pigment yellow 185, an isoindrin-based yellow pigment other than the color index pigment yellow 185, and an azomethine-based yellow pigment.
    A coloring composition in which the content of Color Index Pigment Yellow 185 in the colorant is 10% by mass or more.
  2. 　前記着色剤中における前記黄色顔料の含有量が６０～１００質量％である、請求項１に記載の着色組成物。 The coloring composition according to claim 1, wherein the content of the yellow pigment in the coloring agent is 60 to 100% by mass.
  3. 　前記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が４０質量％以上である、請求項１または２に記載の着色組成物。 The coloring composition according to claim 1 or 2, wherein the content of Color Index Pigment Yellow 185 in the colorant is 40% by mass or more.
  4. 　カラーインデックスピグメントイエロー１８５と前記イソインドリン系黄色顔料との合計の１００質量部に対して、前記アゾメチン系黄色顔料を１０～６０質量部含む、請求項１～３のいずれか１項に記載の着色組成物。 The coloring according to any one of claims 1 to 3, wherein the azomethine-based yellow pigment is contained in an amount of 10 to 60 parts by mass with respect to 100 parts by mass of the total of the color index pigment yellow 185 and the isoindoline-based yellow pigment. Composition.
  5. 　カラーインデックスピグメントイエロー１８５の１００質量部に対して、前記イソインドリン系黄色顔料を１０～７０質量部含む、請求項１～４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 4, which contains 10 to 70 parts by mass of the isoindoline-based yellow pigment with respect to 100 parts by mass of Color Index Pigment Yellow 185.
  6. 　前記イソインドリン系黄色顔料がカラーインデックスピグメントイエロー１３９であり、
    　前記アゾメチン系黄色顔料がカラーインデックスピグメントイエロー１５０である、請求項１～５のいずれか１項に記載の着色組成物。     The isoindoline-based yellow pigment is Color Index Pigment Yellow 139.
    The coloring composition according to any one of claims 1 to 5, wherein the azomethine-based yellow pigment is Color Index Pigment Yellow 150.
  7. 　前記着色剤中におけるカラーインデックスピグメントイエロー１８５の含有量が４０～７０質量％であり、カラーインデックスピグメントイエロー１３９の含有量が１０～３０質量％であり、カラーインデックスピグメントイエロー１５０の含有量が１０～３０質量％である、請求項６に記載の着色組成物。 The content of Color Index Pigment Yellow 185 in the colorant is 40 to 70% by mass, the content of Color Index Pigment Yellow 139 is 10 to 30% by mass, and the content of Color Index Pigment Yellow 150 is 10 to 10 to 70% by mass. The coloring composition according to claim 6, which is 30% by mass.
  8. 　前記光重合開始剤はオキシム化合物を含む、請求項１～７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 7, wherein the photopolymerization initiator contains an oxime compound.
  9. 　前記樹脂は、架橋性基を有する樹脂を含む、請求項１～８のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 8, wherein the resin contains a resin having a crosslinkable group.
  10. 　前記樹脂は、環状エーテル基を有する樹脂を含む、請求項１～８のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 8, wherein the resin contains a resin having a cyclic ether group.
  11. 　前記重合性化合物は、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートおよびこれらの変性体からなる群より選択される少なくとも１種を含む、請求項１～１０のいずれか１項に記載の着色組成物。 Any one of claims 1 to 10, wherein the polymerizable compound contains at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and a modified product thereof. The coloring composition according to the section.
  12. 　前記着色組成物を用いて膜厚０．６μｍの膜を形成した際に、前記膜の波長４００～４７５ｎｍの範囲における透過率の平均値が４％未満であり、波長５５０～７００ｎｍの範囲における透過率の平均値が９０％以上である、請求項１～１１のいずれか１項に記載の着色組成物。 When a film having a film thickness of 0.6 μm is formed using the coloring composition, the average value of the transmittance of the film in the wavelength range of 400 to 475 nm is less than 4%, and the transmittance in the wavelength range of 550 to 700 nm. The coloring composition according to any one of claims 1 to 11, wherein the average value of the rate is 90% or more.
  13. 　黄色着色組成物である、請求項１～１２のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 12, which is a yellow coloring composition.
  14. 　請求項１～１３のいずれか１項に記載の着色組成物を用いて得られる膜。 A film obtained by using the coloring composition according to any one of claims 1 to 13.
  15. 　請求項１４に記載の膜を含むカラーフィルタ。 A color filter containing the film according to claim 14.
  16. 　請求項１４に記載の膜を含む光センサ。 An optical sensor including the film according to claim 14.
  17. 　請求項１４に記載の膜を含む表示装置。 A display device including the film according to claim 14.
PCT/JP2021/033195 2020-10-13 2021-09-09 Coloring composition, film, color filter, optical sensor, and display device WO2022080046A1 (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2011075759A (en) * 2009-09-30 2011-04-14 Toyo Ink Mfg Co Ltd Green colored composition for color filter, and color filter
WO2015182285A1 (en) * 2014-05-28 2015-12-03 富士フイルム株式会社 Coloring composition, method for producing coloring composition, color filter, and organic electroluminescent display element
WO2019039172A1 (en) * 2017-08-22 2019-02-28 富士フイルム株式会社 Structure, method for producing structure, composition for forming absorbent layer, solid-state imaging element, and image display device

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JP6270424B2 (en) 2013-11-15 2018-01-31 東洋インキＳｃホールディングス株式会社 Coloring composition and color filter for solid-state imaging device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011075759A (en) * 2009-09-30 2011-04-14 Toyo Ink Mfg Co Ltd Green colored composition for color filter, and color filter
WO2015182285A1 (en) * 2014-05-28 2015-12-03 富士フイルム株式会社 Coloring composition, method for producing coloring composition, color filter, and organic electroluminescent display element
WO2019039172A1 (en) * 2017-08-22 2019-02-28 富士フイルム株式会社 Structure, method for producing structure, composition for forming absorbent layer, solid-state imaging element, and image display device

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