WO2022196450A1 - Colored composition, method for producing film, method for producing color filter, method for producing solid imaging element, and method for producing image display device - Google Patents

Colored composition, method for producing film, method for producing color filter, method for producing solid imaging element, and method for producing image display device Download PDF

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Publication number
WO2022196450A1
WO2022196450A1 PCT/JP2022/010052 JP2022010052W WO2022196450A1 WO 2022196450 A1 WO2022196450 A1 WO 2022196450A1 JP 2022010052 W JP2022010052 W JP 2022010052W WO 2022196450 A1 WO2022196450 A1 WO 2022196450A1
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Prior art keywords
group
mass
coloring composition
solvent
pigment
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PCT/JP2022/010052
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French (fr)
Japanese (ja)
Inventor
拓貴 本橋
和也 尾田
翔一 中村
全弘 森
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富士フイルム株式会社
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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 KR1020237027081A priority Critical patent/KR20230130697A/en
Priority to JP2023507001A priority patent/JPWO2022196450A1/ja
Publication of WO2022196450A1 publication Critical patent/WO2022196450A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays

Definitions

  • the present invention relates to a coloring composition containing a pigment.
  • the present invention also relates to a method for producing a film, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
  • CCD charge-coupled device
  • Color filters are manufactured using, for example, a coloring composition containing a colorant containing an organic pigment, a polymerizable compound, a photopolymerization initiator, and a solvent.
  • a coloring composition containing a colorant containing an azo pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator containing an oxime ester compound, and a solvent discloses a coloring composition containing a colorant containing an azo pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator containing an oxime ester compound, and a solvent. The manufacture of color filters is described.
  • the concentration of the coloring agent in the total solid content of the coloring composition increases, the proportion of components other than the coloring agent decreases relatively.
  • the viscosity of the coloring composition tended to increase.
  • the viscosity of the coloring composition tends to increase over time.
  • the inventor of the present invention has extensively studied a coloring composition containing a coloring agent containing an organic pigment, a polymerizable compound, a photopolymerization initiator, and a solvent. Furthermore, the inventors have found that the above objects can be achieved by using a solvent containing a predetermined amount of a cyclic ketone solvent, and have completed the present invention. Accordingly, the present invention provides the following.
  • ⁇ 1> containing a coloring agent, a polymerizable compound, a photopolymerization initiator, and a solvent
  • the coloring agent contains an organic pigment
  • the photopolymerization initiator contains an oxime compound
  • the solvent contains a cyclic ketone solvent, and the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass.
  • coloring composition ⁇ 2> The colored composition according to ⁇ 1>, wherein the cyclic ketone solvent is cyclopentanone.
  • ⁇ 3> The colored composition according to ⁇ 1> or ⁇ 2>, wherein the content of the cyclic ketone solvent in the solvent is 5 to 13% by mass.
  • the organic pigment contains at least one selected from quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments and azomethine pigments, ⁇ 1> to ⁇ 4> The colored composition according to any one of items 4>.
  • the organic pigment contains two or more diketopyrrolopyrrole pigments.
  • the organic pigment includes at least one selected from Color Index Pigment Red 254 and Color Index Pigment Red 272.
  • ⁇ 11> A method for producing a film, comprising the step of applying the coloring composition according to any one of ⁇ 1> to ⁇ 10> to a support.
  • ⁇ 12> A method for producing a color filter, including the method for producing a film according to ⁇ 11>.
  • ⁇ 13> A method for manufacturing a solid-state imaging device, including the method for manufacturing a film according to ⁇ 11>.
  • ⁇ 14> A method for manufacturing an image display device, including the method for manufacturing a film according to ⁇ 11>.
  • the present invention it is possible to provide a coloring composition that has good storage stability and is capable of forming a film with little unevenness in thickness.
  • the present invention can provide methods for manufacturing films, color filters, solid-state imaging devices, and image display devices.
  • ⁇ is used to include the numerical values before and after it as lower and upper limits.
  • a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents both or either acrylate and methacrylate
  • (meth)acryl represents both or either acrylic and methacrylic
  • (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
  • Me in the structural formulas represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • total solid content refers to the total mass of all components of the composition excluding the solvent.
  • a pigment means a coloring agent that is difficult to dissolve in a solvent.
  • the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • the coloring composition of the present invention is including a coloring agent, a polymerizable compound, a photopolymerization initiator, and a solvent;
  • the coloring agent contains an organic pigment
  • the photopolymerization initiator contains an oxime compound
  • the solvent contains a cyclic ketone solvent, and the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass.
  • the coloring composition of the present invention it is possible to form a film with good storage stability and small thickness unevenness. Although the detailed reason why such an effect is obtained is unknown, it is presumed to be due to the following.
  • the coloring composition of the present invention contains a predetermined amount of a cyclic ketone solvent, so that the cyclic ketone solvent adsorbs to the organic pigment in the coloring composition, presumably because the dispersion state of the organic pigment can be stabilized. be done. For this reason, it is presumed that aggregation of the organic pigment can be suppressed during storage or coating of the coloring composition.
  • the colored composition of the present invention was able to form a film having good storage stability and less unevenness in thickness.
  • an organic pigment containing a diketopyrrolopyrrole pigment because the above effects are more remarkably exhibited.
  • the heat resistance of the resulting film can be further improved.
  • the coloring composition of the present invention is preferably used as a coloring composition for color filters. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter. Pixel types include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and yellow pixels are preferred. More preferably, it is a red pixel.
  • the coloring composition of the present invention contains a coloring agent.
  • Colorants include chromatic colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants.
  • a pigment derivative can also be used as the colorant.
  • an organic pigment is a pigment composed of an organic compound.
  • organic pigments examples include quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments, azomethine pigments, naphthol pigments, xanthene pigments, thioindigo pigments, phthalocyanine pigments, squarylium pigments, and dioxazine pigments.
  • diketopyrrolopyrrole pigments contains at least one selected from quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments and azomethine pigments. More preferably, it contains at least one selected from diketopyrrolopyrrole pigments and isoindoline pigments, and particularly preferably contains a diketopyrrolopyrrole pigment.
  • two types of diketopyrrolopyrrole pigments are used. It is preferable to include the above.
  • the average primary particle size of the organic 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, and even more preferably 100 nm or less.
  • the primary particle size of the organic pigment can be determined from a photograph obtained by observing the primary particles of the organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the organic pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the organic pigment.
  • the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the organic pigment.
  • the primary particles of the organic pigment refer to independent particles without agglomeration.
  • the coloring agent contained in the coloring composition of the present invention preferably contains an organic pigment and a pigment derivative.
  • Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Details of the pigment derivative will be described later.
  • the ratio of the two is preferably 1 to 30 parts by weight of the pigment derivative per 100 parts by weight of the organic pigment.
  • the lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • organic pigments examples include yellow pigments, orange pigments, red pigments, green pigments, purple pigments and blue pigments, and preferably contain at least one selected from red pigments and yellow pigments, and contain red pigments. It is more preferable that the
  • red pigments examples include diketopyrrolopyrrole pigments, anthraquinone pigments, azo pigments, naphthol pigments, azomethine pigments, xanthene pigments, quinacridone pigments, perylene pigments, and thioindigo pigments. , preferably a naphthol pigment, more preferably a diketopyrrolopyrrole pigment.
  • red pigments include C.I. I. (Color Index) 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, 294, 295, 296, 297 and the like.
  • red pigments diketopyrrolopyrrole compounds having at least one bromine atom substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrroles described in paragraphs 0016 to 0022 of Japanese Patent No.
  • 6248838 compounds diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, brominated diketopyrrolopyrroles described in JP 2020-085947 compounds, naphthol azo compounds described in JP-A-2012-229344, red pigments described in JP-A-6516119, red pigments described in JP-A-6525101, paragraph number 0229 of JP-A-2020-090632 Brominated diketopyrrolopyrrole compound described, anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compound described in Korean Patent Publication No.
  • JP 2020-079396 Perylene compounds described in publications diketopyrrolopyrrole compounds described in paragraphs 0025 to 0041 of JP-A-2020-066702, and the like can also be used.
  • a red pigment a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.
  • C.I. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 and 291 are preferred, C.I. I. Pigment Red 254, 264, 272 are more preferred, and C.I. I. Pigment Red 254, 272 are more preferred.
  • the organic pigment used in the present invention is C.I. I. Pigment Red 254 and C.I. I. Pigment Red 272 preferably contains at least one selected from the reason that the storage stability of the coloring composition can be further improved, the thickness unevenness is smaller, and a film having excellent heat resistance can be formed.
  • C. I. Pigment Red 254 and C.I. I. Pigment Red 272 is more preferred.
  • C.I. I. Pigment Red 254 and C.I. I. Pigment Red 272 is used in combination with C.I. I. pigment red 254,
  • C.I. I. Pigment Red 272 is preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight, even more preferably 50 to 100 parts by weight. If the ratio of both is within the above range, the heat resistance of the obtained film is particularly excellent.
  • yellow pigments examples include azo pigments, azomethine pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments and perylene pigments.
  • Specific examples of 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, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162,
  • an azobarbiturate nickel complex having the following structure can also be used.
  • quinophthalone compounds described in JP-T-2020-517791 the following formula ( A compound represented by QP1) and a compound represented by the following formula (QP2) can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.
  • X 1 to X 16 each 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 formula (QP1) include compounds described in paragraph number 0016 of Japanese Patent No. 6443711 .
  • Y 1 to Y 3 each independently represent a halogen atom.
  • n and m are integers from 0 to 6; p is an integer from 0 to 5; (n+m) is 1 or more.
  • Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
  • C.I. I. Pigment Yellow 129, 138, 139, 150 and 185 are preferred.
  • green pigments examples include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred.
  • Specific examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like.
  • a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used.
  • Specific examples include compounds described in International Publication No. 2015/118720.
  • Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, aluminum phthalocyanine compounds described in JP-A-2020-070426, JP-A-2020-076995 Core-shell type dyes and the like described can also be used.
  • a green pigment C.I. I. Pigment Green 7, 36, 58, 62 and 63 are preferred, C.I. I. Pigment Greens 36 and 58 are more preferably used.
  • 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. is mentioned.
  • C.I. I. Pigment Violet 1 19, 23, 27, 32, 37, 42, 60, 61 and the like.
  • 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. be done.
  • an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
  • the diketopyrrolopyrrole pigment has a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes ( ⁇ 1 ⁇ 1 ⁇ 1) of the crystal lattice planes. It is also preferred to use one.
  • the physical properties of the diketopyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
  • organic pigment it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of enhancing spectral characteristics.
  • organic pigment it is also preferable to use a dioxazine pigment with a controlled contact angle described in WO 2019/107166 from the viewpoint of viscosity adjustment.
  • Dyes can also be used as coloring agents.
  • the dye is not particularly limited, and known dyes can be used.
  • a pigment multimer can also be used as a coloring agent.
  • the dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
  • the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
  • a dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • a plurality of dye structures in one molecule may be the same dye structure or different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
  • the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
  • Colorants include diarylmethane compounds described in JP-A-2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and those described in JP-A-2020-117638.
  • a xanthene compound, a phthalocyanine compound described in International Publication No. 2020/174991, an isoindoline compound described in JP-A-2020-160279, or a salt thereof can be used.
  • a pigment derivative can also be used as a coloring agent.
  • Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons.
  • diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton , thiazineindigo dye skeleton, thioindigo dye skeleton, isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, iminium dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, pyrromethene dye skeleton, and the like.
  • Pyrrolopyrrole dye skeletons benzoisoindole dye skeletons, anthraquinone dye skeletons, dianthraquinone dye skeletons, thiazineindigo dye skeletons, azo dye skeletons, quinophthalone dye skeletons, phthalocyanine dye skeletons, and quinacridone dye skeletons are preferred, and diketo Pyrrolopyrrole dye skeletons, benzoisoindole dye skeletons, anthraquinone dye skeletons, azo dye skeletons, quinophthalone dye skeletons, phthalocyanine dye skeletons, and quinacridone dye skeletons are more preferred.
  • the pigment derivative is preferably a diketopyrrolopyrrole dye skeleton, that is, a diketopyrrolopyrrole compound.
  • a film having a higher red color value can be formed, and it is more preferably used as a coloring composition for red pixels.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
  • the carboxylic acid amide group a group represented by —NHCOR X1 is preferable.
  • sulfonic acid amide group a group represented by —NHSO 2 R X2 is preferable.
  • the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 .
  • R X1 to R X6 each independently represent an alkyl group or an aryl group.
  • the alkyl groups and aryl groups represented by R X1 to R X6 may have substituents.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • the pigment derivative include the compounds described in Examples below, the compounds described in JP-A-56-118462, the compounds described in JP-A-63-264674, and JP-A-01-217077.
  • Compounds described in, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, described in JP-A-03-045662 The compound, the compound described in JP-A-04-285669, the compound described in JP-A-06-145546, the compound described in JP-A-06-212088, the compound described in JP-A-06-240158 , the compound described in JP-A-10-030063, the compound described in JP-A-10-195326, the compound described in paragraph numbers 0086 to 0098 of WO 2011/024896, WO 2012/102399
  • the content of the coloring agent in the total solid content of the coloring composition is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and 55% by mass. % or more, and particularly preferably 60 mass % or more.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
  • the content of the organic pigment in the total solid content of the coloring composition is preferably 35-80% by mass.
  • the lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, even more preferably 55% by mass or more, and 60% by mass or more. is particularly preferred.
  • the upper limit is preferably 75% by mass or less, more preferably 70% by mass or less.
  • the content of the organic pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
  • the upper limit can be 100% by mass or less, and can also be 95% by mass or less.
  • the total content of the organic pigment and the pigment derivative in the total solid content of the coloring composition is preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass or more is more preferable, 55% by mass or more is even more preferable, and 60% by mass or more is particularly preferable.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.
  • the total content of the organic pigment and the pigment derivative in the colorant is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass. is more preferred.
  • the content of the diketopyrrolopyrrole pigment in the total solid content of the coloring composition is preferably 20 to 65% by mass.
  • the lower limit is preferably 25% by mass or more, more preferably 35% by mass or more.
  • the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less.
  • the content of the diketopyrrolopyrrole pigment in the colorant is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
  • the coloring composition of the present invention is used as a coloring composition for forming red pixels of a color filter, it is preferable to use a coloring agent containing a red coloring agent and a yellow coloring agent.
  • the red colorant is preferably a red pigment.
  • the yellow colorant is preferably a yellow pigment.
  • the ratio of the red colorant and the yellow colorant is preferably 10 to 100 parts by mass of the yellow colorant per 100 parts by mass of the red colorant.
  • the lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more.
  • the upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less.
  • the coloring composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
  • examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
  • 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 monomer, prepolymer, oligomer, etc., but monomer is preferred.
  • the molecular weight of the polymerizable compound is preferably 100-3000.
  • the upper limit is preferably 2000 or less, 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 even more 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, more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less, from the viewpoint of the stability of the colored composition over time.
  • the polymerizable compound is preferably a tri- or more functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound. is more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred.
  • polymerizable compounds examples include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. mentioned.
  • Modified compounds include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded via an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate. Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).
  • E is each 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 each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth)acryloyl groups is 3 or 4
  • the sum of m is an integer of 0 to 40.
  • the total number of (meth)acryloyl groups is 5 or 6
  • each n independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.
  • m is preferably an integer of 0-6, more preferably an integer of 0-4.
  • the sum of 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 0-6, more preferably an integer of 0-4.
  • the sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.
  • E in formula (Z-4) or formula (Z-5), that is, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- is A form in which the end on the oxygen atom side is bonded to X is preferred.
  • Polypentaerythritol poly(meth)acrylates represented by the following formula (Z-6) can also be used as the polymerizable compound.
  • X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1-10. 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. Seeds are preferred.
  • Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, TPOA-50 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. mentioned.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetra (meth) acrylate manufactured by Shin-Nakamura Chemical 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 Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL80 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate) and the like can also be used.
  • trimethylolpropane tri(meth)acrylate trimethylolpropane propyleneoxy-modified tri(meth)acrylate
  • trimethylolpropane ethyleneoxy-modified tri(meth)acrylate trimethylolpropane ethyleneoxy-modified tri(meth)acrylate
  • ethyleneoxy isocyanurate-modified tri(meth) It is also preferable to use trifunctional (meth)acrylate compounds such as acrylates and pentaerythritol tri(meth)acrylates.
  • Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
  • M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
  • a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can be used as the polymerizable compound.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • a compound having a caprolactone structure can also be used as the polymerizable compound.
  • the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
  • Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances.
  • a compound such as toluene that does not substantially contain environmentally regulated substances.
  • Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765
  • urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418.
  • the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical 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, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the content of the polymerizable compound in the total solid content of the coloring composition is preferably 1 to 35% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the coloring composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention contains a photopolymerization initiator.
  • an oxime compound is used as the photopolymerization initiator.
  • the oxime compound is preferably a photoradical polymerization initiator.
  • the oxime compound is preferably a compound having photosensitivity to light in the ultraviolet region to the visible region.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S.
  • a bifunctional or trifunctional oxime compound can also be used.
  • bifunctional or trifunctional oxime compounds include JP 2010-527339, JP 2011-524436, WO 2015/004565, paragraph numbers 0407 to 0412 of JP 2016-532675, Dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, International Publication No.
  • oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) and the like.
  • An oxime compound having a fluorene ring can also be used as the oxime compound.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
  • 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 oxime compounds include compounds described in WO2013/083505.
  • An oxime compound having a fluorine atom can also be used as the oxime compound.
  • Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
  • an oxime compound having a nitro group can be used as the oxime compound.
  • 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 paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
  • An oxime compound having a benzofuran skeleton can also be used as the oxime compound.
  • Specific examples include OE-01 to OE-75 described in WO 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 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing 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.
  • a benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, 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.
  • a sulfanyl group or an amino group is more preferred.
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
  • R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
  • R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
  • electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups, with acyl groups and nitro groups being preferred.
  • An acyl group is more preferred, and a benzoyl group is even more preferred, because a film having excellent properties can be easily formed.
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
  • the coloring composition of the present invention can contain a photopolymerization initiator other than the oxime compound (another photopolymerization initiator) as a photopolymerization initiator.
  • a photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
  • hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
  • ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
  • 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.
  • the content of the oxime compound in the photopolymerization initiator is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass.
  • the photopolymerization initiator is substantially only the oxime compound.
  • the case where the photopolymerization initiator is substantially only an oxime compound means that the content of the oxime compound in the photopolymerization initiator is 99% by mass or more, and 99.9% by mass. % by mass or more is more preferable, and it is particularly preferable to contain only the oxime compound.
  • the coloring composition of the present invention only one type of photopolymerization initiator may be used, or two or more types 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 contains a solvent.
  • Solvents contained in the coloring composition of the present invention include cyclic ketone solvents.
  • a ketone compound having a ring structure is preferable as the cyclic ketone solvent.
  • the cyclic ketone solvent may have a substituent on the ring structure. An alkyl group etc. are mentioned as a substituent.
  • the cyclic ketone solvent preferably has 3 to 20 carbon atoms. Examples of the cyclic ketone solvent include cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclopentanone, etc. Cyclopentanone is preferred.
  • the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass, preferably 5 to 13% by mass, more preferably 6 to 10% by mass. Also, the content of cyclopentanone in the solvent is preferably 1 to 15% by mass, more preferably 5 to 13% by mass, even more preferably 6 to 10% by mass.
  • the solvent contained in the coloring composition of the present invention includes solvents other than cyclic ketone solvents (referred to as other solvents).
  • Other solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like.
  • Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
  • the other solvent preferably contains at least one selected from an ester solvent, an ether solvent and an alcohol solvent for the reason that the thickness unevenness of the resulting film can be reduced. More preferably, it contains at least one selected from solvent-based solvents, and more preferably contains an ester-based solvent.
  • an ester-based solvent means an organic solvent having an ester bond in its molecule.
  • an ether-based solvent means an organic solvent having an ether bond in its molecule.
  • an alcohol-based solvent means an organic solvent having a hydroxy group in its molecule.
  • an organic solvent having an ester bond, an ether bond and/or a hydroxy group in its molecule corresponds to an ester solvent.
  • an organic solvent that does not have an ester bond in its molecule and has both an ether bond and a hydroxy group corresponds to an alcohol-based solvent.
  • the content of the ester solvent in the solvent is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. Also, the total content of the cyclic ketone solvent and the ester solvent is preferably 95 to 100% by mass, more preferably 97 to 100% by mass, and even more preferably 98 to 100% by mass.
  • a preferred embodiment of the other solvent includes an embodiment in which the other solvent is substantially only an ester solvent. According to this aspect, the storage stability of the coloring composition can be further improved, and the thickness unevenness of the obtained film can be further reduced.
  • the other solvent is substantially only an ester solvent, it means that the content of the ester solvent in the other solvent is 99% by mass or more, and is 99.9% by mass or more. is preferable, and it is more preferable to use only an ester solvent.
  • Another preferred embodiment of the other solvent includes an embodiment in which the other solvent contains an ester solvent and an alcohol solvent. According to this aspect, the occurrence of coating defects can be further suppressed.
  • the ratio of the ester solvent and the alcohol solvent is preferably 0.1 to 3.0 parts by mass, preferably 0.3 to 2.5 parts by mass, per 100 parts by mass of the ester solvent. more preferably 0.5 to 2.0 parts by mass.
  • solvents 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, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexyl acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole
  • a solvent with a low metal content it is preferable to use a solvent with a low metal content.
  • the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). .
  • Examples of methods for removing impurities such as metals from solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
  • the content of peroxide in the 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 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.
  • the content of the cyclic ketone solvent in the coloring composition is preferably 1 to 10% by mass, more preferably 3 to 9% by mass, and even more preferably 5 to 8% by mass.
  • the coloring composition of the present invention preferably does not substantially contain environmentally regulated substances.
  • substantially free of environmentally regulated substances means that the content of environmentally regulated substances in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • distillation off a small amount of environmentally regulated substances it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency.
  • a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking.
  • These distillation methods are the raw material stage, the reaction product of the raw materials (for example, the resin solution or polyfunctional monomer solution after polymerization), or the colored composition stage produced by mixing these compounds. It is possible at any stage such as
  • the coloring composition of the present invention preferably contains a resin.
  • the resin is blended, for example, for dispersing a pigment or the like in a coloring composition or as a binder.
  • a resin mainly used for dispersing a pigment or the like in a coloring composition is also called a dispersant.
  • such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • resins examples include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, and polyarylene resins.
  • ether phosphine oxide resins polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins and the like.
  • the resin described in the examples of International Publication No.
  • the resin it is preferable to use a resin having an acid group.
  • acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
  • the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
  • the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
  • the upper limit is more preferably 400 mgKOH/g or less, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000.
  • the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin.
  • the upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less.
  • the lower limit of the content of repeating units having an acid group in the side chain is preferably 10 mol % or more, more preferably 20 mol % or more.
  • resin having an acid group JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408
  • the descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein.
  • resin which has an acid group can also use a commercial item.
  • the method for introducing the acid group into the resin is not particularly limited, but includes, for example, the method described in Japanese Patent No. 6349629 .
  • a method for introducing an acid group into a resin a method of reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce an acid group can also be mentioned.
  • the coloring composition of the present invention also preferably contains a resin having a basic group.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain. It is more preferably a polymer, and more preferably a block copolymer having a repeating unit having a basic group on its side chain and a repeating unit containing no basic group. Resins having basic groups can also be used as dispersants.
  • the amine value of the resin having basic groups is preferably 5-300 mgKOH/g.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
  • resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 33090500, 39090500, 390500 56000, 7100 (manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF) and the like.
  • the resin having a basic group is a block copolymer (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and described in paragraph numbers 0046-0076 of JP-A-2018-156021. It is also possible to use the block copolymer A1 described above and vinyl resins having basic groups described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein.
  • the coloring composition of the present invention preferably contains a resin having an acid group and a resin having a basic group. According to this aspect, the storage stability of the coloring composition can be further improved.
  • a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is 20 to 500 parts by mass with respect to 100 parts by mass of the resin having an acid group. It is preferably from 30 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass.
  • 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 an "ether dimer"). It is also preferable to use a resin containing a repeating unit that
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • 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 0-15.
  • the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
  • 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 formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
  • Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic 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 the group represented by the formula (e-2) It is more preferable that the group is When n in formula (e-1) is 0, the group represented by formula (e-1) is an epoxy group, and when n is 1, it is represented by formula (e-1) The group is an oxetanyl group. Also, the group represented by formula (e-2) is an alicyclic epoxy group.
  • R E1 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 represents a ring, and * represents a bond.
  • the number of carbon atoms in the alkyl group represented by R E1 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group represented by R E1 is preferably linear or branched, more preferably linear.
  • R E1 is preferably a hydrogen atom.
  • R 1 E1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • formula (e-1) is a group represented by formula (e-1a) below.
  • the aliphatic hydrocarbon ring represented by ring A E1 in formula (e-2) may be a monocyclic aliphatic hydrocarbon ring or a condensed aliphatic hydrocarbon ring.
  • the aliphatic hydrocarbon ring represented by Ring A E1 may have a crosslinked structure.
  • a condensed aliphatic hydrocarbon ring is preferable because a film having excellent moisture resistance can be easily formed, and a condensed aliphatic hydrocarbon ring having a crosslinked structure is preferable.
  • Specific examples of the aliphatic hydrocarbon ring represented by ring A E1 include the groups shown below, and the group represented by formula (e-2-3) and represented by formula (e-2-4) groups are preferred. In the following formulas, * represents a bond.
  • resins having a cyclic ether group include, for example, naphthalene-modified epoxy resins such as EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation).
  • naphthalene-modified epoxy resins such as EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation).
  • alkyldiphenol-type epoxy resins include EPICLON 820 (manufactured by DIC Corporation).
  • jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (and Co., Ltd.) and the like.
  • Phenol novolac type epoxy resins include jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and the like. mentioned.
  • EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) as cresol novolak type epoxy resins , and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S manufactured by ADEKA Corporation
  • Celoxide 2021P Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like.
  • resin Ac a resin having an aromatic carboxy group
  • the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
  • Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxyl group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxyl group
  • L 11 represents -COO- or -CONH-
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer represents a chain.
  • Examples of the aromatic carboxy group-containing group represented by Ar 1 in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like.
  • Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
  • the group containing an aromatic carboxyl group represented by Ar 1 may have a crosslinkable group.
  • the crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, more preferably an ethylenically unsaturated bond-containing group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). and the like.
  • n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2.
  • n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- 1) or a group represented by the above formula (Q-2).
  • * 1 represents the bonding position with L1.
  • L 1 represents -COO- or -CONH-, preferably -COO-.
  • the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the alkylene group may be linear, branched or cyclic.
  • the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • An alkylene group and an arylene group may have a substituent. A hydroxy group etc.
  • the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
  • L 2a is an alkylene group; an arylene group; a combination of an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group; Examples include groups in which at least one selected from —NH— and —S— are combined, and alkylene groups are preferred.
  • the number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
  • the group containing an aromatic carboxy group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
  • L 11 represents -COO- or -CONH-, preferably -COO-.
  • the trivalent linking group represented by L 12 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included.
  • Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10.
  • the hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown.
  • the trivalent linking group represented by L 12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- is preferably a hydrocarbon group or a group of a combination of a hydrocarbon group and —O—.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown.
  • the trivalent linking group represented by L 12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.
  • P 10 in formula (Ac-2) represents a polymer chain.
  • the polymer chain represented by P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units.
  • the weight average molecular weight of the polymer chain P10 is preferably 500-20,000 .
  • the lower limit is preferably 1000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition is good.
  • the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P10 may contain crosslinkable groups.
  • Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the coloring composition of the present invention preferably contains a resin as a dispersant.
  • Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater 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 possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
  • a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
  • a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
  • the basic group possessed by the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is also preferably a graft resin.
  • graft resin for details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • the resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains.
  • the polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
  • a resin having 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 JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core.
  • resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
  • the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
  • the content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
  • resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
  • the content of the resin in the total solid content of the coloring composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the coloring composition of the present invention may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can also contain a polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersing aids for pigments.
  • a dispersing aid is a material for enhancing dispersibility of a pigment in a coloring composition.
  • a polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has at least a secondary amino group.
  • the polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group.
  • the polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group.
  • the alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, still more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
  • the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
  • the value of the number average molecular weight measured by the viscosity method is used.
  • the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
  • the content of polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain a curing accelerator.
  • Curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
  • the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379.
  • the content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the coloring composition of the present invention can contain an ultraviolet absorber.
  • ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814.
  • UV absorbers examples include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
  • Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016).
  • the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No.
  • a thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used.
  • the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types 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 can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain a silane coupling agent.
  • a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
  • Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
  • silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM
  • silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
  • the content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
  • surfactants reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
  • the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the coloring composition.
  • JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
  • Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
  • the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
  • fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
  • fluorosurfactant 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 as the fluorosurfactant.
  • fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant 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) (meta)
  • 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 fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol %.
  • a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant.
  • Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K.
  • compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, 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 company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
  • Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
  • 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% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention can contain an antioxidant.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
  • antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds 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. Only one kind of antioxidant may be used, or two or more kinds thereof 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 may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein.
  • auxiliaries e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the coloring composition of the present invention may contain a latent antioxidant, if desired.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
  • metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 and SiO 2 .
  • the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
  • Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.
  • the coloring composition of the present invention may contain a light resistance improver.
  • a light resistance improver compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds
  • the coloring composition of the present invention preferably does not substantially contain terephthalic acid ester.
  • substantially free means that the content of 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.
  • perfluoroalkylsulfonic acid and its salts may be regulated.
  • perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • fluoroalkylcarboxylic acid especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the coloring composition.
  • the coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts.
  • 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 and salts thereof may be selected.
  • Compounds that can substitute for regulated compounds include, for example, compounds excluded from regulation due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
  • the coloring composition of the present invention may contain perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts within the maximum allowable range.
  • the water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass.
  • the water content can be measured by the Karl Fischer method.
  • the coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and adjusting the film thickness.
  • the viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa ⁇ s to 50 mPa ⁇ s, more preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s at 25°C.
  • a method for measuring the viscosity for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
  • the container for the coloring composition is not particularly limited, and known containers can be used.
  • a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-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, enhancing the storage stability of the coloring composition, and suppressing deterioration of components.
  • the coloring composition of the present invention can be prepared by mixing the aforementioned ingredients.
  • all components may be simultaneously dissolved and / or dispersed in a solvent to prepare a colored composition, and if necessary, each component may be appropriately mixed into two or more solutions or dispersions. , these may be mixed at the time of use (at the time of coating) to prepare a colored composition.
  • a process of dispersing the pigment when preparing the coloring composition.
  • mechanical forces used for dispersing pigments include 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.
  • 2015-157893 can be suitably used.
  • the particles may be made finer in the salt milling step.
  • Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.
  • 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)
  • polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
  • PP polypropylene
  • nylon including high density polypropylene
  • nylon including high density polypropylene
  • the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
  • Various filters provided by Nihon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as the filter. .
  • fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
  • 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.
  • filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
  • the method for producing the membrane of the present invention includes the step of applying the coloring composition of the present invention to a support.
  • the film thickness of the film manufactured by the film manufacturing method of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even 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, and even more preferably 0.3 ⁇ m or more.
  • the film manufactured by the film manufacturing method of the present invention can be used for colored pixels of color filters.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and yellow pixels are preferred, and red pixels are more preferred. preferable.
  • the method for producing a film of the present invention preferably further includes a step of forming a pattern (pixels).
  • a method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable.
  • Pattern formation by photolithography includes the steps of forming a colored composition layer on a support using the colored composition of the present invention, a step of patternwise exposing the colored composition layer, and a step of exposing the colored composition layer. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the coloring composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
  • the colored composition layer of the present invention is used to form the colored composition layer on the support.
  • the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, 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.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • the silicon substrate is formed with a black matrix that isolates each pixel.
  • the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • the underlayer may be formed using a composition obtained by removing the coloring agent from the colored composition described herein, or a composition containing the resin, polymerizable compound, surfactant, etc. described herein. good.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.
  • a known method can be used as a method for applying the coloring composition.
  • dropping method drop cast
  • slit coating method spray method
  • roll coating method spin coating
  • methods described in publications inkjet
  • ejection system printing ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. various printing methods; a transfer method using a mold or the like; and a nanoimprint method.
  • the application method for inkjet is not particularly limited.
  • the colored composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process.
  • the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
  • the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
  • the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using 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 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
  • Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
  • Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable.
  • a long-wave light source of 300 nm or more can also be used.
  • the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
  • the dose 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 selected as appropriate.
  • the exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done.
  • the oxygen concentration and exposure illuminance may be appropriately combined.
  • the illuminance may be 10000 W/m 2 at an oxygen concentration of 10% by volume and 20000 W/m 2 at an oxygen concentration of 35% by volume.
  • the unexposed areas of the colored composition layer are removed by development to form a pattern (pixels).
  • the development and removal of the unexposed portion of the colored composition layer can be performed using a developer.
  • the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion.
  • the temperature of the developer is preferably 20 to 30° C., for example.
  • the development time is preferably 20 to 180 seconds. Further, in order to effectively remove the residue, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
  • the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
  • an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
  • alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, 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
  • examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate.
  • a compound having a large molecular weight is preferable for the alkaline agent from the standpoint 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 transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse solution to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed.
  • the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
  • the moving speed of the nozzle may be gradually decreased.
  • Additional exposure processing and post-baking are post-development curing treatments for complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
  • the light used for exposure preferably has a wavelength of 400 nm or less.
  • the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • Pattern formation by a dry etching method is 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 layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas.
  • a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable.
  • pattern formation by a dry etching method descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.
  • the method for manufacturing the color filter of the present invention includes the method for manufacturing the film of the present invention described above. That is, the method for producing a color filter of the present invention includes the step of applying the coloring composition of the present invention described above onto a support.
  • a color filter preferably has the film of the present invention as its pixels.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the width of pixels included in the color filter is preferably 0.1 to 10.0 ⁇ m.
  • the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and even more preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
  • a method for manufacturing a solid-state imaging device according to the present invention includes the above-described method for manufacturing a film according to the present invention. That is, the method for producing a solid-state imaging device of the present invention includes the step of applying the coloring composition of the present invention described above to a support.
  • the configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
  • Transfer electrodes made of polysilicon or the like, and a plurality of photodiodes forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a substrate.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • a light-shielding film is provided on the photodiode and the transfer electrode so that only the light-receiving portion of the photodiode is opened. It has a device protective film with a thickness of 1.5 mm, and has a color filter on the device protective film.
  • the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654.
  • an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance.
  • An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.
  • a method for manufacturing an image display device of the present invention includes the above-described method for manufacturing a film of the present invention. That is, the method for producing an image display device of the present invention includes the step of applying the coloring composition of the present invention described above to a support.
  • image display devices include liquid crystal display devices and organic electroluminescence display devices.
  • Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
  • the weight average molecular weight (Mw) of the resin was calculated by GPC (Gel permeation chromatography) measurement under the following measurement conditions.
  • Column type Column connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran
  • Apparatus name HLC-8220GPC manufactured by Tosoh Corporation Detector: Differential refractometer (RI detector)
  • a mixture of a total of 16 parts by mass of a pigment and a pigment derivative, 4 parts by mass of a dispersant in terms of solid content, and 80 parts by mass of a solvent is processed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm). Mixed and dispersed. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a dispersion.
  • the materials shown in the table below were used for the pigment, pigment derivative, dispersant and solvent.
  • pigment (pigment) P-1: C.I. I. Pigment Red 177 (red pigment, anthraquinone pigment)
  • P-2 C.I. I. Pigment Red 254 (red pigment, diketopyrrolopyrrole pigment)
  • P-4 C.I. I. Pigment Red 269 (red pigment, naphthol pigment)
  • P-5 C.I. I. Pigment Red 272 (red pigment, diketopyrrolopyrrole pigment)
  • P-6 C.I. I. Pigment Red 291 (red pigment, diketopyrrolopyrrole pigment)
  • P-7 C.I. I.
  • Pigment Yellow 129 (yellow pigment, azomethine pigment)
  • P-8 C.I. I. Pigment Yellow 138 (yellow pigment, quinophthalone pigment)
  • P-9 C.I. I. Pigment Yellow 139 (yellow pigment, isoindoline pigment)
  • P-10 C.I. I. Pigment Yellow 150 (yellow pigment, azo pigment)
  • P-11 C.I. I. Pigment Yellow 185 (yellow pigment, isoindoline pigment)
  • P-12 C.I. I. Pigment Green 58 (green pigment, phthalocyanine pigment)
  • P-13 C.I. I. Pigment Blue 15:6 (blue pigment, phthalocyanine pigment)
  • (pigment derivative) Syn-1 a compound having the following structure
  • Syn-2 a compound having the following structure
  • Syn-3 a compound having the following structure
  • Syn-4 a compound having the following structure
  • Syn-5 a compound having the following structure
  • Syn-6 a compound having the following structure
  • Syn-7 a compound having the following structure
  • Syn-8 a compound having the following structure
  • Syn-9 a compound having the following structure
  • Syn-10 a compound having the following structure
  • (dispersant) D-1 Resin D-1 synthesized by the following method 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into a reaction vessel, and the atmosphere was The gas was replaced with nitrogen gas. Heat the inside of the reaction vessel to 70° C., add 6 parts by mass of 3-mercapto-1,2-propanediol, add 0.12 parts by mass of AIBN (azobisisobutyronitrile), and react for 12 hours. let me Solid content measurement confirmed that 95% had reacted.
  • PMEA propylene glycol monomethyl ether acetate
  • Resin D-2 Resin D-2 synthesized by the following method 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel, and after replacing the atmospheric gas with nitrogen gas, It was made to react at 120 degreeC for 5 hours (1st process). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified.
  • D-3 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 16000, acid value: 67 mgKOH/g)
  • D-4 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 21000, acid value: 36 mgKOH/g)
  • D-5 Disperbyk-111 (manufactured by BYK-Chemie)
  • D-6 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 18000, acid value 82. 1 mg KOH/g)
  • Each material is mixed in the ratio of prescription 1, prescription 2, prescription 3, prescription 4, prescription c1 or prescription c2 shown below, and filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 ⁇ m.
  • Each coloring composition was produced.
  • the content of the coloring agent in the total solid content of the coloring composition (the total amount of the pigment and the pigment derivative) is described in the column “coloring agent concentration”, and the content of the cyclic ketone solvent in the total solvent The amount is given in the column "Proportion of cyclic ketone solvent”.
  • Dispersions 1 to 31, c1, c2 Dispersions 1 to 31, c1, c2 described above
  • I-1 Irgacure OXE01 (manufactured by BASF, oxime compound)
  • I-2 Irgacure OXE02 (manufactured by BASF, oxime compound)
  • I-3 A compound having the following structure (oxime compound)
  • I-4 Irgacure OXE04 (manufactured by BASF, oxime compound)
  • binder B-1 A 30% by mass PGMEA solution of a resin having the following structure (weight average molecular weight: 11000, the numerical value attached to the main chain represents the molar ratio of repeating units)
  • B-2 30% by mass of a resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
  • (Surfactant) Su-1 A compound having the following structure (weight average molecular weight: 14,000). In the following formulas, % indicating the ratio of repeating units is mol %.
  • solvent 1 Propylene glycol monomethyl ether acetate (ester solvent)
  • S-2 2-butanol (alcohol solvent)
  • S-3 Propylene glycol monomethyl ether (alcohol solvent)
  • S-4 3-methoxybutanol (alcohol solvent)
  • the colored compositions of Examples were excellent in storage stability and film thickness uniformity.
  • the films obtained using the colored composition of Example 9 with a high colorant concentration were , 50, 51, and 52 had better light resistance than the films obtained using the coloring compositions.
  • the heat resistance of the films obtained using the colored compositions of Examples 2, 5 and 9 was evaluated. It had better heat resistance than 5.
  • the films obtained using the colored compositions of Examples 57 to 59 containing a cyclic ketone solvent, an ester solvent and an alcohol solvent had fewer coating defects than other examples.
  • Example 1 Similar results can be obtained by replacing the surfactant in Example 1 with KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant). Similar results are obtained in Example 1 when no polymerization inhibitor is added.
  • a film obtained using the colored composition of each example can be suitably used for a color filter, a solid-state imaging device, and an image display device.
  • the colored composition of each example can also be used for i-line exposure or KrF line exposure.

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Abstract

Provided is a colored composition which has satisfactory storage stability and can form films reduced in thickness unevenness. The colored composition comprises a colorant, a polymerizable compound, a photopolymerization initiator, and solvents, wherein the colorant comprises an organic pigment, the photopolymerization initiator comprises an oxime compound, and the solvents include a cyclic ketone solvent, the content of the cyclic ketone solvent in the solvents being 1-15 mass%.

Description

着色組成物、膜の製造方法、カラーフィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法Coloring composition, method for producing film, method for producing color filter, method for producing solid-state imaging device, and method for producing image display device
　本発明は、顔料を含む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、固体撮像素子および画像表示装置の製造方法に関する。 The present invention relates to a coloring composition containing a pigment. The present invention also relates to a method for producing a film, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
　近年、デジタルカメラ、カメラ付き携帯電話等の普及から、電荷結合素子（ＣＣＤ）イメージセンサなどの固体撮像素子の需要が大きく伸びている。ディスプレイや光学素子のキーデバイスとしてカラーフィルタが使用されている。 In recent years, due to the spread of digital cameras, camera-equipped mobile phones, etc., the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements.
　カラーフィルタは、例えば、有機顔料を含む着色剤と、重合性化合物と、光重合開始剤と、溶剤とを含む着色組成物を用いて製造することが行われている。例えば、特許文献１には、アゾ顔料を含む着色剤と、バインダー樹脂と、光重合性単量体と、オキシムエステル化合物を含む光重合開始剤と、溶剤とを含有する着色組成物を用いてカラーフィルタを製造することが記載されている。 Color filters are manufactured using, for example, a coloring composition containing a colorant containing an organic pigment, a polymerizable compound, a photopolymerization initiator, and a solvent. For example, Patent Document 1 discloses a coloring composition containing a colorant containing an azo pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator containing an oxime ester compound, and a solvent. The manufacture of color filters is described.
特開２０１６－２１２３７２号公報JP 2016-212372 A
　近年、固体撮像素子においては、小型化や薄膜化の要求が強い。このため、固体撮像素子に用いられるカラーフィルタなどの着色剤を含む膜についても、近年では、より薄膜化されることが望まれている。所望の分光性能を維持しつつ薄膜化を達成するためには、膜形成に用いる着色組成物中の着色剤濃度を高めることが必要である。 In recent years, there has been a strong demand for smaller and thinner solid-state imaging devices. Therefore, in recent years, it is desired that films containing colorants such as color filters used in solid-state imaging devices be made thinner. In order to achieve a thin film while maintaining desired spectral performance, it is necessary to increase the colorant concentration in the coloring composition used for film formation.
　しかしながら、着色組成物の全固形分中の着色剤濃度が高くなるに伴い、相対的に着色剤以外の成分の割合が少なくなるので、着色組成物の保管時に、着色剤が凝集するなどして着色組成物の粘度が増加しやすい傾向にあった。特に、有機顔料を含む着色剤を用いた場合においては、着色組成物の粘度が経時的に上昇しやすい傾向にあった。 However, as the concentration of the coloring agent in the total solid content of the coloring composition increases, the proportion of components other than the coloring agent decreases relatively. The viscosity of the coloring composition tended to increase. In particular, when a coloring agent containing an organic pigment is used, the viscosity of the coloring composition tends to increase over time.
　また、着色組成物を用いて膜を形成するに際し、厚みムラが小さいことが求められている。 In addition, when forming a film using a coloring composition, it is required that thickness unevenness is small.
　本発明者の検討によれば、特許文献１に記載された着色組成物では、着色組成物の保存安定性や、着色組成物を用いて得られる膜の厚みムラについて、更なる改善の余地があることが分かった。 According to the study of the present inventor, in the coloring composition described in Patent Document 1, there is room for further improvement with respect to the storage stability of the coloring composition and the thickness unevenness of the film obtained using the coloring composition. It turns out there is.
　よって、本発明の目的は、保存安定性が良好で、厚みムラの小さい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、本発明は、着色組成物を用いた膜、カラーフィルタ、固体撮像素子および画像表示装置の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a coloring composition that has good storage stability and is capable of forming a film with little unevenness in thickness. Another object of the present invention is to provide a method for producing a film, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
　本発明者が有機顔料を含む着色剤と、重合性化合物と、光重合開始剤と、溶剤とを含む着色組成物について鋭意検討を進めたところ、光重合開始剤としてオキシム化合物を含むものを用い、かつ、溶剤として環状ケトン溶剤を所定量含む溶剤を用いることにより、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。よって、本発明は以下を提供する。 The inventor of the present invention has extensively studied a coloring composition containing a coloring agent containing an organic pigment, a polymerizable compound, a photopolymerization initiator, and a solvent. Furthermore, the inventors have found that the above objects can be achieved by using a solvent containing a predetermined amount of a cyclic ketone solvent, and have completed the present invention. Accordingly, the present invention provides the following.
　＜１＞　着色剤と、重合性化合物と、光重合開始剤と、溶剤とを含み、
　上記着色剤は有機顔料を含み、
　上記光重合開始剤はオキシム化合物を含み、
　上記溶剤は環状ケトン溶剤を含み、かつ、上記溶剤中における上記環状ケトン溶剤の含有量が１～１５質量％である、
　着色組成物。
　＜２＞　上記環状ケトン溶剤はシクロペンタノンである、＜１＞に記載の着色組成物。
　＜３＞　上記溶剤中における上記環状ケトン溶剤の含有量が５～１３質量％である、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　上記溶剤は、エステル系溶剤と、アルコール系溶剤と、をさらに含む、＜１＞～＜３＞のいずれか１つに記載の着色組成物。
　＜５＞　上記有機顔料は、キナクリドン顔料、アントラキノン顔料、アゾ顔料、ジケトピロロピロール顔料、イソインドリン顔料、キノフタロン顔料、プテリジン顔料およびアゾメチン顔料から選択される少なくとも１種を含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　上記有機顔料は、ジケトピロロピロール顔料およびイソインドリン顔料から選択される少なくとも１種を含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜７＞　上記有機顔料はジケトピロロピロール顔料を含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜８＞　上記有機顔料はジケトピロロピロール顔料を２種以上含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜９＞　上記有機顔料は、カラーインデックスピグメントレッド２５４およびカラーインデックスピグメントレッド２７２から選択される少なくとも１種を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　上記着色組成物の全固形分中における上記着色剤の含有量が５５質量％以上である、＜１＞～＜９＞のいずれか１つに記載の着色組成物。
　＜１１＞　＜１＞～＜１０＞のいずれか１つに記載の着色組成物を支持体に塗布する工程を含む膜の製造方法。
　＜１２＞　＜１１＞に記載の膜の製造方法を含むカラーフィルタの製造方法。
　＜１３＞　＜１１＞に記載の膜の製造方法を含む固体撮像素子の製造方法。
　＜１４＞　＜１１＞に記載の膜の製造方法を含む画像表示装置の製造方法。 <1> containing a coloring agent, a polymerizable compound, a photopolymerization initiator, and a solvent,
The coloring agent contains an organic pigment,
The photopolymerization initiator contains an oxime compound,
The solvent contains a cyclic ketone solvent, and the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass.
coloring composition.
<2> The colored composition according to <1>, wherein the cyclic ketone solvent is cyclopentanone.
<3> The colored composition according to <1> or <2>, wherein the content of the cyclic ketone solvent in the solvent is 5 to 13% by mass.
<4> The colored composition according to any one of <1> to <3>, wherein the solvent further includes an ester solvent and an alcohol solvent.
<5> The organic pigment contains at least one selected from quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments and azomethine pigments, <1> to <4> The colored composition according to any one of items 4>.
<6> The coloring composition according to any one of <1> to <4>, wherein the organic pigment contains at least one selected from diketopyrrolopyrrole pigments and isoindoline pigments.
<7> The coloring composition according to any one of <1> to <4>, wherein the organic pigment comprises a diketopyrrolopyrrole pigment.
<8> The coloring composition according to any one of <1> to <4>, wherein the organic pigment contains two or more diketopyrrolopyrrole pigments.
<9> The coloring composition according to any one of <1> to <8>, wherein the organic pigment includes at least one selected from Color Index Pigment Red 254 and Color Index Pigment Red 272.
<10> The coloring composition according to any one of <1> to <9>, wherein the content of the coloring agent in the total solid content of the coloring composition is 55% by mass or more.
<11> A method for producing a film, comprising the step of applying the coloring composition according to any one of <1> to <10> to a support.
<12> A method for producing a color filter, including the method for producing a film according to <11>.
<13> A method for manufacturing a solid-state imaging device, including the method for manufacturing a film according to <11>.
<14> A method for manufacturing an image display device, including the method for manufacturing a film according to <11>.
　本発明によれば、保存安定性が良好で、厚みムラの小さい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、膜、カラーフィルタ、固体撮像素子および画像表示装置の製造方法を提供することができる。 According to the present invention, it is possible to provide a coloring composition that has good storage stability and is capable of forming a film with little unevenness in thickness. In addition, the present invention can provide methods for manufacturing films, color filters, solid-state imaging devices, and image display devices.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはそ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意味で使用される。
　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。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。
　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、水銀灯の輝線スペクトル、エキシマレーザ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、「（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、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。
　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総質量をいう。
　本明細書において、顔料とは、溶剤に対して溶解しにくい着色剤を意味する。
　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。 The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "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. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a coloring agent that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
＜着色組成物＞
　本発明の着色組成物は、
　着色剤と、重合性化合物と、光重合開始剤と、溶剤とを含み、
　上記着色剤は有機顔料を含み、
　上記光重合開始剤はオキシム化合物を含み、
　上記溶剤は環状ケトン溶剤を含み、かつ、溶剤中における環状ケトン溶剤の含有量が１～１５質量％である。 <Coloring composition>
The coloring composition of the present invention is
including a coloring agent, a polymerizable compound, a photopolymerization initiator, and a solvent;
The coloring agent contains an organic pigment,
The photopolymerization initiator contains an oxime compound,
The solvent contains a cyclic ketone solvent, and the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass.
　本発明の着色組成物によれば、保存安定性が良好で、厚みムラの小さい膜を形成することができる。このような効果が得られる詳細な理由は不明であるが、以下によるものであると推測される。本発明の着色組成物は、環状ケトン溶剤を所定量含むことにより、着色組成物中において、有機顔料に環状ケトン溶剤が吸着して、有機顔料の分散状態を安定化させることができるためと推測される。このため、着色組成物の保管時や塗布時における有機顔料の凝集を抑制することができると推測される。更に、溶剤として環状ケトン溶剤を含むものを用いることで、光重合開始剤として用いているオキシム化合物の加水分解反応を抑制でき、着色組成物の保存安定性をより向上させることができたと推測される。このような理由により、本発明の着色組成物によれば、保存安定性が良好で、厚みムラの小さい膜を形成することができたと推測される。 According to the coloring composition of the present invention, it is possible to form a film with good storage stability and small thickness unevenness. Although the detailed reason why such an effect is obtained is unknown, it is presumed to be due to the following. The coloring composition of the present invention contains a predetermined amount of a cyclic ketone solvent, so that the cyclic ketone solvent adsorbs to the organic pigment in the coloring composition, presumably because the dispersion state of the organic pigment can be stabilized. be done. For this reason, it is presumed that aggregation of the organic pigment can be suppressed during storage or coating of the coloring composition. Furthermore, it is presumed that by using a solvent containing a cyclic ketone solvent, the hydrolysis reaction of the oxime compound used as the photopolymerization initiator can be suppressed, and the storage stability of the colored composition can be further improved. be. For these reasons, it is presumed that the colored composition of the present invention was able to form a film having good storage stability and less unevenness in thickness.
　なかでも、有機顔料としてジケトピロロピロール顔料を含むものを用いた場合において、上記の効果がより顕著に奏されるので好ましい。特に、ジケトピロロピロール顔料を２種以上併用した場合においては、上述した効果がより一層顕著に奏されるので好ましい。更には、得られる膜の耐熱性をより向上させることもできる。 Among them, it is preferable to use an organic pigment containing a diketopyrrolopyrrole pigment, because the above effects are more remarkably exhibited. In particular, it is preferable to use two or more diketopyrrolopyrrole pigments in combination, because the above-described effects are exhibited more remarkably. Furthermore, the heat resistance of the resulting film can be further improved.
　本発明の着色組成物は、カラーフィルタ用の着色組成物として好ましく用いられる。より詳しくは、カラーフィルタの画素形成用の着色組成物として好ましく用いることができる。画素の種類としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、黄色画素などが挙げられ、赤色画素、緑色画素および黄色画素であることが好ましく、赤色画素または緑色画素であることがより好ましく、赤色画素であることが更に好ましい。 The coloring composition of the present invention is preferably used as a coloring composition for color filters. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter. Pixel types include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and yellow pixels are preferred. More preferably, it is a red pixel.
　以下、本発明の着色組成物に用いられる各成分について説明する。 Each component used in the coloring composition of the present invention will be described below.
＜＜着色剤＞＞
　本発明の着色組成物は着色剤を含有する。着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などの有彩色着色剤が挙げられる。また、着色剤には顔料誘導体を用いることもできる。 <<coloring agent>>
The coloring composition of the present invention contains a coloring agent. Colorants include chromatic colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. A pigment derivative can also be used as the colorant.
　本発明の着色組成物において、着色剤には有機顔料を含むものが用いられる。なお、有機顔料とは、有機化合物で構成された顔料のことである。 In the coloring composition of the present invention, a coloring agent containing an organic pigment is used. In addition, an organic pigment is a pigment composed of an organic compound.
　有機顔料としては、キナクリドン顔料、アントラキノン顔料、アゾ顔料、ジケトピロロピロール顔料、イソインドリン顔料、キノフタロン顔料、プテリジン顔料、アゾメチン顔料、ナフトール顔料、キサンテン顔料、チオインジゴ顔料、フタロシアニン顔料、スクアリリウム顔料、ジオキサジン顔料およびペリレン顔料から選ばれる少なくとも１種を含むものであることが好ましく、キナクリドン顔料、アントラキノン顔料、アゾ顔料、ジケトピロロピロール顔料、イソインドリン顔料、キノフタロン顔料、プテリジン顔料およびアゾメチン顔料から選ばれる少なくとも１種を含むものであることがより好ましく、ジケトピロロピロール顔料およびイソインドリン顔料から選択される少なくとも１種を含むものであることが更に好ましく、ジケトピロロピロール顔料を含むものであることが特に好ましい。なかでも、着色組成物の保存安定性をより向上でき、かつ、厚みムラがより小さく、耐熱性に優れた膜を形成することができるという理由から有機顔料は、ジケトピロロピロール顔料を２種以上含むことが好ましい。 Examples of organic pigments include quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments, azomethine pigments, naphthol pigments, xanthene pigments, thioindigo pigments, phthalocyanine pigments, squarylium pigments, and dioxazine pigments. and perylene pigments, and at least one selected from quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments and azomethine pigments. More preferably, it contains at least one selected from diketopyrrolopyrrole pigments and isoindoline pigments, and particularly preferably contains a diketopyrrolopyrrole pigment. Among them, since the storage stability of the coloring composition can be further improved, and the thickness unevenness is smaller, and the organic pigment can form a film having excellent heat resistance, two types of diketopyrrolopyrrole pigments are used. It is preferable to include the above.
　有機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。有機顔料の平均一次粒子径が上記範囲であれば、着色組成物中における有機顔料の分散安定性が良好である。なお、本発明において、有機顔料の一次粒子径は、有機顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。具体的には、有機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有機顔料の一次粒子径として算出する。また、本発明における平均一次粒子径は、４００個の有機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、有機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 organic 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, and even more preferably 100 nm or less. When the average primary particle size of the organic pigment is within the above range, the dispersion stability of the organic pigment in the coloring composition is good. In the present invention, the primary particle size of the organic pigment can be determined from a photograph obtained by observing the primary particles of the organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the organic pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the organic pigment. Further, the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the organic pigment. Further, the primary particles of the organic pigment refer to independent particles without agglomeration.
　本発明の着色組成物に含まれる着色剤は、有機顔料と顔料誘導体とを含むものであることが好ましい。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。顔料誘導体の詳細については後述する。有機顔料と顔料誘導体とを併用する場合、両者の割合は有機顔料１００質量部に対して顔料誘導体が１～３０質量部であることが好ましい。下限は２質量部以上であることが好ましく、４質量部以上であることがより好ましい。上限は２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。 The coloring agent contained in the coloring composition of the present invention preferably contains an organic pigment and a pigment derivative. Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. Details of the pigment derivative will be described later. When an organic pigment and a pigment derivative are used together, the ratio of the two is preferably 1 to 30 parts by weight of the pigment derivative per 100 parts by weight of the organic pigment. The lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
　有機顔料としては、黄色顔料、オレンジ色顔料、赤色顔料、緑色顔料、紫色顔料および青色顔料などが挙げられ、赤色顔料および黄色顔料から選ばれる少なくとも１種を含むものであることが好ましく、赤色顔料を含むものであることがより好ましい。 Examples of organic pigments include yellow pigments, orange pigments, red pigments, green pigments, purple pigments and blue pigments, and preferably contain at least one selected from red pigments and yellow pigments, and contain red pigments. It is more preferable that the
　赤色顔料としては、ジケトピロロピロール顔料、アントラキノン顔料、アゾ顔料、ナフトール顔料、アゾメチン顔料、キサンテン顔料、キナクリドン顔料、ペリレン顔料、チオインジゴ顔料などが挙げられ、ジケトピロロピロール顔料、アントラキノン顔料、アゾ顔料、ナフトール顔料であることが好ましく、ジケトピロロピロール顔料であることがより好ましい。 Examples of red pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, azo pigments, naphthol pigments, azomethine pigments, xanthene pigments, quinacridone pigments, perylene pigments, and thioindigo pigments. , preferably a naphthol pigment, more preferably a diketopyrrolopyrrole pigment.
　赤色顔料の具体例としては、Ｃ．Ｉ．（カラーインデックス）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等が挙げられる。また、赤色顔料として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つの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２０２０－０８５９４７号公報に記載の臭素化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顔料、特許第６５２５１０１号公報に記載の赤色顔料、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、特開２０２０－０６６７０２号公報の段落番号００２５～００４１に記載のジケトピロロピロール化合物などを用いることもできる。また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 Specific examples of red pigments include C.I. I. (Color Index) 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, 294, 295, 296, 297 and the like. Further, as red pigments, diketopyrrolopyrrole compounds having at least one bromine atom substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrroles described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 compounds, diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, brominated diketopyrrolopyrroles described in JP 2020-085947 compounds, naphthol azo compounds described in JP-A-2012-229344, red pigments described in JP-A-6516119, red pigments described in JP-A-6525101, paragraph number 0229 of JP-A-2020-090632 Brominated diketopyrrolopyrrole compound described, anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compound described in Korean Patent Publication No. 10-2019-0140744, JP 2020-079396 Perylene compounds described in publications, diketopyrrolopyrrole compounds described in paragraphs 0025 to 0041 of JP-A-2020-066702, and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１２２，１７７，２５４，２５５，２６４，２６９，２７２，２９１が好ましく、Ｃ．Ｉ．ピグメントレッド２５４，２６４，２７２がより好ましく、Ｃ．Ｉ．ピグメントレッド２５４，２７２が更に好ましい。 As a red pigment, C.I. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 and 291 are preferred, C.I. I. Pigment Red 254, 264, 272 are more preferred, and C.I. I. Pigment Red 254, 272 are more preferred.
　本発明で用いられる有機顔料は、Ｃ．Ｉ．ピグメントレッド２５４およびＣ．Ｉ．ピグメントレッド２７２から選ばれる少なくとも１種を含むことが好ましく、着色組成物の保存安定性をより向上でき、かつ、厚みムラがより小さく、耐熱性に優れた膜を形成することができるという理由からＣ．Ｉ．ピグメントレッド２５４とＣ．Ｉ．ピグメントレッド２７２とを含むことがより好ましい。また、Ｃ．Ｉ．ピグメントレッド２５４とＣ．Ｉ．ピグメントレッド２７２とを併用する場合、両者の割合は、Ｃ．Ｉ．ピグメントレッド２５４の１００質量部に対して、Ｃ．Ｉ．ピグメントレッド２７２が１０～２００量部であることが好ましく、３０～１５０質量部であることがより好ましく、５０～１００質量部であることが更に好ましい。両者の割合が上記範囲であれば、得られる膜の耐熱性が特に優れる。 The organic pigment used in the present invention is C.I. I. Pigment Red 254 and C.I. I. Pigment Red 272 preferably contains at least one selected from the reason that the storage stability of the coloring composition can be further improved, the thickness unevenness is smaller, and a film having excellent heat resistance can be formed. C. I. Pigment Red 254 and C.I. I. Pigment Red 272 is more preferred. Also, C.I. I. Pigment Red 254 and C.I. I. Pigment Red 272 is used in combination with C.I. I. pigment red 254, C.I. I. Pigment Red 272 is preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight, even more preferably 50 to 100 parts by weight. If the ratio of both is within the above range, the heat resistance of the obtained film is particularly excellent.
　黄色顔料としては、アゾ顔料、アゾメチン顔料、イソインドリン顔料、プテリジン顔料、キノフタロン顔料およびペリレン顔料などが挙げられる。黄色顔料の具体例としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２１５，２２８，２３１，２３２，２３３，２３４，２３５，２３６等が挙げられる。 Examples of yellow pigments include azo pigments, azomethine pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments and perylene pigments. Specific examples of 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, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and the like.
　また、黄色顔料として、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
 Moreover, as a yellow pigment, an azobarbiturate nickel complex having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000001
　また、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２０１８－０６２６４４号公報に記載のイソインドリン化合物、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２０２０－０３３５２５号公報に記載の化合物、特開２０２０－０３３５２４号公報に記載の化合物、特開２０２０－０３３５２３号公報に記載の化合物、特開２０２０－０３３５２２号公報に記載の化合物、特開２０２０－０３３５２１号公報に記載の化合物、国際公開第２０２０／０４５２００号に記載の化合物、国際公開第２０２０／０４５１９９号に記載の化合物、国際公開第２０２０／０４５１９７号に記載の化合物、特開２０２０－０９３９９４号公報に記載のアゾ化合物、特開２０２０－０８３９８２号公報に記載のペリレン化合物、国際公開第２０２０／１０５３４６号に記載のペリレン化合物、特表２０２０－５１７７９１号公報に記載のキノフタロン化合物、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。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。
Figure JPOXMLDOC01-appb-C000002
 Further, as the yellow pigment, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraph numbers 0011-0062 of JP-A-2017-171912, described in 0137-0276 Compounds, compounds described in paragraph numbers 0010 to 0062, 0138 to 0295 of JP 2017-171913, compounds described in paragraph numbers 0011 to 0062, 0139 to 0190 of JP 2017-171914, JP 2017- Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-171915, quinophthalone compounds described in paragraph numbers 0011-0034 of JP-A-2013-054339, paragraph numbers 0013-0058 of JP-A-2014-026228 Quinophthalone compounds described in, isoindoline compounds described in JP-A-2018-062644, quinophthalone compounds described in JP-A-2018-203798, quinophthalone compounds described in JP-A-2018-062578, Patent No. 6432076 Quinophthalone compounds described in the publication, quinophthalone compounds described in JP-A-2018-155881, quinophthalone compounds described in JP-A-2018-111757, quinophthalone compounds described in JP-A-2018-040835, JP-A-2017- Quinophthalone compounds described in 197640, quinophthalone compounds described in JP-A-2016-145282, quinophthalone compounds described in JP-A-2014-085565, quinophthalone compounds described in JP-A-2014-021139, JP-A quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622, Quinophthalone compounds described in JP-A-2013-032486, quinophthalone compounds described in JP-A-2012-226110, quinophthalone compounds described in JP-A-2008-074987, quinophthalones described in JP-A-2008-081565 Compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A-2 008-031281, the quinophthalone compound described in JP-B-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in Japanese Patent No. 6607427, the Korean publication Compounds described in Patent No. 10-2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, Compounds described in JP-A-2020-033525, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020 - compound described in WO 2020/045200, compound described in WO 2020/045199, compound described in WO 2020/045197, JP 2020-093994 Azo compounds described in JP-A-2020-083982, perylene compounds described in JP-A-2020-083982, perylene compounds described in International Publication No. 2020/105346, quinophthalone compounds described in JP-T-2020-517791, the following formula ( A compound represented by QP1) and a compound represented by the following formula (QP2) can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.
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 formula (QP1), X 1 to X 16 each 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 formula (QP1) include compounds described in paragraph number 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 formula (QP2), Y 1 to Y 3 each independently represent a halogen atom. n and m are integers from 0 to 6; p is an integer from 0 to 5; (n+m) is 1 or more. Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１２９，１３８，１３９，１５０，１８５が好ましい。 As a yellow pigment, C.I. I. Pigment Yellow 129, 138, 139, 150 and 185 are preferred.
　緑色顔料としては、フタロシアニン顔料、スクアリリウム顔料などが挙げられ、フタロシアニン顔料であることが好ましい。緑色顔料の具体例としては、Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等が挙げられる。また、緑色顔料として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色顔料として中国特許出願第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、特開２０２０－０７０４２６号公報に記載のアルミニウムフタロシアニン化合物、特開２０２０－０７６９９５号公報に記載のコアシェル型色素などを用いることもできる。緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，６２，６３が好ましく、Ｃ．Ｉ．ピグメントグリーン３６，５８がより好ましく用いられる。 Examples of green pigments include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred. Specific examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like. Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green pigment, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, and the phthalocyanine compound described in JP 2019-008014. Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, aluminum phthalocyanine compounds described in JP-A-2020-070426, JP-A-2020-076995 Core-shell type dyes and the like described can also be used. As a green pigment, C.I. I. Pigment Green 7, 36, 58, 62 and 63 are preferred, C.I. I. Pigment Greens 36 and 58 are more preferably used.
　オレンジ色顔料しては、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等が挙げられる。 As an orange pigment, 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. is mentioned.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等が挙げられる。 As a purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 and the like.
　青色顔料としては、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等が挙げられる。また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落番号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。 As a blue pigment, 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. be done. Also, an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
　各種有機顔料が有していることが好ましい回折角については、特許第６５６１８６２号公報、特許第６４１３８７２号公報、特許第６２８１３４５号公報、特開２０２０－０２６５０３号公報、特開２０２０－０３３５２６号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、ジケトピロロピロール顔料としては結晶格子面のうち（±１±１±１）の８個の面の中でＸ線回折パターンにおける最大ピークに対応する面方向の結晶子サイズが１４０Å以下であるものを用いることも好ましい。また、ジケトピロロピロール顔料の物性については、特開２０２０－０９７７４４号公報の段落番号００２８～００７３に記載の通り設定することも好ましい。 Regarding the diffraction angle that various organic pigments preferably have, Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Unexamined Patent Publication No. 2020-026503, Japanese Unexamined Patent Publication No. 2020-033526. The descriptions can be consulted and their contents are incorporated herein. In addition, the diketopyrrolopyrrole pigment has a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes (±1±1±1) of the crystal lattice planes. It is also preferred to use one. Further, the physical properties of the diketopyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
　また、有機顔料としては、特許６７４４００２号公報に記載のラマンスペクトルを有するハロゲン化亜鉛フタロシアニン顔料を使用することも、分光特性を高める観点で好ましい。また、有機顔料としては、国際公開第２０１９／１０７１６６号に記載の接触角を制御したジオキサジン顔料を使用することも粘度調整の観点で好ましい。 In addition, as the organic pigment, it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of enhancing spectral characteristics. As the organic pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in WO 2019/107166 from the viewpoint of viscosity adjustment.
　着色剤には染料を用いることもできる。染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が挙げられる。 Dyes can also be used as coloring agents. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used.
　着色剤には色素多量体を用いることもできる。色素多量体は、溶剤に溶解して用いられる染料であることが好ましい。また、色素多量体は、粒子を形成していてもよい。色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開２０１５－２１４６８２号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、一分子中に、色素構造を２以上有するものであり、色素構造を３以上有することが好ましい。上限は、特に限定はないが、１００以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量（Ｍｗ）は、２０００～５００００が好ましい。下限は、３０００以上がより好ましく、６０００以上がさらに好ましい。上限は、３００００以下がより好ましく、２００００以下がさらに好ましい。色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報、国際公開第２０１６／０３１４４２号等に記載されている化合物を用いることもできる。 A pigment multimer can also be used as a coloring agent. The dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
　着色剤には、特表２０２０－５０４７５８号公報に記載のジアリールメタン化合物、韓国公開特許第１０－２０２０－００２８１６０号公報に記載されたトリアリールメタン染料ポリマー、特開２０２０－１１７６３８号公報に記載のキサンテン化合物、国際公開第２０２０／１７４９９１号に記載のフタロシアニン化合物、特開２０２０－１６０２７９号公報に記載のイソインドリン化合物又はそれらの塩を用いることができる。 Colorants include diarylmethane compounds described in JP-A-2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and those described in JP-A-2020-117638. A xanthene compound, a phthalocyanine compound described in International Publication No. 2020/174991, an isoindoline compound described in JP-A-2020-160279, or a salt thereof can be used.
　着色剤には顔料誘導体を用いることもできる。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。 A pigment derivative can also be used as a coloring agent. Pigment derivatives 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、キノリン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾイソインドール色素骨格、ベンゾチアゾール色素骨格、イミニウム色素骨格、スクアリリウム色素骨格、クロコニウム色素骨格、オキソノール色素骨格、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、アゾ色素骨格、アゾメチン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、キナクリドン色素骨格、ジオキサジン色素骨格、ペリノン色素骨格、ペリレン色素骨格、チアジンインジゴ色素骨格、チオインジゴ色素骨格、イソインドリン色素骨格、イソインドリノン色素骨格、キノフタロン色素骨格、イミニウム色素骨格、ジチオール色素骨格、トリアリールメタン色素骨格、ピロメテン色素骨格等が挙げられ、ジケトピロロピロール色素骨格、ベンゾイソインドール色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、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、およびキナクリドン色素骨格であることが好ましく、ジケトピロロピロール色素骨格、ベンゾイソインドール色素骨格、アントラキノン色素骨格、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、およびキナクリドン色素骨格であることがより好ましい。また、顔料誘導体はジケトピロロピロール色素骨格、すなわち、ジケトピロロピロール化合物であることが好ましい。この態様によれば、赤色の色価のより高い膜を形成することができ、赤色画素用の着色組成物としてより好ましく用いられる。 Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton , thiazineindigo dye skeleton, thioindigo dye skeleton, isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, iminium dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, pyrromethene dye skeleton, and the like. Pyrrolopyrrole dye skeletons, benzoisoindole dye skeletons, anthraquinone dye skeletons, dianthraquinone dye skeletons, thiazineindigo dye skeletons, azo dye skeletons, quinophthalone dye skeletons, phthalocyanine dye skeletons, and quinacridone dye skeletons are preferred, and diketo Pyrrolopyrrole dye skeletons, benzoisoindole dye skeletons, anthraquinone dye skeletons, azo dye skeletons, quinophthalone dye skeletons, phthalocyanine dye skeletons, and quinacridone dye skeletons are more preferred. Also, the pigment derivative is preferably a diketopyrrolopyrrole dye skeleton, that is, a diketopyrrolopyrrole compound. According to this aspect, a film having a higher red color value can be formed, and it is more preferably used as a coloring composition for red pixels.
　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、スルホン酸アミド基、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。スルホン酸アミド基としては、－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。 The acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like. As the carboxylic acid amide group, a group represented by —NHCOR X1 is preferable. As the sulfonic acid amide group, a group represented by —NHSO 2 R X2 is preferable. The imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 . R X1 to R X6 each independently represent an alkyl group or an aryl group. The alkyl groups and aryl groups represented by R X1 to R X6 may have substituents. 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。 Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
　顔料誘導体の具体例としては、後述の実施例に記載の化合物、特開昭５６－１１８４６２号公報に記載の化合物、特開昭６３－２６４６７４号公報に記載の化合物、特開平０１－２１７０７７号公報に記載の化合物、特開平０３－００９９６１号公報に記載の化合物、特開平０３－０２６７６７号公報に記載の化合物、特開平０３－１５３７８０号公報に記載の化合物、特開平０３－０４５６６２号公報に記載の化合物、特開平０４－２８５６６９号公報に記載の化合物、特開平０６－１４５５４６号公報に記載の化合物、特開平０６－２１２０８８号公報に記載の化合物、特開平０６－２４０１５８号公報に記載の化合物、特開平１０－０３００６３号公報に記載の化合物、特開平１０－１９５３２６号公報に記載の化合物、国際公開第２０１１／０２４８９６号の段落番号００８６～００９８に記載の化合物、国際公開第２０１２／１０２３９９号の段落番号００６３～００９４に記載の化合物、国際公開第２０１７／０３８２５２号の段落番号００８２に記載の化合物、特開２０１５－１５１５３０号公報の段落番号０１７１に記載の化合物、特開２０１１－２５２０６５号公報の段落番号０１６２～０１８３に記載の化合物、特開２００３－０８１９７２号公報に記載の化合物、特許第５２９９１５１号公報に記載の化合物、特開２０１５－１７２７３２号公報に記載の化合物、特開２０１４－１９９３０８号公報に記載の化合物、特開２０１４－０８５５６２号公報に記載の化合物、特開２０１４－０３５３５１号公報に記載の化合物、特開２００８－０８１５６５号公報に記載の化合物、特開２０１９－１０９５１２号公報に記載の化合物、特開２０１９－１３３１５４号公報に記載の化合物、国際公開第２０２０／００２１０６号に記載のチオール連結基を有するジケトピロロピロール化合物が挙げられる。 Specific examples of the pigment derivative include the compounds described in Examples below, the compounds described in JP-A-56-118462, the compounds described in JP-A-63-264674, and JP-A-01-217077. Compounds described in, compounds described in JP-A-03-009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, described in JP-A-03-045662 The compound, the compound described in JP-A-04-285669, the compound described in JP-A-06-145546, the compound described in JP-A-06-212088, the compound described in JP-A-06-240158 , the compound described in JP-A-10-030063, the compound described in JP-A-10-195326, the compound described in paragraph numbers 0086 to 0098 of WO 2011/024896, WO 2012/102399 The compound described in paragraph numbers 0063 to 0094 of, the compound described in paragraph number 0082 of WO 2017/038252, the compound described in paragraph number 0171 of JP 2015-151530, JP 2011-252065 Compounds described in paragraph numbers 0162 to 0183 of, compounds described in JP-A-2003-081972, compounds described in Patent No. 5299151, compounds described in JP-A-2015-172732, JP-A-2014-199308 Compounds described in JP-A-2014-085562, compounds described in JP-A-2014-035351, compounds described in JP-A-2008-081565, JP-A-2019-109512 Compounds described in, compounds described in JP-A-2019-133154, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020/002106.
　着色組成物の全固形分中における着色剤の含有量は、４０質量％以上であることが好ましく、４５質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、５５質量％以上であることがより一層好ましく、６０質量％以上であることが特に好ましい。上限は８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることが更に好ましい。 The content of the coloring agent in the total solid content of the coloring composition is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and 55% by mass. % or more, and particularly preferably 60 mass % or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
　着色組成物の全固形分中における有機顔料の含有量は、３５～８０質量％であることが好ましい。下限は４０質量％以上であることが好ましく、４５質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、５５質量％以上であることがより一層好ましく、６０質量％以上であることが特に好ましい。上限は７５質量％以下であることが好ましく、７０質量％以下であることがより好ましい。また、着色剤中における有機顔料の含有量は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。上限は１００質量％以下とすることができ、９５質量％以下とすることもできる。 The content of the organic pigment in the total solid content of the coloring composition is preferably 35-80% by mass. The lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, even more preferably 55% by mass or more, and 60% by mass or more. is particularly preferred. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less. Also, the content of the organic pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The upper limit can be 100% by mass or less, and can also be 95% by mass or less.
　着色組成物の全固形分中における有機顔料と顔料誘導体との合計の含有量は、４０質量％以上であることが好ましく、４５質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、５５質量％以上であることがより一層好ましく、６０質量％以上であることが特に好ましい。上限は８０質量％以下であることが好ましく、７５質量％以下であることがより好ましい。また、着色剤中における有機顔料と顔料誘導体との合計の含有量は、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い。 The total content of the organic pigment and the pigment derivative in the total solid content of the coloring composition is preferably 40% by mass or more, more preferably 45% by mass or more, and 50% by mass or more is more preferable, 55% by mass or more is even more preferable, and 60% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less. Further, the total content of the organic pigment and the pigment derivative in the colorant is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass. is more preferred.
　着色組成物の全固形分中におけるジケトピロロピロール顔料の含有量は、２０～６５質量％であることが好ましい。下限は２５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い。上限は５０質量％以下であることが好ましく、４０質量％以下であることがより好ましい。また、着色剤中におけるジケトピロロピロール顔料の含有量は、４５質量％以上であることが好ましく、５０質量％以上であることがより好ましく、５５質量％以上であることが更に好ましい。上限は８０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 The content of the diketopyrrolopyrrole pigment in the total solid content of the coloring composition is preferably 20 to 65% by mass. The lower limit is preferably 25% by mass or more, more preferably 35% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less. The content of the diketopyrrolopyrrole pigment in the colorant is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
　本発明の着色組成物をカラーフィルタの赤色画素形成用の着色組成物として用いる場合、着色剤には赤色着色剤と黄色着色剤を含むものを用いることが好ましい。また、赤色着色剤は赤色顔料であることが好ましい。また、黄色着色剤は黄色顔料であることが好ましい。また、赤色着色剤と黄色着色剤との割合は、赤色着色剤１００質量部に対して黄色着色剤が１０～１００質量部であることが好ましい。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。上限は、８０質量部以下であることが好ましく、６０質量部以下であることがより好ましい。 When the coloring composition of the present invention is used as a coloring composition for forming red pixels of a color filter, it is preferable to use a coloring agent containing a red coloring agent and a yellow coloring agent. Also, the red colorant is preferably a red pigment. Also, the yellow colorant is preferably a yellow pigment. Further, the ratio of the red colorant and the yellow colorant is preferably 10 to 100 parts by mass of the yellow colorant per 100 parts by mass of the red colorant. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less.
＜＜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 ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. 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 monomer, prepolymer, oligomer, etc., but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100-3000. The upper limit is preferably 2000 or less, 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 group 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 of the colored composition over time. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more 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, more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups. The upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less, from the viewpoint of the stability of the colored composition over time. Further, the polymerizable compound is preferably a tri- or more functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound. is more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred.
　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、エトキシ化ジペンタエリスリトールヘキサ（メタ）アクリレートなど、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 polymerizable compounds include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds. mentioned. Modified compounds include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded via an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate. Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　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 each 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 each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the sum of m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, each n independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.
　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Ｅ、すなわち－（（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 formula (Z-4), m is preferably an integer of 0-6, more preferably an integer of 0-4. The sum of 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 formula (Z-5), n is preferably an integer of 0-6, more preferably an integer of 0-4. The sum of n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.
Further, E in formula (Z-4) or formula (Z-5), that is, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- is A form in which the end on the oxygen atom side is bonded to X is preferred.
　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-C000005
 　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。 Polypentaerythritol poly(meth)acrylates represented by the following formula (Z-6) can also be used as the polymerizable compound.
Figure JPOXMLDOC01-appb-C000005
 In formula (Z-6), X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1-10. 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. Seeds are preferred. Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, TPOA-50 (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. 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）、ＥＢＥＣＲＹＬ８０（ダイセル・オルネクス社製、アミン含有４官能アクリレート）などを用いることもできる。 Further, 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 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 Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL80 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate) and the like 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。 Further, as the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, ethyleneoxy isocyanurate-modified tri(meth) It is also preferable to use trifunctional (meth)acrylate compounds such as acrylates and pentaerythritol tri(meth)acrylates. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.
　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。 Also, as the polymerizable compound, a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can be used. Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
　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。 A compound having a caprolactone structure can also be used as the polymerizable compound. For compounds having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
　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。 In addition, as the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals 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。 As the polymerizable compound, it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances. 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 such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Also suitable are urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418. 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-01-105238. Further, the polymerizable compound includes UA-7200 (manufactured by Shin-Nakamura Chemical 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, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
　着色組成物の全固形分中における重合性化合物の含有量は、１～３５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、２質量％以上であることが好ましく、５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 in the total solid content of the coloring composition is preferably 1 to 35% by mass. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more. The coloring composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.
＜光重合開始剤＞＞
　本発明の着色組成物は光重合開始剤を含有する。本発明では、光重合開始剤としては、オキシム化合物が用いられる。オキシム化合物は光ラジカル重合開始剤であることが好ましい。また、オキシム化合物は紫外線領域から可視領域の光線に対して感光性を有する化合物であることが好ましい。また、オキシム化合物は波長３５０～５００ｎｍの範囲に極大吸収波長が存在する化合物であることが好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長が存在する化合物であることがより好ましい。 <Photoinitiator>>
The coloring composition of the present invention contains a photopolymerization initiator. In the present invention, an oxime compound is used as the photopolymerization initiator. The oxime compound is preferably a photoradical polymerization initiator. Further, the oxime compound is preferably a compound having photosensitivity to light in the ultraviolet region to the visible region. The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
　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２０１３－１９０４５９号公報に記載のオキシム系光重合開始剤、特開２０１４－１３０１７３号公報の段落００７４～０１０９に記載の化合物、特許第６３０１４８９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、特開２０２０－１７２６１９号公報に記載の重合体などが挙げられる。 Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, oxime-based photopolymerization initiators described in JP-A-2013-190459, compounds described in paragraphs 0074 to 0109 of JP-A-2014-130173, Japanese Patent No. 6301489 Compounds described in publications, compounds described in JP 2017-019766, compounds described in Patent No. 6065596, compounds described in WO 2015/152153, described in WO 2017/051680 Compounds, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, compounds described in WO 2013/167515, JP 2020-172619 Examples thereof include polymers described in publications.
　また、オキシム化合物として、２官能あるいは３官能以上のオキシム化合物を用いることもできる。２官能あるいは３官能以上のオキシム化合物としては、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化合物などが挙げられる。 As the oxime compound, a bifunctional or trifunctional oxime compound can also be used. Examples of bifunctional or trifunctional oxime compounds include JP 2010-527339, JP 2011-524436, WO 2015/004565, paragraph numbers 0407 to 0412 of JP 2016-532675, Dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, International Publication No. Cmpd 1 to 7 described in 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, paragraph numbers 0020 to 0033 of JP 2017-167399 described photoinitiators, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, oxime compounds described in Japanese Patent No. 6469669, and the like. .
　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。 Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronly), and Adeka Optomer N-1919 (manufactured by Tronly). ) manufactured by ADEKA, photopolymerization initiator 2) described in JP-A-2012-014052. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).
　オキシム化合物としては、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、特許第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。 An oxime compound having a fluorene ring can also be used as the oxime compound. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
　オキシム化合物としては、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 oxime compound, 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 oxime compounds include compounds described in WO2013/083505.
　オキシム化合物としては、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。 An oxime compound having a fluorine atom can also be used as the oxime compound. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
　オキシム化合物としては、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 oxime compound, 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 paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
　オキシム化合物としては、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。 An oxime compound having a benzofuran skeleton can also be used as the oxime compound. Specific examples include OE-01 to OE-75 described in WO 2015/036910.
　オキシム化合物としては、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 oxime compound, 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.
　オキシム化合物としては、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、ヘテロ環基、ヘテロ環オキシ基、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、ヘテロ環オキシ基、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 oxime compound, an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing 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 preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclicoxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, 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. A sulfanyl group or an amino group is more preferred.
　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-C000006
 　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、ヘテロ環基、ヘテロ環オキシ基、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、ヘテロ環基、ヘテロ環オキシ基、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 compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
Figure JPOXMLDOC01-appb-C000006
 In the formula, R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R X3 to R X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R X10 to R X14 is an electron-withdrawing group.
　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。 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups, with acyl groups and nitro groups being preferred. An acyl group is more preferred, and a benzoyl group is even more preferred, because a film having excellent properties can be easily formed.
　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, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 and R X14 are preferably 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 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 oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明の着色組成物は、光重合開始剤として、オキシム化合物以外の光重合開始剤（他の光重合開始剤）を含有することができる。他の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。 The coloring composition of the present invention can contain a photopolymerization initiator other than the oxime compound (another photopolymerization initiator) as a photopolymerization initiator. Other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like.
　ヘキサアリールビイミダゾール化合物の具体例としては、２，２’，４－トリス（２－クロロフェニル）－５－（３，４－ジメトキシフェニル）－４，５－ジフェニル－１，１’－ビイミダゾールなどが挙げられる。 Specific examples of hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
　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 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
　また、他の光重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～００７２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などを用いることもできる。 In addition, as other photopolymerization initiators, compounds described in paragraphs 0065 to 0072 of JP-A-2014-130173, MATERIAL STAGE 37-60, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, the peroxide-based initiator described in JP-A-2020-055992. Aminoacetophenone-based initiators having an oxazolidine group as described can also be used.
　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。
　また、光重合開始剤中におけるオキシム化合物の含有量は、５０～１００質量％であることが好ましく、７０～１００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い。光重合開始剤は、実質的にオキシム化合物のみであることが好ましい。なお、本明細書において、光重合開始剤が実質的にオキシム化合物のみである場合とは、光重合開始剤中におけるオキシム化合物の含有量が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、オキシム化合物のみであることが特に好ましい。
　本発明の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.
The content of the oxime compound in the photopolymerization initiator is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass. Preferably, the photopolymerization initiator is substantially only the oxime compound. In this specification, the case where the photopolymerization initiator is substantially only an oxime compound means that the content of the oxime compound in the photopolymerization initiator is 99% by mass or more, and 99.9% by mass. % by mass or more is more preferable, and it is particularly preferable to contain only the oxime compound.
In the coloring composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types 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。本発明の着色組成物に含まれる溶剤は、環状ケトン溶剤を含む。 <<Solvent>>
The coloring composition of the present invention contains a solvent. Solvents contained in the coloring composition of the present invention include cyclic ketone solvents.
　環状ケトン溶剤としては、環構造を有するケトン化合物が好ましい。環状ケトン溶剤は環構造上に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。環状ケトン溶剤の炭素数は３～２０であることが好ましい。環状ケトン溶剤としては、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、シクロペンタノンなどが挙げられ、シクロペンタノンであることが好ましい。 A ketone compound having a ring structure is preferable as the cyclic ketone solvent. The cyclic ketone solvent may have a substituent on the ring structure. An alkyl group etc. are mentioned as a substituent. The cyclic ketone solvent preferably has 3 to 20 carbon atoms. Examples of the cyclic ketone solvent include cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclopentanone, etc. Cyclopentanone is preferred.
　溶剤中における環状ケトン溶剤の含有量は１～１５質量％であり、５～１３質量％であることが好ましく、６～１０質量％であることがより好ましい。また、溶剤中におけるシクロペンタノンの含有量は１～１５質量％であることが好ましく、５～１３質量％であることがより好ましく、６～１０質量％であることが更に好ましい。 The content of the cyclic ketone solvent in the solvent is 1 to 15% by mass, preferably 5 to 13% by mass, more preferably 6 to 10% by mass. Also, the content of cyclopentanone in the solvent is preferably 1 to 15% by mass, more preferably 5 to 13% by mass, even more preferably 6 to 10% by mass.
　本発明の着色組成物に含まれる溶剤は、環状ケトン溶剤以外の溶剤（他の溶剤という）も含む。他の溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。他の溶剤は、得られる膜の厚みムラをより小さくすることができるという理由からエステル系溶剤、エーテル系溶剤およびアルコール系溶剤から選ばれる少なくとも１種を含むものであることが好ましく、エステル系溶剤およびアルコール系溶剤から選ばれる少なくとも１種を含むものであることがより好ましく、エステル系溶剤を含むものであることが更に好ましい。 The solvent contained in the coloring composition of the present invention includes solvents other than cyclic ketone solvents (referred to as other solvents). Other solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. The other solvent preferably contains at least one selected from an ester solvent, an ether solvent and an alcohol solvent for the reason that the thickness unevenness of the resulting film can be reduced. More preferably, it contains at least one selected from solvent-based solvents, and more preferably contains an ester-based solvent.
　なお、本明細書において、エステル系溶剤とは、分子内にエステル結合を有する有機溶剤のことを意味する。また、エーテル系溶剤とは、分子内にエーテル結合を有する有機溶剤のことを意味する。また、アルコール系溶剤とは、分子内にヒドロキシ基を有する有機溶剤のことを意味する。また、本明細書において、分子内にエステル結合と、エーテル結合及び／またはヒドロキシ基をそれぞれ有する有機溶剤は、エステル系溶剤に該当するものとする。また、分子内にエステル結合を有さず、かつ、エーテル結合とヒドロキシ基とをそれぞれ有する有機溶剤は、アルコール系溶剤に該当するものとする。 In this specification, an ester-based solvent means an organic solvent having an ester bond in its molecule. Further, an ether-based solvent means an organic solvent having an ether bond in its molecule. Also, an alcohol-based solvent means an organic solvent having a hydroxy group in its molecule. Further, in this specification, an organic solvent having an ester bond, an ether bond and/or a hydroxy group in its molecule corresponds to an ester solvent. Moreover, an organic solvent that does not have an ester bond in its molecule and has both an ether bond and a hydroxy group corresponds to an alcohol-based solvent.
　溶剤中におけるエステル系溶剤の含有量は８０質量％以上であることが好ましく、８５質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。また、環状ケトン溶剤とエステル系溶剤の合計の含有量は９５～１００質量％であることが好ましく、９７～１００質量％であることがより好ましく、９８～１００質量％であることが更に好ましい。 The content of the ester solvent in the solvent is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. Also, the total content of the cyclic ketone solvent and the ester solvent is preferably 95 to 100% by mass, more preferably 97 to 100% by mass, and even more preferably 98 to 100% by mass.
　他の溶剤の好ましい態様として、他の溶剤が実質的にエステル系溶剤のみである態様が挙げられる。この態様によれば、着色組成物の保存安定性をより向上でき、更には、得られる膜の厚みムラをより小さくすることができる。なお、他の溶剤が実質的にエステル系溶剤のみである場合とは、他の溶剤中におけるエステル系溶剤の含有量が９９質量％以上であることを意味し、９９．９質量％以上であることが好ましく、エステル系溶剤のみであることがより好ましい。 A preferred embodiment of the other solvent includes an embodiment in which the other solvent is substantially only an ester solvent. According to this aspect, the storage stability of the coloring composition can be further improved, and the thickness unevenness of the obtained film can be further reduced. In addition, when the other solvent is substantially only an ester solvent, it means that the content of the ester solvent in the other solvent is 99% by mass or more, and is 99.9% by mass or more. is preferable, and it is more preferable to use only an ester solvent.
　また、他の溶剤の別の好ましい態様として、他の溶剤がエステル系溶剤とアルコール系溶剤とを含む態様が挙げられる。この態様によれば、塗布欠陥の発生をより抑制することができる。エステル系溶剤とアルコール系溶剤との割合は、エステル系溶剤１００質量部に対してアルコール系溶剤が０．１～３．０質量部であることが好ましく、０．３～２．５質量部であることがより好ましく、０．５～２．０質量部であることが更に好ましい。 Another preferred embodiment of the other solvent includes an embodiment in which the other solvent contains an ester solvent and an alcohol solvent. According to this aspect, the occurrence of coating defects can be further suppressed. The ratio of the ester solvent and the alcohol solvent is preferably 0.1 to 3.0 parts by mass, preferably 0.3 to 2.5 parts by mass, per 100 parts by mass of the ester solvent. more preferably 0.5 to 2.0 parts by mass.
　他の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、２－ペンタノン、３－ペンタノン、４－ヘプタノン、酢酸シクロヘキシル、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（別名として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）、２－メトキシプロピルアセテート、２－メトキシ－１－プロパノール、イソプロピルアルコール、２－ブタノール、３－メトキシブタノールなどが挙げられ、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、２－ブタノールおよび３－メトキシブタノールであることが好ましい。 Specific examples of other solvents 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, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexyl acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, diacetic acid butane-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1 -propanol, isopropyl alcohol, 2-butanol, 3-methoxybutanol, etc., preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-butanol and 3-methoxybutanol.
　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い。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）レベルの有機溶剤を用いてもよく、そのような有機溶剤は，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 with a low metal content. The metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (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 methods for removing impurities such as metals from solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　溶剤は、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
　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。 The content of peroxide in the 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、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、３０～９０質量％であることが更に好ましい。
　また、着色組成物中における環状ケトン溶剤の含有量は、１～１０質量％であることが好ましく、３～９質量％であることがより好ましく、５～８質量％であることが更に好ましい。 The content of the solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.
The content of the cyclic ketone solvent in the coloring composition is preferably 1 to 10% by mass, more preferably 3 to 9% by mass, and even more preferably 5 to 8% by mass.
　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、着色組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として着色組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば、重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した着色組成物の段階などのいずれの段階でも可能である。 From the viewpoint of environmental regulations, the coloring composition of the present invention preferably does not substantially contain environmentally regulated substances. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmental controlled substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) Regulations, the Pollutant Release and Transfer Register (PRTR) Law, and the VOC (Volatile Organic Compounds) Regulations. methods are strictly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of safety to humans and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the amount of environmentally regulated substances, there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking. may These distillation methods are the raw material stage, the reaction product of the raw materials (for example, the resin solution or polyfunctional monomer solution after polymerization), or the colored composition stage produced by mixing these compounds. It is possible at any stage such as
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含有することが好ましい。樹脂は、例えば、顔料など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、主に顔料など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 preferably contains a resin. The resin is blended, for example, for dispersing a pigment or the like in a coloring composition or as a binder. A resin mainly used for dispersing a pigment or the like in a coloring composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
　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 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 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、樹脂としては、国際公開第２０１６／０８８６４５号の実施例に記載された樹脂、特開２０１７－０５７２６５号公報に記載された樹脂、特開２０１７－０３２６８５号公報に記載された樹脂、特開２０１７－０７５２４８号公報に記載された樹脂、特開２０１７－０６６２４０号公報に記載された樹脂、特開２０１７－１６７５１３号公報に記載された樹脂、特開２０１７－１７３７８７号公報に記載された樹脂、特開２０１７－２０６６８９号公報の段落番号００４１～００６０に記載された樹脂、特開２０１８－０１０８５６号公報の段落番号００２２～００７１に記載された樹脂、特開２０１６－２２２８９１号公報に記載されたブロックポリイソシアネート樹脂、特開２０２０－１２２０５２号公報に記載された樹脂、特開２０２０－１１１６５６号公報に記載された樹脂、特開２０２０－１３９０２１号公報に記載された樹脂、特開２０１７－１３８５０３号公報に記載の主鎖に環構造を有する構成単位と側鎖にビフェニル基を有する構成単位とを含む樹脂を用いることもできる。 Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, and polyarylene resins. ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins and the like. Further, as the resin, the resin described in the examples of International Publication No. 2016/088645, the resin described in JP-A-2017-057265, the resin described in JP-A-2017-032685, JP Resins described in JP-A-2017-075248, resins described in JP-A-2017-066240, resins described in JP-A-2017-167513, resins described in JP-A-2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, resins described in paragraph numbers 0022-0071 of JP-A-2018-010856, blocks described in JP-A-2016-222891 Polyisocyanate resin, resin described in JP-A-2020-122052, resin described in JP-A-2020-111656, resin described in JP-A-2020-139021, JP-A-2017-138503 A resin containing a structural unit having a ring structure in its main chain and a structural unit having a biphenyl group in its side chain as described in 1) can also be used.
　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 acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups.
　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 acid groups is preferably 30-500 mgKOH/g. The lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, still more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the acid group-containing resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Moreover, the number average molecular weight (Mn) of the resin having an acid group is preferably 1,000 to 20,000.
　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 on its side chain, and more preferably contains 5 to 70 mol % of repeating units having an acid group on its side chain in all repeating units of the resin. The upper limit of the content of repeating units having an acid group in a side chain is preferably 50 mol % or less, more preferably 30 mol % or less. The lower limit of the content of repeating units 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。 For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item. Moreover, the method for introducing the acid group into the resin is not particularly limited, but includes, for example, the method described in Japanese Patent No. 6349629 . Furthermore, as a method for introducing an acid group into a resin, a method of reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce an acid group can also be mentioned.
　本発明の着色組成物は、塩基性基を有する樹脂を含むことも好ましい。塩基性基を有する樹脂は、塩基性基を側鎖に有する繰り返し単位を含む樹脂であることが好ましく、塩基性基を側鎖に有する繰り返し単位と塩基性基を含まない繰り返し単位とを有する共重合体であることがより好ましく、塩基性基を側鎖に有する繰り返し単位と、塩基性基を含まない繰り返し単位とを有するブロック共重合体であることが更に好ましい。塩基性基を有する樹脂は分散剤として用いることもできる。塩基性基を有する樹脂のアミン価は、５～３００ｍｇＫＯＨ／ｇが好ましい。下限は、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、２００ｍｇＫＯＨ／ｇ以下が好ましく、１００ｍｇＫＯＨ／ｇ以下がより好ましい。 The coloring composition of the present invention also preferably contains a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain. It is more preferably a polymer, and more preferably a block copolymer having a repeating unit having a basic group on its side chain and a repeating unit containing no basic group. Resins having basic groups can also be used as dispersants. The amine value of the resin having basic groups is preferably 5-300 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
　塩基性基を有する樹脂の市販品としては、ＤＩＳＰＥＲＢＹＫ－１６１、１６２、１６３、１６４、１６６、１６７、１６８、１７４、１８２、１８３、１８４、１８５、２０００、２００１、２０５０、２１５０、２１６３、２１６４、ＢＹＫ－ＬＰＮ６９１９（以上、ビックケミー社製）、ソルスパース１１２００、１３２４０、１３６５０、１３９４０、２４０００、２６０００、２８０００、３２０００、３２５００、３２５５０、３２６００、３３０００、３４７５０、３５１００、３５２００、３７５００、３８５００、３９０００、５３０９５、５６０００、７１００（以上、日本ルーブリゾール社製）、Ｅｆｋａ　ＰＸ　４３００、４３３０、４０４６、４０６０、４０８０（以上、ＢＡＳＦ社製）等が挙げられる。また、塩基性基を有する樹脂は、特開２０１４－２１９６６５号公報の段落番号００６３～０１１２に記載されたブロック共重合体（Ｂ）、特開２０１８－１５６０２１号公報の段落番号００４６～００７６に記載されたブロック共重合体Ａ１、特開２０１９－１８４７６３号公報の段落番号０１５０～０１５３に記載された塩基性基を有するビニル樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。 Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 33090500, 39090500, 390500 56000, 7100 (manufactured by Nippon Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (manufactured by BASF) and the like. Further, the resin having a basic group is a block copolymer (B) described in paragraph numbers 0063 to 0112 of JP-A-2014-219665, and described in paragraph numbers 0046-0076 of JP-A-2018-156021. It is also possible to use the block copolymer A1 described above and vinyl resins having basic groups described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein.
　本発明の着色組成物は、酸基を有する樹脂と塩基性基を有する樹脂とをそれぞれ含むことも好ましい。この態様によれば、着色組成物の保存安定性をより向上できる。酸基を有する樹脂と塩基性基を有する樹脂とを併用する場合、塩基性基を有する樹脂の含有量は、酸基を有する樹脂の１００質量部に対して２０～５００質量部であることが好ましく、３０～３００質量部であることがより好ましく、５０～２００質量部であることが更に好ましい。 The coloring composition of the present invention preferably contains a resin having an acid group and a resin having a basic group. According to this aspect, the storage stability of the coloring composition can be further improved. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is 20 to 500 parts by mass with respect to 100 parts by mass of the resin having an acid group. It is preferably from 30 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass.
　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 an "ether dimer"). It is also preferable to use a resin containing a repeating unit that
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　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-C000011
 　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 formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Figure JPOXMLDOC01-appb-C000011
 In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, the contents of which are incorporated herein.
　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 number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.
　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-C000012
 　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 formula (X).
Figure JPOXMLDOC01-appb-C000012
 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 0-15. The number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and 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 formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
　樹脂としては、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。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、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-C000013
 　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。 As the resin, it is also preferable to use a resin having a crosslinkable group. Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The epoxy group may be a cycloaliphatic 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 the group represented by the formula (e-2) It is more preferable that the group is When n in formula (e-1) is 0, the group represented by formula (e-1) is an epoxy group, and when n is 1, it is represented by formula (e-1) The group is an oxetanyl group. Also, the group represented by formula (e-2) is an alicyclic epoxy group.
Figure JPOXMLDOC01-appb-C000013
 In formula (e-1), R E1 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 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 in the alkyl group represented by R E1 is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group represented by R E1 is preferably linear or branched, 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, R E1 is preferably a hydrogen atom. When n is 1, R 1 E1 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-C000014
 Here, when n in formula (e-1) is 0, formula (e-1) is a group represented by formula (e-1a) below.
Figure JPOXMLDOC01-appb-C000014
　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-C000015
 The aliphatic hydrocarbon ring represented by ring A E1 in formula (e-2) may be a monocyclic aliphatic hydrocarbon ring or a condensed aliphatic hydrocarbon ring. In addition, the aliphatic hydrocarbon ring represented by Ring A E1 may have a crosslinked structure. Among them, a condensed aliphatic hydrocarbon ring is preferable because a film having excellent moisture resistance can be easily formed, and a condensed aliphatic hydrocarbon ring having a crosslinked structure is preferable. Specific examples of the aliphatic hydrocarbon ring represented by ring A E1 include the groups shown below, and the group represented by formula (e-2-3) and represented by formula (e-2-4) groups are preferred. In the following formulas, * represents a bond.
Figure JPOXMLDOC01-appb-C000015
　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。 Commercial products of resins having a cyclic ether group include, for example, naphthalene-modified epoxy resins such as EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation). Examples of alkyldiphenol-type epoxy resins include EPICLON 820 (manufactured by DIC Corporation). As bisphenol A type epoxy resins, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (and Co., Ltd.) and the like. As bisphenol F type epoxy resins, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (manufactured by DIC Corporation), LCE-21, RE-602S ( and Nippon Kayaku Co., Ltd.). Phenol novolac type epoxy resins include jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and the like. mentioned. EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) as cresol novolak type epoxy resins , and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.). As aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like. Further, as the resin having a cyclic ether group, resins described in paragraphs 0034 to 0036 of JP-A-2013-011869, resins described in paragraphs 0147-0156 of JP-A-2014-043556, in particular Resins described in paragraph numbers 0085 to 0092 of JP-A-2014-089408, resins described in JP-A-2017-179172, paragraph numbers 0027-0055 and 0096 of JP-A-2018-180081 Resins, resins described in Paragraph Nos. 0117 to 0120 of JP-T-2020-515680, and resins described in Paragraph No. 0084 of International Publication No. 2020/175011 can also be used.
　樹脂としては、芳香族カルボキシ基を有する樹脂（以下、樹脂Ａｃともいう）を用いることも好ましい。樹脂Ａｃにおいて、芳香族カルボキシ基は繰り返し単位の主鎖に含まれていてもよく、繰り返し単位の側鎖に含まれていてもよい。芳香族カルボキシ基は繰り返し単位の主鎖に含まれていることが好ましい。なお、本明細書において、芳香族カルボキシ基とは、芳香族環にカルボキシ基が１個以上結合した構造の基のことである。芳香族カルボキシ基において、芳香族環に結合したカルボキシ基の数は、１～４個であることが好ましく、１～２個であることがより好ましい。 As the resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In Resin Ac, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
　樹脂Ａｃは、式（Ａｃ－１）で表される繰り返し単位および式（Ａｃ－２）で表される繰り返し単位から選ばれる少なくとも１種の繰り返し単位を含む樹脂であることが好ましい。
Figure JPOXMLDOC01-appb-C000016
 　式（Ａｃ－１）中、Ａｒ１は芳香族カルボキシ基を含む基を表し、Ｌ１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ２は、２価の連結基を表す。
　式（Ａｃ－２）中、Ａｒ１０は芳香族カルボキシ基を含む基を表し、Ｌ１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ１２は３価の連結基を表し、Ｐ１０はポリマー鎖を表す。 Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).
Figure JPOXMLDOC01-appb-C000016
 In formula (Ac-1), Ar 1 represents a group containing an aromatic carboxyl group, L 1 represents -COO- or -CONH-, and L 2 represents a divalent linking group.
In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 represents -COO- or -CONH-, L 12 represents a trivalent linking group, and P 10 represents a polymer represents a chain.
　式（Ａｃ－１）においてＡｒ１が表す芳香族カルボキシ基を含む基としては、芳香族トリカルボン酸無水物から由来する構造、芳香族テトラカルボン酸無水物から由来する構造などが挙げられる。芳香族トリカルボン酸無水物および芳香族テトラカルボン酸無水物としては、下記構造の化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000017
 Examples of the aromatic carboxy group-containing group represented by Ar 1 in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like. Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.
Figure JPOXMLDOC01-appb-C000017
　上記式中、Ｑ１は、単結合、－Ｏ－、－ＣＯ－、－ＣＯＯＣＨ２ＣＨ２ＯＣＯ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、下記式（Ｑ－１）で表される基または下記式（Ｑ－２）で表される基を表す。
Figure JPOXMLDOC01-appb-C000018
 In the above formula, Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
Figure JPOXMLDOC01-appb-C000018
　Ａｒ１が表す芳香族カルボキシ基を含む基は、架橋性基を有していてもよい。架橋性基は、エチレン性不飽和結合含有基および環状エーテル基であることが好ましく、エチレン性不飽和結合含有基であることがより好ましい。Ａｒ１が表す芳香族カルボキシ基を含む基の具体例としては、式（Ａｒ－１１）で表される基、式（Ａｒ－１２）で表される基、式（Ａｒ－１３）で表される基などが挙げられる。
Figure JPOXMLDOC01-appb-C000019
 The group containing an aromatic carboxyl group represented by Ar 1 may have a crosslinkable group. The crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). and the like.
Figure JPOXMLDOC01-appb-C000019
　式（Ａｒ－１１）中、ｎ１は１～４の整数を表し、１または２であることが好ましく、２であることがより好ましい。
　式（Ａｒ－１２）中、ｎ２は１～８の整数を表し、１～４の整数であることが好ましく、１または２であることがより好ましく、２であることが更に好ましい。
　式（Ａｒ－１３）中、ｎ３およびｎ４はそれぞれ独立して０～４の整数を表し、０～２の整数であることが好ましく、１または２であることがより好ましく、１であることが更に好ましい。ただし、ｎ３およびｎ４の少なくとも一方は１以上の整数である。
　式（Ａｒ－１３）中、Ｑ１は、単結合、－Ｏ－、－ＣＯ－、－ＣＯＯＣＨ２ＣＨ２ＯＣＯ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、上記式（Ｑ－１）で表される基または上記式（Ｑ－２）で表される基を表す。
　式（Ａｒ－１１）～（Ａｒ－１３）中、＊１はＬ１との結合位置を表す。 In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2.
In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-13), Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), * 1 represents the bonding position with L1.
　式（Ａｃ－１）においてＬ１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、－ＣＯＯ－を表すことが好ましい。 In formula (Ac-1), L 1 represents -COO- or -CONH-, preferably -COO-.
　式（Ａｃ－１）においてＬ２が表す２価の連結基としては、アルキレン基、アリーレン基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。Ｌ２が表す２価の連結基は、－Ｌ２ａ－Ｏ－で表される基であることが好ましい。Ｌ２ａは、アルキレン基；アリーレン基；アルキレン基とアリーレン基とを組み合わせた基；アルキレン基およびアリーレン基から選ばれる少なくとも１種と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、アルキレン基であることが好ましい。アルキレン基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよい。アルキレン基およびアリーレン基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。 The divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-. L 2a is an alkylene group; an arylene group; a combination of an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group; Examples include groups in which at least one selected from —NH— and —S— are combined, and alkylene groups are preferred. The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
　式（Ａｃ－２）においてＡｒ１０が表す芳香族カルボキシ基を含む基としては、式（Ａｃ－１）のＡｒ１と同義であり、好ましい範囲も同様である。 The group containing an aromatic carboxy group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
　式（Ａｃ－２）においてＬ１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、－ＣＯＯ－を表すことが好ましい。 In formula (Ac-2), L 11 represents -COO- or -CONH-, preferably -COO-.
　式（Ａｃ－２）においてＬ１２が表す３価の連結基としては、炭化水素基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。炭化水素基は、脂肪族炭化水素基、芳香族炭化水素基が挙げられる。脂肪族炭化水素基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよい。芳香族炭化水素基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。炭化水素基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。Ｌ１２が表す３価の連結基は、式（Ｌ１２－１）で表される基であることが好ましく、式（Ｌ１２－２）で表される基であることがより好ましい。
Figure JPOXMLDOC01-appb-C000020
 The trivalent linking group represented by L 12 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).
Figure JPOXMLDOC01-appb-C000020
　式（Ｌ１２－１）中、Ｌ１２ｂは３価の連結基を表し、Ｘ１はＳを表し、＊１は式（Ａｃ－２）のＬ１１との結合位置を表し、＊２は式（Ａｃ－２）のＰ１０との結合位置を表す。Ｌ１２ｂが表す３価の連結基としては、炭化水素基；炭化水素基と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、炭化水素基または炭化水素基と－Ｏ－とを組み合わせた基であることが好ましい。 In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown. The trivalent linking group represented by L 12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- is preferably a hydrocarbon group or a group of a combination of a hydrocarbon group and —O—.
　式（Ｌ１２－２）中、Ｌ１２ｃは３価の連結基を表し、Ｘ１はＳを表し、＊１は式（Ａｃ－２）のＬ１１との結合位置を表し、＊２は式（Ａｃ－２）のＰ１０との結合位置を表す。Ｌ１２ｃが表す３価の連結基としては、炭化水素基；炭化水素基と、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－および－Ｓ－から選ばれる少なくとも１種とを組み合わせた基などが挙げられ、炭化水素基であることが好ましい。 In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, *1 represents the bonding position with L 11 of formula (Ac-2), *2 represents formula ( The binding position of Ac- 2 ) with P10 is shown. The trivalent linking group represented by L 12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.
　式（Ａｃ－２）においてＰ１０はポリマー鎖を表す。Ｐ１０が表すポリマー鎖は、ポリ（メタ）アクリル繰り返し単位、ポリエーテル繰り返し単位、ポリエステル繰り返し単位およびポリオール繰り返し単位から選ばれる少なくとも１種の繰り返し単位を有することが好ましい。ポリマー鎖Ｐ１０の重量平均分子量は５００～２００００が好ましい。下限は１０００以上が好ましい。上限は１００００以下が好ましく、５０００以下がより好ましく、３０００以下が更に好ましい。Ｐ１０の重量平均分子量が上記範囲であれば組成物中における顔料の分散性が良好である。芳香族カルボキシ基を有する樹脂が式（Ａｃ－２）で表される繰り返し単位を有する樹脂である場合は、この樹脂は分散剤として好ましく用いられる。 P 10 in formula (Ac-2) represents a polymer chain. The polymer chain represented by P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units. The weight average molecular weight of the polymer chain P10 is preferably 500-20,000 . The lower limit is preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.
　Ｐ１０が表すポリマー鎖は、架橋性基を含んでいてもよい。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。 The polymer chain represented by P10 may contain crosslinkable groups. Crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
　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. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater 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 possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by 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。 The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
　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。 The resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having 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 JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
　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。 The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
　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 its side chain. The content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is 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 a dispersant, resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, 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 BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.
　着色組成物の全固形分中における樹脂の含有量は１～５０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、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 content of the resin in the total solid content of the coloring composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The coloring composition of the present invention may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.
＜＜ポリアルキレンイミン＞＞
　本発明の着色組成物は、ポリアルキレンイミンを含有することもできる。ポリアルキレンイミンは例えば顔料の分散助剤として用いられる。分散助剤とは、着色組成物中において顔料の分散性を高めるための素材のことである。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーであって、２級アミノ基を少なくとも有するポリマーである。ポリアルキレンイミンは、２級アミノ基の他に、１級アミノ基や３級アミノ基を含んでいてもよい。ポリアルキレンイミンは、１級アミノ基と、２級アミノ基と、３級アミノ基とをそれぞれ含む分岐構造を有するポリマーであることが好ましい。アルキレンイミンの炭素数は２～６が好ましく、２～４がより好ましく、２または３であることが更に好ましく、２であることが特に好ましい。 <<Polyalkyleneimine>>
The coloring composition of the present invention can also contain a polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersing aids for pigments. A dispersing aid is a material for enhancing dispersibility of a pigment in a coloring composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has at least a secondary amino group. The polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group. The polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, still more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
　ポリアルキレンイミンの分子量は、２００以上であることが好ましく、２５０以上であることがより好ましい。上限は、１０００００以下であることが好ましく、５００００以下であることがより好ましく、１００００以下であることが更に好ましく、２０００以下であることが特に好ましい。なお、ポリアルキレンイミンの分子量の値について、構造式から分子量が計算できる場合は、ポリアルキレンイミンの分子量は構造式から計算した値である。一方、特定アミン化合物の分子量が構造式から計算できない、あるいは、計算が困難な場合には、沸点上昇法で測定した数平均分子量の値を用いる。また、沸点上昇法でも測定できない、あるいは、測定が困難な場合は、粘度法で測定した数平均分子量の値を用いる。また、粘度法でも測定できない、あるいは、粘度法での測定が困難な場合は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値での数平均分子量の値を用いる。 The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the value of the molecular weight of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. When the boiling point elevation method cannot be used or the measurement is difficult, the value of the number average molecular weight measured by the viscosity method is used. In addition, when measurement by the viscosity method is not possible or measurement by the viscosity method is difficult, the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
　ポリアルキレンイミンのアミン価は５ｍｍｏｌ／ｇ以上であることが好ましく、１０ｍｍｏｌ／ｇ以上であることがより好ましく、１５ｍｍｏｌ／ｇ以上であることが更に好ましい。 The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
　アルキレンイミンの具体例としては、エチレンイミン、プロピレンイミン、１，２－ブチレンイミン、２，３－ブチレンイミンなどが挙げられ、エチレンイミンまたはプロピレンイミンであることが好ましく、エチレンイミンであることがより好ましい。ポリアルキレンイミンは、ポリエチレンイミンであることが特に好ましい。また、ポリエチレンイミンは、１級アミノ基を、１級アミノ基と２級アミノ基と３級アミノ基との合計に対して１０モル％以上含むことが好ましく、２０モル％以上含むことがより好ましく、３０モル％以上含むことが更に好ましい。ポリエチレンイミンの市販品としては、エポミンＳＰ－００３、ＳＰ－００６、ＳＰ－０１２、ＳＰ－０１８、ＳＰ－２００、Ｐ－１０００（以上、（株）日本触媒製）などが挙げられる。 Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
　着色組成物の全固形分中におけるポリアルキレンイミンの含有量は０．１～５質量％であることが好ましい。下限は０．２質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１質量％以上であることが更に好ましい。上限は４．５質量％以下であることが好ましく、４質量％以下であることがより好ましく、３質量％以下であることが更に好ましい。また、ポリアルキレンイミンの含有量は、顔料１００質量部に対して０．５～２０質量部であることが好ましい。下限は０．６質量部以上であることが好ましく、１質量部以上であることがより好ましく、２質量部以上であることが更に好ましい。上限は１０質量部以下であることが好ましく、８質量部以下であることがより好ましい。ポリアルキレンイミンは、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であることが好ましい。 The content of polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Also, the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜硬化促進剤＞＞
　本発明の着色組成物は、硬化促進剤を含有することができる。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第２０１８／０５６１８９号の段落番号００９４～００９７に記載の化合物、特開２０１５－０３４９６３号公報の段落番号０２４６～０２５３に記載の化合物、特開２０１３－０４１１６５号公報の段落番号０１８６～０２５１に記載の化合物、特開２０１４－０５５１１４号公報に記載のイオン性化合物、特開２０１２－１５０１８０号公報の段落番号００７１～００８０に記載の化合物、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、特許第５７６５０５９号公報の段落番号００８５～００９２に記載の化合物、特開２０１７－０３６３７９号公報に記載のカルボキシ基含有エポキシ硬化剤などが挙げられる。着色組成物の全固形分中における硬化促進剤の含有量は０．３～８．９質量％であることが好ましく、０．８～６．４質量％であることがより好ましい。 <<Curing accelerator>>
The coloring composition of the present invention can contain a curing accelerator. Curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like. Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379. The content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
＜＜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。紫外線吸収剤としては、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が挙げられる。このような化合物の具体例としては、特開２００９－２１７２２１号公報の段落番号００３８～００５２、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に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。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）、ＢＡＳＦ社製のＴｉｎｕｖｉｎシリーズ、Ｕｖｉｎｕｌ（ユビナール）シリーズ、住化ケムテックス（株）製のＳｕｍｉｓｏｒｂシリーズなどが挙げられる。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、紫外線吸収剤は、特許第６２６８９６７号公報の段落番号００４９～００５９に記載された化合物、国際公開第２０１６／１８１９８７号の段落番号００５９～００７６に記載された化合物、国際公開第２０２０／１３７８１９号に記載されたチオアリール基置換ベンゾトリアゾール型紫外線吸収剤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紫外線吸収剤の含有量は、０．０１～１０質量％であることが好ましく、０．０１～５質量％であることがより好ましい。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、それらの合計量が上記範囲となることが好ましい。 <<Ultraviolet absorber>>
The coloring composition of the present invention can contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814. 0334, and compounds described in paragraphs 0061 to 0080 of JP-A-2016-162946, the contents of which are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. . Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). In addition, the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of WO 2016/181987, and WO 2020/137819. A thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more kinds are used, 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－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔｅｒｔ－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－ｔｅｒｔ－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）が挙げられる。中でも、ｐ－メトキシフェノールが好ましい。着色組成物の全固形分中における重合禁止剤の含有量は、０．０００１～５質量％であることが好ましい。重合禁止剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、それらの合計量が上記範囲となることが好ましい。 <<polymerization inhibitor>>
The coloring composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜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ができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、Ｎ－β－アミノエチル－γ－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、商品名　ＫＢＭ－６０２）、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－６０３）、Ｎ－β－アミノエチル－γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－６０２）、γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－９０３）、γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－９０３）、３－メタクリロキシプロピルメチルジメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－５０２）、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、商品名　ＫＢＭ－５０３）等がある。また、シランカップリング剤の具体例については、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６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。着色組成物の全固形分中におけるシランカップリング剤の含有量は、０．０１～１５．０質量％であることが好ましく、０．０５～１０．０質量％であることがより好ましい。シランカップリング剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、それらの合計量が上記範囲となることが好ましい。 <<Silane coupling agent>>
The coloring composition of the present invention can contain a silane coupling agent. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy Propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503), and the like. Further, specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein. The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
＜＜界面活性剤＞＞
　本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコ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。界面活性剤はシリコーン系界面活性剤またはフッ素系界面活性剤であることが好ましい。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を参照することができ、この内容は本明細書に組み込まれる。 <<Surfactant>>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. For surfactants, reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
　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 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the 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、Ｒ－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。 As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and 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, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH- 40 (manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS , FTX-218 (manufactured by NEOS Corporation) and the like.
　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。 The fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Available. Examples of such fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
　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。 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 as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。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-C000021
 　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。 A block polymer can also be used as the fluorosurfactant. The fluorosurfactant 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) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
Figure JPOXMLDOC01-appb-C000021
 The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units 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。 A fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, as the fluorosurfactant, 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 regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for the surfactant having a perfluoroalkyl group with 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-C000022
 　式（ｆｉ－１）中、ｍは１または２を表し、ｎは１～４の整数を表し、ａは１または２を表し、Ｘａ＋はａ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 formula (fi-1) as a surfactant.
Figure JPOXMLDOC01-appb-C000022
 In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
　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（富士フイルム和光純薬（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 (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, 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 company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) and the like.
　シリコーン系界面活性剤としては、ＤＯＷＳＩＬ　ＳＨ８４００、ＳＨ８４００　ＦＬＵＩＤ、ＦＺ－２１２２、６７　Ａｄｄｉｔｉｖｅ、７４　Ａｄｄｉｔｉｖｅ、Ｍ　Ａｄｄｉｔｉｖｅ、ＳＦ　８４１９　ＯＩＬ（以上、ダウ・東レ（株）製）、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－６０００、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３（以上、信越化学工業（株）製）、ＢＹＫ－３０７、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３３０、ＢＹＫ－３３３、ＢＹＫ－３７６０、ＢＹＫ－ＵＶ３５１０（以上、ビックケミー社製）等が挙げられる。 Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
　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-C000023
 A compound having the following structure can also be used as the silicone-based surfactant.
Figure JPOXMLDOC01-appb-C000023
　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％であることが好ましく、０．００５～３．０質量％であることがより好ましい。界面活性剤は、１種類のみでもよく、２種類以上でもよい。２種類以上の場合は、それらの合計量が上記範囲となることが好ましい。 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% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably 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。リン系酸化防止剤としてはトリス［２－［［２，４，８，１０－テトラキス（１，１－ジメチルエチル）ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル］オキシ］エチル］アミン、トリス［２－［（４，６，９，１１－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－２－イル）オキシ］エチル］アミン、亜リン酸エチルビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ　ＡＯ－２０、アデカスタブ　ＡＯ－３０、アデカスタブ　ＡＯ－４０、アデカスタブ　ＡＯ－５０、アデカスタブ　ＡＯ－５０Ｆ、アデカスタブ　ＡＯ－６０、アデカスタブ　ＡＯ－６０Ｇ、アデカスタブ　ＡＯ－８０、アデカスタブ　ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。また、酸化防止剤は、特許第６２６８９６７号公報の段落番号００２３～００４８に記載された化合物、国際公開第２０１７／００６６００号に記載された化合物、国際公開第２０１７／１６４０２４号に記載された化合物、韓国公開特許第１０－２０１９－００５９３７１号公報に記載された化合物を使用することもできる。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。酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。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。 <<Antioxidant>>
The coloring composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds 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. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof 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、フィラー、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、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、本発明の着色組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、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 optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. In addition, the coloring composition of the present invention may contain a latent antioxidant, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
　本発明の着色組成物は、得られる膜の屈折率を調整するために金属酸化物を含有させてもよい。金属酸化物としては、ＴｉＯ２、ＺｒＯ２、Ａｌ２Ｏ３、ＳｉＯ２等が挙げられる。金属酸化物の一次粒子径は１～１００ｎｍが好ましく、３～７０ｎｍがより好ましく、５～５０ｎｍが更に好ましい。金属酸化物はコア－シェル構造を有していてもよい。また、この場合、コア部は中空状であってもよい。 The coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 and SiO 2 . The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.
　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 improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 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。 The coloring composition of the present invention preferably does not substantially contain terephthalic acid ester. Here, "substantially free" means that the content of 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。本発明の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。本発明の着色組成物は、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。本発明の着色組成物は、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 perspective of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be regulated. In the coloring composition of the present invention, when the content of the above compounds is reduced, perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and salts thereof, and per The content of fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the coloring composition. is preferably in the range of , more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts. 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 and salts thereof may be selected. Compounds that can substitute for regulated compounds include, for example, compounds excluded from regulation due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. The coloring composition of the present invention may contain perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts within the maximum allowable range.
　本発明の着色組成物の含水率は、通常３質量％以下であり、０．０１～１．５質量％が好ましく、０．１～１．０質量％の範囲であることがより好ましい。含水率は、カールフィッシャー法にて測定することができる。 The water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.
　本発明の着色組成物は、膜面状（平坦性など）の調整、膜厚の調整などを目的として粘度を調整して用いることができる。粘度の値は必要に応じて適宜選択することができるが、例えば、２５℃において０．３ｍＰａ・ｓ～５０ｍＰａ・ｓが好ましく、０．５ｍＰａ・ｓ～２０ｍＰａ・ｓがより好ましい。粘度の測定方法としては、例えば、コーンプレートタイプの粘度計を使用し、２５℃に温度調整を施した状態で測定することができる。 The coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s at 25°C. As a method for measuring the viscosity, for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
＜＜収容容器＞＞
　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、着色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。 <<Container>>
The container for the coloring composition is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, 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, enhancing the storage stability of the coloring composition, and suppressing deterioration of components.
＜着色組成物の調製方法＞
　本発明の着色組成物は、前述の成分を混合して調製できる。着色組成物の調製に際しては、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調製してもよいし、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調製してもよい。 <Method for preparing coloring composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the colored composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare a colored composition, and if necessary, each component may be appropriately mixed into two or more solutions or dispersions. , these may be mixed at the time of use (at the time of coating) to prepare a colored composition.
　また、着色組成物の調製に際して、顔料を分散させるプロセスを含むことが好ましい。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。 In addition, it is preferable to include a process of dispersing the pigment when preparing the coloring composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include 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. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling step. Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.
　着色組成物の調製にあたり、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 preparing the colored composition, it is preferable to filter the colored 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), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹ、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 size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, and even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nihon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as the filter. .
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. 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.
　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。また組成物の親疎水性に合わせて、適宜フィルタを選択することができる。 When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
＜膜の製造方法＞
　本発明の膜の製造方法は、本発明の着色組成物を支持体に塗布する工程を含む。 <Method for producing membrane>
The method for producing the membrane of the present invention includes the step of applying the coloring composition of the present invention to a support.
　本発明の膜の製造方法によって製造される膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は、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。 The film thickness of the film manufactured by the film manufacturing method of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even 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, and even more preferably 0.3 μm or more.
　本発明の膜の製造方法によって製造される膜は、カラーフィルタの着色画素などに用いることができる。着色画素としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、黄色画素などが挙げられ、赤色画素、緑色画素および黄色画素であることが好ましく、赤色画素であることがより好ましい。 The film manufactured by the film manufacturing method of the present invention can be used for colored pixels of color filters. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and yellow pixels are preferred, and red pixels are more preferred. preferable.
　本発明の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。 The method for producing a film of the present invention preferably further includes a step of forming a pattern (pixels). A method for forming the pattern (pixels) includes 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。 Pattern formation by photolithography includes the steps of forming a colored composition layer on a support using the colored composition of the present invention, a step of patternwise exposing the colored composition layer, and a step of exposing the colored composition layer. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the coloring 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。下地層は、本明細書に記載の着色組成物から着色剤を除いた組成物や、本明細書記載の樹脂、重合性化合物、界面活性剤などを含む組成物などを用いて形成してもよい。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。 In the step of forming the colored composition layer, the colored composition layer of the present invention is used to form the colored composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, 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. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. The underlayer may be formed using a composition obtained by removing the coloring agent from the colored composition described herein, or a composition containing the resin, polymerizable compound, surfactant, etc. described herein. good. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.
　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。 A known method can be used as a method for applying the coloring composition. For example, dropping method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., 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, etc. various printing methods; a transfer method using a mold or the like; and a nanoimprint method. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the coloring composition, the descriptions of WO2017/030174 and WO2017/018419 can be referred to, and the contents thereof are incorporated herein.
　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 (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using 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 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source 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。 In addition, when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
　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 dose (exposure dose) 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 selected as appropriate. The exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m 2 at an oxygen concentration of 10% by volume and 20000 W/m 2 at an oxygen concentration of 35% by volume.
　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、残渣の除去を効果的に行うために、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 areas of the colored composition layer are removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored composition layer can be performed using a developer. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to effectively remove the residue, the process of shaking off the developer every 60 seconds and then supplying 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。 The developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, 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 include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint 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. Moreover, the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse solution to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.
　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。 After development, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, 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。 Pattern formation by a dry etching method is 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 layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.
＜カラーフィルタの製造方法＞
　本発明のカラーフィルタの製造方法は、上述した本発明の膜の製造方法を含む。すなわち、本発明のカラーフィルタの製造方法は、上述した本発明の着色組成物を支持体に塗布する工程を含む。カラーフィルタは、その画素として本発明の膜を有することが好ましい。 <Manufacturing method of color filter>
The method for manufacturing the color filter of the present invention includes the method for manufacturing the film of the present invention described above. That is, the method for producing a color filter of the present invention includes the step of applying the coloring composition of the present invention described above onto a support. A color filter preferably has the film of the present invention as its pixels.
　カラーフィルタにおいて本発明の膜の膜厚は、目的に応じて適宜調整できる。膜厚は、２μｍ以下が好ましく、１μｍ以下がより好ましく、０．５μｍ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。 In the color filter, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
　カラーフィルタに含まれる画素の幅は０．１～１０．０μｍであることが好ましい。下限は、０．４μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましく、０．６μｍ以上であることが更に好ましい。上限は、５．０μｍ以下であることが好ましく、２．０μｍ以下であることがより好ましく、１．０μｍ以下であることが更に好ましく、０．８μｍ以下であることがより一層好ましい。 The width of pixels included in the color filter is preferably 0.1 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less.
＜固体撮像素子の製造方法＞
　本発明の固体撮像素子の製造方法は、上述した本発明の膜の製造方法を含む。すなわち、本発明の固体撮像素子の製造方法は、上述した本発明の着色組成物を支持体に塗布する工程を含む。固体撮像素子の構成としては、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 <Manufacturing method of solid-state imaging device>
A method for manufacturing a solid-state imaging device according to the present invention includes the above-described method for manufacturing a film according to the present invention. That is, the method for producing a solid-state imaging device of the present invention includes the step of applying the coloring composition of the present invention described above to a support. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
　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から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から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。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号に記載の装置が挙げられる。また、特開２０１９－２１１５５９号公報の中で示しているように固体撮像素子の構造内に紫外線吸収層を設けて耐光性を改良してもよい。本発明の固体撮像素子を備えた撮像装置は、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用としても用いることができる。 Transfer electrodes made of polysilicon or the like, and a plurality of photodiodes forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a substrate. A light-shielding film is provided on the photodiode and the transfer electrode so that only the light-receiving portion of the photodiode is opened. It has a device protective film with a thickness of 1.5 mm, and has a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. Further, as disclosed in Japanese Patent Application Laid-Open No. 2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.
＜画像表示装置の製造方法＞
　本発明の画像表示装置の製造方法は、上述した本発明の膜の製造方法を含む。すなわち、本発明の画像表示装置の製造方法は、上述した本発明の着色組成物を支持体に塗布する工程を含む。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木昭夫著、（株）工業調査会、１９９０年発行）」、「ディスプレイデバイス（伊吹順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田龍男編集、（株）工業調査会、１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Method for manufacturing image display device>
A method for manufacturing an image display device of the present invention includes the above-described method for manufacturing a film of the present invention. That is, the method for producing an image display device of the present invention includes the step of applying the coloring composition of the present invention described above to a support. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
　以下に実施例を挙げて本発明をさらに具体的に説明する。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 described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.
＜重量平均分子量の測定方法＞
　樹脂の重量平均分子量（Ｍｗ）は、下記測定条件の下、ＧＰＣ（Ｇｅｌ　ｐｅｒｍｅａｔｉｏｎ　ｃｈｒｏｍａｔｏｇｒａｐｈｙ）測定により算出した。
　カラムの種類：ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｈと、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００と、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００とを連結したカラム
　展開溶媒：テトラヒドロフラン
　カラム温度：４０℃
　流量（サンプル注入量）：１．０μＬ（サンプル濃度０．１質量％）
　装置名：東ソー（株）製　ＨＬＣ－８２２０ＧＰＣ
　検出器：示差屈折計（ＲＩ検出器） <Method for measuring weight average molecular weight>
The weight average molecular weight (Mw) of the resin was calculated by GPC (Gel permeation chromatography) measurement under the following measurement conditions.
Column type: Column connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1% by mass)
Apparatus name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: Differential refractometer (RI detector)
＜分散液の製造＞
　顔料と顔料誘導体とを合計で１６質量部と、分散剤を固形分換算で４質量部と、溶剤を８０質量部との混合液を、ビーズミル（ジルコニアビーズ０．１ｍｍ径）を用いて３時間混合および分散した。その後、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、圧力２０００ｋｇ／ｃｍ２および流量５００ｇ／ｍｉｎの条件の下、分散処理を行なった。この分散処理を全１０回まで繰り返して、分散液を得た。なお、顔料、顔料誘導体、分散剤および溶剤はそれぞれ下記表に示す素材を用いた。 <Production of dispersion liquid>
A mixture of a total of 16 parts by mass of a pigment and a pigment derivative, 4 parts by mass of a dispersant in terms of solid content, and 80 parts by mass of a solvent is processed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm). Mixed and dispersed. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism, dispersion treatment was carried out under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersing treatment was repeated up to 10 times to obtain a dispersion. The materials shown in the table below were used for the pigment, pigment derivative, dispersant and solvent.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　上記分散液の処方を示す表中の略語で示す素材の詳細は下記の通りである。 The details of the materials indicated by the abbreviations in the table showing the formulation of the dispersion are as follows.
（顔料）
　Ｐ－１：　Ｃ．Ｉ．ピグメントレッド１７７（赤色顔料、アントラキノン顔料）
　Ｐ－２：　Ｃ．Ｉ．ピグメントレッド２５４（赤色顔料、ジケトピロロピロール顔料）
　Ｐ－３：　Ｃ．Ｉ．ピグメントレッド２６４（赤色顔料、ジケトピロロピロール顔料）
　Ｐ－４：　Ｃ．Ｉ．ピグメントレッド２６９（赤色顔料、ナフトール顔料）
　Ｐ－５：　Ｃ．Ｉ．ピグメントレッド２７２（赤色顔料、ジケトピロロピロール顔料）
　Ｐ－６：　Ｃ．Ｉ．ピグメントレッド２９１（赤色顔料、ジケトピロロピロール顔料）
　Ｐ－７：　Ｃ．Ｉ．ピグメントイエロー１２９（黄色顔料、アゾメチン顔料）
　Ｐ－８：　Ｃ．Ｉ．ピグメントイエロー１３８（黄色顔料、キノフタロン顔料）
　Ｐ－９：　Ｃ．Ｉ．ピグメントイエロー１３９（黄色顔料、イソインドリン顔料）
　Ｐ－１０：　Ｃ．Ｉ．ピグメントイエロー１５０（黄色顔料、アゾ顔料）
　Ｐ－１１：　Ｃ．Ｉ．ピグメントイエロー１８５（黄色顔料、イソインドリン顔料）
　Ｐ－１２：　Ｃ．Ｉ．ピグメントグリーン５８（緑色顔料、フタロシアニン顔料）
　Ｐ－１３：　Ｃ．Ｉ．ピグメントブルー１５：６（青色顔料、フタロシアニン顔料） (pigment)
P-1: C.I. I. Pigment Red 177 (red pigment, anthraquinone pigment)
P-2: C.I. I. Pigment Red 254 (red pigment, diketopyrrolopyrrole pigment)
P-3: C.I. I. Pigment Red 264 (red pigment, diketopyrrolopyrrole pigment)
P-4: C.I. I. Pigment Red 269 (red pigment, naphthol pigment)
P-5: C.I. I. Pigment Red 272 (red pigment, diketopyrrolopyrrole pigment)
P-6: C.I. I. Pigment Red 291 (red pigment, diketopyrrolopyrrole pigment)
P-7: C.I. I. Pigment Yellow 129 (yellow pigment, azomethine pigment)
P-8: C.I. I. Pigment Yellow 138 (yellow pigment, quinophthalone pigment)
P-9: C.I. I. Pigment Yellow 139 (yellow pigment, isoindoline pigment)
P-10: C.I. I. Pigment Yellow 150 (yellow pigment, azo pigment)
P-11: C.I. I. Pigment Yellow 185 (yellow pigment, isoindoline pigment)
P-12: C.I. I. Pigment Green 58 (green pigment, phthalocyanine pigment)
P-13: C.I. I. Pigment Blue 15:6 (blue pigment, phthalocyanine pigment)
（顔料誘導体）
　Ｓｙｎ－１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000026
 　Ｓｙｎ－２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000027
 　Ｓｙｎ－３：下記構造の化合物
Figure JPOXMLDOC01-appb-C000028
 　Ｓｙｎ－４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000029
 　Ｓｙｎ－５：下記構造の化合物
Figure JPOXMLDOC01-appb-C000030
 　Ｓｙｎ－６：下記構造の化合物
Figure JPOXMLDOC01-appb-C000031
 　Ｓｙｎ－７：下記構造の化合物
Figure JPOXMLDOC01-appb-C000032
 　Ｓｙｎ－８：下記構造の化合物
Figure JPOXMLDOC01-appb-C000033
 　Ｓｙｎ－９：下記構造の化合物
Figure JPOXMLDOC01-appb-C000034
 　Ｓｙｎ－１０：下記構造の化合物
Figure JPOXMLDOC01-appb-C000035
 (pigment derivative)
Syn-1: a compound having the following structure
Figure JPOXMLDOC01-appb-C000026
 Syn-2: a compound having the following structure
Figure JPOXMLDOC01-appb-C000027
 Syn-3: a compound having the following structure
Figure JPOXMLDOC01-appb-C000028
 Syn-4: a compound having the following structure
Figure JPOXMLDOC01-appb-C000029
 Syn-5: a compound having the following structure
Figure JPOXMLDOC01-appb-C000030
 Syn-6: a compound having the following structure
Figure JPOXMLDOC01-appb-C000031
 Syn-7: a compound having the following structure
Figure JPOXMLDOC01-appb-C000032
 Syn-8: a compound having the following structure
Figure JPOXMLDOC01-appb-C000033
 Syn-9: a compound having the following structure
Figure JPOXMLDOC01-appb-C000034
 Syn-10: a compound having the following structure
Figure JPOXMLDOC01-appb-C000035
（分散剤）
　Ｄ－１：以下の方法で合成した樹脂Ｄ－１
　メチルメタクリレート５０質量部、ｎ－ブチルメタクリレート３０質量部、（３－エチルオキセタン－３－イル）メチルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）４５．４質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を７０℃に加熱して、３－メルカプト－１，２－プロパンジオール６質量部を添加して、さらにＡＩＢＮ（アゾビスイソブチロニトリル）０．１２質量部を加え、１２時間反応させた。固形分測定により９５％が反応したことを確認した。次に、ピロメリット酸無水物９．７質量部、ＰＧＭＥＡ７０．３質量部、触媒としてＤＢＵ（１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン）０．２０質量部を追加し、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化していることを確認し反応を終了したのち、乾燥して溶剤を除去し、酸価４３ｍｇＫＯＨ／ｇ、重量平均分子量９０００の下記構造の樹脂Ｄ－１を得た。
Figure JPOXMLDOC01-appb-C000036
 (dispersant)
D-1: Resin D-1 synthesized by the following method
50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into a reaction vessel, and the atmosphere was The gas was replaced with nitrogen gas. Heat the inside of the reaction vessel to 70° C., add 6 parts by mass of 3-mercapto-1,2-propanediol, add 0.12 parts by mass of AIBN (azobisisobutyronitrile), and react for 12 hours. let me Solid content measurement confirmed that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added. , and 120° C. for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value and completing the reaction, the solvent is removed by drying, and the acid value is 43 mgKOH / g and the weight average molecular weight is 9000. A resin D-1 was obtained.
Figure JPOXMLDOC01-appb-C000036
　Ｄ－２：以下の方法で合成した樹脂Ｄ－２
　１－チオグリセロール１０８質量部、ピロメリット酸無水物１７４質量部、メトキシプロピルアセテート６５０質量部、触媒としてモノブチルスズオキシド０．２質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した後、１２０℃で５時間反応させた（第一工程）。酸価の測定で９５％以上の酸無水物がハーフエステル化していることを確認した。次に、第一工程で得られた化合物を固形分換算で１６０質量部、２－ヒドロキシプロピルメタクリレート２００質量部、エチルアクリレート２００質量部、ｔ－ブチルアクリレート１５０質量部、２－メトキシエチルアクリレート２００質量部、メチルアクリレート２００質量部、メタクリル酸５０質量部、ＰＧＭＥＡ６６３質量部を反応容器に仕込み、反応容器内を８０℃に加熱して、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１．２質量部を添加し、１２時間反応させた（第二工程）。固形分測定により９５％が反応したことを確認した。最後に、第二工程で得られた化合物の５０質量％ＰＧＭＥＡ溶液５００質量部、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）２７．０質量部、ヒドロキノン０．１質量部を反応容器に仕込み、イソシアネート基に基づく２２７０ｃｍ－１のピークの消失を確認するまで反応を行った（第三工程）。ピーク消失の確認後、反応溶液を冷却したのち、乾燥して溶剤を除去して、酸価６８ｍｇＫＯＨ／ｇ、エチレン性不飽和結合基価０．６２ｍｍｏｌ／ｇ、重量平均分子量１３０００の下記構造の樹脂Ｄ－２を得た。
Figure JPOXMLDOC01-appb-C000037
 D-2: Resin D-2 synthesized by the following method
108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel, and after replacing the atmospheric gas with nitrogen gas, It was made to react at 120 degreeC for 5 hours (1st process). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, 200 parts by mass of 2-methoxyethyl acrylate Parts, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are charged into a reaction vessel, and the inside of the reaction vessel is heated to 80 ° C. to obtain 2,2′-azobis(2,4-dimethylvaleronitrile) 1 .2 mass parts were added and reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts by mass of a 50% by mass PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part by mass of hydroquinone were charged into a reaction vessel, isocyanate group The reaction was carried out until the disappearance of the peak at 2270 cm −1 based on Δ was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and then dried to remove the solvent. D-2 was obtained.
Figure JPOXMLDOC01-appb-C000037
　Ｄ－３：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１６０００、酸価６７ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000038
 D-3: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 16000, acid value: 67 mgKOH/g)
Figure JPOXMLDOC01-appb-C000038
　Ｄ－４：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-C000039
 D-4: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 21000, acid value: 36 mgKOH/g)
Figure JPOXMLDOC01-appb-C000039
　Ｄ－５：Ｄｉｓｐｅｒｂｙｋ－１１１（ビックケミー社製） D-5: Disperbyk-111 (manufactured by BYK-Chemie)
　Ｄ－６：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。酸基を有する樹脂、重量平均分子量１８０００、酸価８２．１ｍｇＫＯＨ／ｇ）
Figure JPOXMLDOC01-appb-C000040
 D-6: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 18000, acid value 82. 1 mg KOH/g)
Figure JPOXMLDOC01-appb-C000040
（溶剤）
　Ｓ－１：プロピレングリコールモノメチルエーテルアセテート（エステル系溶剤） (solvent)
S-1: Propylene glycol monomethyl ether acetate (ester solvent)
＜着色組成物の製造＞
　各素材を、以下に示す処方１、処方２、処方３、処方４、処方ｃ１または処方ｃ２の割合で混合し、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して各着色組成物を製造した。下記表において、着色組成物の全固形分中における着色剤の含有量（顔料と顔料誘導体の合計量）の値を「着色剤濃度」の欄に記載し、全溶剤中における環状ケトン溶剤の含有量を、「環状ケトン溶剤の割合」の欄に記載する。 <Production of coloring composition>
Each material is mixed in the ratio of prescription 1, prescription 2, prescription 3, prescription 4, prescription c1 or prescription c2 shown below, and filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm. Each coloring composition was produced. In the table below, the content of the coloring agent in the total solid content of the coloring composition (the total amount of the pigment and the pigment derivative) is described in the column "coloring agent concentration", and the content of the cyclic ketone solvent in the total solvent The amount is given in the column "Proportion of cyclic ketone solvent".
　（処方１）
　下記表に記載の分散液　　　・・・６０．０質量部
　下記表に記載のモノマー　　　・・・６．０質量部
　下記表に記載のバインダー　　　・・・１１．５質量部
　下記表に記載の光重合開始剤　　　・・・３．０質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・１４質量部
　下記表に記載の環状ケトン溶剤　　　・・・５．５質量部 (Prescription 1)
Dispersion listed in the table below...60.0 parts by mass Monomer listed in the table below...6.0 parts by mass Binder listed in the table below...11.5 parts by mass Photopolymerization listed in the table below Initiator ... 3.0 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below ... 14 parts by mass Cyclic ketone solvent listed in the table below ... 5.5 parts by mass
　（処方２）
　下記表に記載の分散液　　　・・・７０．０質量部
　下記表に記載のモノマー　　　・・・３．０質量部
　下記表に記載のバインダー　　　・・・９．０質量部
　下記表に記載の光重合開始剤　　　・・・２．５質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・１０質量部
　下記表に記載の環状ケトン溶剤　　　・・・５．５質量部 (Prescription 2)
Dispersions listed in the table below...70.0 parts by mass Monomers listed in the table below...3.0 parts by mass Binders listed in the table below...9.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.5 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below ... 10 parts by mass Cyclic ketone solvent described in the table below ... 5.5 parts by mass
　（処方３）
　下記表に記載の分散液　　　・・・７５．０質量部
　下記表に記載のモノマー　　　・・・２．５質量部
　下記表に記載のバインダー　　　・・・９．０質量部
　下記表に記載の光重合開始剤　　　・・・２．０質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・６質量部
　下記表に記載の環状ケトン溶剤　　　・・・５．５質量部 (Prescription 3)
Dispersion listed in the table below...75.0 parts by mass Monomer listed in the table below...2.5 parts by mass Binder listed in the table below...9.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.0 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below ... 6 parts by mass Cyclic ketone solvent described in the table below ... 5.5 parts by mass
　（処方４）
　下記表に記載の分散液　　　・・・８０．０質量部
　下記表に記載のモノマー　　　・・・２．０質量部
　下記表に記載のバインダー　　　・・・６．０質量部
　下記表に記載の光重合開始剤　　　・・・２．０質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・４．５質量部
　下記表に記載の環状ケトン溶剤　　　・・・５．５質量部 (Prescription 4)
Dispersion listed in the table below...80.0 parts by mass Monomer listed in the table below...2.0 parts by mass Binder listed in the table below...6.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.0 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below 4.5 parts by mass Cyclic ketone solvent listed in the table below 5.5 parts by mass
　（処方５）
　下記表に記載の分散液　　　・・・８０．０質量部
　下記表に記載のモノマー　　　・・・２．０質量部
　下記表に記載のバインダー　　　・・・６．０質量部
　下記表に記載の光重合開始剤　　　・・・２．０質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・４．５質量部
　下記表に記載の溶剤２　　　・・・１質量部
　下記表に記載の環状ケトン溶剤　　　・・・４．５質量部 (Prescription 5)
Dispersion listed in the table below...80.0 parts by mass Monomer listed in the table below...2.0 parts by mass Binder listed in the table below...6.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.0 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below ... 4.5 parts by mass Solvent 2 listed in the table below... 1 part by mass Cyclic ketone solvent listed in the table below... 4.5 parts by mass
　（処方ｃ１）
　下記表に記載の分散液　　　・・・７０．０質量部
　下記表に記載のモノマー　　　・・・３．０質量部
　下記表に記載のバインダー　　　・・・９．０質量部
　下記表に記載の光重合開始剤　　　・・・２．５質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・１５質量部
　下記表に記載の環状ケトン溶剤　　　・・・０．５質量部 (Prescription c1)
Dispersions listed in the table below...70.0 parts by mass Monomers listed in the table below...3.0 parts by mass Binders listed in the table below...9.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.5 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below ... 15 parts by mass Cyclic ketone solvent described in the table below ... 0.5 parts by mass
　（処方ｃ２）
　下記表に記載の分散液　　　・・・７０．０質量部
　下記表に記載のモノマー　　　・・・３．０質量部
　下記表に記載のバインダー　　　・・・９．０質量部
　下記表に記載の光重合開始剤　　　・・・２．５質量部
　下記表に記載の界面活性剤　　　・・・０．０００１質量部
　下記表に記載の重合禁止剤　　　・・・０．００１３５質量部
　下記表に記載の溶剤１　　　・・・０．５質量部
　下記表に記載の環状ケトン溶剤　　　・・・１５質量部 (Prescription c2)
Dispersions listed in the table below...70.0 parts by mass Monomers listed in the table below...3.0 parts by mass Binders listed in the table below...9.0 parts by mass Photopolymerization listed in the table below Initiator ... 2.5 parts by mass Surfactant listed in the table below ... 0.0001 part by mass Polymerization inhibitor listed in the table below ... 0.00135 parts by mass Solvent 1 listed in the table below 0.5 parts by mass Cyclic ketone solvent listed in the table below 15 parts by mass
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
　上記着色組成物の処方を示す表中の略語で示す素材の詳細は下記の通りである。 The details of the materials indicated by the abbreviations in the table showing the formulation of the coloring composition are as follows.
（分散液）
　分散液１～３１、ｃ１、ｃ２：上述した分散液１～３１、ｃ１、ｃ２ (dispersion liquid)
Dispersions 1 to 31, c1, c2: Dispersions 1 to 31, c1, c2 described above
（モノマー（重合性化合物））
　Ｍ－１：下記構造の化合物の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000047
 　Ｍ－２：下記構造の化合物の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000048
 　Ｍ－３：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（株）製）にＰＧＭＥＡを加えて固形分濃度を３０質量％に調整した溶液
　Ｍ－４：下記構造の化合物の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000049
 (Monomer (polymerizable compound))
M-1: 30% by mass PGMEA solution of a compound having the following structure
Figure JPOXMLDOC01-appb-C000047
 M-2: 30% by mass PGMEA solution of a compound having the following structure
Figure JPOXMLDOC01-appb-C000048
 M-3: A solution obtained by adding PGMEA to KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) to adjust the solid content concentration to 30% by mass M-4: A 30% by mass PGMEA solution of a compound having the following structure
Figure JPOXMLDOC01-appb-C000049
（光重合開始剤）
　Ｉ－１：Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（ＢＡＳＦ社製、オキシム化合物）
　Ｉ－２：Ｉｒｇａｃｕｒｅ　ＯＸＥ０２（ＢＡＳＦ社製、オキシム化合物）
　Ｉ－３：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000050
 　Ｉ－４：Ｉｒｇａｃｕｒｅ　ＯＸＥ０４（ＢＡＳＦ社製、オキシム化合物） (Photoinitiator)
I-1: Irgacure OXE01 (manufactured by BASF, oxime compound)
I-2: Irgacure OXE02 (manufactured by BASF, oxime compound)
I-3: A compound having the following structure (oxime compound)
Figure JPOXMLDOC01-appb-C000050
 I-4: Irgacure OXE04 (manufactured by BASF, oxime compound)
（バインダー）
　Ｂ－１：下記構造の樹脂（重量平均分子量１１０００、主鎖に付記された数値は、繰り返し単位のモル比を表す。）の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000051
 　Ｂ－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１６０００、酸価６７ｍｇＫＯＨ／ｇ）の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000052
 (binder)
B-1: A 30% by mass PGMEA solution of a resin having the following structure (weight average molecular weight: 11000, the numerical value attached to the main chain represents the molar ratio of repeating units)
Figure JPOXMLDOC01-appb-C000051
 B-2: 30% by mass of a resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH/g) PGMEA solution
Figure JPOXMLDOC01-appb-C000052
　Ｂ－３：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。酸基を有する樹脂、重量平均分子量１８０００、酸価８２．１ｍｇＫＯＨ／ｇ）の３０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000053
 B-3: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 18000, acid value 82. 1 mg KOH/g) of 30 wt% PGMEA solution
Figure JPOXMLDOC01-appb-C000053
（界面活性剤）
　Ｓｕ－１：下記構造の化合物（重量平均分子量１４０００）。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-C000054
 (Surfactant)
Su-1: A compound having the following structure (weight average molecular weight: 14,000). In the following formulas, % indicating the ratio of repeating units is mol %.
Figure JPOXMLDOC01-appb-C000054
（重合禁止剤）
　Ｉｎ－１：ｐ－メトキシフェノール (Polymerization inhibitor)
In-1: p-methoxyphenol
（溶剤１、溶剤２）（環状ケトン溶剤以外の溶剤）
　Ｓ－１：プロピレングリコールモノメチルエーテルアセテート（エステル系溶剤）
　Ｓ－２：２－ブタノール（アルコール系溶剤）
　Ｓ－３：プロピレングリコールモノメチルエーテル（アルコール系溶剤）
　Ｓ－４：３－メトキシブタノール（アルコール系溶剤） (Solvent 1, solvent 2) (solvents other than cyclic ketone solvents)
S-1: Propylene glycol monomethyl ether acetate (ester solvent)
S-2: 2-butanol (alcohol solvent)
S-3: Propylene glycol monomethyl ether (alcohol solvent)
S-4: 3-methoxybutanol (alcohol solvent)
（環状ケトン溶剤）
　Ｓ－１０１：シクロペンタノン
　Ｓ－１０２：シクロヘキサノン
　Ｓ－１０３：シクロヘプタノン
　Ｓ－１０４：シクロオクタノン
　Ｓ－１０５：３－メチルシクロヘキサノン (Cyclic ketone solvent)
S-101: cyclopentanone S-102: cyclohexanone S-103: cycloheptanone S-104: cyclooctanone S-105: 3-methylcyclohexanone
＜保存安定性の評価＞
　製造直後の着色組成物の粘度（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。粘度差（ΔＶｉｓ）の数値が小さいほど、着色組成物の保存安定性が良好であるといえる。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。
－評価基準－
　５：ΔＶｉｓが０．２ｍＰａ・ｓ以下であった。
　４：ΔＶｉｓが０．２ｍＰａ・ｓを超え、０．４ｍＰａ・ｓ以下であった。
　３：ΔＶｉｓが０．４ｍＰａ・ｓを超え、０．６ｍＰａ・ｓ以下であった。
　２：ΔＶｉｓが０．８ｍＰａ・ｓを超え、１．０ｍＰａ・ｓ以下であった。
　１：ΔＶｉｓが１．０ｍＰａ・ｓを超えた。 <Evaluation of storage stability>
The viscosity (mPa·s) of the colored composition immediately after production was measured with "RE-85L" manufactured by Toki Sangyo Co., Ltd. After the above measurement, the colored composition was allowed to stand under conditions of 45° C. and light shielding for 3 days, and the viscosity (mPa·s) was measured again. Storage stability was evaluated according to the following evaluation criteria from the difference in viscosity (ΔVis) before and after standing. It can be said that the smaller the numerical value of the viscosity difference (ΔVis), the better the storage stability of the colored composition. All of the viscosity measurements were carried out in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, and the temperature of the colored composition was adjusted to 25°C.
-Evaluation criteria-
5: ΔVis was 0.2 mPa·s or less.
4: ΔVis exceeded 0.2 mPa·s and was 0.4 mPa·s or less.
3: ΔVis exceeded 0.4 mPa·s and was 0.6 mPa·s or less.
2: ΔVis exceeded 0.8 mPa·s and was 1.0 mPa·s or less.
1: ΔVis exceeded 1.0 mPa·s.
＜膜厚均一性の評価＞
　着色組成物を８インチ（２０．３２ｃｍ）のシリコンウエハ上に膜厚０．４μｍとなるよう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。得られた膜を光学式膜厚計（フィルメトリクス（株）、Ｆ５０）を用い、膜厚を測定し、膜厚の最も薄い部分の膜厚と最も厚い部分の膜厚の差（以下、膜厚差という）を算出した。膜厚差が小さいほど膜厚均一性が良好であるといえる。
－評価基準－
　５：膜厚差が０．０２μｍ以下である。
　４：膜厚差が０．０２μｍより大きく０．０３μｍ以下である。
　３：膜厚差が０．０３μｍより大きく０．０４μｍ以下である。
　２：膜厚差が０．０４μｍより大きく０．０５μｍ以下である。
　１：膜厚差が０．０５μｍより大きい。 <Evaluation of film thickness uniformity>
The coloring composition was applied onto an 8-inch (20.32 cm) silicon wafer by spin coating to a thickness of 0.4 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. The film thickness is measured using an optical film thickness meter (Filmetrics Co., Ltd., F50). thickness difference) was calculated. It can be said that the smaller the film thickness difference, the better the film thickness uniformity.
-Evaluation criteria-
5: The film thickness difference is 0.02 μm or less.
4: The film thickness difference is more than 0.02 μm and 0.03 μm or less.
3: The film thickness difference is greater than 0.03 μm and 0.04 μm or less.
2: The film thickness difference is greater than 0.04 μm and 0.05 μm or less.
1: The film thickness difference is greater than 0.05 μm.
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
　上記表に示すように、実施例の着色組成物は、保存安定性および膜厚均一性が良好であった。
　また、実施例９、５０、５１、５２の着色組成物を用いて得られた膜の耐光性について評価したところ、着色剤濃度の高い実施例９の着色組成物を用いた得られた膜は、５０、５１、５２の着色組成物を用いて得られた膜よりも、より優れた耐光性を有していた。
　また、実施例２、５、９の着色組成物を用いて得られた膜の耐熱性について評価したところ、有機顔料としてジケトピロロピロール顔料を２種併用した実施例９は、実施例２、５よりもより優れた耐熱性を有していた。
　また、環状ケトン溶剤とエステル系溶剤とアルコール系溶剤とを含む実施例５７～５９の着色組成物を用いて得られた膜は、他の実施例よりも塗布欠陥が少なかった。 As shown in the above table, the colored compositions of Examples were excellent in storage stability and film thickness uniformity.
In addition, when the light resistance of the films obtained using the colored compositions of Examples 9, 50, 51, and 52 was evaluated, the films obtained using the colored composition of Example 9 with a high colorant concentration were , 50, 51, and 52 had better light resistance than the films obtained using the coloring compositions.
In addition, the heat resistance of the films obtained using the colored compositions of Examples 2, 5 and 9 was evaluated. It had better heat resistance than 5.
In addition, the films obtained using the colored compositions of Examples 57 to 59 containing a cyclic ketone solvent, an ester solvent and an alcohol solvent had fewer coating defects than other examples.
　実施例１において、界面活性剤をＫＦ－６００１（信越化学工業製、シリコーン系界面活性剤）に置き換えても同様の結果が得られる。実施例１において、重合禁止剤を添加しない場合も同様の結果が得られる。各実施例の着色組成物を用いて得られた膜は、カラーフィルタ、固体撮像素子および画像表示装置に好適に使用できる。各実施例の着色組成物は、ｉ線露光用またはＫｒＦ線露光用としても使用できる。 Similar results can be obtained by replacing the surfactant in Example 1 with KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant). Similar results are obtained in Example 1 when no polymerization inhibitor is added. A film obtained using the colored composition of each example can be suitably used for a color filter, a solid-state imaging device, and an image display device. The colored composition of each example can also be used for i-line exposure or KrF line exposure.

Claims (14)

  1. 　着色剤と、重合性化合物と、光重合開始剤と、溶剤とを含み、
    　前記着色剤は有機顔料を含み、
    　前記光重合開始剤はオキシム化合物を含み、
    　前記溶剤は環状ケトン溶剤を含み、かつ、前記溶剤中における前記環状ケトン溶剤の含有量が１～１５質量％である、
    　着色組成物。     including a coloring agent, a polymerizable compound, a photopolymerization initiator, and a solvent;
    the coloring agent comprises an organic pigment;
    The photoinitiator comprises an oxime compound,
    The solvent contains a cyclic ketone solvent, and the content of the cyclic ketone solvent in the solvent is 1 to 15% by mass.
    coloring composition.
  2. 　前記環状ケトン溶剤はシクロペンタノンである、請求項１に記載の着色組成物。 The coloring composition according to claim 1, wherein the cyclic ketone solvent is cyclopentanone.
  3. 　前記溶剤中における前記環状ケトン溶剤の含有量が５～１３質量％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 the cyclic ketone solvent in the solvent is 5 to 13% by mass.
  4. 　前記溶剤は、エステル系溶剤と、アルコール系溶剤と、をさらに含む、請求項１～３のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 3, wherein the solvent further contains an ester solvent and an alcohol solvent.
  5. 　前記有機顔料は、キナクリドン顔料、アントラキノン顔料、アゾ顔料、ジケトピロロピロール顔料、イソインドリン顔料、キノフタロン顔料、プテリジン顔料およびアゾメチン顔料から選択される少なくとも１種を含む、請求項１～４のいずれか１項に記載の着色組成物。 5. The organic pigment comprises at least one selected from quinacridone pigments, anthraquinone pigments, azo pigments, diketopyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, pteridine pigments and azomethine pigments. 1. The coloring composition according to item 1.
  6. 　前記有機顔料は、ジケトピロロピロール顔料およびイソインドリン顔料から選択される少なくとも１種を含む、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, wherein the organic pigment contains at least one selected from diketopyrrolopyrrole pigments and isoindoline pigments.
  7. 　前記有機顔料は、ジケトピロロピロール顔料を含む、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, wherein the organic pigment comprises a diketopyrrolopyrrole pigment.
  8. 　前記有機顔料は、ジケトピロロピロール顔料を２種以上含む、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, wherein the organic pigment contains two or more diketopyrrolopyrrole pigments.
  9. 　前記有機顔料は、カラーインデックスピグメントレッド２５４およびカラーインデックスピグメントレッド２７２から選択される少なくとも１種を含む、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 organic pigment comprises at least one selected from Color Index Pigment Red 254 and Color Index Pigment Red 272.
  10. 　前記着色組成物の全固形分中における前記着色剤の含有量が５５質量％以上である、請求項１～９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 9, wherein the content of the coloring agent in the total solid content of the coloring composition is 55% by mass or more.
  11. 　請求項１～１０のいずれか１項に記載の着色組成物を支持体に塗布する工程を含む膜の製造方法。 A method for producing a film, comprising the step of applying the coloring composition according to any one of claims 1 to 10 to a support.
  12. 　請求項１１に記載の膜の製造方法を含むカラーフィルタの製造方法。 A method for manufacturing a color filter, including the method for manufacturing the film according to claim 11.
  13. 　請求項１１に記載の膜の製造方法を含む固体撮像素子の製造方法。 A method for manufacturing a solid-state imaging device, including the method for manufacturing the film according to claim 11.
  14. 　請求項１１に記載の膜の製造方法を含む画像表示装置の製造方法。 A method for manufacturing an image display device including the method for manufacturing the film according to claim 11.
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WO2017141723A1 (en) * 2016-02-19 2017-08-24 富士フイルム株式会社 Curable composition, light-shielding film, solid-state imaging device, and color filter
JP2019200343A (en) * 2018-05-17 2019-11-21 東洋インキＳｃホールディングス株式会社 Red coloring composition for color filter and manufacturing method for color filter
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