WO2023176335A1 - Coloring composition, film, optical filter, solid-state imaging element, and image display device - Google Patents

Coloring composition, film, optical filter, solid-state imaging element, and image display device Download PDF

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Publication number
WO2023176335A1
WO2023176335A1 PCT/JP2023/006340 JP2023006340W WO2023176335A1 WO 2023176335 A1 WO2023176335 A1 WO 2023176335A1 JP 2023006340 W JP2023006340 W JP 2023006340W WO 2023176335 A1 WO2023176335 A1 WO 2023176335A1
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group
compound
resin
compounds
mass
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PCT/JP2023/006340
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French (fr)
Japanese (ja)
Inventor
貴洋 大谷
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富士フイルム株式会社
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Publication of WO2023176335A1 publication Critical patent/WO2023176335A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a colored composition containing a coloring agent, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.
  • the present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the colored composition.
  • a color filter is used as key devices for displays and optical elements.
  • a color filter usually includes pixels of three primary colors, red, green, and blue, and serves to separate transmitted light into the three primary colors.
  • Pixels of color filters are manufactured by using a coloring composition containing a colorant and forming a pattern using a method such as photolithography.
  • Patent Document 1 describes manufacturing a color filter using a coloring composition containing a colorant, a resin having an epoxy group, a photopolymerization initiator, a polymerizable compound, and a solvent.
  • the film formed using the coloring composition has low thermal shrinkage and that voids are unlikely to occur even when the pixels are exposed to a high humidity environment. In recent years, higher standards have been required for these characteristics.
  • the present invention provides the following.
  • ⁇ 1> Contains a colorant, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
  • the photopolymerization initiator contains an oxime compound having a hydroxy group
  • the above-mentioned resin is a colored composition containing a resin having an alicyclic epoxy group.
  • ⁇ 2> The colored composition according to ⁇ 1>, wherein the alicyclic epoxy group is a group having a polycyclic aliphatic hydrocarbon ring.
  • ⁇ 3> The colored composition according to ⁇ 1> or ⁇ 2>, wherein the polymerizable compound includes an alkylene oxide-modified (meth)acrylate compound.
  • ⁇ 4> The colored composition according to any one of ⁇ 1> to ⁇ 3>, wherein the oxime compound having a hydroxy group is an oxime compound containing a hydroxy group and a thioether group.
  • ⁇ 5> The colored composition according to any one of ⁇ 1> to ⁇ 4>, wherein the photopolymerization initiator further contains a photopolymerization initiator other than the oxime compound having a hydroxy group.
  • ⁇ 6> The colored composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a cyclic siloxane compound.
  • ⁇ 7> A film obtained using the colored composition according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 8> An optical filter having the film according to ⁇ 7>.
  • ⁇ 9> A solid-state imaging device having the film according to ⁇ 7>.
  • ⁇ 10> An image display device comprising the film according to ⁇ 7>.
  • the present invention it is possible to provide a colored composition that can suppress the generation of development residues and form a film with excellent heat shrinkage resistance and moisture resistance. Further, the present invention can provide a film, a color filter, a solid-state image sensor, and an image display device.
  • ⁇ is used to include the numerical values described before and after it as a lower limit and an upper limit.
  • the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents acrylate and/or methacrylate
  • (meth)acrylic represents both acrylic and/or methacrylic
  • (meth)acrylate” represents acrylic and/or methacrylate.
  • Acryloyl refers to either or both of acryloyl and methacryloyl.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • pigment means a compound that is difficult to dissolve in a solvent.
  • the term "process” is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
  • the colored composition of the present invention includes a colorant, a resin, a polymerizable compound, a photoinitiator, and a solvent,
  • the photopolymerization initiator contains an oxime compound having a hydroxy group,
  • the resin is characterized by containing a resin having an alicyclic epoxy group.
  • the generation of development residues can be suppressed, and a film with excellent heat shrinkage resistance and moisture resistance can be formed.
  • the coloring composition of the present invention contains a resin having an alicyclic epoxy group and an oxime compound having a hydroxy group, during film formation, the alicyclic epoxy group is It is possible to accelerate the curing of the resin having the following properties, and it is possible to form a film with a high crosslinking density. Therefore, a film with excellent heat shrinkage resistance and moisture resistance can be formed.
  • an oxime compound having a hydroxyl group as a photopolymerization initiator, the hydrophilicity of the film can be improved, and the composition layer in unexposed areas can be efficiently removed by a developer. Therefore, generation of development residues can also be suppressed.
  • the colored composition of the present invention can be preferably used as a colored composition for forming an optical filter.
  • the optical filter include color filters and infrared cut filters, and color filters are preferred.
  • the color filter examples include a filter having colored pixels that transmit light of a specific wavelength, and at least one type of colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. It is preferable that the filter has the following.
  • the infrared transmission filter is a filter that transmits at least a portion of infrared rays.
  • the infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared rays.
  • the infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a minimum transmittance in the wavelength range of 1100 to 1300 nm.
  • Preferred examples include filters that satisfy spectral characteristics with a value of 70% or more (preferably 75% or more, more preferably 80% or more).
  • the infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
  • 70% or more preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the solid content concentration of the colored composition of the present invention is preferably 5 to 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
  • the colored composition of the present invention contains a coloring agent.
  • the coloring agent include a yellow coloring agent, an orange coloring agent, a red coloring agent, a green coloring agent, a purple coloring agent, a blue coloring agent, and the like.
  • the coloring agent may be a pigment or a dye.
  • the pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoint of wide color variations, ease of dispersion, safety, and the like.
  • the average primary particle diameter of the 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 average primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles.
  • the primary particles of pigment refer to independent particles without agglomeration.
  • the crystallite size of the organic pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm.
  • the crystallite size can be determined from the half width of the peak of the diffraction angle using an X-ray diffraction device, and is calculated using the Scherrer equation.
  • the crystallite size of the organic pigment can be adjusted by known methods such as adjusting production conditions or pulverizing after production.
  • green colorant examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
  • Specific examples of green colorants include C.I. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
  • halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720.
  • a green colorant a compound described in Chinese Patent Application No.
  • a phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395 and a phthalocyanine compound described in JP-A No. 2019-008014 Phthalocyanine compounds described in JP 2018-180023, compounds described in JP 2019-038958, aluminum phthalocyanine compounds described in JP 2020-070426, JP 2020-076995 It is also possible to use core-shell type dyes described in , diarylmethane compounds described in Japanese Patent Publication No. 2020-504758, and the like.
  • the green colorant is C. I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred; I. Pigment Green 7, 36, 58, and 59 are more preferred.
  • red colorant examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and the like.
  • red colorants include C.I. I.
  • a red coloring agent a diketopyrrolopyrrole compound having at least one bromine atom substituted in the structure described in JP 2017-201384A, a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Patent No. 6248838, Pyrrole compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No.
  • the diketopyrrolopyrrole compounds described above can also be used.
  • a red colorant a compound having a structure in which an aromatic ring group into which a group to which an oxygen atom, sulfur atom, or nitrogen atom is bonded is bonded to a diketopyrrolopyrrole skeleton may be used. You can also do it.
  • Lumogen F Orange 240 manufactured by BASF, red pigment, perylene pigment
  • the red colorant is C. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, 291 are preferred; I. Pigment Red 254, 264, and 272 are more preferred.
  • yellow colorants examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • Specific examples of yellow colorants 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
  • an azobarbituric acid nickel complex having the following structure can also be used.
  • the compound described in JP 2017-201003 As a yellow coloring agent, the compound described in JP 2017-201003, the compound described in JP 2017-197719, the compound described in paragraph numbers 0011 to 0062, 0137 to 0276 of JP 2017-171912, , 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 2017-171915 Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of Japanese Patent Publication No. 2013-054339, quinophthalone compounds described in paragraph numbers 0011 to 0034 of Japanese Patent Application Publication No.
  • X 1 to X 16 each independently represent a hydrogen atom or a halogen atom
  • Z 1 represents an alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the compound represented by formula (QP1) include the compound described in paragraph number 0016 of Japanese Patent No. 6443711.
  • Y 1 to Y 3 each independently represent a halogen atom.
  • n and m represent integers from 0 to 6, and p represents 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 paragraph numbers 0047 to 0048 of Japanese Patent No. 6432077.
  • the yellow colorant is C. I. Pigment Yellow 117, 129, 138, 139, 150, and 185 are preferred.
  • the orange colorant is C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
  • C. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • 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. It will be done.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
  • Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight ( ⁇ 1 ⁇ 1 ⁇ 1) crystal lattice planes is 140 ⁇ or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.
  • the 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 improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 2019/107166 from the viewpoint of viscosity adjustment.
  • Dyes can also be used as the coloring agent.
  • the dye There are no particular restrictions on the dye, and known dyes can be used.
  • pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
  • a pigment multimer can also be used as the colorant.
  • the dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent.
  • the dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682.
  • the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
  • the lower limit is preferably 3000 or more, more preferably 6000 or more.
  • the upper limit is preferably 30,000 or less, more preferably 20,000 or less.
  • Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.
  • the coloring agent includes a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP2020-117638, and a phthalocyanine described in International Publication No. 2020/174991.
  • the isoindoline compounds described in can be used.
  • the coloring agent may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
  • Two or more colorants may be used in combination. Moreover, when using a combination of two or more types of colorants, black may be formed by a combination of two or more types of colorants. Examples of such combinations include the following embodiments (1) to (7).
  • Embodiment containing a red colorant and a blue colorant (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant.
  • An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant An embodiment containing a red colorant, a blue colorant, and a green colorant.
  • Embodiment containing a yellow colorant and a purple colorant Embodiment containing a yellow colorant and a purple colorant.
  • such a coloring composition contains two or more types of colorants and a black color is produced by a combination of the two or more types of colorants
  • a coloring composition is a coloring composition for forming an infrared transmission filter. It can be preferably used as
  • the content of the coloring agent in the total solid content of the coloring composition is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by 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 colored composition of the present invention contains a resin.
  • the resin is blended, for example, for use in dispersing pigments in coloring compositions, or for use as a binder.
  • a resin used mainly for dispersing pigments and the like in a coloring composition is also referred to as a dispersant.
  • this use of the resin is just an example, and the resin can also be used for purposes other than this use.
  • the resin contained in the coloring composition of the present invention includes a resin having an alicyclic epoxy group (hereinafter also referred to as an alicyclic epoxy resin).
  • the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and an aliphatic hydrocarbon ring are condensed.
  • the alicyclic epoxy group is preferably a group having a polycyclic aliphatic hydrocarbon ring because it facilitates the formation of a film with better heat shrinkage resistance. That is, the alicyclic epoxy group is preferably a group in which a polycyclic aliphatic hydrocarbon ring and an epoxy ring are condensed.
  • the polycyclic aliphatic hydrocarbon ring refers to an aliphatic hydrocarbon ring having a structure in which two or more monocyclic aliphatic hydrocarbon rings share one or more carbon atoms in the ring.
  • Specific examples of the polycyclic aliphatic hydrocarbon ring include an isobornyl ring, an adamantane ring, a dicyclopentene ring, a dicyclopentane ring, a tricyclodecane ring, a norbornene ring, and a norbornane ring.
  • Examples of the alicyclic epoxy group include a group represented by formula (e-1).
  • ring A E1 represents an aliphatic hydrocarbon ring, and * represents a bond.
  • the aliphatic hydrocarbon ring represented by ring A E1 in formula (e-1) may be a monocyclic aliphatic hydrocarbon ring or a polycyclic aliphatic hydrocarbon ring, but A polycyclic aliphatic hydrocarbon ring is preferred because it facilitates the formation of a membrane with excellent shrinkability.
  • alicyclic epoxy group examples include the groups shown below, with the group represented by formula (e-1-3) and the group represented by formula (e-1-4) being preferred.
  • * represents a bond.
  • the alicyclic epoxy resin is preferably a resin containing a repeating unit having an alicyclic epoxy group.
  • Examples of the repeating unit having an alicyclic epoxy group include a repeating unit represented by formula (E1).
  • X a1 represents a trivalent linking group
  • L a1 represents a single bond or a divalent linking group
  • Z a1 represents an alicyclic epoxy group
  • the trivalent linking group represented by X a1 in formula (E1) includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, and a polyamide linking group.
  • Linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolak-based linking groups, etc. include poly(meth)acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups, etc.
  • a linking group and a novolak-based linking group are preferred, a polyether-based linking group, a novolak-based linking group, and a poly(meth)acrylic-based linking group are more preferred, and a poly(meth)acrylic-based linking group is even more preferred.
  • the divalent linking group represented by L a1 in formula (E1) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH- , -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these.
  • the alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • Examples of the alicyclic epoxy group represented by Z a1 in formula (E1) include the group represented by formula (e-1) described above, the group represented by formula (e-1-3), and the group represented by formula (e-1). -1-4) is preferred.
  • the resin containing a repeating unit having an alicyclic epoxy group has at least one repeating unit selected from a repeating unit represented by formula (E1-1) and a repeating unit represented by formula (E1-2). It is preferable.
  • the resin may contain only one of the repeating units represented by formula (E1-1) and the repeating unit represented by formula (E1-2), It may contain each of the repeating unit represented by 1) and the repeating unit represented by formula (E1-2).
  • the ratio of the repeating unit represented by formula (E1-1) to the repeating unit represented by formula (E1-2) is the molar ratio, which is expressed by formula (E1-1).
  • repeating unit: repeating unit represented by formula (E1-2) preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferable.
  • L E1 represents a single bond or a divalent linking group
  • R E10 represents a hydrogen atom or a substituent.
  • substituent represented by R E10 include an alkyl group and an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • R E10 is preferably a hydrogen atom or a methyl group.
  • the divalent linking group represented by L E1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, Examples thereof include -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these.
  • the alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • the content of the repeating unit having an alicyclic epoxy group is preferably 1 to 100 mol% of the total repeating units of the resin containing the repeating unit having an alicyclic epoxy group.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the resin containing a repeating unit having an alicyclic epoxy group may have other repeating units in addition to the repeating unit having an alicyclic epoxy group.
  • Examples of other repeating units include repeating units having an acid group and repeating units having an ethylenically unsaturated bond-containing group.
  • Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, with a phenolic hydroxy group or a carboxy group being preferred, and a carboxy group being more preferred.
  • ethylenically unsaturated bond-containing groups examples include vinyl groups, styrene groups, (meth)allyl groups, (meth)acryloyl groups, and the like.
  • Examples of the repeating unit having an acid group include a repeating unit represented by the following formula (E2).
  • Examples of the repeating unit having an ethylenically unsaturated bond-containing group include a repeating unit represented by the following formula (E3).
  • X b1 represents a trivalent linking group
  • L b1 represents a single bond or a divalent linking group
  • Z b1 represents an acid group.
  • X c1 represents a trivalent linking group
  • L c1 represents a single bond or a divalent linking group
  • Z c1 represents an ethylenically unsaturated bond-containing group.
  • the trivalent linking group represented by X b1 in formula (E2) and the trivalent linking group represented by X c1 in formula (E3) include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, and a polyester linking group. groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolac-based linking groups, etc., and poly(meth)acrylic-based linking groups.
  • polyether-based linking groups polyester-based linking groups, bisphenol-based linking groups, and novolak-based linking groups are preferred, polyether-based linking groups, novolak-based linking groups, and poly(meth)acrylic-based linking groups are more preferred; ) Acrylic linking groups are more preferred.
  • the divalent linking group represented by L b1 in formula (E2) and the divalent linking group represented by L c1 in formula (E3) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group ( (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and two or more of these Examples include groups formed in combination.
  • the alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • the acid group represented by Z b1 in formula (E2) includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, and a carboxy group. is more preferable.
  • Examples of the ethylenically unsaturated bond-containing group represented by Z c2 in formula (E3) include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group.
  • the content of the repeating unit having an acid group is the total repeating unit of the resin including a repeating unit having an alicyclic epoxy group. It is preferably 10 to 80 mol%.
  • the upper limit is preferably 70 mol% or less, more preferably 60 mol% or less.
  • the lower limit is preferably 15 mol% or more, more preferably 20 mol% or more.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group is 1 to 20 mol% of the total repeating units of the resin containing the repeating unit.
  • the upper limit is preferably 18 mol% or less, more preferably 15 mol% or less.
  • the lower limit is preferably 3 mol% or more, more preferably 5 mol% or more.
  • the resin containing a repeating unit having an alicyclic epoxy group further contains a repeating unit having an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring.
  • the aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group.
  • the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 65% of the total repeating units of the resin having a cyclic ether group. Preferably it is mol%.
  • the upper limit is preferably 45 mol% or less, more preferably 30 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
  • the repeating unit having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth)acrylate.
  • the weight average molecular weight of the alicyclic epoxy resin is preferably 5,000 to 30,000.
  • the lower limit is preferably 7,000 or more, more preferably 9,000 or more.
  • the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the epoxy equivalent of the alicyclic epoxy resin is preferably 50 to 500 g/eq.
  • the lower limit is preferably 100 g/eq or more, more preferably 150 g/eq or more.
  • the upper limit is preferably 450 g/eq or less, more preferably 400 g/eq or less.
  • the epoxy equivalent of the alicyclic epoxy resin is a value calculated by dividing the molecular weight of the alicyclic epoxy resin by the number of alicyclic epoxy groups contained in the alicyclic epoxy resin.
  • the acid value of the alicyclic epoxy resin is preferably 50 to 200 mgKOH/g.
  • the lower limit is preferably 75 mgKOH/g or more, more preferably 100 mgKOH/g or more.
  • the upper limit is preferably 175 mgKOH/g or less, more preferably 150 mgKOH/g or less.
  • the coloring composition of the present invention can contain resins other than the above-mentioned alicyclic epoxy resins (hereinafter also referred to as other resins).
  • Examples of other resins include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, Examples include polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
  • the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685.
  • Polyisocyanate resin resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP-A-2020-186373, resin described in paragraphs 0199 to 0233 of JP-A No. 2020-186325 Alkali-soluble resins described in the publication and resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 can also be used.
  • the weight average molecular weight (Mw) of the other 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.
  • the other resin it is preferable to use a resin having an acid group.
  • the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the acid value of the resin having acid groups is preferably 30 to 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, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin.
  • the upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
  • resins having basic groups can also be used.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group.
  • a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable.
  • a resin having a basic group can also be used as a dispersant.
  • the amine value of the resin having a basic group is preferably 5 to 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, 3 8500, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
  • the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
  • the storage stability of the resin composition can be further improved.
  • the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group.
  • the amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
  • resins include monomer components containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). It is also preferable to use a resin containing repeating units derived from.
  • 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 to 15.
  • the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, 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.).
  • the other resin it is also preferable to use a resin having a polymerizable group.
  • the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • an aromatic carboxy group refers to 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 to 4, more preferably 1 to 2.
  • the resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxy group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxy 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 group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
  • Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride 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 aromatic carboxy group-containing group represented by Ar 1 may have a polymerizable group.
  • the polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and 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). Examples include groups such as
  • n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even 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, and 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- Represents a group represented by 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L 1 .
  • L 1 represents -COO- or -CONH-, and preferably represents -COO-.
  • the divalent linking group represented by L 2 includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the alkylene group and arylene group may have 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 group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the aromatic carboxy group-containing 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 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and 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 the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
  • 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 ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group is preferable.
  • P 10 represents a polymer chain.
  • the polymer chain represented by P 10 preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the weight average molecular weight of the polymer chain P 10 is preferably 500 to 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 P 10 is within the above range, the pigment will have good dispersibility in the composition.
  • the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P 10 may contain a polymerizable group.
  • examples of the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • At least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is capped with an acid group can also be used.
  • Such resins are preferably used as dispersants.
  • Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above-mentioned formula (Ac-2).
  • Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like.
  • alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
  • graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.
  • star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion.
  • Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
  • the block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer.
  • the block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.
  • the resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
  • examples include resins with a structure sealed with acid groups.
  • acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphoric acid groups.
  • the dispersant examples include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
  • the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
  • the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group that the basic dispersant has is preferably an amino group.
  • Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
  • Disperbyk series manufactured by Byk Chemie for example, Disperbyk-111, 161, 2001, etc.
  • the content of resin in the total solid content of the coloring composition is preferably 20 to 60% by mass.
  • the upper limit is preferably 55% by mass or less, more preferably 50% by mass or less.
  • the lower limit is preferably 25% by mass or more, more preferably 30% by mass or more.
  • the content of the alicyclic epoxy resin in the total solid content of the coloring composition is preferably 10 to 55% by mass.
  • the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less.
  • the lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.
  • the content of the alicyclic epoxy resin in the resin contained in the coloring composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. .
  • the upper limit can be 100% by mass or less, and can also be 90% by mass or less.
  • the colored composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the coloring composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but monomers are preferred.
  • the molecular weight of the polymerizable compound is preferably 100 to 2,500.
  • 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 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 storage stability of the coloring composition.
  • 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 a 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.
  • the polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four 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, and even more preferably 6 or less from the viewpoint of storage stability of the coloring composition.
  • the polymerizable compound is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound.
  • polymerizable compounds include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and The compounds described in paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, and JP 6031807 are , the contents of which are incorporated herein.
  • the polymerizable compound is an alkylene oxide modified (meth)acrylate compound.
  • alkylene oxide-modified (meth)acrylate compounds include compounds having a structure in which (meth)acryloyl groups of a (meth)acrylate compound are bonded via an alkyleneoxy group.
  • the alkylene oxide modified (meth)acrylate compound is preferably an ethylene oxide modified (meth)acrylate compound.
  • the alkylene oxide modified (meth)acrylate compound is preferably a compound represented by formula (Z-4) or a compound represented by formula (Z-5).
  • E is each independently -((CH 2 ) y CH 2 O)-, or -((CH 2 ) y CH(CH 3 )O)- , each y 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
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth)acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • alkylene oxide-modified (meth)acrylate compounds include alkylene oxide-modified dipentaerythritol tri(meth)acrylate, alkylene oxide-modified dipentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol penta(meth)acrylate, Examples include alkylene oxide-modified dipentaerythritol hexa(meth)acrylate.
  • alkylene oxide-modified (meth)acrylate compounds include NK ester M-DPH-6E, M-DPH-12E, A-DPH-6E, and A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • polypentaerythritol poly(meth)acrylate as shown in the following formula (Z-6) can also be used.
  • X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1 to 10. However, at least one of X 1 to X 6 is a (meth)acryloyl group.
  • polymerizable compounds examples include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320) ; made by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available: M-460; Toa) Synthetic), pentaery
  • Polymerizable compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol.
  • Trifunctional (meth)acrylate compounds such as tri(meth)acrylate can also be used.
  • Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
  • M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.
  • a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can also be used.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
  • a compound having a caprolactone structure can also be used.
  • the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein.
  • Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain environmentally controlled substances such as toluene.
  • environmentally controlled substances such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • polymerizable compounds 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.
  • the polymerizable compounds include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, 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, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the colored composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types of polymerizable compounds are included, it is preferable that the total amount thereof falls within the above range.
  • the colored composition of the present invention contains a photopolymerization initiator.
  • a photopolymerization initiator containing an oxime compound having a hydroxy group is used.
  • the oxime compound having a hydroxyl group used as a photopolymerization initiator will also be referred to as a specific oxime compound.
  • the number of hydroxy groups that the specific oxime compound has is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • the specific oxime compound preferably has a molecular weight of 200 to 800.
  • the lower limit is preferably 250 or more, more preferably 300 or more.
  • the upper limit is preferably 750 or less, more preferably 700 or less.
  • the hydroxyl value of the specific oxime compound is preferably 0.5 to 10.0 mmol/g because it is possible to both accelerate the curing reaction and suppress development residue at a higher level.
  • the lower limit is preferably 1.0 mmol/g or more, more preferably 1.5 mmol/g or more.
  • the upper limit is preferably 8.0 mmol/g or less, more preferably 6.0 mmol/g or less.
  • the hydroxy value of the specific oxime compound is a value calculated by dividing the number of hydroxy groups contained in one molecule of the specific oxime compound by the molecular weight of the specific oxime compound.
  • the specific oxime compound is preferably an oxime compound containing a hydroxy group and a thioether group. By using such an oxime compound, the effects of the present invention are more prominently exhibited.
  • Specific examples of the specific oxime compound include compounds having the following structure.
  • the photopolymerization initiator contained in the coloring composition of the present invention may be substantially only the above-mentioned specific oxime compound, or may be a photopolymerization initiator other than the above-mentioned specific oxime compound (hereinafter, other photopolymerization initiator). ) may also be included.
  • the photopolymerization initiator is substantially only a specific oxime compound because the rectangularity of the pattern shape can be further improved.
  • the case where the photopolymerization initiator is substantially only a specific oxime compound means that the specific oxime compound in the photopolymerization initiator is 99% by mass or more, and 99.9% by mass % or more, and more preferably only the specific oxime compound.
  • the photopolymerization initiator further contains another photopolymerization initiator in addition to the specific oxime compound, since the adhesion of the pattern after development can be further improved.
  • the content of the other photopolymerization initiators is 10 to 50 parts by mass based on 100 parts by mass of the specific oxime compound. It is preferable that there be.
  • the lower limit is preferably 20 parts by mass or more, more preferably 25 parts by mass or more.
  • the upper limit is preferably 45 parts by mass or less, more preferably 40 parts by mass or less.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, and organic peroxides. , thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphines, etc.
  • halogenated hydrocarbon derivatives for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
  • acylphosphine compounds for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
  • a coumarin compound is preferable, a compound selected from an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound is more preferable, and an oxime compound is even more preferable.
  • other photopolymerization initiators include compounds described in paragraphs 0065 to 0111 of JP-A No.
  • hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 1. 173, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure.
  • acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
  • Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 - Compounds described in Publication No. 066385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No.
  • oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • oxime compounds having a fluorene ring can also be used.
  • Specific examples of oxime compounds having a fluorene ring include the compounds described in JP-A No. 2014-137466, the compounds described in Japanese Patent No. 6636081, and the compounds described in Korean Patent Publication No. 10-2016-0109444. Can be mentioned.
  • oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring.
  • Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.
  • oxime compounds having a fluorine atom can also be used.
  • Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).
  • oxime compounds having a nitro group can be used as other photopolymerization initiators. It is also preferable that the oxime compound having a nitro group is in the form of a dimer.
  • Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
  • oxime compounds having a benzofuran skeleton can also be used.
  • Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
  • oxime compounds used as other photopolymerization initiators include the compounds shown below.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • difunctional or trifunctional or more functional photopolymerization initiators may be used as other photopolymerization initiators.
  • a photopolymerization initiator two or more radicals are generated from one molecule of the photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the coloring composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photopolymerization initiators include the paragraphs of Japanese Translated Patent Publication No. 2010-527339, Japanese Translated Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator in the total solid content of the colored composition is preferably 0.1 to 20% 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 15% by mass or less, more preferably 10% by mass or less.
  • the content of the specific oxime compound in the total solid content of the coloring composition is preferably 0.1 to 20% 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 15% by mass or less, more preferably 10% by mass or less.
  • the content of the specific oxime compound is preferably 10 to 50 parts by mass based on 100 parts by mass of the alicyclic epoxy resin.
  • the upper limit is preferably 45 parts by mass or less, more preferably 40 parts by mass or less.
  • the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
  • the number of photoinitiators may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic 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, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, 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 by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
  • the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
  • the content of the solvent in the coloring composition is preferably 10 to 95% by mass.
  • the upper limit is preferably 92.5% by mass or less, more preferably 90% by mass or less.
  • the lower limit is preferably 30% by mass or more, more preferably 50% by mass, even more preferably 70% by mass or more, even more preferably 75% by mass or more, and even more preferably 80% by mass or more. It is particularly preferable that
  • the colored composition of the present invention preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
  • "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHemicals
  • PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • the method is 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 human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible.
  • methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
  • distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of colored compositions prepared by mixing these compounds. This is possible at any stage.
  • the coloring composition of the present invention can contain a compound having a cyclic ether group (also referred to as another compound having a cyclic ether group) other than the above-mentioned alicyclic epoxy resin.
  • the colored composition of the present invention does not substantially contain other compounds having a cyclic ether group. According to this aspect, heat shrinkage resistance can be further improved.
  • substantially not containing compounds having other cyclic ether groups means that the content of compounds having other cyclic ether groups in the total solid content of the coloring composition is 0.1% by mass. It is preferably 0.01% by mass or less, and more preferably does not contain any other cyclic ether group-containing compound.
  • Examples of compounds having a cyclic ether group other than alicyclic epoxy resins include compounds having a group represented by formula (e-2).
  • R e2 represents a hydrogen atom or an alkyl group
  • n represents 0 or 1
  • * represents a bond.
  • the number of carbon atoms in the alkyl group represented by R e2 is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group represented by R e2 is preferably linear or branched, more preferably linear.
  • R e2 is preferably a hydrogen atom.
  • R e2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the other compound having a cyclic ether group may be a monomer or a polymer compound.
  • its molecular weight is preferably less than 1,500, more preferably from 100 to 1,250, and even more preferably from 300 to 1,000.
  • its weight average molecular weight is preferably 1,500 or more, more preferably 1,750 or more, and even more preferably 2,000 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less.
  • epoxy resin can be preferably used as another compound having a cyclic ether group.
  • epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, aliphatic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, and halogenated phenols.
  • Epoxy resins that are glycidylated, condensates of silicon compounds with epoxy groups and other silicon compounds, copolymers of polymerizable unsaturated compounds with epoxy groups and other polymerizable unsaturated compounds, etc. can be mentioned.
  • Examples of commercially available compounds having other cyclic ether groups include EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation) as naphthalene-modified epoxy resins.
  • Examples of the alkyl diphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation).
  • jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, Mitsubishi Ke Mical Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Co., Ltd.), etc.
  • Bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (manufactured by DIC Corporation), LCE-21, RE-602S ( The above examples include those manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of phenol novolac type epoxy resins include jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (manufactured by DIC Corporation). ) etc. Can be mentioned.
  • EPICLON N-660 As cresol novolak type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-6 95 (manufactured by DIC Corporation) , EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.).
  • ADEKA RESIN EP-4080S, EP-4085S, EP-4088S manufactured by ADEKA Co., Ltd.
  • Celoxide 2021P Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD Examples include PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation).
  • the content of the compound having another cyclic ether group is 5 to 30 parts by mass based on 100 parts by mass of the alicyclic epoxy resin. It is preferable.
  • the lower limit is preferably 7 parts by mass or more, more preferably 10 parts by mass or more.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.
  • the colored composition of the present invention may contain only one type of compound having another cyclic ether group, or may contain two or more types of compounds. When two or more types of compounds having other cyclic ether groups are included, the total amount thereof is preferably within the above range.
  • the colored composition of the present invention can contain a pigment derivative.
  • the coloring agent used in the coloring composition of the present invention contains a pigment
  • Pigment derivatives are used, for example, as dispersion aids.
  • a dispersion aid is a material for improving the dispersibility of pigments in a coloring composition.
  • Examples of pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzimidazolone pigment skeleton, benzisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrrolopyrrole pigment.
  • diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton
  • Examples include isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, and pyrromethene dye skeleton.
  • Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide 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, Examples include phosphonium ions.
  • As 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 imide 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 , and -SO 2 NHSO 2 R X3 is more preferred.
  • R X1 to R X6 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R X1 to R X6 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
  • Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used.
  • the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and preferably 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less. is more preferable, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, and JP-A-03-1999.
  • Compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in JP-A No. 06-145546, compounds described in JP-A No. 06-212088, compounds described in JP-A No. 06-240158, compounds described in JP-A No.
  • the content of the pigment derivative is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the pigment. Further, the total content of the pigment derivative and the colorant is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more based on the total solid content of the coloring composition.
  • the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the colored composition of the present invention may contain only one kind of pigment derivative, or may contain two or more kinds of pigment derivatives. When two or more types of pigment derivatives are included, the total amount thereof is preferably within the above range.
  • the colored composition of the present invention can also contain polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersion aids for pigments.
  • Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
  • the polyalkyleneimine is preferably a polymer having 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 containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
  • the alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the molecular weight of the polyalkylene imine 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 polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
  • the molecular weight of a 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. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) 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, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more.
  • Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all 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 polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight 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 type of polyalkylene imine 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 colored composition of the present invention can contain a curing accelerator.
  • the curing accelerator 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 International Publication No. 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, and JP 2013-041165. Compounds described in paragraph numbers 0186 to 0251 of JP-A No.
  • the content of the curing accelerator in the total solid content of the colored composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the colored composition of the present invention can contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A.
  • UV absorbers include compounds having the following structures.
  • Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
  • examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016).
  • the ultraviolet absorbers include compounds described in paragraph numbers 0049 to 0059 of Patent No. 6268967, compounds described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and compounds described in International Publication No. 2020/137819. It is also possible to use the thioaryl group-substituted benzotriazole type ultraviolet absorbers described in .
  • 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.
  • the number of ultraviolet absorbers may be one type or two or more types. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the colored 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), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 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.
  • the number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the colored 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.
  • hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is 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 groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
  • silane coupling agents 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 No. 2009-288703 and compounds described in paragraph numbers 0056 to 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 type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the colored 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 surfactant or a fluorine surfactant.
  • fluorine-based surfactants examples include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and the like; Examples include the surfactants described in paragraph numbers 0117 to 0132 of Publication No. 132503 and the 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, F-144.
  • Fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is severed and the fluorine atom volatizes. Can be used.
  • fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)); Fuck DS-21 is an example.
  • fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • fluorine-based surfactants include the fluorine-based surfactants described in JP-A No. 2016-216602, the content of which is incorporated herein.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraph numbers 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used.
  • Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K.
  • compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a+ represents an a-valent metal ion, a primary ammonium ion
  • a Re represents a secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
  • 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 Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa
  • silicone surfactants examples include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TS.
  • F-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 surfactant.
  • the content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass.
  • the number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the colored composition of the present invention can contain a cyclic siloxane compound.
  • the colored composition of the present invention contains a silicone surfactant, it is preferable that the colored composition further contains a cyclic siloxane compound.
  • the cyclic siloxane compound means a cyclic compound formed by siloxane bonds.
  • the cyclic siloxane compound is preferably a compound represented by formula (Si-1).
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and m represents an integer of 3 to 20.
  • Examples of the substituent represented by R 1 and R 2 in formula (Si-1) include an alkyl group and an aryl group, with an alkyl group being preferred.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1.
  • the alkyl group may be linear or branched, but is preferably linear.
  • the number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6.
  • R 1 and R 2 are each independently preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a methyl group.
  • n in formula (Si-1) represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and even more preferably an integer of 3 to 6.
  • an integer of 4 to 6 is particularly preferable.
  • the molecular weight of the cyclic siloxane compound is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.
  • the lower limit can be 100 or more.
  • cyclic siloxane compounds include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethylcyclotrisiloxane, etc.; Preferably, it is at least one selected from methylcyclohexasiloxane.
  • the colored composition of the present invention may contain only one type of cyclic siloxane compound, but preferably contains two or more types of cyclic siloxane compounds.
  • a compound in which m in the above formula (1) is 3 or 4 (preferably a compound in which m is 4), and a compound in which m in the above formula (1) is an integer of 5 or more.
  • a certain compound preferably a compound where m is an integer of 5 to 10, more preferably a compound where m is an integer of 5 to 8, a compound where m is 5 or 6) is preferably included.
  • the ratio of the compound in which m in the above formula (Si-1) is 3 or 4 and the compound in which m in the above formula (Si-1) is an integer of 5 or more is
  • the compound in the above formula (Si-1) where m is an integer of 5 or more is preferably 10 to 1000 parts by mass, and 25 to 750 parts by mass. More preferably, the amount is 50 to 500 parts by mass.
  • the cyclic siloxane compound preferably contains at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; More preferably, it contains sasiloxane.
  • the cyclic siloxane compound is preferably at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, More preferably, it is composed of dodecamethylcyclohexasiloxane.
  • octamethylcyclotetrasiloxane When using a cyclic siloxane compound containing octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are used.
  • the ratio of octamethylcyclotetrasiloxane to 100 parts by mass of dodecamethylcyclohexasiloxane and siloxane is preferably 1 to 100 parts by mass, and 50 to 200 parts by mass of decamethylcyclopentasiloxane.
  • the amount of octamethylcyclotetrasiloxane is preferably 1 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of dodecamethylcyclohexasiloxane.
  • the amount of decamethylcyclopentasiloxane is preferably 1 to 200 parts by weight, more preferably 50 to 150 parts by weight, per 100 parts by weight of dodecamethylcyclohexasiloxane.
  • the content of the cyclic siloxane compound in the total solid content of the coloring composition is preferably 0.001 to 1% by mass, more preferably 0.0015 to 0.5% by mass.
  • the content of the cyclic siloxane compound is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the silicone surfactant.
  • the lower limit is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more.
  • the upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.
  • the composition of the present invention contains two or more types of cyclic siloxane compounds, it is preferable that the total amount thereof is within the above range.
  • the colored composition of the present invention can contain an antioxidant.
  • the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
  • phenolic antioxidants include hindered phenol compounds.
  • the phenolic antioxidant is preferably a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position).
  • the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
  • a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
  • phosphorus-based antioxidants can also be suitably used.
  • antioxidants include, for example, 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 Co., Ltd.).
  • antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 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 type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the coloring composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.) may also be included.
  • auxiliary agents e.g., conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.
  • the colored composition of the present invention may contain a latent antioxidant, if necessary.
  • a latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the colored 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 diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
  • the metal oxide may have a core-shell structure. Further, in this case, the core portion may be hollow.
  • the colored composition of the present invention may also contain a lightfastness improver.
  • a lightfastness improver compounds described in paragraph numbers 0036 to 0037 of JP 2017-198787, compounds described in paragraph numbers 0029 to 0034 of JP 2017-146350, JP 2017-129774, Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674, compounds described in paragraph numbers 0031 to 0034, 0058 to 0059 of JP 2017-122803, paragraph numbers 0036 to 0037 of JP 2017-122803. , compounds described in paragraph numbers 0025 to 0039 of International Publication No.
  • the colored composition of the present invention is substantially free of terephthalic acid ester.
  • substantially not containing means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
  • the colored composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less.
  • the type of metal is not particularly limited, but examples include alkali metals, alkaline earth metals, transition metals, Al, Sn, Pb, Bi, and the like.
  • the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the colored composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with emphasis on ion exchange.
  • perfluoroalkyl sulfonic acids and their salts may be regulated.
  • perfluoroalkylsulfonic acids particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms
  • salts thereof and perfluoroalkylsulfonic acids
  • the content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the coloring composition.
  • the coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt.
  • a coloring composition that is substantially free of and salts thereof.
  • Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
  • the colored compositions of the present invention may include perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, to the maximum extent permissible.
  • the water content of the colored composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass.
  • the water content can be measured by the Karl Fischer method.
  • the colored composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface condition (flatness, etc.), adjusting the film thickness, etc.
  • the value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa ⁇ s to 50 mPa ⁇ s is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
  • the viscosity can be measured using, for example, a cone plate type viscometer with the temperature adjusted to 25°C.
  • the container for storing the coloring composition is not particularly limited, and any known container can be used.
  • any known container can be used.
  • 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, increasing the storage stability of the coloring composition, and suppressing component deterioration.
  • the colored composition of the present invention can be prepared by mixing the above-mentioned components.
  • the colored composition may be prepared by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be prepared as two or more solutions or dispersions as appropriate.
  • a colored composition may be prepared by mixing these at the time of use (at the time of application).
  • the preparation of the colored composition includes a process of dispersing the pigment.
  • 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.
  • the particles may be made finer in a salt milling step.
  • Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
  • an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads.
  • the composition may contain 1 to 10,000 ppm of the beads.
  • any filter that has been conventionally used for filtration and the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
  • polyamide resins such as nylon (for example, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP)
  • filters using materials such as high-density, ultra-high molecular weight polyolefin resins.
  • polypropylene (including high-density polypropylene) and nylon are preferred.
  • the pore diameter of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the pore size value of the filter reference can be made to the nominal value of the filter manufacturer.
  • various filters provided by Nippon Pole Co., Ltd. DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.
  • Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used. .
  • a fiber-like filter medium examples include polypropylene fiber, nylon fiber, and glass fiber.
  • Commercially available products include the SBP type series (SBP008, etc.), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003, etc.) manufactured by Loki Techno.
  • 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 two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed. Further, a filter can be appropriately selected depending on the hydrophilicity and hydrophobicity of the colored composition.
  • the film of the present invention is a film obtained from the colored composition of the present invention described above.
  • the film of the present invention can be used for optical filters such as color filters and infrared transmission filters.
  • the film thickness of the film of the present invention can be adjusted as appropriate depending on 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 of the present invention When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue, more preferably a green, red, or yellow hue. preferable. Further, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the film of the present invention preferably has any of the following spectral properties (1) to (4).
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is
  • the minimum value of the ratio in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light with wavelengths exceeding 700 nm.
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1300 nm.
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm.
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1300 nm.
  • a film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 940 nm.
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm.
  • a film having such spectral characteristics can block light in a wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1040 nm.
  • the method for manufacturing a pixel includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer to light in a pattern, and an unexposed part of the colored composition layer. It is preferable to include a step of developing and removing to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
  • a colored composition layer is formed on a support using the colored composition of the present invention.
  • the support is not particularly limited and can be appropriately selected depending on the application.
  • a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate.
  • CMOS complementary metal oxide semiconductor
  • a black matrix that isolates each pixel may be formed on the silicon substrate.
  • the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
  • a known method can be used to apply the coloring composition.
  • dropping method drop casting
  • slit coating method spray method; roll coating method; spin coating method; casting coating method; slit and spin method;
  • inkjet for example, on-demand method, piezo method, thermal method
  • ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
  • Examples include various printing methods; transfer method using a mold, etc.; nanoimprint method, etc.
  • the application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115).
  • the colored composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed.
  • the prebaking 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, or 80°C or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, 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 it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
  • Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
  • the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
  • the oxygen concentration during exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
  • the exposure may be carried out in an oxygen-free environment (without oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 vol% (for example, 22 vol%, 30 vol%, or 50 vol%).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). I can do it.
  • the oxygen concentration and the exposure illuminance may be appropriately combined.
  • the illumination intensity may be 10,000 W/m 2 at an oxygen concentration of 10% by volume, or 20,000 W/m 2 at an oxygen concentration of 35% by volume.
  • the unexposed portions of the colored composition layer are developed and removed to form a pattern (pixel).
  • the unexposed areas of the colored composition layer can be removed by development using a developer.
  • the unexposed portions of the colored composition layer in the exposure step are eluted into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
  • an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water is preferable.
  • alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • ethyltrimethylammonium hydroxide ethyltrimethylammonium hydroxide
  • benzyltrimethylammonium hydroxide dimethylbis(2-hydroxyethyl)ammonium hydroxide
  • choline pyrrole
  • piperidine 1,8-diazabicyclo-[5.4.0]-7-undecene
  • alkali agent compounds with a large molecular weight are preferable from the environmental and safety standpoints.
  • 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.
  • the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use.
  • the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, rinsing is preferably performed by supplying a rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed.
  • the nozzle that discharges the rinsing liquid from the center of the support it is also preferable to move the nozzle that discharges the rinsing liquid from the center of the support to the peripheral edge of the support.
  • the nozzle may be moved while gradually decreasing its moving speed.
  • Additional exposure processing and post-bake are post-development curing processing to complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C.
  • Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
  • the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • optical filter of the present invention has the film of the present invention described above.
  • Types of optical filters include color filters and infrared transmission filters, and color filters are preferred.
  • the color filter has the film of the present invention as its colored pixels.
  • the film thickness of the film of the present invention can be adjusted as appropriate depending on 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 width of the pixels included in the optical filter is preferably 0.4 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.
  • the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • each pixel included in the optical filter has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be set to a suitable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.).
  • the volume resistance value of the pixel is high.
  • the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more.
  • the upper limit is not specified, it is preferably 10 14 ⁇ cm or less, for example.
  • the volume resistance value of a pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the film of the present invention.
  • various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Examples of the method for forming the protective layer include a method of applying a composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • the protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain.
  • organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • the absorber for light of a specific wavelength a known absorber can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
  • the protective layer the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.
  • the solid-state imaging device of the present invention has the film of the present invention described above.
  • the configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, but examples include the following configurations.
  • the substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like.
  • a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls.
  • the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No.
  • an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance.
  • An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.
  • the image display device of the present invention has the film of the present invention described above.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • Examples of an image display device and details of each image display device see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by 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 Chosenkai Co., Ltd., 1994)".
  • Next Generation Liquid Crystal Display Technology edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994.
  • the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • (dispersant) A-1 Resin synthesized by the following method (resin having an alicyclic epoxy group having a polycyclic aliphatic hydrocarbon ring) An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 340 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was added thereto and heated to 80° C. with stirring.
  • PGMEA propylene glycol monomethyl ether acetate
  • the temperature was maintained at 80° C. for 3 hours, and then cooled to room temperature to obtain a resin having the following structure.
  • the weight average molecular weight of the obtained resin was 9400, the dispersity was 1.89, and the acid value was 114 mgKOH/g.
  • A-2 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 24,000)
  • A-3 Resin with the following structure (the numerical value appended to the main chain is the molar ratio. Weight average molecular weight 11000)
  • A-4 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
  • A-5 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 16,000)
  • A-6 Resin with the following structure (the number appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
  • A-7 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
  • A-8 Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 7000)
  • A-9 Resin synthesized by the following method (resin having an alicyclic epoxy group) In the synthesis of resin A-1, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 A resin having the following structure was obtained in the same manner as Resin A - 1 except that the mixture of decane-9-yl acrylate was changed to 3,4-epoxycyclohexylmethyl methacrylate. The weight average molecular weight of the obtained resin was 10,000.
  • Dye solutions X-1 to X-3 were prepared by mixing the materials listed in the table below.
  • the unit of the numerical value described in the column of compounding amount is mass parts.
  • Dye 1 Xanthene dye with the following structure
  • Dye 2 Xanthene dye with the following structure
  • Dye 3 Xanthene dye with the following structure (weight average molecular weight 10,000)
  • a colored composition was produced by mixing the raw materials listed in the table below.
  • the unit of the numerical value described in the column of compounding amount is mass parts.
  • binder B-1 PGMEA solution (solid content concentration 40% by mass) of resin synthesized by the following method (resin having an alicyclic epoxy group having a polycyclic aliphatic hydrocarbon ring) An appropriate amount of nitrogen was passed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 371 parts by mass of PGMEA was added thereto, and the flask was heated to 85° C. with stirring.
  • B-2 PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are molar ratios.
  • B-3 PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are molar ratios.
  • B-4 PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are mass ratios.
  • Weight average molecular weight 14600) B-5 PGMEA solution (solid content concentration 40% by mass) of resin with the following structure (weight average molecular weight 10600) BM: A mixed solution containing equal amounts of the binders B-1 to B-5 described above (solid content concentration 40% by mass)
  • C-1 Compound with the following structure (oxime compound having a hydroxy group)
  • C-2 Compound with the following structure (oxime compound having a hydroxy group)
  • C-3 Compound with the following structure (oxime compound containing a hydroxy group and a thioether group)
  • C-4 Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
  • C-5 Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
  • C-6 Compound with the following structure (oxime compound having a hydroxy group)
  • C-7 Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
  • C-8 Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
  • C-9 Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
  • C-10 Compound with the
  • D-1 Compound with the following structure
  • D-2 NK ester M-DPH-6E (ethoxylated dipentaerythritol hexamethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • D-3 Mixture of compounds with the following structure (mixture with a molar ratio of 7:3 between the compound on the left (hexafunctional (meth)acrylate compound) and the compound on the right (pentafunctional (meth)acrylate compound))
  • D-4 Compound with the following structure
  • D-5 Trimethylolpropane ethyleneoxy modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350)
  • D-6 EBECRYL80 (manufactured by Daicel Allnex Corporation, amine-containing tetrafunctional acrylate)
  • DM mixture of equal amounts of the above-mentioned polymerizable compounds D-1 to D-6
  • E-1 Compound with the following structure (ultraviolet absorber)
  • E-2 Compound with the following structure (weight average molecular weight 3500)
  • E-3 Compound with the following structure (weight average molecular weight 2300)
  • E-4 Compound with the following structure (silane coupling agent)
  • E-5 3-methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
  • E-6 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
  • E-7 ADEKA STAB AO-80 (manufactured by ADEKA Co., Ltd., antioxidant)
  • EM A mixture of the above-mentioned compounds E-1 to E-7 in equal amounts
  • F-3 Megafac F-551 (manufactured by DIC Corporation, fluorine-based surfactant)
  • F-4 DISPERBYK BYK-330 (manufactured by BYK, silicone surfactant)
  • F-5 Emulgen 103 (manufactured by Kao Corporation, nonionic surfactant)
  • F-6 A mixture of equal amounts of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane (cyclic siloxane compound)
  • FM A mixture of the above-mentioned surfactants F-1 to F-5 in equal amounts
  • Each coloring composition was applied onto a silicon wafer using a spin coater (manufactured by Mikasa Co., Ltd.) so that the film thickness after post-baking was 1.0 ⁇ m, and then coated at 100°C using a hot plate. A composition layer was obtained by heating for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), this composition layer was exposed to light at a wavelength of 365 nm at an exposure dose of 1000 mJ/cm 2 using a mask having a Bayer pattern of 1 ⁇ m square. exposed through.
  • the exposed silicon wafer with the composition layer formed thereon was placed on a horizontal rotary table of a spin shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and tetramethylammonium hydroxide ( Paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the silicon wafer is fixed on a horizontal rotary table using a vacuum chuck method, and while the silicon wafer is rotated by a rotating device at a rotation speed of 50 rpm, pure water is supplied in a shower form from a spout nozzle from above the center of rotation to perform rinsing processing. and further washed with pure water.
  • pixels were formed by heating (post-baking) at 200° C. for 5 minutes using a hot plate.
  • the areas between the patterns (unexposed areas) were observed using a scanning electron microscope (SEM, magnification: 10000), and development residues were evaluated according to the following evaluation criteria.
  • 3 10 areas in the unexposed area. On average, 2 to 5 residues with a diameter of 200 nm or less were confirmed.
  • 2 In the unexposed area, 6 or more residues with a diameter of 200 nm or less were confirmed on an average of 10 locations.
  • Occurrence rate Number of pixels where voids have occurred inside the pixel / Number of observed pixels 5: Occurrence rate of voids is 0 4: The occurrence rate of voids is greater than 0 and less than 0.1 3: The occurrence rate of voids is greater than 0.1 and less than 0.2 2: The occurrence rate of voids is greater than 0.2 and less than 0.5 1 : Occurrence rate of voids is greater than 0.5 and less than 1.0
  • the colored compositions of Examples had little residue and were excellent in heat shrinkage resistance and moisture resistance. Furthermore, the film obtained using the colored composition of Example 50 had particularly excellent surface smoothness.

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Abstract

Provided are: a colored composition which can suppress the occurrence of a development residue and from which a film having excellent heat shrinkage resistance and moisture resistance can be formed; a film; a color filter; a solid-state imaging element; and an image display device. The coloring composition comprises a coloring agent, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator includes an oxime compound having a hydroxy group, and the resin includes a resin having an alicyclic epoxy group.

Description

着色組成物、膜、光学フィルタ、固体撮像素子および画像表示装置Colored compositions, films, optical filters, solid-state imaging devices, and image display devices
　本発明は、着色剤と樹脂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関する。また、本発明は、着色組成物を用いた膜、光学フィルタ、固体撮像素子および画像表示装置に関する。 The present invention relates to a colored composition containing a coloring agent, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the colored 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。カラーフィルタは、通常、赤、緑及び青の３原色の画素を備えており、透過光を３原色へ分解する役割を果たしている。 In recent years, with the spread of digital cameras, camera-equipped mobile phones, etc., demand for solid-state image sensors such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements. A color filter usually includes pixels of three primary colors, red, green, and blue, and serves to separate transmitted light into the three primary colors.
　カラーフィルタの画素は、着色剤を含む着色組成物を用い、フォトリソグラフィ法などの方法でパターン形成して製造されている。 Pixels of color filters are manufactured by using a coloring composition containing a colorant and forming a pattern using a method such as photolithography.
　特許文献１には、着色剤と、エポキシ基を有する樹脂と、光重合開始剤と、重合性化合物と、溶剤とを含む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。 Patent Document 1 describes manufacturing a color filter using a coloring composition containing a colorant, a resin having an epoxy group, a photopolymerization initiator, a polymerizable compound, and a solvent.
国際公開第２０２１／０３９４９１号International Publication No. 2021/039491
　着色組成物を用い、フォトリソグラフィ法でパターン形成して画素を製造するにあたり、現像残渣の発生が少ないことが好ましい。 When manufacturing pixels by forming a pattern using a colored composition using a photolithography method, it is preferable that little development residue is generated.
　また、着色組成物を用いて形成される膜について、熱収縮が小さいこと、画素を湿度の高い環境下に曝してもボイドが発生しにくいことが望まれている。近年では、これらの特性について、より高い水準が求められている。 It is also desired that the film formed using the coloring composition has low thermal shrinkage and that voids are unlikely to occur even when the pixels are exposed to a high humidity environment. In recent years, higher standards have been required for these characteristics.
　本発明者の検討によれば、特許文献１に開示されている着色組成物では、これらの特性を並立させることが困難であり、更なる改善の余地があることが分かった。 According to the studies of the present inventors, it was found that it is difficult to achieve these characteristics simultaneously in the colored composition disclosed in Patent Document 1, and there is room for further improvement.
　よって、本発明の目的は、現像残渣の発生を抑制でき、耐熱収縮性および耐湿性に優れた膜を形成できる着色組成物を提供することにある。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を提供することにある。 Therefore, an object of the present invention is to provide a colored composition that can suppress the generation of development residue and form a film with excellent heat shrinkage resistance and moisture resistance. Another object of the present invention is to provide a film, a color filter, a solid-state image sensor, and an image display device.
　本発明者の検討によれば、後述する着色組成物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。 According to the studies of the present inventors, it was discovered that the above object can be achieved by the coloring composition described below, and the present invention was completed. Accordingly, the present invention provides the following.
　＜１＞　着色剤と、樹脂と、重合性化合物と、光重合開始剤と、溶剤とを含み、
　上記光重合開始剤は、ヒドロキシ基を有するオキシム化合物を含み、
　上記樹脂は、脂環式エポキシ基を有する樹脂を含む、着色組成物。
　＜２＞　上記脂環式エポキシ基は、多環式脂肪族炭化水素環を有する基である、＜１＞に記載の着色組成物。
　＜３＞　上記重合性化合物は、アルキレンオキシド変性（メタ）アクリレート化合物を含む、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　上記ヒドロキシ基を有するオキシム化合物は、ヒドロキシ基とチオエ―テル基とを含むオキシム化合物である、＜１＞～＜３＞のいずれか１つに記載の着色組成物。
　＜５＞　上記光重合開始剤は、更に上記ヒドロキシ基を有するオキシム化合物以外の光重合開始剤を含む、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
　＜６＞　さらに環状シロキサン化合物を含む、＜１＞～＜５＞のいずれか１つに記載の着色組成物。
　＜７＞　＜１＞～＜６＞のいずれか１つに記載の着色組成物を用いて得られる膜。
　＜８＞　＜７＞に記載の膜を有する光学フィルタ。
　＜９＞　＜７＞に記載の膜を有する固体撮像素子。
　＜１０＞　＜７＞に記載の膜を有する画像表示装置。 <1> Contains a colorant, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The photopolymerization initiator contains an oxime compound having a hydroxy group,
The above-mentioned resin is a colored composition containing a resin having an alicyclic epoxy group.
<2> The colored composition according to <1>, wherein the alicyclic epoxy group is a group having a polycyclic aliphatic hydrocarbon ring.
<3> The colored composition according to <1> or <2>, wherein the polymerizable compound includes an alkylene oxide-modified (meth)acrylate compound.
<4> The colored composition according to any one of <1> to <3>, wherein the oxime compound having a hydroxy group is an oxime compound containing a hydroxy group and a thioether group.
<5> The colored composition according to any one of <1> to <4>, wherein the photopolymerization initiator further contains a photopolymerization initiator other than the oxime compound having a hydroxy group.
<6> The colored composition according to any one of <1> to <5>, further comprising a cyclic siloxane compound.
<7> A film obtained using the colored composition according to any one of <1> to <6>.
<8> An optical filter having the film according to <7>.
<9> A solid-state imaging device having the film according to <7>.
<10> An image display device comprising the film according to <7>.
　本発明によれば、現像残渣の発生を抑制でき、耐熱収縮性および耐湿性に優れた膜を形成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を提供することができる。 According to the present invention, it is possible to provide a colored composition that can suppress the generation of development residues and form a film with excellent heat shrinkage resistance and moisture resistance. Further, the present invention can provide a film, a color filter, a solid-state image sensor, and an image display device.
　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、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化合物を意味する。
　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 content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to either or both of acryloyl and methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, pigment means a compound that is difficult to dissolve in a solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process 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、樹脂と、重合性化合物と、光重合開始剤と、溶剤とを含み、
　上記光重合開始剤は、ヒドロキシ基を有するオキシム化合物を含み、
　上記樹脂は、脂環式エポキシ基を有する樹脂を含むことを特徴とする。 <Colored composition>
The colored composition of the present invention includes a colorant, a resin, a polymerizable compound, a photoinitiator, and a solvent,
The photopolymerization initiator contains an oxime compound having a hydroxy group,
The resin is characterized by containing a resin having an alicyclic epoxy group.
　本発明の着色組成物によれば、現像残渣の発生を抑制でき、耐熱収縮性および耐湿性に優れた膜を形成できる。本発明の着色組成物は、脂環式エポキシ基を有する樹脂と、ヒドロキシ基を有するオキシム化合物とを含むので、製膜時に、ヒドロキシ基を有するオキシム化合物由来のヒドロキシ基によって、脂環式エポキシ基を有する樹脂の硬化を促進させることができ、架橋密度の高い膜を形成することができる。このため、耐熱収縮性および耐湿性に優れた膜を形成できる。そして、光重合開始剤としてヒドロキシ基を有するオキシム化合物を用いることにより、膜の親水性を向上させることができ、現像液によって未露光部の組成物層を効率よく除去することができる。このため、現像残渣の発生も抑制することができる。 According to the colored composition of the present invention, the generation of development residues can be suppressed, and a film with excellent heat shrinkage resistance and moisture resistance can be formed. Since the coloring composition of the present invention contains a resin having an alicyclic epoxy group and an oxime compound having a hydroxy group, during film formation, the alicyclic epoxy group is It is possible to accelerate the curing of the resin having the following properties, and it is possible to form a film with a high crosslinking density. Therefore, a film with excellent heat shrinkage resistance and moisture resistance can be formed. By using an oxime compound having a hydroxyl group as a photopolymerization initiator, the hydrophilicity of the film can be improved, and the composition layer in unexposed areas can be efficiently removed by a developer. Therefore, generation of development residues can also be suppressed.
　本発明の着色組成物は、光学フィルタ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。光学フィルタとしては、カラーフィルタおよび赤外線カットフィルタなどが挙げられ、カラーフィルタであることが好ましい。 The colored composition of the present invention can be preferably used as a colored composition for forming an optical filter. Examples of the optical filter include color filters and infrared cut filters, and color filters are preferred.
　カラーフィルタとしては、特定の波長の光を透過させる着色画素を有するフィルタが挙げられ、赤色画素、青色画素、緑色画素、黄色画素、シアン色画素及びマゼンタ色画素から選ばれる少なくとも１種の着色画素を有するフィルタであることが好ましい。 Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength, and at least one type of colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, and magenta pixels. It is preferable that the filter has the following.
　赤外線透過フィルタは、赤外線の少なくとも一部を透過させるフィルタである。赤外線透過フィルタは、可視光の少なくとも一部を遮光し、赤外線の少なくとも一部を透過させるフィルタであることが好ましい。赤外線透過フィルタとしては、波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１３００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である分光特性を満たしているフィルタなどが好ましく挙げられる。赤外線透過フィルタは、以下の（１）～（５）のいずれかの分光特性を満たしているフィルタであることが好ましい。
　（１）：波長４００～６４０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長８００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（２）：波長４００～７５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長９００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（３）：波長４００～８３０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（４）：波長４００～９５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１１００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。
　（５）：波長４００～１０５０ｎｍの範囲における透過率の最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１２００～１５００ｎｍの範囲における透過率の最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）であるフィルタ。 The infrared transmission filter is a filter that transmits at least a portion of infrared rays. The infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared rays. The infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a minimum transmittance in the wavelength range of 1100 to 1300 nm. Preferred examples include filters that satisfy spectral characteristics with a value of 70% or more (preferably 75% or more, more preferably 80% or more). The infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
(1): The maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less). 70% or more (preferably 75% or more, more preferably 80% or more).
(2): The maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(3): The maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(4): The maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(5): The maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　本発明の着色組成物の固形分濃度は、５～３０質量％であることが好ましい。下限は、７．５質量％以上が好ましく、１０質量％以上がより好ましい。上限は、２５質量％以下が好ましく、２０質量％以下がより好ましい。 The solid content concentration of the colored composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
　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。 Hereinafter, each component used in the colored composition of the present invention will be explained.
＜＜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、黄色着色剤、オレンジ色着色剤、赤色着色剤、緑色着色剤、紫色着色剤、青色着色剤などが挙げられる。着色剤は、顔料であってもよく、染料であってもよい。顔料は、無機顔料または有機顔料のいずれでもよいが、カラーバリエーションの多さ、分散の容易性、安全性等の観点から有機顔料であることが好ましい。 <<Colorant>>
The colored composition of the present invention contains a coloring agent. Examples of the coloring agent include a yellow coloring agent, an orange coloring agent, a red coloring agent, a green coloring agent, a purple coloring agent, a blue coloring agent, and the like. The coloring agent may be a pigment or a dye. The pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoint of wide color variations, ease of dispersion, safety, and the like.
　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。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顔料の分散安定性が良好である。なお、本発明において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本発明における平均一次粒子径は、４００個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The average primary particle diameter of the 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 diameter of the pigment is within the above range, the dispersion stability of the pigment in the coloring composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.
　有機顔料の結晶子サイズは、０．１～５０ｎｍであることが好ましく、０．５～３０ｎｍであることがより好ましく、１～１５ｎｍであることが更に好ましい。結晶子サイズはＸ線回折装置を用いて回折角のピークの半値幅より求めることができ、シェラーの式を用いて算出される。有機顔料の結晶子サイズは、製造条件の調整、製造後に粉砕するなどの公知の方法で調整することができる。 The crystallite size of the organic pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the half width of the peak of the diffraction angle using an X-ray diffraction device, and is calculated using the Scherrer equation. The crystallite size of the organic pigment can be adjusted by known methods such as adjusting production conditions or pulverizing after production.
　緑色着色剤としては、フタロシアニン化合物およびスクアリリウム化合物が挙げられ、フタロシアニン化合物であることが好ましい。緑色着色剤の具体例としては、Ｃ．Ｉ．ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等の緑色顔料が挙げられる。また、緑色着色剤として、１分子中のハロゲン原子数が平均１０～１４個であり、臭素原子数が平均８～１２個であり、塩素原子数が平均２～５個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第２０１５／１１８７２０号に記載の化合物が挙げられる。また、緑色着色剤として中国特許出願第１０６９０９０２７号明細書に記載の化合物、国際公開第２０１２／１０２３９５号に記載のリン酸エステルを配位子として有するフタロシアニン化合物、特開２０１９－００８０１４号公報に記載のフタロシアニン化合物、特開２０１８－１８００２３号公報に記載のフタロシアニン化合物、特開２０１９－０３８９５８号公報に記載の化合物、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、特表２０２０－５０４７５８号公報に記載のジアリールメタン化合物などを用いることもできる。 Examples of the green colorant include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Specific examples of green colorants include C.I. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, as a green coloring agent, halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395, and a phthalocyanine compound described in JP-A No. 2019-008014 Phthalocyanine compounds described in JP 2018-180023, compounds described in JP 2019-038958, aluminum phthalocyanine compounds described in JP 2020-070426, JP 2020-076995 It is also possible to use core-shell type dyes described in , diarylmethane compounds described in Japanese Patent Publication No. 2020-504758, and the like.
　緑色着色剤は、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，５９，６２，６３が好ましく、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，５９がより好ましい。 The green colorant is C. I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred; I. Pigment Green 7, 36, 58, and 59 are more preferred.
　赤色着色剤としては、ジケトピロロピロール化合物、アントラキノン化合物、アゾ化合物、ナフトール化合物、アゾメチン化合物、キサンテン化合物、キナクリドン化合物、ペリレン化合物、チオインジゴ化合物などが挙げられる。赤色着色剤の具体例としては、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等の赤色顔料が挙げられる。また、赤色着色剤として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つ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着色剤、特許第６５２５１０１号公報に記載の赤色着色剤、特開２０２０－０９０６３２号公報の段落番号０２２９に記載の臭素化ジケトピロロピロール化合物、韓国公開特許第１０－２０１９－０１４０７４１号公報に記載のアントラキノン化合物、韓国公開特許第１０－２０１９－０１４０７４４号公報に記載のアントラキノン化合物、特開２０２０－０７９３９６号公報に記載のペリレン化合物、特開２０２０－０８３９８２号公報に記載のペリレン化合物、特開２０１８－０３５３４５号公報に記載のキサンテン化合物、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、赤色着色剤として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。赤色着色剤として、Ｌｕｍｏｇｅｎ　Ｆ　Ｏｒａｎｇｅ　２４０（ＢＡＳＦ製、赤色顔料、ペリレン顔料）を用いることもできる。 Examples of the red colorant include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and the like. Specific examples of red colorants 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, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like. In addition, as a red coloring agent, a diketopyrrolopyrrole compound having at least one bromine atom substituted in the structure described in JP 2017-201384A, a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Patent No. 6248838, Pyrrole compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, brominated diketopyrrolopyrrole compounds described in JP2020-085947A Pyrrole compound, naphthol azo compound described in JP 2012-229344, red colorant described in JP 6516119, red coloring agent described in JP 6525101, paragraph of JP 2020-090632 Brominated diketopyrrolopyrrole compound described in No. 0229, anthraquinone compound described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compound described in Korean Publication Patent No. 10-2019-0140744, JP-A-2020 Perylene compounds described in -079396, perylene compounds described in JP 2020-083982, xanthene compounds described in JP 2018-035345, paragraph numbers 0025 to 0041 of JP 2020-066702, The diketopyrrolopyrrole compounds described above can also be used. Furthermore, as a red colorant, a compound having a structure in which an aromatic ring group into which a group to which an oxygen atom, sulfur atom, or nitrogen atom is bonded is bonded to a diketopyrrolopyrrole skeleton may be used. You can also do it. As the red colorant, Lumogen F Orange 240 (manufactured by BASF, red pigment, perylene pigment) can also be used.
　赤色着色剤は、Ｃ．Ｉ．ピグメントレッド１２２，１７７，１７９，２５４，２５５，２６４，２６９，２７２，２９１が好ましく、Ｃ．Ｉ．ピグメントレッド２５４，２６４，２７２がより好ましい。 The red colorant is C. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, 291 are preferred; I. Pigment Red 254, 264, and 272 are more preferred.
　黄色着色剤としては、アゾ化合物、アゾメチン化合物、イソインドリン化合物、プテリジン化合物、キノフタロン化合物およびペリレン化合物などが挙げられる。黄色着色剤の具体例としては、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等の黄色顔料が挙げられる。 Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow colorants 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, Examples include yellow pigments such as 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236.
　黄色着色剤として、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。
As a yellow coloring agent, an azobarbituric acid nickel complex having the following structure can also be used.
　黄色着色剤として、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、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。
As a yellow coloring agent, the compound described in JP 2017-201003, the compound described in JP 2017-197719, the compound described in paragraph numbers 0011 to 0062, 0137 to 0276 of JP 2017-171912, , 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 2017-171915 Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of Japanese Patent Publication No. 2013-054339, quinophthalone compounds described in paragraph numbers 0011 to 0034 of Japanese Patent Application Publication No. 2014-026228, and paragraph numbers 0013 to 0058 of Japanese Patent Application Publication No. 2014-026228. The quinophthalone compounds described in JP-A No. 2018-062644, the quinophthalone compounds described in JP-A No. 2018-203798, the quinophthalone compounds described in JP-A No. 2018-062578, the quinophthalone compounds described in Japanese Patent No. 6432076 The quinophthalone compound described in JP2018-155881, the quinophthalone compound described in JP2018-111757, the quinophthalone compound described in JP2018-040835, the quinophthalone compound described in JP2017-197640 Quinophthalone compounds described in Japanese Patent Publication No. 2016-145282, Quinophthalone compounds described in Japanese Patent Application Publication No. 2014-085565, Quinophthalone compounds described in Japanese Patent Application Publication No. 2014-021139, Quinophthalone compounds described in Japanese Patent Application Publication No. 2014-021139, The quinophthalone compounds described in JP-A-209614, the quinophthalone compounds described in JP-A-2013-209435, the quinophthalone compounds described in JP-A-2013-181015, the quinophthalone compounds described in JP-A-2013-061622, Quinophthalone compounds described in JP-A No. 2013-032486, quinophthalone compounds described in JP-A No. 2012-226110, quinophthalone compounds described in JP-A No. 2008-074987, quinophthalone compounds described in JP-A No. 2008-081565 , quinophthalone compounds described in JP2008-074986A, quinophthalone compounds described in JP2008-074985A, quinophthalone compounds described in JP2008-050420A, quinophthalone compounds described in JP2008-031281A Quinophthalone compound, Quinophthalone compound described in Japanese Patent Publication No. 48-032765, Quinophthalone compound described in Japanese Patent Application Publication No. 2019-008014, Quinophthalone compound described in Patent No. 6607427, Korean Published Patent No. 10-2014-0034963 Compounds described in the publication, 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 2020-033525 Compounds described in JP 2020-033524, Compounds described in JP 2020-033523, Compounds described in JP 2020-033522, Compounds described in JP 2020-033521 , the compound described in International Publication No. 2020/045200, the compound described in International Publication No. 2020/045199, the compound described in International Publication No. 2020/045197, the azo compound described in JP 2020-093994, Using the perylene compound described in International Publication No. 2020/105346, the quinophthalone compound described in Japanese Patent Publication No. 2020-517791, the compound represented by the following formula (QP1), and the compound represented by the following formula (QP2) You can also do it. Furthermore, polymerized versions of these compounds are also preferably used from the viewpoint of improving color value.
　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。
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 the compound described in paragraph number 0016 of Japanese Patent No. 6443711.
　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 represent integers from 0 to 6, and p represents 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 paragraph numbers 0047 to 0048 of Japanese Patent No. 6432077.
　黄色着色剤は、Ｃ．Ｉ．ピグメントイエロー１１７，１２９，１３８，１３９，１５０，１８５が好ましい。 The yellow colorant is C. I. Pigment Yellow 117, 129, 138, 139, 150, and 185 are preferred.
　オレンジ色着色剤しては、Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等のオレンジ色顔料が挙げられる。 The orange colorant is C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
　紫色着色剤としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等の紫色顔料が挙げられる。 As the purple colorant, C. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
　青色着色剤としては、Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等が挙げられる。また、青色着色剤として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開２０１２－２４７５９１号公報の段落番号００２２～００３０、特開２０１１－１５７４７８号公報の段落番号００４７に記載の化合物が挙げられる。 As the blue colorant, C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88 etc. It will be done. Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
　各種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、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、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 angles that various pigments preferably have, see the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Publication No. 2020-026503, and Japanese Patent Application Publication No. 2020-033526. , the contents of which are incorporated herein. Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight (±1±1±1) crystal lattice planes is 140 Å or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.
　また、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、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。 Further, as the 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 improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 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 the coloring agent. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
　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以上が好ましく、６０００以上がより好ましい。上限は、３００００以下が好ましく、２００００以下がより好ましい。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 the colorant. The dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is preferably 3000 or more, more preferably 6000 or more. The upper limit is preferably 30,000 or less, more preferably 20,000 or less. Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.
　着色剤には、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、韓国公開特許第１０－２０２０－００６９４４２号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９７３０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０７０号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６７号公報に記載の式１で表される化合物、韓国公開特許第１０－２０２０－００６９０６２号公報に記載の式１で表される化合物、特許第６８０９６４９号に記載のハロゲン化亜鉛フタロシアニン顔料、特開２０２０－１８０１７６号公報に記載のイソインドリン化合物を用いることができる。着色剤は、ロタキサンであってもよく、色素骨格はロタキサンの環状構造に使用されていてもよく、棒状構造に使用されていてもよく、両方の構造に使用されていてもよい。 The coloring agent includes a triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, a xanthene compound described in JP2020-117638, and a phthalocyanine described in International Publication No. 2020/174991. Compound, isoindoline compound or salt thereof described in JP-A No. 2020-160279, compound represented by formula 1 described in Korean Unexamined Patent Publication No. 10-2020-0069442, Korean Unexamined Patent No. 10-2020- Compounds represented by formula 1 described in Korean Publication No. 0069730, compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069070, compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069067, Compound represented by formula 1, compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Publication The isoindoline compounds described in can be used. The coloring agent may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
　着色剤は、２種以上組み合わせて用いてもよい。また、着色剤を２種以上組み合わせて用いる場合、２種以上の着色剤の組み合わせで黒色を形成していてもよい。そのような組み合わせとしては、例えば以下の（１）～（７）の態様が挙げられる。
（１）赤色着色剤と青色着色剤とを含有する態様。
（２）赤色着色剤と青色着色剤と黄色着色剤とを含有する態様。
（３）赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤とを含有する態様。
（４）赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤とを含有する態様。
（５）赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤とを含有する態様。
（６）赤色着色剤と青色着色剤と緑色着色剤とを含有する態様。
（７）黄色着色剤と紫色着色剤とを含有する態様。 Two or more colorants may be used in combination. Moreover, when using a combination of two or more types of colorants, black may be formed by a combination of two or more types of colorants. Examples of such combinations include the following embodiments (1) to (7).
(1) Embodiment containing a red colorant and a blue colorant.
(2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant.
(3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
(4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
(5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
(6) An embodiment containing a red colorant, a blue colorant, and a green colorant.
(7) Embodiment containing a yellow colorant and a purple colorant.
　着色組成物中に着色剤を２種以上含み、かつ、２種以上の着色剤の組み合わせで黒色を呈している場合においては、このような着色組成物は、赤外線透過フィルタ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。 In cases where the coloring composition contains two or more types of colorants and a black color is produced by a combination of the two or more types of colorants, such a coloring composition is a coloring composition for forming an infrared transmission filter. It can be preferably used as
　着色組成物の全固形分中における着色剤の含有量は、２５質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。上限は、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 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by 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.
＜＜樹脂＞＞
　本発明の着色組成物は樹脂を含む。樹脂は、例えば、顔料など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 colored composition of the present invention contains a resin. The resin is blended, for example, for use in dispersing pigments in coloring compositions, or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a coloring composition is also referred to as a dispersant. However, this use of the resin is just an example, and the resin can also be used for purposes other than this use.
（脂環式エポキシ基を有する樹脂）
　本発明の着色組成物に含まれる樹脂は、脂環式エポキシ基を有する樹脂（以下、脂環式エポキシ樹脂ともいう）を含む。なお、脂環式エポキシ基とは、エポキシ環と脂肪族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。より耐熱収縮性に優れた膜を形成しやすい理由から、脂環式エポキシ基は、多環式脂肪族炭化水素環を有する基であることが好ましい。すなわち、脂環式エポキシ基は、多環式脂肪族炭化水素環とエポキシ環とが縮合した基であることが好ましい。ここで、多環式脂肪族炭化水素環とは、２以上の単環式脂肪族炭化水素環が環中の炭素原子を１又は２以上共有する構造の脂肪族炭化水素環のことである。多環式脂肪族炭化水素環の具体例としては、イソボルニル環、アダマンタン環、ジシクロペンテン環、ジシクロペンタン環、トリシクロデカン環、ノルボルネン環、ノルボルナン環などが挙げられる。 (Resin with alicyclic epoxy group)
The resin contained in the coloring composition of the present invention includes a resin having an alicyclic epoxy group (hereinafter also referred to as an alicyclic epoxy resin). Note that the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and an aliphatic hydrocarbon ring are condensed. The alicyclic epoxy group is preferably a group having a polycyclic aliphatic hydrocarbon ring because it facilitates the formation of a film with better heat shrinkage resistance. That is, the alicyclic epoxy group is preferably a group in which a polycyclic aliphatic hydrocarbon ring and an epoxy ring are condensed. Here, the polycyclic aliphatic hydrocarbon ring refers to an aliphatic hydrocarbon ring having a structure in which two or more monocyclic aliphatic hydrocarbon rings share one or more carbon atoms in the ring. Specific examples of the polycyclic aliphatic hydrocarbon ring include an isobornyl ring, an adamantane ring, a dicyclopentene ring, a dicyclopentane ring, a tricyclodecane ring, a norbornene ring, and a norbornane ring.
　脂環式エポキシ基としては、式（ｅ－１）で表される基が挙げられる。
　式（ｅ－１）中、環ＡＥ１は脂肪族炭化水素環を表し、＊は結合手を表す。 Examples of the alicyclic epoxy group include a group represented by formula (e-1).
In formula (e-1), ring A E1 represents an aliphatic hydrocarbon ring, and * represents a bond.
　式（ｅ－１）の環ＡＥ１が表す脂肪族炭化水素環は、単環式脂肪族炭化水素環であってもよく、多環式脂肪族炭化水素環であってもよいが、より耐熱収縮性に優れた膜を形成しやすい理由から、多環式脂肪族炭化水素環であることが好ましい。 The aliphatic hydrocarbon ring represented by ring A E1 in formula (e-1) may be a monocyclic aliphatic hydrocarbon ring or a polycyclic aliphatic hydrocarbon ring, but A polycyclic aliphatic hydrocarbon ring is preferred because it facilitates the formation of a membrane with excellent shrinkability.
　脂環式エポキシ基の具体例としては、以下に示す基が挙げられ、式（ｅ－１－３）で表される基および式（ｅ－１－４）で表される基が好ましい。以下の式中、＊は結合手を表す。
Specific examples of the alicyclic epoxy group include the groups shown below, with the group represented by formula (e-1-3) and the group represented by formula (e-1-4) being preferred. In the following formula, * represents a bond.
　脂環式エポキシ樹脂は、脂環式エポキシ基を有する繰り返し単位を含む樹脂であることが好ましい。脂環式エポキシ基を有する繰り返し単位としては、式（Ｅ１）で表される繰り返し単位が挙げられる。
The alicyclic epoxy resin is preferably a resin containing a repeating unit having an alicyclic epoxy group. Examples of the repeating unit having an alicyclic epoxy group include a repeating unit represented by formula (E1).
　式（Ｅ１）中、Ｘａ１は３価の連結基を表し、Ｌａ１は単結合または２価の連結基を表し、Ｚａ１は脂環式エポキシ基を表す。 In formula (E1), X a1 represents a trivalent linking group, L a1 represents a single bond or a divalent linking group, and Z a1 represents an alicyclic epoxy group.
　式（Ｅ１）のＸａ１が表す３価の連結基としては、ポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基、ポリエステル系連結基、ポリウレタン系連結基、ポリウレア系連結基、ポリアミド系連結基、ポリエーテル系連結基、ポリスチレン系連結基、ビスフェノール系連結基、ノボラック系連結基などが挙げられ、ポリ（メタ）アクリル系連結基、ポリエーテル系連結基、ポリエステル系連結基、ビスフェノール系連結基およびノボラック系連結基が好ましく、ポリエーテル系連結基、ノボラック系連結基およびポリ（メタ）アクリル系連結基がより好ましく、ポリ（メタ）アクリル系連結基が更に好ましい。 The trivalent linking group represented by X a1 in formula (E1) includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, and a polyamide linking group. Linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolak-based linking groups, etc., include poly(meth)acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups, etc. A linking group and a novolak-based linking group are preferred, a polyether-based linking group, a novolak-based linking group, and a poly(meth)acrylic-based linking group are more preferred, and a poly(meth)acrylic-based linking group is even more preferred.
　式（Ｅ１）のＬａ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシ基、アルコキシ基などが挙げられる。 The divalent linking group represented by L a1 in formula (E1) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH- , -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. The alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
　式（Ｅ１）のＺａ１が表す脂環式エポキシ基は、上述した式（ｅ－１）で表される基が挙げられ、式（ｅ－１－３）で表される基および式（ｅ－１－４）で表される基が好ましい。 Examples of the alicyclic epoxy group represented by Z a1 in formula (E1) include the group represented by formula (e-1) described above, the group represented by formula (e-1-3), and the group represented by formula (e-1). -1-4) is preferred.
　脂環式エポキシ基を有する繰り返し単位を含む樹脂は、式（Ｅ１－１）で表される繰り返し単位および式（Ｅ１－２）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有することが好ましい。上記樹脂は、式（Ｅ１－１）で表される繰り返し単位および式（Ｅ１－２）で表される繰り返し単位のうち、いずれか一方の繰り返し単位のみを含んでいてもよく、式（Ｅ１－１）で表される繰り返し単位と式（Ｅ１－２）で表される繰り返し単位のそれぞれを含んでいてもよい。両方の繰り返し単位を含む場合、式（Ｅ１－１）で表される繰り返し単位と式（Ｅ１－２）で表される繰り返し単位との比率は、モル比で、式（Ｅ１－１）で表される繰り返し単位：式（Ｅ１－２）で表される繰り返し単位＝５：９５～９５：５であることが好ましく、１０：９０～９０：１０であることがより好ましく、２０：８０～８０：２０であることが更に好ましい。
The resin containing a repeating unit having an alicyclic epoxy group has at least one repeating unit selected from a repeating unit represented by formula (E1-1) and a repeating unit represented by formula (E1-2). It is preferable. The resin may contain only one of the repeating units represented by formula (E1-1) and the repeating unit represented by formula (E1-2), It may contain each of the repeating unit represented by 1) and the repeating unit represented by formula (E1-2). When both repeating units are included, the ratio of the repeating unit represented by formula (E1-1) to the repeating unit represented by formula (E1-2) is the molar ratio, which is expressed by formula (E1-1). repeating unit: repeating unit represented by formula (E1-2) = preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferable.
　式（Ｅ１－１）および（Ｅ１－２）中、ＬＥ１は単結合または２価の連結基を表し、ＲＥ１０は水素原子または置換基を表す。ＲＥ１０が表す置換基としては、アルキル基およびアリール基が挙げられ、アルキル基であることが好ましい。アルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。ＲＥ１０は、水素原子またはメチル基であることが好ましい。ＬＥ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシ基、アルコキシ基などが挙げられる。 In formulas (E1-1) and (E1-2), L E1 represents a single bond or a divalent linking group, and R E10 represents a hydrogen atom or a substituent. Examples of the substituent represented by R E10 include an alkyl group and an aryl group, and an alkyl group is preferable. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. R E10 is preferably a hydrogen atom or a methyl group. The divalent linking group represented by L E1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, Examples thereof include -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. The alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
　脂環式エポキシ基を有する繰り返し単位の含有量は、脂環式エポキシ基を有する繰り返し単位を含む樹脂の全繰り返し単位中１～１００モル％であることが好ましい。上限は９０モル％以下であることが好ましく、８０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。 The content of the repeating unit having an alicyclic epoxy group is preferably 1 to 100 mol% of the total repeating units of the resin containing the repeating unit having an alicyclic epoxy group. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more.
　脂環式エポキシ基を有する繰り返し単位を含む樹脂は、脂環式エポキシ基を有する繰り返し単位の他に他の繰り返し単位を有していてもよい。他の繰り返し単位としては、酸基を有する繰り返し単位、エチレン性不飽和結合含有基を有する繰り返し単位などが挙げられる。 The resin containing a repeating unit having an alicyclic epoxy group may have other repeating units in addition to the repeating unit having an alicyclic epoxy group. Examples of other repeating units include repeating units having an acid group and repeating units having an ethylenically unsaturated bond-containing group.
　酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, with a phenolic hydroxy group or a carboxy group being preferred, and a carboxy group being more preferred.
　エチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。 Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, (meth)acryloyl groups, and the like.
　酸基を有する繰り返し単位としては、下記式（Ｅ２）で表される繰り返し単位が挙げられる。エチレン性不飽和結合含有基を有する繰り返し単位としては、下記式（Ｅ３）で表される繰り返し単位が挙げられる。
Examples of the repeating unit having an acid group include a repeating unit represented by the following formula (E2). Examples of the repeating unit having an ethylenically unsaturated bond-containing group include a repeating unit represented by the following formula (E3).
　式（Ｅ２）中、Ｘｂ１は３価の連結基を表し、Ｌｂ１は単結合または２価の連結基を表し、Ｚｂ１は酸基を表す。式（Ｅ３）中、Ｘｃ１は３価の連結基を表し、Ｌｃ１は単結合または２価の連結基を表し、Ｚｃ１はエチレン性不飽和結合含有基を表す。 In formula (E2), X b1 represents a trivalent linking group, L b1 represents a single bond or a divalent linking group, and Z b1 represents an acid group. In formula (E3), X c1 represents a trivalent linking group, L c1 represents a single bond or a divalent linking group, and Z c1 represents an ethylenically unsaturated bond-containing group.
　式（Ｅ２）のＸｂ１が表す３価の連結基および式（Ｅ３）のＸｃ１が表す３価の連結基としてはポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基、ポリエステル系連結基、ポリウレタン系連結基、ポリウレア系連結基、ポリアミド系連結基、ポリエーテル系連結基、ポリスチレン系連結基、ビスフェノール系連結基、ノボラック系連結基などが挙げられ、ポリ（メタ）アクリル系連結基、ポリエーテル系連結基、ポリエステル系連結基、ビスフェノール系連結基およびノボラック系連結基が好ましく、ポリエーテル系連結基、ノボラック系連結基およびポリ（メタ）アクリル系連結基がより好ましく、ポリ（メタ）アクリル系連結基が更に好ましい。 The trivalent linking group represented by X b1 in formula (E2) and the trivalent linking group represented by X c1 in formula (E3) include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, and a polyester linking group. groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolac-based linking groups, etc., and poly(meth)acrylic-based linking groups. , polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups, and novolak-based linking groups are preferred, polyether-based linking groups, novolak-based linking groups, and poly(meth)acrylic-based linking groups are more preferred; ) Acrylic linking groups are more preferred.
　式（Ｅ２）のＬｂ１が表す２価の連結基および式（Ｅ３）のＬｃ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。アルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシ基、アルコキシ基などが挙げられる。 The divalent linking group represented by L b1 in formula (E2) and the divalent linking group represented by L c1 in formula (E3) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group ( (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and two or more of these Examples include groups formed in combination. The alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
　式（Ｅ２）のＺｂ１が表す酸基としては、フェノール性ヒドロキシ基、カルボキシ基、スルホ基、リン酸基が挙げられ、フェノール性ヒドロキシ基またはカルボキシ基であることが好ましく、カルボキシ基であることがより好ましい。 The acid group represented by Z b1 in formula (E2) includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, and a carboxy group. is more preferable.
　式（Ｅ３）のＺｃ２が表すエチレン性不飽和結合含有基としては、ビニル基、スチレン基、（メタ）アリル基、（メタ）アクリロイル基等が挙げられる。 Examples of the ethylenically unsaturated bond-containing group represented by Z c2 in formula (E3) include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group.
　脂環式エポキシ基を有する繰り返し単位を含む樹脂が酸基を有する繰り返し単位を含む場合、酸基を有する繰り返し単位の含有量は、脂環式エポキシ基を有する繰り返し単位を含む樹脂の全繰り返し単位中１０～８０モル％であることが好ましい。上限は７０モル％以下であることが好ましく、６０モル％以下であることがより好ましい。下限は、１５モル％以上が好ましく、２０モル％以上がより好ましい。 When a resin containing a repeating unit having an alicyclic epoxy group contains a repeating unit having an acid group, the content of the repeating unit having an acid group is the total repeating unit of the resin including a repeating unit having an alicyclic epoxy group. It is preferably 10 to 80 mol%. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less. The lower limit is preferably 15 mol% or more, more preferably 20 mol% or more.
　脂環式エポキシ基を有する繰り返し単位を含む樹脂がエチレン性不飽和結合含有基を有する繰り返し単位を含む場合、エチレン性不飽和結合含有基を有する繰り返し単位の含有量は、脂環式エポキシ基を有する繰り返し単位を含む樹脂の全繰り返し単位中１～２０モル％であることが好ましい。上限は１８モル％以下であることが好ましく、１５モル％以下であることがより好ましい。下限は、３モル％以上が好ましく、５モル％以上がより好ましい。 When the resin containing a repeating unit having an alicyclic epoxy group contains a repeating unit having an ethylenically unsaturated bond-containing group, the content of the repeating unit having an ethylenically unsaturated bond-containing group is It is preferable that the amount is 1 to 20 mol% of the total repeating units of the resin containing the repeating unit. The upper limit is preferably 18 mol% or less, more preferably 15 mol% or less. The lower limit is preferably 3 mol% or more, more preferably 5 mol% or more.
　脂環式エポキシ基を有する繰り返し単位を含む樹脂は、更に芳香族炭化水素環を有する繰り返し単位を含むことが好ましい。芳香族炭化水素環としては、ベンゼン環またはナフタレン環であることが好ましく、ベンゼン環であることが好ましい。芳香族炭化水素環は置換基を有していてもよい。置換基としては、アルキル基などが挙げられる。環状エーテル基を有する樹脂が、芳香族炭化水素環を有す繰り返し単位を含む場合、芳香族炭化水素環を有する繰り返し単位の含有量は、環状エーテル基を有する樹脂の全繰り返し単位中１～６５モル％であることが好ましい。上限は４５モル％以下であることが好ましく、３０モル％以下であることがより好ましい。下限は、２モル％以上が好ましく、３モル％以上がより好ましい。芳香族炭化水素環を有す繰り返し単位としては、ビニルトルエン、ベンジル（メタ）アクリレートなどの芳香族炭化水素環を有する単官能の重合性化合物由来の繰り返し単位が挙げられる。 It is preferable that the resin containing a repeating unit having an alicyclic epoxy group further contains a repeating unit having an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group. When the resin having a cyclic ether group contains a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 65% of the total repeating units of the resin having a cyclic ether group. Preferably it is mol%. The upper limit is preferably 45 mol% or less, more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, more preferably 3 mol% or more. Examples of the repeating unit having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth)acrylate.
　脂環式エポキシ樹脂の重量平均分子量は５０００～３００００であることが好ましい。下限は、７０００以上であることが好ましく、９０００以上であることがより好ましい。上限は、２５０００以下であることが好ましく、２００００以下であることがより好ましく、１５０００以下であることが更に好ましい。 The weight average molecular weight of the alicyclic epoxy resin is preferably 5,000 to 30,000. The lower limit is preferably 7,000 or more, more preferably 9,000 or more. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
　脂環式エポキシ樹脂のエポキシ当量は、５０～５００ｇ／ｅｑであることが好ましい。下限は、１００ｇ／ｅｑ以上が好ましく、１５０ｇ／ｅｑ以上がより好ましい。上限は、４５０ｇ／ｅｑ以下が好ましく、４００ｇ／ｅｑ以下がより好ましい。なお、脂環式エポキシ樹脂のエポキシ当量は、脂環式エポキシ樹脂の分子量を脂環式エポキシ樹脂に含まれる脂環式エポキシ基の数で割ることで算出した値である。 The epoxy equivalent of the alicyclic epoxy resin is preferably 50 to 500 g/eq. The lower limit is preferably 100 g/eq or more, more preferably 150 g/eq or more. The upper limit is preferably 450 g/eq or less, more preferably 400 g/eq or less. The epoxy equivalent of the alicyclic epoxy resin is a value calculated by dividing the molecular weight of the alicyclic epoxy resin by the number of alicyclic epoxy groups contained in the alicyclic epoxy resin.
　脂環式エポキシ樹脂の酸価は、５０～２００ｍｇＫＯＨ／ｇが好ましい。下限は、７５ｍｇＫＯＨ／ｇ以上が好ましく、１００ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、１７５ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましい。 The acid value of the alicyclic epoxy resin is preferably 50 to 200 mgKOH/g. The lower limit is preferably 75 mgKOH/g or more, more preferably 100 mgKOH/g or more. The upper limit is preferably 175 mgKOH/g or less, more preferably 150 mgKOH/g or less.
（他の樹脂）
　本発明の着色組成物は、上述した脂環式エポキシ樹脂以外の樹脂（以下、他の樹脂ともいう）を含有することができる。 (other resins)
The coloring composition of the present invention can contain resins other than the above-mentioned alicyclic epoxy resins (hereinafter also referred to as other resins).
　他の樹脂としては、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、特開２０２０－１８６３７３号公報の段落０１９９～０２３３に記載の樹脂、特開２０２０－１８６３２５号公報に記載のアルカリ可溶性樹脂、韓国公開特許第１０－２０２０－００７８３３９号公報に記載の式１で表される樹脂を用いることもできる。 Examples of other resins include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, Examples include polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. In addition, the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685. The resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP 2017-206689, resins described in paragraph numbers 0022 to 0071 of JP 2018-010856, and blocks described in JP 2016-222891. Polyisocyanate resin, resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP-A-2020-186373, resin described in paragraphs 0199 to 0233 of JP-A No. 2020-186325 Alkali-soluble resins described in the publication and resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 can also be used.
　他の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 other 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.
　他の樹脂としては、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 other resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
　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 to 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, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups 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 in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin. The upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。また、樹脂への酸基の導入方法としては、特に制限はないが、例えば、特許第６３４９６２９号公報に記載の方法が挙げられる。更に、樹脂への酸基の導入方法としては、エポキシ基の開環反応で生じたヒドロキシ基に酸無水物を反応させて酸基を導入する方法も挙げられる。 Regarding resins having acid groups, the descriptions in paragraph numbers 0558 to 0571 of JP 2012-208494 (corresponding paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099), JP 2012-198408 The descriptions in paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, commercially available resins having acid groups can also be used. Furthermore, there are no particular limitations on the method for introducing acid groups into the resin, but examples include the method described in Japanese Patent No. 6,349,629. Furthermore, as a method for introducing acid groups into the resin, there is also 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.
　他の樹脂としては、塩基性基を有する樹脂を用いることもできる。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。 As other resins, resins having basic groups can also be used. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group. A polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable. A resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 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, 3 8500, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
　他の樹脂は、酸基を有する樹脂と塩基性基を有する樹脂とを用いることも好ましい。この態様によれば、樹脂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。 It is also preferable to use a resin having an acid group and a resin having a basic group as the other resins. According to this aspect, the storage stability of the resin composition can be further improved. When a resin having an acid group and a resin having a basic group are used together, the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group. The amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
　他の樹脂としては、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。 Other resins include monomer components containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable to use a resin containing repeating units derived from.
　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。
　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.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), the description in JP-A No. 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.
　他の樹脂としては、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。
　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 other resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).
In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, 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.).
　他の樹脂としては、重合性基を有する樹脂を用いることも好ましい。重合性基としては、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る。 As the other resin, it is also preferable to use a resin having a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.
　他の樹脂としては、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 other resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In the resin Ac, the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In addition, in this specification, an aromatic carboxy group refers to 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 to 4, more preferably 1 to 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。
　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。 The resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
In formula (Ac-1), Ar 1 represents a group containing an aromatic carboxy 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 carboxy 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。
Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
　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。
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).
　Ａｒ１が表す芳香族カルボキシ基を含む基は、重合性基を有していてもよい。重合性基は、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。
The aromatic carboxy group-containing group represented by Ar 1 may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and 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). Examples include groups such as
　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, and 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 even 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, and 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- Represents a group represented by 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), *1 represents the bonding position with L 1 .
　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-, and preferably represents -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。 In formula (Ac-1), the divalent linking group represented by L 2 includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group. 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 group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms. The alkylene group may be linear, branched, or cyclic. The alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
　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 aromatic carboxy group-containing 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。
In formula (Ac-2), the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
　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), and *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 . The trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
　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), and *2 represents formula ( It represents the bonding position of Ac-2) with P10 . The trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group is preferable.
　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、ポリエステル構造、ポリエーテル構造、ポリスチレン構造およびポリ（メタ）アクリル構造から選ばれる少なくとも１種の構造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。 In formula (Ac-2), P 10 represents a polymer chain. The polymer chain represented by P 10 preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. The weight average molecular weight of the polymer chain P 10 is preferably 500 to 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 P 10 is within the above range, the pigment will have good dispersibility in the composition. When the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
　Ｐ１０が表すポリマー鎖は、重合性基を含んでいてもよい。重合性基としては、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 P 10 may contain a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
　他の樹脂として、グラフトポリマー、星形ポリマー、ブロック共重合体およびポリマー鎖の少なくとも一方の末端が酸基で封止された樹脂から選ばれる少なくとも１種を用いることもできる。このような樹脂は分散剤として好ましく用いられる。 As the other resin, at least one selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is capped with an acid group can also be used. Such resins are preferably used as dispersants.
　グラフトポリマーとしては、グラフト鎖を有する繰り返し単位を有する樹脂および上述した式（Ａｃ－２）で表される繰り返し単位を有する樹脂などが挙げられる。グラフト鎖としては、ポリエステル構造、ポリエーテル構造、ポリスチレン構造およびポリ（メタ）アクリル構造から選ばれる少なくとも１種の構造を含むグラフト鎖が挙げられる。グラフト鎖の末端構造としては、特に限定されない。水素原子であってもよく、置換基であってもよい。置換基としては、アルキル基、アルコキシ基、アルキルチオエーテル基等が挙げられる。なかでも、顔料の分散性向上の観点から、立体反発効果を有する基が好ましく、炭素数５～３０のアルキル基又はアルコキシ基が好ましい。アルキル基およびアルコキシ基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。 Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above-mentioned formula (Ac-2). Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like. Among these, from the viewpoint of improving the dispersibility of the pigment, groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
　グラフトポリマーの具体例としては、特開２０１２－２５５１２８号公報の段落番号００２５～００９４、特開２００９－２０３４６２号公報の段落番号００２２～００９７、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６に記載された樹脂が挙げられる。 Specific examples of graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.
　星形ポリマーとしては、コア部に複数個のポリマー鎖が結合した構造の樹脂が挙げられる。星型ポ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。 Examples of star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion. Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
　ブロック共重合体としては、酸基または塩基性基を含む繰り返し単位を有する重合体のブロック（以下、ブロックＡともいう）と、酸基および塩基性基を含まない繰り返し単位を有する重合体のブロック（以下、ブロックＢともいう）とのブロック共重合体であることが好ましい。ブロック共重合体には、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。 The block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer. The block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.
　ポリマー鎖の少なくとも一方の末端が酸基で封止された樹脂としては、ポリエステル構造、ポリエーテル構造およびポリ（メタ）アクリル構造から選ばれる少なくとも１種の構造を含むポリマー鎖の少なくとも一方の末端が酸基で封止された構造の樹脂が挙げられる。ポリマー鎖の末端を封止する酸基としては、カルボキシ基、スルホ基、リン酸基が挙げられる。 The resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure. Examples include resins with a structure sealed with acid groups. Examples of acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphoric acid groups.
　他の樹脂は、分散剤としての樹脂を用いることもできる。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）としては、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上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。 Other resins can also be used as dispersants. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.
　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、Ａ２０８Ｆ（第一工業製薬（株）製）、Ｈ－３６０６（第一工業製薬（株）製）、サンデットＥＴ（三洋化成工業（株）製）などが挙げられる。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 include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A 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２０～６０質量％であることが好ましい。上限は、５５質量％以下であることが好ましく、５０質量％以下であることがより好ましい。下限は、２５質量％以上であることが好ましく、３０質量％以上であることがより好ましい。 The content of resin in the total solid content of the coloring composition is preferably 20 to 60% by mass. The upper limit is preferably 55% by mass or less, more preferably 50% by mass or less. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more.
　着色組成物の全固形分中における脂環式エポキシ樹脂の含有量は１０～５５質量％であることが好ましい。上限は、５０質量％以下であることが好ましく、４５質量％以下であることがより好ましい。下限は、１５質量％以上であることが好ましく、２０質量％以上であることがより好ましい。 The content of the alicyclic epoxy resin in the total solid content of the coloring composition is preferably 10 to 55% by mass. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more.
　着色組成物に含まれる樹脂中における脂環式エポキシ樹脂の含有量は、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０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、９０質量％以下とすることもできる。 The content of the alicyclic epoxy resin in the resin contained in the coloring composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. . The upper limit can be 100% by mass or less, and can also be 90% by mass or less.
　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 colored composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
＜＜重合性化合物＞＞
　本発明の着色組成物は重合性化合物を含有する。重合性化合物としては、エチレン性不飽和結合含有基を有する化合物などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。本発明で用いられる重合性化合物は、ラジカル重合性化合物であることが好ましい。 <<Polymerizable compound>>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.
　重合性化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～２５００が好ましい。上限は、２０００以下が好ましく、１５００以下がより好ましい。下限は、１５０以上が好ましく、２５０以上がより好ましい。 The polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 2,500. 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、着色組成物の保存安定性の観点から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 storage stability of the coloring composition. 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 a 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、着色組成物の保存安定性の観点から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。重合性化合物の具体例としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－０２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７、特開２０１３－２５３２２４号公報の段落番号００３４～００３８、特開２０１２－２０８４９４号公報の段落番号０４７７、特開２０１７－０４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物が挙げられ、これらの内容は本明細書に組み込まれる。 The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four 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, and even more preferably 6 or less from the viewpoint of storage stability of the coloring composition. Further, the polymerizable compound is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound. More preferably, it is a tri- to hexa-functional (meth)acrylate compound. Specific examples of polymerizable compounds include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and The compounds described in paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, and JP 6031807 are , the contents of which are incorporated herein.
　重合性化合物は、アルキレンオキシド変性（メタ）アクリレート化合物であることも好ましい。このような重合性化合物を用いることで、現像残渣の発生をより抑制することができる。
　アルキレンオキシド変性（メタ）アクリレート化合物としては、（メタ）アクリレート化合物の（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が挙げられる。アルキレンオキシド変性（メタ）アクリレート化合物は、エチレンオキシド変性（メタ）アクリレート化合物であることが好ましい。 It is also preferable that the polymerizable compound is an alkylene oxide modified (meth)acrylate compound. By using such a polymerizable compound, generation of development residue can be further suppressed.
Examples of alkylene oxide-modified (meth)acrylate compounds include compounds having a structure in which (meth)acryloyl groups of a (meth)acrylate compound are bonded via an alkyleneoxy group. The alkylene oxide modified (meth)acrylate compound is preferably an ethylene oxide modified (meth)acrylate compound.
　アルキレンオキシド変性（メタ）アクリレート化合物は、式（Ｚ－４）で表される化合物または式（Ｚ－５）で表される化合物であることが好ましい。 The alkylene oxide modified (meth)acrylate compound is preferably a compound represented by formula (Z-4) or a compound represented by formula (Z-5).
　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)- , each y 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 total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中の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 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In addition, 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)-, A form in which the terminal on the oxygen atom side is bonded to X is preferable.
　アルキレンオキシド変性（メタ）アクリレート化合物の具体例としては、アルキレンオキシド変性ジペンタエリスリトールトリ（メタ）アクリレート、アルキレンオキシド変性ジペンタエリスリトールテトラ（メタ）アクリレート、アルキレンオキシド変性ジペンタエリスリトールペンタ（メタ）アクリレート、アルキレンオキシド変性ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。 Specific examples of alkylene oxide-modified (meth)acrylate compounds include alkylene oxide-modified dipentaerythritol tri(meth)acrylate, alkylene oxide-modified dipentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol penta(meth)acrylate, Examples include alkylene oxide-modified dipentaerythritol hexa(meth)acrylate.
　アルキレンオキシド変性（メタ）アクリレート化合物の市販品としては、ＮＫエステル　Ｍ－ＤＰＨ－６Ｅ、Ｍ－ＤＰＨ－１２Ｅ、Ａ－ＤＰＨ－６Ｅ、Ａ－ＤＰＨ－１２Ｅ（以上、新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＤＰＥＡ－１２（日本化薬（株）製）などが挙げられる。 Commercially available alkylene oxide-modified (meth)acrylate compounds include NK ester M-DPH-6E, M-DPH-12E, A-DPH-6E, and A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ), KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
　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。
　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。 As the polymerizable compound, polypentaerythritol poly(meth)acrylate as shown in the following formula (Z-6) can also be used.
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 to 10. However, at least one of X 1 to X 6 is a (meth)acryloyl group.
　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（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、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アクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることもできる。 Examples of polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320) ; made by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available: M-460; Toa) Synthetic), pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 ( Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.) ), light acrylate POB-A0 (manufactured by Kyoeisha Kagaku Co., Ltd.), etc. can also be used.
　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ド変性トリ（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ド変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシド変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることもできる。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 Polymerizable compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol. Trifunctional (meth)acrylate compounds such as tri(meth)acrylate can also be used. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.
　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。 As the polymerizable compound, a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can also be used. Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
　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。 As the polymerizable compound, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein.
Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
　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。 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 Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
　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 that does not substantially contain environmentally controlled substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.
　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。 Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. It is also preferable to use polymerizable compounds 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. In addition, the polymerizable compounds include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, 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く、２０質量％以下であることが更に好ましく、１０質量％以下であることが特に好ましい。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, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more. The colored composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types of polymerizable compounds are included, it is preferable that the total amount thereof falls 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。本発明の着色組成物には、光重合開始剤として、ヒドロキシ基を有するオキシム化合物を含むものが用いられる。以下、光重合開始剤として用いるヒドロキシ基を有するオキシム化合物を、特定オキシム化合物ともいう。 <<Photopolymerization initiator>>
The colored composition of the present invention contains a photopolymerization initiator. In the colored composition of the present invention, a photopolymerization initiator containing an oxime compound having a hydroxy group is used. Hereinafter, the oxime compound having a hydroxyl group used as a photopolymerization initiator will also be referred to as a specific oxime compound.
　特定オキシム化合物が有するヒドロキシ基の数は、１～４個であることが好ましく、１または２個であることがより好ましく、１個であることが更に好ましい。 The number of hydroxy groups that the specific oxime compound has is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
　特定オキシム化合物の分子量は、２００～８００であることが好ましい。下限は、２５０以上であることが好ましく、３００以上であることがより好ましい。上限は、７５０以下であることが好ましく、７００以下であることがより好ましい。 The specific oxime compound preferably has a molecular weight of 200 to 800. The lower limit is preferably 250 or more, more preferably 300 or more. The upper limit is preferably 750 or less, more preferably 700 or less.
　特定オキシム化合物のヒドロキシ基価は、硬化反応の促進と現像残渣の抑制をより高い水準で両立できるという理由から０．５～１０．０ｍｍｏｌ／ｇであることが好ましい。下限は、１．０ｍｍｏｌ／ｇ以上であることが好ましく、１．５ｍｍｏｌ／ｇ以上であることがより好ましい。上限は８．０ｍｍｏｌ／ｇ以下であることが好ましく、６．０ｍｍｏｌ／ｇ以下であることがより好ましい。特定オキシム化合物のヒドロキシ基価は、特定オキシム化合物の１分子中に含まれるヒドロキシ基の数を特定オキシム化合物の分子量で割ることで算出した値である。 The hydroxyl value of the specific oxime compound is preferably 0.5 to 10.0 mmol/g because it is possible to both accelerate the curing reaction and suppress development residue at a higher level. The lower limit is preferably 1.0 mmol/g or more, more preferably 1.5 mmol/g or more. The upper limit is preferably 8.0 mmol/g or less, more preferably 6.0 mmol/g or less. The hydroxy value of the specific oxime compound is a value calculated by dividing the number of hydroxy groups contained in one molecule of the specific oxime compound by the molecular weight of the specific oxime compound.
　特定オキシム化合物は、ヒドロキシ基とチオエ―テル基を含むオキシム化合物であることが好ましい。このようなオキシム化合物を用いることで、本発明の効果がより顕著に奏される。 The specific oxime compound is preferably an oxime compound containing a hydroxy group and a thioether group. By using such an oxime compound, the effects of the present invention are more prominently exhibited.
　特定オキシム化合物の具体例としては、下記構造の化合物が挙げられる。
Specific examples of the specific oxime compound include compounds having the following structure.
　本発明の着色組成物に含まれる光重合開始剤は、実質的に上述した特定オキシム化合物のみであってもよく、上述した特定オキシム化合物以外の光重合開始剤（以下、他の光重合開始剤ともいう）を更に含んでいてもよい。 The photopolymerization initiator contained in the coloring composition of the present invention may be substantially only the above-mentioned specific oxime compound, or may be a photopolymerization initiator other than the above-mentioned specific oxime compound (hereinafter, other photopolymerization initiator). ) may also be included.
　光重合開始剤が実質的に特定オキシム化合物のみである場合は、パターン形状の矩形性をより向上させることができるという点で好ましい。なお、本明細書において、光重合開始剤が実質的に特定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特定オキシム化合物が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、特定オキシム化合物のみであることがより好ましい。 It is preferable that the photopolymerization initiator is substantially only a specific oxime compound because the rectangularity of the pattern shape can be further improved. In addition, in this specification, the case where the photopolymerization initiator is substantially only a specific oxime compound means that the specific oxime compound in the photopolymerization initiator is 99% by mass or more, and 99.9% by mass % or more, and more preferably only the specific oxime compound.
　光重合開始剤が特定オキシム化合物の他に、更に他の光重合開始剤を含む場合は、現像後のパターンの密着性をより向上させることができるという点で好ましい。光重合開始剤が特定オキシム化合物の他に、更に他の光重合開始剤を含む場合、他の光重合開始剤の含有量は、特定オキシム化合物の１００質量部に対して１０～５０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、２５質量部以上であることがより好ましい。上限は、４５質量部以下であることが好ましく、４０質量部以下であることがより好ましい。 It is preferable that the photopolymerization initiator further contains another photopolymerization initiator in addition to the specific oxime compound, since the adhesion of the pattern after development can be further improved. When the photopolymerization initiator further contains other photopolymerization initiators in addition to the specific oxime compound, the content of the other photopolymerization initiators is 10 to 50 parts by mass based on 100 parts by mass of the specific oxime compound. It is preferable that there be. The lower limit is preferably 20 parts by mass or more, more preferably 25 parts by mass or more. The upper limit is preferably 45 parts by mass or less, more preferably 40 parts by mass or less.
　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、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられ、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、ヘキサアリールビイミダゾール化合物、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、他の光重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～０１１１に記載された化合物、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤、特開２０２０－０５５９９２号公報に記載のオキサゾリジン基を有するアミノアセトフェノン系開始剤、特開２０１３－１９０４５９号公報に記載のオキシム系光重合開始剤、特開２０２０－１７２６１９号公報に記載の重合体、国際公開第２０２０／１５２１２０号に記載の式１で表される化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 Other photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, and organic peroxides. , thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphines, etc. compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substitutions A coumarin compound is preferable, a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound is more preferable, and an oxime compound is even more preferable. In addition, other photopolymerization initiators include compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3,2019, 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 No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 Examples include compounds represented by Formula 1, the contents of which are incorporated herein.
　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. can be 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, and Irgacure 1. 173, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure. 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３８に記載の化合物、国際公開第２０１３／１６７５１５号に記載の化合物、特許第５４３０７４６号に記載の化合物、特許第５６４７７３８号に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン、１－［４－（フェニルチオ）フェニル］－３－シクロヘキシル－プロパン－１，２－ジオン－２－（Ｏ－アセチルオキシム）などが挙げられる。市販品としては、Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、Ｉｒｇａｃｕｒｅ　ＯＸＥ０２、Ｉｒｇａｃｕｒｅ　ＯＸＥ０３、Ｉｒｇａｃｕｒｅ　ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４、ＴＲ－ＰＢＧ－３２７（ＴＲＯＮＬＹ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。 Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 - Compounds described in Publication No. 066385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017 /051680, the compound described in JP2017-198865, the compound described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515, Examples include compounds described in Japanese Patent No. 5430746 and compounds described in Japanese Patent No. 5647738. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-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), Adeka Optomer N- 1919 (Co., Ltd. ) Photopolymerization initiator 2) manufactured by ADEKA and described in JP-A-2012-014052.
　他の光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物、特許第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。 As other photopolymerization initiators, oxime compounds having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compounds described in JP-A No. 2014-137466, the compounds described in Japanese Patent No. 6636081, and the compounds described in Korean Patent Publication No. 10-2016-0109444. Can be mentioned.
　他の光重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 As other photopolymerization initiators, it is also possible to use oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.
　他の光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 As other photopolymerization initiators, oxime compounds having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).
　他の光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 As other photopolymerization initiators, oxime compounds having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
　他の光重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載されているＯＥ－０１～ＯＥ－７５が挙げられる。 As other photopolymerization initiators, oxime compounds having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
　他の光重合開始剤として用いられるオキシム化合物の具体例としては以下に示す化合物が挙げられる。 Specific examples of oxime compounds used as other photopolymerization initiators include the compounds shown below.
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１０００～３０００００であることがより好ましく、２０００～３０００００であることが更に好ましく、５０００～２０００００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
　他の光重合開始剤としては、２官能あるいは３官能以上の光重合開始剤を用いてもよい。そのような光重合開始剤を用いることにより、光重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、着色組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開第２０１７／０３３６８０号の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）、特許第６４６９６６９号公報に記載されているオキシムエステル光開始剤などが挙げられる。 As other photopolymerization initiators, difunctional or trifunctional or more functional photopolymerization initiators may be used. By using such a photopolymerization initiator, two or more radicals are generated from one molecule of the photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the coloring composition over time. . Specific examples of bifunctional or trifunctional or more functional photopolymerization initiators include the paragraphs of Japanese Translated Patent Publication No. 2010-527339, Japanese Translated Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Translated Patent Publication No. 2016-532675. Nos. 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound (G ), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of Japanese Patent Application Publication No. 2017-523465, paragraph of Japanese Patent Application Publication No. 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, oxime described in Japanese Patent No. 6469669 Examples include ester photoinitiators.
　着色組成物の全固形分中における光重合開始剤の含有量は０．１～２０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、１５質量％以下が好ましく、１０質量％以下がより好ましい。
　着色組成物の全固形分中における特定オキシム化合物の含有量は０．１～２０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、１５質量％以下が好ましく、１０質量％以下がより好ましい。
　特定オキシム化合物の含有量は、脂環式エポキシ樹脂の１００質量部に対して１０～５０質量部であることが好ましい。上限は、４５質量部以下であることが好ましく、４０質量部以下であることがより好ましい。下限は、１５質量部以上であることが好ましく、２０質量部以上であることがより好ましい。
　光重合開始剤は、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 photopolymerization initiator in the total solid content of the colored composition is preferably 0.1 to 20% 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 15% by mass or less, more preferably 10% by mass or less.
The content of the specific oxime compound in the total solid content of the coloring composition is preferably 0.1 to 20% 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 15% by mass or less, more preferably 10% by mass or less.
The content of the specific oxime compound is preferably 10 to 50 parts by mass based on 100 parts by mass of the alicyclic epoxy resin. The upper limit is preferably 45 parts by mass or less, more preferably 40 parts by mass or less. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
The number of photoinitiators may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
＜＜溶剤＞＞
　本発明の着色組成物は、溶剤を含有する。溶剤としては、有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第２０１５／１６６７７９号の段落番号０２２３を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、２－ペンタノン、３－ペンタノン、４－ヘプタノン、シクロヘキサノン、２－メチルシクロヘキサノン、３－メチルシクロヘキサノン、４－メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、プロピレングリコールジアセテート、３－メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、１，４－ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン－１，３－ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール（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などが挙げられる。ただし有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 <<Solvent>>
The colored composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic 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, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy Butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
　本発明においては、金属含有量の少ない有機溶剤を用いることが好ましい。有機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 an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, 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 by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
　有機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 organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　有機溶剤は、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 organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
　有機溶剤中の過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 It is preferable that the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no 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い。上限は、９２．５質量％以下であることが好ましく、９０質量％以下であることがより好ましい。下限は、３０質量％以上であることが好ましく、５０質量％であることがより好ましく、７０質量％以上であることが更に好ましく、７５質量％以上であることがより一層好ましく、８０質量％以上であることが特に好ましい。 The content of the solvent in the coloring composition is preferably 10 to 95% by mass. The upper limit is preferably 92.5% by mass or less, more preferably 90% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 50% by mass, even more preferably 70% by mass or more, even more preferably 75% by mass or more, and even more preferably 80% by mass or more. It is particularly preferable that
　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。 The colored composition of the present invention preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations. In the present invention, "not substantially containing environmentally controlled substances" means that the content of environmentally controlled substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and It is registered as an environmentally regulated substance under the Transfer Register Act, VOC (Volatile Organic Compounds) regulations, etc., and its usage and handling are The method is 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 human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible. Examples of methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is also useful to carry out azeotropy with a solvent having the same boiling point as the relevant solvent in order to increase efficiency. In addition, if a compound that has radical polymerizability is contained, a polymerization inhibitor or the like may be added to prevent the radical polymerization reaction from proceeding during vacuum distillation and crosslinking between molecules. It's okay. These distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of colored compositions prepared by mixing these compounds. This is possible at any stage.
＜＜他の環状エーテル基を有する化合物＞＞
　本発明の着色組成物は、上述した脂環式エポキシ樹脂以外の環状エーテル基を有する化合物（他の環状エーテル基を有する化合物ともいう）を含有することができる。 <<Compounds having other cyclic ether groups>>
The coloring composition of the present invention can contain a compound having a cyclic ether group (also referred to as another compound having a cyclic ether group) other than the above-mentioned alicyclic epoxy resin.
　脂環式エポキシ化合物と、他の環状エーテル基を有する化合物とを併用することで、現像残渣の発生をより抑制することができる。また、本発明の着色組成物は、他の環状エーテル基を有する化合物を実質的に含まないことも好ましい。この態様によれば、耐熱収縮性をより向上させることができる。なお、本明細書において、他の環状エーテル基を有する化合物を実質的に含まないとは、着色組成物の全固形分中における他の環状エーテル基を有する化合物の含有量が０．１質量％以下であることを意味し、０．０１質量％以下であることが好ましく、他の環状エーテル基を有する化合物を含有しないことがより好ましい。 By using an alicyclic epoxy compound and another compound having a cyclic ether group in combination, the generation of development residues can be further suppressed. Moreover, it is also preferable that the colored composition of the present invention does not substantially contain other compounds having a cyclic ether group. According to this aspect, heat shrinkage resistance can be further improved. In addition, in this specification, "substantially not containing compounds having other cyclic ether groups" means that the content of compounds having other cyclic ether groups in the total solid content of the coloring composition is 0.1% by mass. It is preferably 0.01% by mass or less, and more preferably does not contain any other cyclic ether group-containing compound.
　脂環式エポキシ樹脂以外の環状エーテル基を有する化合物としては、式（ｅ－２）で表される基を有する化合物が挙げられる。
　式（ｅ－２）中、Ｒｅ２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。 Examples of compounds having a cyclic ether group other than alicyclic epoxy resins include compounds having a group represented by formula (e-2).
In formula (e-2), R e2 represents a hydrogen atom or an alkyl group, n represents 0 or 1, and * represents a bond.
　Ｒｅ２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。Ｒｅ２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 e2 is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group represented by R e2 is preferably linear or branched, more preferably linear.
　ｎが０のとき、Ｒｅ２は水素原子であることが好ましい。ｎが１のとき、Ｒｅ２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 e2 is preferably a hydrogen atom. When n is 1, R e2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
　他の環状エーテル基を有する化合物は、モノマーであってもよく、高分子化合物であってもよい。他の環状エーテル基を有する化合物がモノマーの場合、その分子量は１５００未満であることが好ましく、１００～１２５０であることがより好ましく、３００～１０００であることが更に好ましい。他の環状エーテル基を有する化合物が高分子化合物の場合、その重量平均分子量は１５００以上であることが好ましく、１７５０以上であることがより好ましく、２０００以上であることが更に好ましい。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い。 The other compound having a cyclic ether group may be a monomer or a polymer compound. When the compound having another cyclic ether group is a monomer, its molecular weight is preferably less than 1,500, more preferably from 100 to 1,250, and even more preferably from 300 to 1,000. When the compound having another cyclic ether group is a polymer compound, its weight average molecular weight is preferably 1,500 or more, more preferably 1,750 or more, and even more preferably 2,000 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less.
　他の環状エーテル基を有する化合物としては、エポキシ樹脂を好ましく用いることができる。エポキシ樹脂としては、例えばフェノール化合物のグリシジルエーテル化物であるエポキシ樹脂、各種ノボラック樹脂のグリシジルエーテル化物であるエポキシ樹脂、脂肪族エポキシ樹脂、グリシジルエステル系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ハロゲン化フェノール類をグリシジル化したエポキシ樹脂、エポキシ基をもつケイ素化合物とそれ以外のケイ素化合物との縮合物、エポキシ基を持つ重合性不飽和化合物とそれ以外の他の重合性不飽和化合物との共重合体等が挙げられる。 As another compound having a cyclic ether group, epoxy resin can be preferably used. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, aliphatic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, and halogenated phenols. Epoxy resins that are glycidylated, condensates of silicon compounds with epoxy groups and other silicon compounds, copolymers of polymerizable unsaturated compounds with epoxy groups and other polymerizable unsaturated compounds, etc. can be mentioned.
　他の環状エーテル基を有する化合物の市販品としては、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、オキセタニル基を有する化合物として、ＯＸＴ－１０１、ＯＸＴ－１２１、ＯＸＴ－２１２、ＯＸＴ－２２１（以上、東亞合成（株）製）、ＯＸＥ－１０、ＯＸＥ－３０（以上、大阪有機化学工業（株）製）などが挙げられる。また、他の環状エーテル基を有する化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６に記載された化合物、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６に記載された化合物、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物、特表２０２０－５１５６８０号公報の段落番号０１１７～０１２０に記載された化合物を用いることもできる。 Examples of commercially available compounds having other cyclic ether groups include EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation) as naphthalene-modified epoxy resins. Examples of the alkyl diphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation). As bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, Mitsubishi Ke Mical Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Co., Ltd.), etc. Bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (manufactured by DIC Corporation), LCE-21, RE-602S ( The above examples include those manufactured by Nippon Kayaku Co., Ltd.). Examples of phenol novolac type epoxy resins include jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (manufactured by DIC Corporation). ) etc. Can be mentioned. As cresol novolak type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-6 95 (manufactured by DIC Corporation) , EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.). As aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD Examples include PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (manufactured by Nagase ChemteX Corporation). In addition, as compounds having an oxetanyl group, OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd.), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Co., Ltd.). In addition, as other compounds having a cyclic ether group, compounds described in paragraph numbers 0034 to 0036 of JP-A No. 2013-011869 and compounds described in paragraph numbers 0147 to 0156 of JP-A-2014-043556 are included. , compounds described in paragraph numbers 0085 to 0092 of JP 2014-089408, compounds described in JP 2017-179172, and paragraphs 0117 to 0120 of JP 2020-515680. Compounds can also be used.
　着色組成物が他の環状エーテル基を有する化合物を含有する場合、他の環状エーテル基を有する化合物の含有量は、脂環式エポキシ樹脂の１００質量部に対して、５～３０質量部であることが好ましい。下限は７質量部以上であることが好ましく、１０質量部以上であることがより好ましい。上限は、２５質量部以下であることが好ましく、２０質量部以下であることがより好ましい。本発明の着色組成物は、他の環状エーテル基を有する化合物を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。他の環状エーテル基を有する化合物を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。 When the coloring composition contains a compound having another cyclic ether group, the content of the compound having another cyclic ether group is 5 to 30 parts by mass based on 100 parts by mass of the alicyclic epoxy resin. It is preferable. The lower limit is preferably 7 parts by mass or more, more preferably 10 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less. The colored composition of the present invention may contain only one type of compound having another cyclic ether group, or may contain two or more types of compounds. When two or more types of compounds having other cyclic ether groups are included, the total amount thereof is preferably within the above range.
＜＜顔料誘導体＞＞
　本発明の着色組成物は顔料誘導体を含有することができる。本発明の着色組成物に用いられる着色剤が顔料を含むものである場合には、本発明の着色組成物は顔料誘導体を含むことが好ましい。顔料誘導体は例えば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。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。 <<Pigment derivative>>
The colored composition of the present invention can contain a pigment derivative. When the coloring agent used in the coloring composition of the present invention contains a pigment, it is preferable that the coloring composition of the present invention contains a pigment derivative. Pigment derivatives are used, for example, as dispersion aids. A dispersion aid is a material for improving the dispersibility of pigments in a coloring composition. Examples of 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、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、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る。 The pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzimidazolone pigment skeleton, benzisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrrolopyrrole pigment. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Examples include isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, and pyrromethene dye skeleton.
　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。 Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide 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, Examples include phosphonium ions. 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 imide 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 , and -SO 2 NHSO 2 R X3 is more preferred. R X1 to R X6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R X1 to R X6 may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.
　塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。 Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
　顔料誘導体には、可視透明性に優れた顔料誘導体（以下、透明顔料誘導体ともいう）を用いることもできる。透明顔料誘導体の４００～７００ｎｍの波長領域におけるモル吸光係数の最大値（εｍａｘ）は３０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることが好ましく、１０００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがより好ましく、１００Ｌ・ｍｏｌ－１・ｃｍ－１以下であることがさらに好ましい。εｍａｘの下限は、例えば１Ｌ・ｍｏｌ－１・ｃｍ－１以上であり、１０Ｌ・ｍｏｌ－１・ｃｍ－１以上でもよい。 As the pigment derivative, a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used. The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L·mol −1 ·cm −1 or less, and preferably 1000 L·mol −1 ·cm −1 or less. is more preferable, and even more preferably 100 L·mol −1 ·cm −1 or less. The lower limit of εmax is, for example, 1 L·mol −1 ·cm −1 or more, and may be 10 L·mol −1 ·cm −1 or more.
　顔料誘導体の具体例としては、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、特開２０１８－１６８２４４号公報に記載のベンゾイミダゾロン化合物又はそれらの塩が挙げられる。 Specific examples of pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, and JP-A-03-1999. Compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in JP-A No. 06-145546, compounds described in JP-A No. 06-212088, compounds described in JP-A No. 06-240158, compounds described in JP-A No. 10-030063 Compounds described in JP-A-10-195326, compounds described in paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399. Compounds, compounds described in paragraph number 0082 of International Publication No. 2017/038252, compounds described in paragraph number 0171 of JP 2015-151530, paragraphs 0162 to 0183 of JP 2011-252065, Compounds, compounds described in JP 2003-081972, compounds described in JP 5299151, compounds described in JP 2015-172732, compounds described in JP 2014-199308, JP Compounds described in JP 2014-085562, compounds described in JP 2014-035351, compounds described in JP 2008-081565, compounds described in JP 2019-109512, JP 2019- Examples include the compound described in JP-A No. 133154, the diketopyrrolopyrrole compound having a thiol linking group described in International Publication No. 2020/002106, and the benzimidazolone compound or salt thereof described in JP-A No. 2018-168244. .
　顔料誘導体の含有量は、顔料１００質量部に対して１～３０質量部が好ましく、３～２０質量部が更に好ましい。また、顔料誘導体と着色剤との合計の含有量は、着色組成物の全固形分中３０質量％以上であることが好ましく、３５質量％以上がより好ましく、４０質量％以上が更に好ましい。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く、６５質量％以下であることが更に好ましい。本発明の着色組成物は、顔料誘導体を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。顔料誘導体を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 pigment derivative is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the pigment. Further, the total content of the pigment derivative and the colorant is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more based on the total solid content of the coloring composition. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. The colored composition of the present invention may contain only one kind of pigment derivative, or may contain two or more kinds of pigment derivatives. When two or more types of pigment derivatives 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。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る。ポリアルキレンイミンは、２級アミノ基を少なくとも有するポリマーであることが好ましい。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 colored composition of the present invention can also contain polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersion aids for pigments. Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine. The polyalkyleneimine is preferably a polymer having 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 containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively. The alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even 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 polyalkylene imine 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 polyalkylene imine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula. On the other hand, if the molecular weight of a 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. In addition, if measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) 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, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all 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. Further, the content of polyalkyleneimine is preferably 0.5 to 20 parts by weight per 100 parts by weight 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 type of polyalkylene imine 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.
＜＜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 colored composition of the present invention can contain a curing accelerator. Examples of the curing accelerator 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 International Publication No. 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, and JP 2013-041165. Compounds described in paragraph numbers 0186 to 0251 of JP-A No. 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP-A-2012-150180, JP-A-2011-253054 Examples include alkoxysilane compounds having an epoxy group as described in Japanese Patent Publication No. 5765059, compounds described in paragraph numbers 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in Japanese Patent Application Publication No. 2017-036379. The content of the curing accelerator in the total solid content of the colored 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、ジベンゾイル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、国際公開第２０２１／１３１３５５号の段落番号００５２、００７４、国際公開第２０２１／１３２２４７号の段落番号００２２～００２４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。紫外線吸収剤の具体例としては、下記構造の化合物などが挙げられる。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。
<<Ultraviolet absorber>>
The colored composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like.
Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A. 0334, paragraph numbers 0061 to 0080 of JP 2016-162946, paragraph numbers 0052 and 0074 of International Publication No. 2021/131355, and paragraph numbers 0022 to 0024 of International Publication No. 2021/132247. , the contents of which are incorporated herein. Specific examples of ultraviolet absorbers include compounds having the following structures. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. . Furthermore, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016). In addition, the ultraviolet absorbers include compounds described in paragraph numbers 0049 to 0059 of Patent No. 6268967, compounds described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and compounds described in International Publication No. 2020/137819. It is also possible to use the thioaryl group-substituted benzotriazole type ultraviolet absorbers described in .
　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％が好ましく、０．０１～５質量％がより好ましい。紫外線吸収剤は、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 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. The number of ultraviolet absorbers may be one type or two or more types. In the case of two or more types, it is preferable that their total amount falls 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 colored 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), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 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. The number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls 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。本明細書において、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 colored composition of the present invention can contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is 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 groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable. Specific examples of silane coupling agents 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 Examples include 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. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and compounds described in paragraph numbers 0056 to 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 type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that their total amount falls 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、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、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 colored 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 surfactant or a fluorine surfactant. Regarding the surfactant, reference can be made to the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.
　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。 Examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and the like; Examples include the surfactants described in paragraph numbers 0117 to 0132 of Publication No. 132503 and the 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, 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), Florado FC430, FC431, FC171 (all manufactured by Sumitomo 3M 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 Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710 FM, 710FS , FTX-218 (manufactured by NEOS Co., Ltd.), 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。 Fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is severed and the fluorine atom volatizes. Can be used. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)); Fuck DS-21 is an example.
　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。 As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Examples of such fluorine-based surfactants include the fluorine-based surfactants described in JP-A No. 2016-216602, the content of which is 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。
　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 fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraph numbers 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion 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。 Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 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。 Furthermore, 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 a surfactant having a perfluoroalkyl group having 6 or more carbon atoms.
　また、式（ｆｉ－１）で表される含フッ素イミド塩化合物を界面活性剤として用いることも好ましい。
　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.
In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X a+ represents an a-valent metal ion, a primary ammonium ion, a Represents a secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（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。 Examples of 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 Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa (manufactured by Hikari Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) ), etc.
　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。 Examples of silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TS. F-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。
Moreover, a compound having the following structure can also be used as the silicone surfactant.
　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% to 3.0% by mass. The number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
＜＜環状シロキサン化合物＞＞
　本発明の着色組成物は、環状シロキサン化合物を含有することができる。本発明の着色組成物がシリコーン系界面活性剤を含む場合、着色組成物は、更に環状シロキサン化合物を含むことが好ましい。環状シロキサン化合物を含有することで、塗布時における膜厚均一性をより向上させることができ、表面の平滑性に優れた膜を形成することができる。ここで、環状シロキサン化合物とは、シロキサン結合により形成された環状化合物のことを意味する。 <<Cyclic siloxane compound>>
The colored composition of the present invention can contain a cyclic siloxane compound. When the colored composition of the present invention contains a silicone surfactant, it is preferable that the colored composition further contains a cyclic siloxane compound. By containing a cyclic siloxane compound, the uniformity of the film thickness during coating can be further improved, and a film with excellent surface smoothness can be formed. Here, the cyclic siloxane compound means a cyclic compound formed by siloxane bonds.
　環状シロキサン化合物は、式（Ｓｉ－１）で表される化合物であることが好ましい。
　式（Ｓｉ－１）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表し、ｍは３～２０の整数を表す。 The cyclic siloxane compound is preferably a compound represented by formula (Si-1).
In formula (Si-1), R 1 and R 2 each independently represent a hydrogen atom or a substituent, and m represents an integer of 3 to 20.
　式（Ｓｉ－１）のＲ１およびＲ２が表す置換基としては、アルキル基およびアリール基が挙げられ、アルキル基であることが好ましい。 Examples of the substituent represented by R 1 and R 2 in formula (Si-1) include an alkyl group and an aryl group, with an alkyl group being preferred.
　アルキル基の炭素数は１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、１が特に好ましい。上記アルキル基は直鎖または分岐のいずれでもよいが、直鎖であることが好ましい。
　アリール基の炭素数は６～２０が好ましく、６～１２がより好ましく、６であることが特に好ましい。
　Ｒ１およびＲ２は、それぞれ独立して、水素原子、メチル基またはフェニル基であることが好ましく、メチル基であることがより好ましい。 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. The alkyl group may be linear or branched, but is preferably linear.
The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6.
R 1 and R 2 are each independently preferably a hydrogen atom, a methyl group or a phenyl group, and more preferably a methyl group.
　式（Ｓｉ－１）のｍは３～２０の整数を表し、３～１０の整数であることが好ましく、３～８の整数であることがより好ましく、３～６の整数であることが更に好ましく、４～６の整数であることが特に好ましい。 m in formula (Si-1) represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and even more preferably an integer of 3 to 6. Preferably, an integer of 4 to 6 is particularly preferable.
　環状シロキサン化合物の分子量は１０００以下であることが好ましく、８００以下であることがより好ましく、６００以下であることが更に好ましい。下限は、１００以上とすることができる。 The molecular weight of the cyclic siloxane compound is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. The lower limit can be 100 or more.
　環状シロキサン化合物の具体例としては、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、ヘキサメチルシクロトリシロキサンなどが挙げられ、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサンおよびドデカメチルシクロヘキサシロキサンから選ばれる少なくとも１種であることが好ましい。 Specific examples of cyclic siloxane compounds include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethylcyclotrisiloxane, etc.; Preferably, it is at least one selected from methylcyclohexasiloxane.
　本発明の着色組成物は、環状シロキサン化合物を１種のみ含んでいてもよいが、環状シロキサン化合物を２種以上含むことが好ましい。環状シロキサン化合物を２種以上含む場合、上記式（１）のｍが３または４である化合物（好ましくは、ｍが４である化合物）と、上記式（１）のｍが５以上の整数である化合物（好ましくは、ｍが５～１０の整数である化合物、より好ましくは、ｍが５～８の整数である化合物、ｍが５または６である化合物）とをそれぞれ含むことが好ましい。また、上記式（Ｓｉ－１）のｍが３または４である化合物と、上記式（Ｓｉ－１）のｍが５以上の整数である化合物との割合は、上記式（Ｓｉ－１）のｍが３または４である化合物の１００質量部に対して、上記式（Ｓｉ－１）のｍが５以上の整数である化合物が１０～１０００質量部であることが好ましく、２５～７５０質量部であることがより好ましく、５０～５００質量部であることが更に好ましい。 The colored composition of the present invention may contain only one type of cyclic siloxane compound, but preferably contains two or more types of cyclic siloxane compounds. When two or more types of cyclic siloxane compounds are included, a compound in which m in the above formula (1) is 3 or 4 (preferably a compound in which m is 4), and a compound in which m in the above formula (1) is an integer of 5 or more. A certain compound (preferably a compound where m is an integer of 5 to 10, more preferably a compound where m is an integer of 5 to 8, a compound where m is 5 or 6) is preferably included. Further, the ratio of the compound in which m in the above formula (Si-1) is 3 or 4 and the compound in which m in the above formula (Si-1) is an integer of 5 or more is For 100 parts by mass of the compound in which m is 3 or 4, the compound in the above formula (Si-1) where m is an integer of 5 or more is preferably 10 to 1000 parts by mass, and 25 to 750 parts by mass. More preferably, the amount is 50 to 500 parts by mass.
　環状シロキサン化合物は、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサンおよびドデカメチルシクロヘキサシロキサン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、オクタメチルシクロテトラシロキサンとデカメチルシクロペンタシロキサンとドデカメチルシクロヘキサシロキサンを含むものであることがより好ましい。
　また、環状シロキサン化合物は、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサンおよびドデカメチルシクロヘキサシロキサンから選ばれる少なくとも１種であることが好ましく、オクタメチルシクロテトラシロキサンと、デカメチルシクロペンタシロキサンと、ドデカメチルシクロヘキサシロキサンとで構成されているものであることがより好ましい。 The cyclic siloxane compound preferably contains at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; More preferably, it contains sasiloxane.
Further, the cyclic siloxane compound is preferably at least one selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, More preferably, it is composed of dodecamethylcyclohexasiloxane.
　環状シロキサン化合物として、オクタメチルシクロテトラシロキサンと、デカメチルシクロペンタシロキサンと、ドデカメチルシクロヘキサシロキサンとを含むものを用いた場合、オクタメチルシクロテトラシロキサンとデカメチルシクロペンタシロキサンと、ドデカメチルシクロヘキサシロキサンとの割合は、ドデカメチルシクロヘキサシロキサンの１００質量部に対してオクタメチルシクロテトラシロキサンが１～１００質量部で、デカメチルシクロペンタシロキサンが５０～２００質量部であることが好ましい。オクタメチルシクロテトラシロキサンは、ドデカメチルシクロヘキサシロキサンの１００質量部に対して１～１００質量部であることが好ましく、１０～５０質量部であることがより好ましい。デカメチルシクロペンタシロキサンは、ドデカメチルシクロヘキサシロキサンの１００質量部に対して１～２００質量部であることが好ましく、５０～１５０質量部であることがより好ましい。 When using a cyclic siloxane compound containing octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are used. The ratio of octamethylcyclotetrasiloxane to 100 parts by mass of dodecamethylcyclohexasiloxane and siloxane is preferably 1 to 100 parts by mass, and 50 to 200 parts by mass of decamethylcyclopentasiloxane. The amount of octamethylcyclotetrasiloxane is preferably 1 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of dodecamethylcyclohexasiloxane. The amount of decamethylcyclopentasiloxane is preferably 1 to 200 parts by weight, more preferably 50 to 150 parts by weight, per 100 parts by weight of dodecamethylcyclohexasiloxane.
　着色組成物の全固形分中における環状シロキサン化合物の含有量は、０．００１～１質量％であることが好ましく、０．００１５～０．５質量％であることがより好ましい。 The content of the cyclic siloxane compound in the total solid content of the coloring composition is preferably 0.001 to 1% by mass, more preferably 0.0015 to 0.5% by mass.
　着色組成物が、シリコーン系界面活性剤と環状シロキサン化合物とを含む場合、環状シロキサン化合物の含有量は、シリコーン系界面活性剤の１００質量部に対して０．０１～１０質量部であることが好ましい。下限は、０．１質量部以上であることが好ましく、０．５質量部以上であることがより好ましい。上限は、５質量部以下であることが好ましく、４質量部以下であることがより好ましく、３質量部以下であることがより好ましい。
　本発明の組成物が環状シロキサン化合物を２種以上含む場合は、それらの合計量が上記範囲であることが好ましい。 When the coloring composition contains a silicone surfactant and a cyclic siloxane compound, the content of the cyclic siloxane compound is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the silicone surfactant. preferable. The lower limit is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more. The upper limit is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less.
When the composition of the present invention contains two or more types of cyclic siloxane compounds, it is preferable that the total amount thereof is within the above range.
＜＜酸化防止剤＞＞
　本発明の着色組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤などが挙げられる。フェノール系酸化防止剤としては、ヒンダードフェノール化合物が挙げられる。フェノール系酸化防止剤は、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 colored composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Examples of phenolic antioxidants include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position). The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-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, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, 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 Co., Ltd.). In addition, antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 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 type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls 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 contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.) may also be included. By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, the colored composition of the present invention may contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles 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 colored 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 diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. Further, 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 colored composition of the present invention may also contain a lightfastness improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP 2017-198787, compounds described in paragraph numbers 0029 to 0034 of JP 2017-146350, JP 2017-129774, Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674, compounds described in paragraph numbers 0031 to 0034, 0058 to 0059 of JP 2017-122803, paragraph numbers 0036 to 0037 of JP 2017-122803. , compounds described in paragraph numbers 0025 to 0039 of International Publication No. 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 No. 2012-145604, compounds described in paragraph numbers 0018 to 0021 of JP-A-2012-103475, Compounds described in paragraph numbers 0015 to 0018 of JP 2011-257591, compounds described in paragraph numbers 0017 to 0021 of JP 2011-191483, and paragraph numbers 0108 to 0116 of JP 2011-145668. and the compounds described in paragraph numbers 0103 to 0153 of JP-A No. 2011-253174.
　本発明の着色組成物は、テレフタル酸エステルを実質的に含まないことも好ましい。ここで、「実質的に含まない」とは、テレフタル酸エステルの含有量が、着色組成物の全量中、１０００質量ｐｐｂ以下であることを意味し、１００質量ｐｐｂ以下であることがより好ましく、ゼロであることが特に好ましい。 It is also preferable that the colored composition of the present invention is substantially free of terephthalic acid ester. Here, "substantially not containing" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
　本発明の着色組成物は、遊離の金属含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましい。金属の種類は特に限定されないが、アルカリ金属、アルカリ土類金属、遷移金属、Ａｌ、Ｓｎ、Ｐｂ、Ｂｉなどが挙げられる。また、遊離のハロゲン含有量は１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましい。着色組成物中の遊離の金属やハロゲンの低減方法としては、イオン交換水による洗浄、ろ過、限外ろ過、イオン交換重視による精製等の方法が挙げられる。 The colored composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The type of metal is not particularly limited, but examples include alkali metals, alkaline earth metals, transition metals, Al, Sn, Pb, Bi, and the like. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the colored composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with emphasis on ion exchange.
　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 perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be regulated. In the coloring composition of the present invention, when reducing the content of the above-mentioned compounds, perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms), salts thereof, and perfluoroalkylsulfonic acids, The content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the coloring composition. It 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 salt, and perfluoroalkylcarboxylic acid and its salt. For example, by using a compound that can be substituted for perfluoroalkylsulfonic acid and its salt, and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid You may select a coloring composition that is substantially free of and salts thereof. Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not preclude the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The colored compositions of the present invention may include perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, to the maximum extent permissible.
　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 colored composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and 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 colored composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface condition (flatness, etc.), adjusting the film thickness, etc. The value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa·s to 50 mPa·s is preferable, and 0.5 mPa·s to 20 mPa·s is more preferable. The viscosity can be measured using, for example, a cone plate type viscometer with the temperature 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。 <<Storage container>>
The container for storing the coloring composition is not particularly limited, and any known container can be used. In addition, for the purpose of suppressing impurities from entering raw materials and coloring compositions, we also use multilayer bottles with container inner walls made of 6 types of 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, increasing the storage stability of the coloring composition, and suppressing component deterioration.
＜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 colored composition>
The colored composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a colored composition, the colored composition may be prepared by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be prepared as two or more solutions or dispersions as appropriate. A colored composition may be prepared by mixing these at the time of use (at the time of application).
　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。分散に使用するビーズの素材としては、ジルコニア、メノウ、石英、チタニア、タングステンカーバイト、窒化ケイ素、アルミナ、ステンレス鋼およびガラスが挙げられる。また、ビーズには、モース硬度が２以上の無機化合物を使用することもできる。組成物中に上記ビーズが１～１００００ｐｐｍ含まれていてもよい。 Preferably, the preparation of the colored composition includes a process of dispersing the pigment. 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 addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the particles may be made finer in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Moreover, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The composition may contain 1 to 10,000 ppm of the beads.
　着色組成物の調製に際して、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）及びナイロンが好ましい。 When 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 and the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) Examples include filters using materials such as high-density, ultra-high molecular weight polyolefin resins. 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）及び株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used. .
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えば、ポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。また着色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。 It is also preferable to use a fiber-like filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003, etc.) manufactured by Loki Techno. 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 two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed. Further, a filter can be appropriately selected depending on the hydrophilicity and hydrophobicity of the colored composition.
＜膜＞
　本発明の膜は、上述した本発明の着色組成物から得られる膜である。本発明の膜は、カラーフィルタや赤外線透過フィルタなどの光学フィルタに用いることができる。 <Membrane>
The film of the present invention is a film obtained from the colored composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters and infrared transmission filters.
　本発明の膜の膜厚は、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 of the present invention can be adjusted as appropriate depending on 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.
　本発明の膜をカラーフィルタとして用いる場合、本発明の膜は、緑色、赤色、青色、シアン色、マゼンタ色または黄色の色相を有することが好ましく、緑色、赤色または黄色の色相を有することがより好ましい。また、本発明の膜は、カラーフィルタの着色画素として好ましく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る。 When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue, more preferably a green, red, or yellow hue. preferable. Further, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
　本発明の膜を赤外線透過フィルタとして用いる場合、本発明の膜は、以下の（１）～（４）のいずれかの分光特性を有することが好ましい。
　（１）：膜の厚み方向における光透過率の、波長４００～６４０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）で、膜の厚み方向における光透過率の、波長８００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である。このような分光特性を有する膜は、波長４００～６４０ｎｍの範囲の光を遮光して、波長７００ｎｍを超える光を透過させることができる。
　（２）：膜の厚み方向における光透過率の、波長４００～７５０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）で、膜の厚み方向における光透過率の、波長９００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である膜。このような分光特性を有する膜は、波長４００～７５０ｎｍの範囲の光を遮光して、波長８５０ｎｍを超える光を透過させることができる。
　（３）：膜の厚み方向における光透過率の、波長４００～８３０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）で、膜の厚み方向における光透過率の、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である膜。このような分光特性を有する膜は、波長４００～８３０ｎｍの範囲の光を遮光して、波長９４０ｎｍを超える光を透過させることができる。
　（４）：膜の厚み方向における光透過率の、波長４００～９５０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）で、膜の厚み方向における光透過率の、波長１１００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である膜。このような分光特性を有する膜は、波長４００～９５０ｎｍの範囲の光を遮光して、波長１０４０ｎｍを超える光を透過させることができる。 When the film of the present invention is used as an infrared transmission filter, the film of the present invention preferably has any of the following spectral properties (1) to (4).
(1): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is The minimum value of the ratio in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light with wavelengths exceeding 700 nm.
(2): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1300 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light with a wavelength exceeding 850 nm.
(3): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1300 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light with a wavelength exceeding 940 nm.
(4): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmission in the thickness direction of the film is A film having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. A film having such spectral characteristics can block light in a wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1040 nm.
＜画素の製造方法＞
　本発明の着色組成物を用いた画素の製造方法について説明する。画素の製造方法は、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。 <Pixel manufacturing method>
A method for manufacturing pixels using the coloring composition of the present invention will be explained. The method for manufacturing a pixel includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer to light in a pattern, and an unexposed part of the colored composition layer. It is preferable to include a step of developing and removing to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
　着色組成物層を形成する工程では、本発明の着色組成物を用いて、支持体上に着色組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下地層が設けられていてもよい。下地層の表面接触角は、ジヨードメタンで測定した際に２０～７０°であることが好ましい。また、水で測定した際に３０～８０°であることが好ましい。 In the step of forming a colored composition layer, a colored composition layer is formed on a support using the colored composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable. Further, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. Further, a black matrix that isolates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 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 to apply the coloring composition. For example, dropping method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; Methods described in publications); inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include various printing methods; transfer method using a mold, etc.; nanoimprint method, etc. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned. Further, regarding the method of applying the coloring composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and the contents of these 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 (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking 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, or 80°C or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, 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 it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to 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 during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, 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。 Furthermore, during exposure, light may be exposed by continuous irradiation, or exposure may be performed by irradiation in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば、酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ２～１０００００Ｗ／ｍ２（例えば、５０００Ｗ／ｍ２、１５０００Ｗ／ｍ２、または、３５０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 . The oxygen concentration during exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be carried out in an oxygen-free environment (without oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 vol% (for example, 22 vol%, 30 vol%, or 50 vol%). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). I can do it. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 10,000 W/m 2 at an oxygen concentration of 10% by volume, or 20,000 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、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the unexposed portions of the colored composition layer are developed and removed to form a pattern (pixel). The unexposed areas of the colored composition layer can be removed by development using a developer. As a result, the unexposed portions of the colored composition layer in the exposure step are eluted into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
　現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液（アルカリ現像液）が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の着色組成物層が形成された支持体を回転させつつ、現像後の着色組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. As for the alkali agent, compounds with a large molecular weight are preferable from the environmental and safety standpoints. 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. For convenience in transportation and storage, the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, rinsing is preferably performed by supplying a rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle that discharges the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when moving the nozzle from the center of the support to the peripheral edge, the nozzle may be moved while gradually decreasing its moving speed. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. The same effect can also be obtained by gradually reducing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.
　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、１００～３００℃が好ましく、２００～２７０℃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 treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions. . When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
＜光学フィルタ＞
　本発明の光学フィルタは、上述した本発明の膜を有する。光学フィルタの種類としては、カラーフィルタおよび赤外線透過フィルタなどが挙げられ、カラーフィルタであることが好ましい。カラーフィルタは、その着色画素として本発明の膜を有することが好ましい。 <Optical filter>
The optical filter of the present invention has the film of the present invention described above. Types of optical filters include color filters and infrared transmission filters, and color filters are preferred. Preferably, the color filter has the film of the present invention as its colored pixels.
　光学フィルタにおいて、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、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。 In the optical filter, the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. 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.
　光学フィルタに含まれる画素の幅は０．４～１０．０μｍ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。また、画素のヤング率は０．５～２０ＧＰａであることが好ましく、２．５～１５ＧＰａがより好ましい。 The width of the pixels included in the optical filter is preferably 0.4 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. Furthermore, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
　光学フィルタに含まれる各画素は高い平坦性を有することが好ましい。具体的には、画素の表面粗さＲａは、１００ｎｍ以下であることが好ましく、４０ｎｍ以下であることがより好ましく、１５ｎｍ以下であることが更に好ましい。下限は規定されないが、例えば０．１ｎｍ以上であることが好ましい。画素の表面粗さは、例えばＶｅｅｃｏ社製のＡＦＭ（原子間力顕微鏡）　Ｄｉｍｅｎｓｉｏｎ３１００を用いて測定することができる。また、画素上の水の接触角は適宜好ましい値に設定することができるが、典型的には、５０～１１０°の範囲である。接触角は、例えば接触角計ＣＶ－ＤＴ・Ａ型（協和界面科学（株）製）を用いて測定できる。また、画素の体積抵抗値は高いことが好ましい。具体的には、画素の体積抵抗値は１０９Ω・ｃｍ以上であることが好ましく、１０１１Ω・ｃｍ以上であることがより好ましい。上限は規定されないが、例えば１０１４Ω・ｃｍ以下であることが好ましい。画素の体積抵抗値は、超高抵抗計５４１０（アドバンテスト社製）を用いて測定することができる。 It is preferable that each pixel included in the optical filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. Further, the contact angle of water on the pixel can be set to a suitable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. Although the upper limit is not specified, it is preferably 10 14 Ω·cm or less, for example. The volume resistance value of a pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
　光学フィルタにおいては、本発明の膜の表面に保護層が設けられていてもよい。保護層を設けることで、酸素遮断化、低反射化、親疎水化、特定波長の光（紫外線、近赤外線等）の遮蔽等の種々の機能を付与することができる。保護層の厚さとしては、０．０１～１０μｍが好ましく、０．１～５μｍがより好ましい。保護層の形成方法としては、保護層形成用の組成物を塗布して形成する方法、化学気相蒸着法、成型した樹脂を接着材で貼りつける方法等が挙げられる。保護層を構成する成分としては、（メタ）アクリル樹脂、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、ポリオール樹脂、ポリ塩化ビニリデン樹脂、メラミン樹脂、ウレタン樹脂、アラミド樹脂、ポリアミド樹脂、アルキド樹脂、エポキシ樹脂、変性シリコーン樹脂、フッ素樹脂、ポリアクリロニトリル樹脂、セルロース樹脂、Ｓｉ、Ｃ、Ｗ、Ａｌ２Ｏ３、Ｍｏ、ＳｉＯ２、Ｓｉ２Ｎ４などが挙げられ、これらの成分を二種以上含有しても良い。例えば、酸素遮断化を目的とした保護層の場合、保護層はポリオール樹脂と、ＳｉＯ２と、Ｓｉ２Ｎ４を含むことが好ましい。また、低反射化を目的とした保護層の場合、保護層は（メタ）アクリル樹脂とフッ素樹脂を含むことが好ましい。 In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended for oxygen blocking, the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 . Furthermore, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
　保護層は、必要に応じて、有機・無機微粒子、特定波長の光（例えば、紫外線、近赤外線等）の吸収剤、屈折率調整剤、酸化防止剤、密着剤、界面活性剤等の添加剤を含有しても良い。有機・無機微粒子の例としては、例えば、高分子微粒子（例えば、シリコーン樹脂微粒子、ポリスチレン微粒子、メラミン樹脂微粒子）、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化インジウム、酸化アルミニウム、窒化チタン、酸窒化チタン、フッ化マグネシウム、中空シリカ、シリカ、炭酸カルシウム、硫酸バリウム等が挙げられる。特定波長の光の吸収剤は公知の吸収剤を用いることができる。これらの添加剤の含有量は適宜調整できるが、保護層の全質量に対して０．１～７０質量％が好ましく、１～６０質量％がさらに好ましい。 The protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain. Examples of organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. As the absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
　また、保護層としては、特開２０１７－１５１１７６号公報の段落番号００７３～００９２に記載の保護層を用いることもできる。 Furthermore, as the protective layer, the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.
　光学フィルタは、隔壁により例えば格子状に仕切られた空間に、各画素が埋め込まれた構造を有していてもよい。 The optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.
＜固体撮像素子＞
　本発明の固体撮像素子は、上述した本発明の膜を有する。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。 <Solid-state image sensor>
The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, but examples include the following configurations.
　基板上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、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な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。 The substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film. Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter, etc. There may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018/043654. Further, as shown in Japanese Patent Application Laid-open No. 2019-211559, an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.
＜画像表示装置＞
　本発明の画像表示装置は、上述した本発明の膜を有する。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。 <Image display device>
The image display device of the present invention has the film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of an image display device and details of each image display device, see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho)”. Co., Ltd., issued in 1989). Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."
　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。また、以下に示す構造式中、Ｅｔはエチル基を表し、ｉＰｒはイソプロピル基を表す。 The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Further, in the structural formula shown below, Et represents an ethyl group, and iPr represents an isopropyl group.
＜分散液の製造＞
　下記表に記載の素材を混合した混合液を、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。次いで、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回繰り返して、分散液を得た。なお、以下の表において、配合量の欄に記載の数値の単位は質量部である。 <Production of dispersion>
A mixture of the materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter). Next, dispersion treatment was performed using a high-pressure dispersion machine NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under conditions of a pressure of 2000 kg/cm 2 and a flow rate of 500 g/min. This dispersion treatment was repeated a total of 10 times to obtain a dispersion liquid. In addition, in the following table, the unit of the numerical value described in the column of compounding amount is mass parts.
　上記表の略語で記載の素材は以下の通りである。 The materials listed with abbreviations in the table above are as follows.
（着色剤）
　ＰＹ１３９　：　Ｃ．Ｉ．ピグメントイエロー１３９
　ＰＹ１５０　：　Ｃ．Ｉ．ピグメントイエロー１５０
　ＰＹ１８５　：　Ｃ．Ｉ．ピグメントイエロー１８５
　ＰＢ１５：４　：　Ｃ．Ｉ．ピグメントブルー１５：４
　ＰＢ１５：６　：　Ｃ．Ｉ．ピグメントブルー１５：６
　ＰＧ７　：　Ｃ．Ｉ．ピグメントグリーン７
　ＰＧ３６　：　Ｃ．Ｉ．ピグメントグリーン３６
　ＰＧ５８　：　Ｃ．Ｉ．ピグメントグリーン５８
　ＰＧ５９　：　Ｃ．Ｉ．ピグメントグリーン５９
　ＰＲ１２２　：　Ｃ．Ｉ．ピグメントレッド１２２
　ＰＲ２５４　：　Ｃ．Ｉ．ピグメントレッド２５４
　ＰＲ２６４　：　Ｃ．Ｉ．ピグメントレッド２６４
　ＰＲ２７２　：　Ｃ．Ｉ．ピグメントレッド２７２
　ＰＲ２９１　：　Ｃ．Ｉ．ピグメントレッド２９１
　ＰＶ２３　：　Ｃ．Ｉ．ピグメントバイオレット２３ (colorant)
PY139: C. I. pigment yellow 139
PY150: C. I. pigment yellow 150
PY185: C. I. pigment yellow 185
PB15:4: C. I. pigment blue 15:4
PB15:6: C. I. pigment blue 15:6
PG7: C. I. pigment green 7
PG36: C. I. pigment green 36
PG58: C. I. pigment green 58
PG59: C. I. pigment green 59
PR122: C. I. pigment red 122
PR254: C. I. pigment red 254
PR264: C. I. pigment red 264
PR272: C. I. pigment red 272
PR291: C. I. pigment red 291
PV23: C. I. pigment violet 23
（分散剤）
　Ａ－１：以下の方法で合成した樹脂（多環式脂肪族炭化水素環を有する脂環式エポキシ基を有する樹脂）
　還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流し、窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）の３４０質量部を入れ、撹拌しながら８０℃まで加熱した。次いで、アクリル酸の５７質量部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（含有比はモル比で１：１）の５４質量部、ベンジルメタクリレートの２３９質量部、ＰＧＭＥＡの７３質量部の混合溶液を５時間かけて滴下した。次いで、重合開始剤（２，２－アゾビス（２，４－ジメチルバレロニトリル））の４０質量部をＰＧＭＥＡの１９７質量部に溶解した溶液を６時間かけて滴下した。重合開始剤溶液の滴下終了後、８０℃で３時間保持した後、室温まで冷却して下記構造の樹脂を得た。得られた樹脂の重量平均分子量は９４００、分散度は１．８９、酸価は１１４ｍｇＫＯＨ／ｇであった。
(dispersant)
A-1: Resin synthesized by the following method (resin having an alicyclic epoxy group having a polycyclic aliphatic hydrocarbon ring)
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 340 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was added thereto and heated to 80° C. with stirring. Then, 57 parts by weight of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 A mixed solution of 54 parts by mass of a mixture of decane-9-yl acrylate (content ratio is 1:1 in molar ratio), 239 parts by mass of benzyl methacrylate , and 73 parts by mass of PGMEA was added dropwise over 5 hours. . Next, a solution of 40 parts by mass of a polymerization initiator (2,2-azobis(2,4-dimethylvaleronitrile)) dissolved in 197 parts by mass of PGMEA was added dropwise over 6 hours. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 80° C. for 3 hours, and then cooled to room temperature to obtain a resin having the following structure. The weight average molecular weight of the obtained resin was 9400, the dispersity was 1.89, and the acid value was 114 mgKOH/g.
　Ａ－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２４０００）
A-2: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 24,000)
　Ａ－３：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１１０００）
A-3: Resin with the following structure (the numerical value appended to the main chain is the molar ratio. Weight average molecular weight 11000)
　Ａ－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２００００）
A-4: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
　Ａ－５：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）
A-5: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 16,000)
　Ａ－６：下記構造の樹脂（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２００００）
A-6: Resin with the following structure (the number appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
　Ａ－７：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２００００）
A-7: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 20,000)
　Ａ－８：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７０００）
A-8: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 7000)
　Ａ－９：以下の方法で合成した樹脂（脂環式エポキシ基を有する樹脂）
　樹脂Ａ－１の合成において、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物を、３，４－エポキシシクロヘキシルメチルメタクリレートに変更した以外は樹脂Ａ－１と同様の方法にて、下記構造の樹脂を得た。得られた樹脂の重量平均分子量は１００００であった。
A-9: Resin synthesized by the following method (resin having an alicyclic epoxy group)
In the synthesis of resin A-1, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 A resin having the following structure was obtained in the same manner as Resin A - 1 except that the mixture of decane-9-yl acrylate was changed to 3,4-epoxycyclohexylmethyl methacrylate. The weight average molecular weight of the obtained resin was 10,000.
（溶剤）
　Ｚ－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（ＰＧＭＥＡ） (solvent)
Z-1: Propylene glycol monomethyl ether acetate (PGMEA)
＜染料溶液の製造＞
　下記表に記載の素材を混合して染料溶液Ｘ－１～Ｘ－３を製造した。なお、以下の表において、配合量の欄に記載の数値の単位は質量部である。 <Manufacture of dye solution>
Dye solutions X-1 to X-3 were prepared by mixing the materials listed in the table below. In addition, in the following table, the unit of the numerical value described in the column of compounding amount is mass parts.
　上記表の略語で記載の素材は以下の通りである。 The materials listed with abbreviations in the table above are as follows.
（染料）
　染料１：下記構造のキサンテン染料
　染料２：下記構造のキサンテン染料
　染料３：下記構造のキサンテン染料（重量平均分子量１００００）
(dye)
Dye 1: Xanthene dye with the following structure
Dye 2: Xanthene dye with the following structure
Dye 3: Xanthene dye with the following structure (weight average molecular weight 10,000)
（溶剤）
　Ｚ－４：シクロヘキサノン (solvent)
Z-4: Cyclohexanone
＜着色組成物の製造＞
　下記の表に記載の原料を混合して、着色組成物を製造した。なお、以下の表において、配合量の欄に記載の数値の単位は質量部である。 <Manufacture of colored composition>
A colored composition was produced by mixing the raw materials listed in the table below. In addition, in the following table, the unit of the numerical value described in the column of compounding amount is mass parts.
　上記表の略語で記載の原料は以下の通りである。 The raw materials listed with abbreviations in the table above are as follows.
（分散液）
　ＤＹ－１～ＤＹ－１４：上述した分散液ＤＹ－１～ＤＹ－１４
　ＤＢ－１、ＤＢ－２：上述した分散液ＤＢ－１、ＤＢ－２
　ＤＧ－１～ＤＧ－４：上述した分散液ＤＧ－１～ＤＧ－４
　ＤＲ－１～ＤＲ－５：上述した分散液ＤＲ－１～ＤＲ－５
　ＤＶ－１：上述した分散液ＤＶ－１ (Dispersion liquid)
DY-1 to DY-14: Dispersions DY-1 to DY-14 described above
DB-1, DB-2: Dispersion liquid DB-1, DB-2 described above
DG-1 to DG-4: Dispersions DG-1 to DG-4 described above
DR-1 to DR-5: Dispersions DR-1 to DR-5 described above
DV-1: Dispersion liquid DV-1 described above
（染料溶液）
　Ｘ－１～Ｘ－３：上述した染料溶液Ｘ－１～Ｘ－３ (dye solution)
X-1 to X-3: Above-mentioned dye solutions X-1 to X-3
（バインダー）
　Ｂ－１：以下の方法で合成した樹脂（多環式脂肪族炭化水素環を有する脂環式エポキシ基を有する樹脂）のＰＧＭＥＡ溶液（固形分濃度４０質量％）
　還流冷却器、滴下ロート及び攪拌機を備えた１Ｌのフラスコ内に窒素を適量流し、窒素雰囲気に置換し、ＰＧＭＥＡの３７１質量部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸の５４質量部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８又は／及び９－イルアクリレートの混合物の２２５質量部、ビニルトルエン（異性体混合物）の８１質量部、ＰＧＭＥＡの８０質量部の混合溶液を４時間かけて滴下した。次いで、重合開始剤（２，２－アゾビス（２，４－ジメチルバレロニトリル））の３０質量部をＰＧＭＥＡの１６０質量部に溶解した溶液を５時間かけて滴下した。重合開始剤溶液の滴下終了後、４時間同温度で保持した後、室温まで冷却して目的の樹脂を得た。得られた樹脂の重量平均分子量は１０６００、分散度は２．０１であった。 (binder)
B-1: PGMEA solution (solid content concentration 40% by mass) of resin synthesized by the following method (resin having an alicyclic epoxy group having a polycyclic aliphatic hydrocarbon ring)
An appropriate amount of nitrogen was passed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 371 parts by mass of PGMEA was added thereto, and the flask was heated to 85° C. with stirring. Then, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8 or/and 9-yl acrylate, vinyltoluene (isomer A mixed solution of 81 parts by mass of the mixture) and 80 parts by mass of PGMEA was added dropwise over 4 hours. Next, a solution of 30 parts by mass of a polymerization initiator (2,2-azobis(2,4-dimethylvaleronitrile)) dissolved in 160 parts by mass of PGMEA was added dropwise over 5 hours. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain the desired resin. The weight average molecular weight of the obtained resin was 10,600, and the degree of dispersion was 2.01.
　Ｂ－２：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量１１０００）のＰＧＭＥＡ溶液（固形分濃度４０質量％）
　Ｂ－３：下記構造の樹脂（主鎖に付記した数値はモル比である。重量平均分子量３００００）のＰＧＭＥＡ溶液（固形分濃度４０質量％）
　Ｂ－４：下記構造の樹脂（主鎖に付記した数値は質量比である。重量平均分子量１４６００）のＰＧＭＥＡ溶液（固形分濃度４０質量％）
　Ｂ－５：下記構造の樹脂（重量平均分子量１０６００）のＰＧＭＥＡ溶液（固形分濃度４０質量％）
　Ｂ－Ｍ：上述したバインダーＢ－１～Ｂ－５を等量混合した混合液（固形分濃度４０質量％） B-2: PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are molar ratios. Weight average molecular weight 11000)
B-3: PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are molar ratios. Weight average molecular weight 30000)
B-4: PGMEA solution (solid content concentration 40% by mass) of a resin with the following structure (the numbers appended to the main chain are mass ratios. Weight average molecular weight 14600)
B-5: PGMEA solution (solid content concentration 40% by mass) of resin with the following structure (weight average molecular weight 10600)
BM: A mixed solution containing equal amounts of the binders B-1 to B-5 described above (solid content concentration 40% by mass)
（光重合開始剤）
　Ｃ－１：下記構造の化合物（ヒドロキシ基を有するオキシム化合物）
　Ｃ－２：下記構造の化合物（ヒドロキシ基を有するオキシム化合物）
　Ｃ－３：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－４：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－５：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－６：下記構造の化合物（ヒドロキシ基を有するオキシム化合物）
　Ｃ－７：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－８：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－９：下記構造の化合物（ヒドロキシ基とチオエ―テル基を含むオキシム化合物）
　Ｃ－１０：下記構造の化合物（ヒドロキシ基を有するオキシム化合物）
　Ｃ－１１～Ｃ－１４：下記構造の化合物（ヒドロキシ基を含まないオキシム化合物）
　Ｃ－１５：２，２’，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
　Ｃ－Ｍ：上述した光重合開始剤Ｃ－１～Ｃ－１０を等量混合した混合物 (Photopolymerization initiator)
C-1: Compound with the following structure (oxime compound having a hydroxy group)
C-2: Compound with the following structure (oxime compound having a hydroxy group)
C-3: Compound with the following structure (oxime compound containing a hydroxy group and a thioether group)
C-4: Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
C-5: Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
C-6: Compound with the following structure (oxime compound having a hydroxy group)
C-7: Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
C-8: Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
C-9: Compound with the following structure (oxime compound containing a hydroxyl group and a thioether group)
C-10: Compound with the following structure (oxime compound having a hydroxy group)
C-11 to C-14: Compounds with the following structure (oxime compounds containing no hydroxy group)
C-15: 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole CM: Photopolymerization as described above Mixture of equal amounts of initiators C-1 to C-10
（重合性化合物）
　Ｄ－１：下記構造の化合物
　Ｄ－２：ＮＫエステル　Ｍ－ＤＰＨ－６Ｅ（エトキシ化ジペンタエリスリトールヘキサメタクリレート、新中村化学工業（株）製）
　Ｄ－３：下記構造の化合物の混合物（左側化合物（６官能の（メタ）アクリレート化合物）と右側化合物（５官能の（メタ）アクリレート化合物）とのモル比が７：３の混合物）
　Ｄ－４：下記構造の化合物
　Ｄ－５：トリメチロールプロパンエチレンオキシ変性トリアクリレート（東亞合成（株）製、アロニックスＭ－３５０）
　Ｄ－６：ＥＢＥＣＲＹＬ８０（ダイセル・オルネクス（株）製、アミン含有４官能アクリレート）
　Ｄ－Ｍ：上述した重合性化合物Ｄ－１～Ｄ－６を等量混合した混合物 (Polymerizable compound)
D-1: Compound with the following structure
D-2: NK ester M-DPH-6E (ethoxylated dipentaerythritol hexamethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-3: Mixture of compounds with the following structure (mixture with a molar ratio of 7:3 between the compound on the left (hexafunctional (meth)acrylate compound) and the compound on the right (pentafunctional (meth)acrylate compound))
D-4: Compound with the following structure
D-5: Trimethylolpropane ethyleneoxy modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350)
D-6: EBECRYL80 (manufactured by Daicel Allnex Corporation, amine-containing tetrafunctional acrylate)
DM: mixture of equal amounts of the above-mentioned polymerizable compounds D-1 to D-6
（添加剤）
　Ｅ－１：下記構造の化合物（紫外線吸収剤）

　Ｅ－２：下記構造の化合物（重量平均分子量３５００）
　Ｅ－３：下記構造の化合物（重量平均分子量２３００）

　Ｅ－４：下記構造の化合物（シランカップリング剤）
　Ｅ－５：３－メタクリロキシプロピルメチルジメトキシシラン（ＫＢＭ－５０２、信越化学工業（株）製、シランカップリング剤）
　Ｅ－６：３－メタクリロキシプロピルトリメトキシシラン（ＫＢＭ－５０３、信越化学工業（株）製、シランカップリング剤）
　Ｅ－７：アデカスタブ　ＡＯ－８０（（株）ＡＤＥＫＡ製、酸化防止剤）
　Ｅ－Ｍ：上述した化合物Ｅ－１～Ｅ－７を等量混合した混合物 (Additive)
E-1: Compound with the following structure (ultraviolet absorber)

E-2: Compound with the following structure (weight average molecular weight 3500)
E-3: Compound with the following structure (weight average molecular weight 2300)

E-4: Compound with the following structure (silane coupling agent)
E-5: 3-methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
E-6: 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
E-7: ADEKA STAB AO-80 (manufactured by ADEKA Co., Ltd., antioxidant)
EM: A mixture of the above-mentioned compounds E-1 to E-7 in equal amounts
（界面活性剤類）
　Ｆ－１：ＳＨ－８４００（東レ・ダウコーニング（株）製、シリコーン系界面活性剤）
　Ｆ－２：下記構造の化合物（シリコーン系界面活性剤、水酸基価６２ｍｇＫＯＨ／ｇ）。
　Ｆ－３：メガファック　Ｆ－５５１（ＤＩＣ（株）製、フッ素系界面活性剤）
　Ｆ－４：ＤＩＳＰＥＲＢＹＫ　ＢＹＫ－３３０（ＢＹＫ社製、シリコーン系界面活性剤）
　Ｆ－５：エマルゲン１０３（花王（株）製、ノ二オン系界面活性剤）
　Ｆ－６：オクタメチルシクロテトラシロキサンと、デカメチルシクロペンタシロキサンと、ドデカメチルシクロヘキサシロキサンを等量混合した混合物（環状シロキサン化合物）
　Ｆ－Ｍ：上述した界面活性剤類Ｆ－１～Ｆ－５を等量混合した混合物 (Surfactants)
F-1: SH-8400 (manufactured by Dow Corning Toray Co., Ltd., silicone surfactant)
F-2: Compound with the following structure (silicone surfactant, hydroxyl value 62 mgKOH/g).
F-3: Megafac F-551 (manufactured by DIC Corporation, fluorine-based surfactant)
F-4: DISPERBYK BYK-330 (manufactured by BYK, silicone surfactant)
F-5: Emulgen 103 (manufactured by Kao Corporation, nonionic surfactant)
F-6: A mixture of equal amounts of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane (cyclic siloxane compound)
FM: A mixture of the above-mentioned surfactants F-1 to F-5 in equal amounts
（重合禁止剤）
　Ｇ－１：ｐ－メトキシフェノール (Polymerization inhibitor)
G-1: p-methoxyphenol
（溶剤）
　Ｚ－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（ＰＧＭＥＡ）
　Ｚ－２：プロピレングリコールモノメチルエーテル（ＰＧＭＥ）
　Ｚ－３：シクロペンタノン
　Ｚ－４：シクロヘキサノン
　Ｚ－５：アニソール
　Ｚ－６：ジアセトンアルコール
　Ｚ－７：酢酸シクロヘキシル
　Ｚ－８：プロピレングリコールジアセテート
　Ｚ－９：３－メトキシブタノール
　Ｚ－Ｍ：上述した溶剤Ｚ－１～Ｚ－６を等量混合した混合物 (solvent)
Z-1: Propylene glycol monomethyl ether acetate (PGMEA)
Z-2: Propylene glycol monomethyl ether (PGME)
Z-3: Cyclopentanone Z-4: Cyclohexanone Z-5: Anisole Z-6: Diacetone alcohol Z-7: Cyclohexyl acetate Z-8: Propylene glycol diacetate Z-9: 3-methoxybutanol Z-M: A mixture of equal amounts of the above-mentioned solvents Z-1 to Z-6
＜現像残渣の評価＞
　シリコンウエハ上に、各着色組成物をポストベーク後の膜厚が１．０μｍになるようにスピンコーター（ミカサ（株）製）を用いて塗布し、次いで、ホットプレートを用いて、１００℃で２分間加熱して組成物層を得た。次いで、この組成物層に対して、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（Ｃａｎｏｎ（株）製）を用い、３６５ｎｍの波長の光を１０００ｍＪ／ｃｍ２の露光量で１μｍ四方のＢａｙｅｒパターンを有するマスクを介して露光した。次いで、露光後の組成物層が形成されているシリコンウエハをスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用いて２３℃で６０秒間パドル現像を行った。その後、シリコンウエハを真空チャック方式で水平回転テーブルに固定し、回転装置によってシリコンウエハを回転数５０ｒｐｍで回転させつつ、その回転の中心上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、さらに純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱（ポストベーク）することで画素（着色パターン）を形成した。パターン間（未露光部）について、走査型電子顕微鏡（ＳＥＭ、倍率：１００００）を用いて観測し、以下の評価基準に従って現像残渣を評価した。
　５：未露光部には、残渣が確認されなかった
　４：未露光部に、１０箇所を平均して、直径２００ｎｍ以下のサイズの残渣が１個確認された
　３：未露光部に、１０箇所を平均して、直径２００ｎｍ以下のサイズの残渣が２～５個確認された
　２：未露光部に、１０箇所を平均して、直径２００ｎｍ以下のサイズの残渣が６個以上確認された
　１：未露光部に、直径２００ｎｍ以上のサイズの残渣が確認されたか、または、未露光部がほとんど溶解しなかった <Evaluation of development residue>
Each coloring composition was applied onto a silicon wafer using a spin coater (manufactured by Mikasa Co., Ltd.) so that the film thickness after post-baking was 1.0 μm, and then coated at 100°C using a hot plate. A composition layer was obtained by heating for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), this composition layer was exposed to light at a wavelength of 365 nm at an exposure dose of 1000 mJ/cm 2 using a mask having a Bayer pattern of 1 μm square. exposed through. Next, the exposed silicon wafer with the composition layer formed thereon was placed on a horizontal rotary table of a spin shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and tetramethylammonium hydroxide ( Paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution (TMAH). After that, the silicon wafer is fixed on a horizontal rotary table using a vacuum chuck method, and while the silicon wafer is rotated by a rotating device at a rotation speed of 50 rpm, pure water is supplied in a shower form from a spout nozzle from above the center of rotation to perform rinsing processing. and further washed with pure water. Next, pixels (colored patterns) were formed by heating (post-baking) at 200° C. for 5 minutes using a hot plate. The areas between the patterns (unexposed areas) were observed using a scanning electron microscope (SEM, magnification: 10000), and development residues were evaluated according to the following evaluation criteria.
5: No residue was observed in the unexposed area. 4: One residue with a diameter of 200 nm or less was observed in the unexposed area, on average of 10 areas. 3: 10 areas in the unexposed area. On average, 2 to 5 residues with a diameter of 200 nm or less were confirmed. 2: In the unexposed area, 6 or more residues with a diameter of 200 nm or less were confirmed on an average of 10 locations. 1: Residue with a diameter of 200 nm or more was observed in the unexposed area, or the unexposed area was hardly dissolved.
＜耐熱収縮性の評価＞
　現像残渣の評価で作製した画素（着色パターン）を、ホットプレートを用いて２６０℃で３０分間加熱した。Ｄｅｋｔａｋ（Ｂｒｕｋｅｒ社製）を用いて、加熱前後の画素の膜厚を測定し、以下の基準に従って耐熱収縮性を評価した。画素の膜厚は、５個のサンプル（画素）の平均値を用いた。
　５：（加熱後の画素の膜厚／加熱前の画素の膜厚）の値が０．９以上
　４：（加熱後の画素の膜厚／加熱前の画素の膜厚）の値が０．８８以上、０．９未満
　３：（加熱後の画素の膜厚／加熱前の画素の膜厚）の値が０．８５以上、０．８８未満
　２：（加熱後の画素の膜厚／加熱前の画素の膜厚）の値が０．８以上、０．８５未満
　１：（加熱後の画素の膜厚／加熱前の画素の膜厚）の値が０．８未満 <Evaluation of heat shrinkage resistance>
The pixels (coloring pattern) prepared for evaluation of development residue were heated at 260° C. for 30 minutes using a hot plate. Using Dektak (manufactured by Bruker), the film thickness of the pixel before and after heating was measured, and the heat shrinkage resistance was evaluated according to the following criteria. For the film thickness of the pixel, the average value of five samples (pixels) was used.
5: The value of (pixel thickness after heating/pixel thickness before heating) is 0.9 or more. 4: The value of (pixel thickness after heating/pixel thickness before heating) is 0. 88 or more and less than 0.9 3: The value of (pixel thickness after heating/pixel thickness before heating) is 0.85 or more and less than 0.88 2: (pixel thickness after heating/pixel thickness before heating) The value of (film thickness of previous pixel) is 0.8 or more and less than 0.85 1: The value of (film thickness of pixel after heating / film thickness of pixel before heating) is less than 0.8
＜耐湿性の評価＞
　現像残渣の評価で作製した画素（着色パターン）を、温度５０℃、湿度８５％の条件下に２０００時間曝す恒温恒湿試験を実施した。恒温恒湿試験後、透過型電子顕微鏡を用いて、画素の断面を４万倍の倍率で観察し、画素の空隙（ボイド）の発生率（画素内部に空隙が発生した画素の数／観察した画素の数）を求め、以下の基準に従って耐湿性を評価した。なお、空隙の発生率は、ランダムに２０箇所の断面を選択し、１断面ごとに、１０個の画素において、空隙の有無を観察することで、計２００箇所の境界を観察して算出した。
　発生率＝画素内部に空隙が発生した画素の数／観察した画素の数
　５：空隙の発生率が０
　４：空隙の発生率が０より大きく、０．１以下
　３：空隙の発生率が０．１より大きく、０．２以下
　２：空隙の発生率が０．２より大きく、０．５以下
　１：空隙の発生率が０．５より大きく、１．０以下 <Evaluation of moisture resistance>
A constant temperature and humidity test was conducted in which the pixels (coloring patterns) prepared for evaluation of development residue were exposed for 2000 hours at a temperature of 50° C. and a humidity of 85%. After the constant temperature and humidity test, the cross section of the pixel was observed using a transmission electron microscope at a magnification of 40,000 times, and the incidence of voids in the pixel (number of pixels with voids inside the pixel/observed) was determined. (number of pixels) was determined, and moisture resistance was evaluated according to the following criteria. The occurrence rate of voids was calculated by randomly selecting 20 cross sections and observing the presence or absence of voids in 10 pixels for each cross section, observing a total of 200 boundaries.
Occurrence rate = Number of pixels where voids have occurred inside the pixel / Number of observed pixels 5: Occurrence rate of voids is 0
4: The occurrence rate of voids is greater than 0 and less than 0.1 3: The occurrence rate of voids is greater than 0.1 and less than 0.2 2: The occurrence rate of voids is greater than 0.2 and less than 0.5 1 : Occurrence rate of voids is greater than 0.5 and less than 1.0
　上記表に示すように、実施例の着色組成物は、残渣が少なく、耐熱収縮性および耐湿性に優れていた。
　また、実施例５０の着色組成物を用いて得られた膜は、表面の平滑性が特に優れていた。 As shown in the table above, the colored compositions of Examples had little residue and were excellent in heat shrinkage resistance and moisture resistance.
Furthermore, the film obtained using the colored composition of Example 50 had particularly excellent surface smoothness.

Claims (10)

  1. 　着色剤と、樹脂と、重合性化合物と、光重合開始剤と、溶剤とを含み、
    　前記光重合開始剤は、ヒドロキシ基を有するオキシム化合物を含み、
    　前記樹脂は、脂環式エポキシ基を有する樹脂を含む、着色組成物。     Contains a colorant, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
    The photopolymerization initiator contains an oxime compound having a hydroxy group,
    A colored composition, wherein the resin includes a resin having an alicyclic epoxy group.
  2. 　前記脂環式エポキシ基は、多環式脂肪族炭化水素環を有する基である、請求項１に記載の着色組成物。 The colored composition according to claim 1, wherein the alicyclic epoxy group is a group having a polycyclic aliphatic hydrocarbon ring.
  3. 　前記重合性化合物は、アルキレンオキシド変性（メタ）アクリレート化合物を含む、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the polymerizable compound includes an alkylene oxide-modified (meth)acrylate compound.
  4. 　前記ヒドロキシ基を有するオキシム化合物は、ヒドロキシ基とチオエ―テル基とを含むオキシム化合物である、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the oxime compound having a hydroxy group is an oxime compound containing a hydroxy group and a thioether group.
  5. 　前記光重合開始剤は、更に前記ヒドロキシ基を有するオキシム化合物以外の光重合開始剤を含む、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, wherein the photopolymerization initiator further contains a photopolymerization initiator other than the oxime compound having a hydroxy group.
  6. 　さらに環状シロキサン化合物を含む、請求項１または２に記載の着色組成物。 The colored composition according to claim 1 or 2, further comprising a cyclic siloxane compound.
  7. 　請求項１または２に記載の着色組成物を用いて得られる膜。 A film obtained using the colored composition according to claim 1 or 2.
  8. 　請求項７に記載の膜を有する光学フィルタ。 An optical filter comprising the film according to claim 7.
  9. 　請求項７に記載の膜を有する固体撮像素子。 A solid-state imaging device comprising the film according to claim 7.
  10. 　請求項７に記載の膜を有する画像表示装置。 An image display device comprising the film according to claim 7.
PCT/JP2023/006340 2022-03-17 2023-02-22 Coloring composition, film, optical filter, solid-state imaging element, and image display device WO2023176335A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017027029A (en) * 2015-07-21 2017-02-02 東京応化工業株式会社 Coloring photosensitive composition
JP2017133009A (en) * 2016-01-27 2017-08-03 住友化学株式会社 Colored curable resin composition, color filter and display device comprising the same
CN107561861A (en) * 2016-06-30 2018-01-09 奇美实业股份有限公司 Photosensitive resin composition and application thereof
JP2021103294A (en) * 2019-12-24 2021-07-15 ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド Colored photosensitive resin composition and black matrix prepared therefrom
JP2021167905A (en) * 2020-04-10 2021-10-21 東京応化工業株式会社 Photosensitive composition, patterned cured film production method, and patterned cured film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017027029A (en) * 2015-07-21 2017-02-02 東京応化工業株式会社 Coloring photosensitive composition
JP2017133009A (en) * 2016-01-27 2017-08-03 住友化学株式会社 Colored curable resin composition, color filter and display device comprising the same
CN107561861A (en) * 2016-06-30 2018-01-09 奇美实业股份有限公司 Photosensitive resin composition and application thereof
JP2021103294A (en) * 2019-12-24 2021-07-15 ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド Colored photosensitive resin composition and black matrix prepared therefrom
JP2021167905A (en) * 2020-04-10 2021-10-21 東京応化工業株式会社 Photosensitive composition, patterned cured film production method, and patterned cured film

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