WO2022004683A1 - Coloring composition, film, color filter, solid-state imaging element, and image display device - Google Patents

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

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Publication number
WO2022004683A1
WO2022004683A1 PCT/JP2021/024431 JP2021024431W WO2022004683A1 WO 2022004683 A1 WO2022004683 A1 WO 2022004683A1 JP 2021024431 W JP2021024431 W JP 2021024431W WO 2022004683 A1 WO2022004683 A1 WO 2022004683A1
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Prior art keywords
group
compound
mass
coloring composition
resin
Prior art date
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PCT/JP2021/024431
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French (fr)
Japanese (ja)
Inventor
宏明 出井
Original Assignee
富士フイルム株式会社
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Priority to JP2022534012A priority Critical patent/JP7574295B2/en
Publication of WO2022004683A1 publication Critical patent/WO2022004683A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • 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

Definitions

  • the present invention relates to a coloring composition containing an organic pigment.
  • the present invention also relates to a film, a color filter, a solid-state image pickup device, and an image display device using a coloring composition.
  • color filters are used as key devices for displays and optical elements.
  • a color filter usually includes pixels of the three primary colors of red, green, and blue, and plays a role of decomposing transmitted light into the three primary colors.
  • the colored pixels of each color of the color filter are manufactured by using a coloring composition containing a coloring material such as a pigment.
  • Patent Document 1 describes an invention relating to a coloring composition containing a latent antioxidant (A) and a coloring agent (B).
  • the present inventor found that the spectral fluctuation of the film after a long-term heat treatment (for example, heat treatment at 130 ° C. for 1000 hours) was observed. It was found that there is room for further improvement in color unevenness. In particular, as the content of the coloring material in the film increases, the spectral fluctuation and color unevenness of the film after a long-term heat resistance test tend to increase.
  • a long-term heat treatment for example, heat treatment at 130 ° C. for 1000 hours
  • an object of the present invention is a coloring composition, a film, a color filter, a solid-state image pickup device, and an image display device capable of obtaining a film in which spectral fluctuation is small even after a long-term heat treatment and the occurrence of color unevenness is suppressed. Is to provide.
  • the present invention provides the following.
  • the coloring composition according to ⁇ 1> or ⁇ 2> which contains 2 to 25 parts by mass of the compound A with respect to 100 parts by mass of the organic pigment.
  • R 11 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group.
  • R 12 and R 13 independently represent a hydrogen atom or an alkyl group, respectively.
  • LR1 represents an alkylene group q represents 0 or 1 and represents When q is 1, L R1 and R 14 may be combined to form a ring.
  • m represents an integer from 0 to 4 and represents n represents an integer from 1 to 10 and represents X 1 represents an n-valent group.
  • ⁇ 7> The coloring composition according to any one of ⁇ 1> to ⁇ 6>, wherein the organic pigment contains at least one selected from a green pigment, a yellow pigment and a red pigment.
  • the organic pigment contains a green pigment, and the green pigment contains a phthalocyanine compound.
  • the resin contains a graft resin having an acid group.
  • the acid value of the graft resin is 20 to 150 mgKOH / g.
  • ⁇ 11> The coloring composition according to ⁇ 9> or ⁇ 10>, wherein the graft resin has a weight average molecular weight of 3000 to 35000.
  • ⁇ 12> The coloring composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a photopolymerization initiator and a polymerizable compound.
  • ⁇ 13> The coloring composition according to ⁇ 12>, wherein the photopolymerization initiator contains an oxime compound having an aromatic ring group in which an electron-attracting group is introduced into the aromatic ring.
  • ⁇ 14> The coloring composition according to any one of ⁇ 1> to ⁇ 13>, further containing a phenolic antioxidant.
  • ⁇ 15> A film obtained by using the coloring composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> A color filter containing the film according to ⁇ 15>.
  • ⁇ 17> A solid-state image sensor including the film according to ⁇ 15>.
  • ⁇ 18> An image display device including the film according to ⁇ 15>.
  • a coloring composition a film, a color filter, a solid-state image pickup device, and an image display device capable of obtaining a film in which spectral fluctuation is small even after a long-term heat treatment and the occurrence of color unevenness is suppressed. can do.
  • the contents of the present invention will be described in detail.
  • "to” is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the term "exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • EUV light extreme ultraviolet rays
  • (meth) acrylate” represents both acrylate and methacrylate, or either
  • “(meth) acrylic” represents both acrylic and methacrylic, or either.
  • Acryloyl represents both acryloyl and / or methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • a first aspect of the coloring composition of the present invention comprises a coloring material containing an organic pigment, a resin, and a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protective group that can be desorbed by heating. It is a coloring composition containing 40% by mass or more of a coloring material in the total solid content of the coloring composition.
  • the second aspect of the coloring composition of the present invention is a coloring composition containing a coloring material containing an organic pigment, a resin, and a compound represented by the formula (AO-1). It is characterized by containing 40% by mass or more of a coloring material in the total solid content of the above.
  • the compound A described above and the compound represented by the formula (AO-1) are collectively referred to as a specific compound.
  • the coloring composition of the present invention contains 40% by mass or more of a coloring material containing an organic pigment in the total solid content of the coloring composition, it is heated for a long period of time by containing the above-mentioned specific compound. Even after the treatment, the spectral fluctuation is small, and it is possible to form a film in which the occurrence of color unevenness is suppressed. The detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following.
  • the above-mentioned specific compound contained in the coloring composition of the present invention has a protective group desorbed at the time of film formation (for example, at the time of post-baking) to generate a phenolic hydroxy group, and exhibits a function as an antioxidant. It is presumed. It is presumed that the action of the component that functions as an antioxidant produced from the specific compound could suppress the deterioration and aggregation of the organic pigment at high temperatures. Therefore, it is presumed that the coloring composition of the present invention can form a film in which spectral fluctuation is small and the occurrence of color unevenness is suppressed even after a long-term heat treatment.
  • the antioxidant when a film is formed using a coloring composition containing an antioxidant, the antioxidant is decomposed or denatured by heating or exposure during film formation, and a sufficient amount of the antioxidant remains in the film. I may not have done it.
  • the above-mentioned specific compound has a small content of the specific compound because the protecting group is desorbed at the time of film formation to generate a phenolic hydroxy group and the specific compound exhibits a function as an antioxidant. Even so, the membrane can contain a sufficient amount of a component that functions as an antioxidant. Therefore, the coloring composition of the present invention can further increase the degree of freedom in formulation design.
  • the coloring composition of the present invention is preferably used as a coloring composition for a color filter. Specifically, it can be preferably used as a coloring composition for forming colored pixels of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, a yellow pixel, and the like, and a green pixel or a cyan color pixel is preferable. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a solid-state image sensor, and more preferably as a coloring composition for forming colored pixels of a color filter used for a solid-state image sensor.
  • the coloring composition of the present invention contains a coloring material.
  • the coloring material contained in the coloring composition of the present invention contains an organic pigment.
  • the organic pigment is a pigment composed of an organic compound.
  • the pigment means a coloring material that is difficult to dissolve in a solvent.
  • the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
  • the average primary particle size of the organic pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less.
  • the average primary particle size of the organic pigment can be obtained from an image photograph obtained by observing the primary particles of the organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments.
  • the primary particles of the pigment refer to independent particles without aggregation.
  • the organic pigment is preferably a chromatic organic pigment.
  • the chromatic organic pigment include a yellow pigment, an orange pigment, a red pigment, a green pigment, a purple pigment, and a blue pigment.
  • the organic pigment used in the present invention preferably contains at least one selected from a green pigment, a yellow pigment and a red pigment, and more preferably contains a green pigment.
  • the green pigment examples include phthalocyanine compounds and squarylium compounds.
  • the phthalocyanine compound also referred to as phthalocyanine green pigment
  • the phthalocyanine green pigment tends to be easily heat-diffused in the film, and the phthalocyanine green pigment aggregates in the heated film to improve the spectral characteristics of the heated film.
  • the coloring composition of the present invention fluctuations in spectral characteristics and occurrence of color unevenness are effectively suppressed even when a phthalocyanine green pigment is used. can do. Therefore, a particularly remarkable effect can be obtained when a phthalocyanine compound (phthalocyanine green pigment) is used as the green pigment.
  • the phthalocyanine green pigment examples include a phthalocyanine compound having Cu, Al, Co, Ni, Ti or Zn as a central metal, and the phthalocyanine green pigment is described as Cu, because the effect of the present invention is more prominently exhibited. It is more preferably a phthalocyanine compound having Zn or Al as a central metal, and even more preferably a phthalocyanine compound having Cu or Zn as a central metal. A ligand may be further coordinated to the central metal. Further, the phthalocyanine compound is preferably a halogenated phthalocyanine compound.
  • the halogenated phthalocyanine compound is a phthalocyanine compound having a halogen atom as a substituent.
  • the green pigment examples include Color Index (CI) Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like. Further, as a green pigment, a halogen having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5.
  • a halogen having an average number of halogen atoms in one molecule of 10 to 14 an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5.
  • Halogenated zinc phthalocyanine pigments can also be used. Specific examples include the phthalocyanine pigment described in International Publication No. 2015/118720. Further, as a green pigment, the compound described in Chinese Patent Application No. 106900927, the phthalocyanine compound having a phosphate ester described in International Publication No.
  • Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, and the like can also be used.
  • C.I. I. Pigment greens 7, 36, 58, 59, 62, 63 are preferred.
  • yellow pigment examples include azo compounds, azomethine compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, pteridine compounds, anthraquinone compounds and the like.
  • yellow pigments include C.I. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1,36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179, 180,181,182,185,187,188,193,194,199,213,214,215,228,231,232,233,234,235,236 and the like can be mentioned.
  • a nickel azobarbituric acid complex having the following structure can also be used.
  • the yellow pigment the quinophthalone compound described in paragraphs 0011 to 0034 of JP2013-054339, the quinophthalone compound described in paragraphs 0013 to 0058 of JP2014-026228, and JP-A-2018-0626444.
  • the isoindrin compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, the quinophthalone compound described in JP-A-6432076, JP-A-2018-155881 The quinophthalone compound described in JP-A-2018-11757, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2017-197640, JP-A-2016
  • the compound described in JP-A-2020-033523, the compound described in JP-A-2020-033522, the compound described in JP-A-2020-033521, International Publication No. 2 The compound described in 020/045200, the compound described in International Publication No. 2020/045199, and the compound described in International Publication No. 2020/045197 can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value.
  • yellow pigment a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.
  • X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the compound represented by the formula (QP1) include the compound described in paragraph No. 0016 of Japanese Patent No. 6443711.
  • Y 1 ⁇ Y 3 represents a halogen atom independently.
  • n and m represent integers of 0 to 6, and p represents an integer of 0 to 5.
  • N + m is 1 or more.
  • Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
  • C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 215 is preferred, and C.I. I. Pigment Yellow 139, 150, 185 is more preferred.
  • red pigment examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds and thioindigo compounds.
  • red pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48: 2,48:3,48:4 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 294, 295, 296, 297 and the like can be mentioned.
  • red pigment a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole described in paragraphs 0016 to 0022 of Patent No. 6248838.
  • the red pigment described in Japanese Patent No. 6516119, the red pigment described in Japanese Patent No. 6525101, and the like can also be used.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. ..
  • C.I. I. Pigment Violet 1 19, 23, 27, 32, 37, 42, 60, 61 and the like.
  • Japanese Patent No. 6561862 Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Laid-Open No. 2020-026553, and Japanese Patent Application Laid-Open No. 2020-033526 are described. These contents are incorporated herein by reference.
  • Two or more kinds of chromatic organic pigments may be used in combination.
  • the coloring composition of the present invention when used for forming green pixels of a color filter, it is preferable to use a green pigment and a yellow pigment in combination.
  • the ratio of the green pigment to the yellow pigment is preferably 10 to 120 parts by mass, more preferably 20 to 100 parts by mass, and 25 to 75 parts by mass with respect to 100 parts by mass of the green pigment. It is more preferably by mass.
  • a dye may be further used in addition to the organic pigment.
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound, xanthene compound examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds.
  • the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and the azo compound described in JP-A-2011-145540 can also be used.
  • a dye multimer can also be used.
  • 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 have the same dye structure or may have different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
  • the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • the compounds described in 031442 and the like can also be used.
  • the content of the coloring material in the total solid content of the coloring composition is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more. Further, the upper limit of the content of the coloring material in the total solid content of the coloring composition is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. preferable.
  • the content of the organic pigment in the total solid content of the coloring composition is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more. It is particularly preferable that it is 45% by mass or more.
  • the upper limit of the content of the organic pigment in the total solid content of the coloring composition is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. preferable.
  • the content of the organic pigment in the coloring material is preferably 50% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. It is particularly preferable to have.
  • the upper limit may be 100% by mass or less.
  • the coloring composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing the pigment in the coloring composition or for the purpose of a binder.
  • the resin mainly used for dispersing the pigment is also referred to as a dispersant.
  • such use of the resin is an example, and it can be used for purposes other than such use.
  • the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • the resin examples include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyimine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resin described in paragraph numbers 0041 to 0060 of JP-A-2017-206689 and the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856 can also be used.
  • a resin having an acid group as the resin.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable.
  • the resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the resin having an acid group is a monomer 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 include repeating units derived from the components.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the resin used in the present invention preferably contains a repeating unit derived from the compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms.
  • n represents an integer from 1 to 15.
  • the acid value of the resin having an acid group is preferably 5 to 200 mgKOH / g.
  • the upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.
  • the lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.
  • the weight average molecular weight (Mw) of the resin having an acid group is preferably 3000 to 35000.
  • the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
  • the coloring composition of the present invention can also use a resin having a basic group.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, and has both a repeating unit having a basic group in the 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 the side chain and a repeating unit not containing a basic group is further 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, and more preferably 20 mgKOH / g or more.
  • the upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less.
  • Examples of the resin having a basic group are described in the block copolymers (B) described in paragraphs 0063 to 0112 of JP2014-219665A and paragraphs 0046 to 0076 of JP-A-2018-156021.
  • the block copolymer A1 can be mentioned.
  • the coloring composition of the present invention preferably contains a graft resin having an acid group (hereinafter, also referred to as an acidic graft resin).
  • a graft resin having an acid group hereinafter, also referred to as an acidic graft resin.
  • the aggregation of the organic pigment can be suppressed by the graft chain of the acidic graft resin, and further, the deterioration and aggregation of the organic pigment at high temperature are suppressed by the action of the component which functions as an antioxidant produced from the specific compound. It is speculated that it can be done. For this reason, it is presumed that the spectral fluctuation of the film after a long-term heat treatment and the occurrence of color unevenness can be further suppressed.
  • the acidic graft resin can be preferably used as a dispersant.
  • the graft resin means a resin containing a repeating unit having a graft chain.
  • the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit.
  • the graft chain is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure, and the polyester structure, More preferably, it is a polymer chain containing at least one structure selected from a polyether 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.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, an amino group and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferable.
  • the weight average molecular weight of the graft chain is preferably 500 to 10000.
  • the upper limit is preferably 5000 or less, and more preferably 3000 or less.
  • the lower limit is preferably 800 or more, and more preferably 1000 or more.
  • the weight average molecular weight of the graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit having the graft chain.
  • repeating units with graft chains can be formed by polymerizing macromonomers.
  • the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer.
  • the value of the weight average molecular weight of the raw material monomer the polystyrene-equivalent value measured by the GPC (gel permeation chromatography) method is used.
  • Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
  • the acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g.
  • the upper limit is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.
  • the lower limit is preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 35 mgKOH / g or more.
  • the weight average molecular weight of the acidic graft resin is preferably 3000 to 35000.
  • the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
  • the acidic graft resin examples include a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, a resin having a repeating unit represented by the following formula (Ac-2), and the like.
  • the acidic graft resin may further contain other repeating units such as repeating units having a polymerizable group.
  • the polymerizable group examples include an ethylenically unsaturated bond-containing group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the acidic graft resin is a resin containing a repeating unit having a graft chain and a repeating unit having an acid group
  • the acidic graft resin contains 1 mol of the repeating unit having a graft chain in all the repeating units of the acidic graft resin.
  • % Or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more is further preferable.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
  • the acidic graft resin preferably contains 1 mol% or more of the repeating units having an acid group in all the repeating units of the acidic graft resin, more preferably 2 mol% or more, and 3 mol% or more. Is more preferable.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
  • Ar 10 represents a group containing an aromatic carboxyl group
  • L 11 represents -COO- or -CONH-
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer. Represents a chain.
  • Examples of the group containing an aromatic carboxyl group represented by Ar 10 in the formula (Ac-2) 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 acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.
  • Q 1 is represented by a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).
  • the group containing an aromatic carboxyl group represented by Ar 10 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 carboxyl group represented by Ar 10 include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13). Examples include the base.
  • 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-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
  • * 1 represents the bonding position with L 11.
  • L 11 is preferably —COO ⁇ .
  • the trivalent linking group represented by L 12 in the formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these.
  • a group that combines species or more can be mentioned.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the number of carbon atoms of 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 number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the hydrocarbon group may have a substituent.
  • substituent include a hydroxy group and the like.
  • the trivalent linking group represented by L 12 is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • * 1 represents the bonding position with L 11 in the formula (Ac-2)
  • * 2 represents the bonding position with L 11 in the formula (Ac-2). It represents a bonding position to P 10 of the Ac-2).
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined with, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • * 1 represents the bonding position with L 11 of the formula (Ac-2)
  • * 2 represents the bonding position of the formula (Ac-2). It represents a bonding position to P 10 of the Ac-2).
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.
  • Polymer chains represented by P 10 of the formula (Ac-2) comprises a polyester structure, a polyether structure, poly (meth) acrylic structure, polystyrene structure, polyurethane structure, at least one structure selected from a polyurea structure and polyamide structure
  • the polymer chain is mentioned, and is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly (meth) acrylic structure.
  • the weight average molecular weight of the polymer chain represented by P 10 is preferably 500 to 10000.
  • the upper limit is preferably 5000 or less, and more preferably 3000 or less.
  • the lower limit is preferably 800 or more, and more preferably 1000 or more.
  • the polymer chain represented by P 10 preferably contains a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain.
  • the proportion of the repeating units containing an ethylenically unsaturated bond-containing group in the total repeating units constituting the P 10 in a side chain is preferably 5 mass% or more, more preferably 10 mass% or more , 20% by mass or more is more preferable.
  • the upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.
  • the polymer chain represented by P 10 contains a repeating unit containing an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the ratio of the repeating unit containing an acid group in all the repeating units constituting P 10 is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 10% by mass. Is even more preferable.
  • the acidic graft resin examples include resins B-1 to B-7 described in Examples described later. Further, as the acidic graft resin, the resin described in paragraphs 0025 to 0094 of JP2012-255128 and the polyimine resin described in paragraphs 0102 to 0166 of JP2012-255128 may be used. can.
  • the coloring composition of the present invention preferably contains a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger 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 the amount of acid groups and the amount of basic groups is 100 mol%.
  • the basic group of the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
  • a resin such as the above-mentioned acidic graft resin can also be used as a dispersant.
  • the resin used as the dispersant is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
  • the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.
  • Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.
  • the content of the resin in the total solid content of the coloring composition is preferably 1 to 45% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the acidic graft resin in the total solid content of the coloring composition is preferably 1 to 45% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of the acidic graft resin is preferably 100 to 3000 parts by mass with respect to 100 parts by mass of the specific compound.
  • the lower limit is preferably 200 parts by mass or more, and more preferably 300 parts by mass or more.
  • the upper limit is preferably 2500 parts by mass or less, more preferably 2000 parts by mass or less.
  • the coloring composition of the present invention contains a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protective group that can be desorbed by heating, or a compound represented by the formula (AO-1).
  • a compound represented by the formula (AO-1) a compound represented by the formula (AO-1)
  • the compound A described above and the compound represented by the formula (AO-1) are collectively referred to as a specific compound.
  • the compound A is preferably a compound in which the protecting group is removed by heating to 180 ° C. or higher to generate a phenolic hydroxy group.
  • the protecting group in compound A include acid anhydrides, acid acid compounds, tert-butoxycarbonylating agents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, reaction residues of metalyl ether compounds and the like.
  • Specific examples of the protecting group include a group having a structure represented by R 2 of the formula (AO-1).
  • the formula amount of the protecting group is preferably 30 to 200, more preferably 35 to 100, and even more preferably 40 to 70 because it is preferable that the protecting group volatilizes and does not remain at the time of baking.
  • Compound A is preferably a compound containing 1 to 10 phenolic hydroxy groups (hereinafter, also referred to as protected hydroxy groups) protected by the protecting group in one molecule.
  • the lower limit is preferably 2 or more, and more preferably 3 or more.
  • the upper limit is preferably 6 or less, and more preferably 4 or less.
  • Compound A is preferably a compound represented by the formula (AO-1).
  • R 11 , R 12 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group.
  • R 13 represents a hydrogen atom or an alkyl group.
  • LR1 represents an alkylene group q represents 0 or 1 and represents When q is 1, L R1 and R 14 may be combined to form a ring.
  • m represents an integer from 0 to 4 and represents n represents an integer from 1 to 10 and represents X 1 represents an n-valent group.
  • Examples of the substituent represented by R 1 in the formula (AO-1) include a substituent T described later, which is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic, but is preferably branched or cyclic because of its good function as a phenolic antioxidant after desorption, and more preferably branched. ..
  • R 11 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group
  • R 12 and R 13 independently represent a hydrogen atom or an alkyl group
  • L R 1 represents an alkylene group.
  • q represents 0 or 1, and when q is 1, L R1 and R 14 may be combined to form a ring.
  • the number of carbon atoms of the alkyl group represented by R 11 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkyl group may be linear, branched or cyclic, but is preferably a branched alkyl group because the desorption temperature is appropriate.
  • the alkyl group represented by R 11 may have a substituent. Examples of the substituent include a substituent T described later, and an aryl group is preferable. Specific examples of R 11 include a tert-butyl group and a benzyl group.
  • the number of carbon atoms of the alkyl group represented by R 12 and R 13 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkyl group represented by R 11 and R 12 may be linear, branched or cyclic, but is preferably a linear or branched alkyl group because it can be produced at a lower cost, and is preferably a linear alkyl. It is more preferable that it is a group.
  • R 12 and R 13 are preferably independent alkyl groups, and more preferably methyl groups.
  • the number of carbon atoms of the alkyl group represented by R 14 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group because it can be produced at a lower cost.
  • the number of carbon atoms of the alkyl group represented by R 15 to R 17 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group because it can be produced at a lower cost.
  • the alkylene group L R1 represents is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, 1 to 3 particularly preferred.
  • the alkylene group may be linear, branched or cyclic, but is preferably a linear or branched alkylene group because it can be produced at a lower cost. Further, L R1 and R 14 may form a ring.
  • the group represented by "-CH 2 (-OL R1 ) q- OR 14 " when q is 0, the group of the structure represented by -CH 2- OR 14 Is.
  • the n-valent group represented by X 1 in the formula (AO-1) includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, —O—, —S—, —CO—, —COO—, -OCO-, -SO 2- , -NR X- , -NR X CO-, -CONR X- , -NR X SO 2- , -SO 2 NR X- and a group consisting of a combination thereof can be mentioned.
  • X represents a hydrogen atom, an alkyl group or an aryl group.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, further preferably 2 to 10, and particularly preferably 2 to 5.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. Further, the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
  • the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
  • the aromatic hydrocarbon group is preferably a monocyclic or an aromatic hydrocarbon group having a condensed ring having 2 to 4 condensation numbers.
  • the aromatic hydrocarbon group is preferably a benzene ring group.
  • the heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • Aliphatic hydrocarbon groups, aromatic hydrocarbon groups and heterocyclic groups may have substituents. Examples of the substituent include the groups listed in Substituent T described later.
  • the number of carbon atoms of the alkyl group represented by R X is preferably 1-20, more preferably 1-15, 1-8 is more preferable.
  • the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
  • Alkyl group R X represents may further have a substituent. Examples of the substituent include a substituent T described later.
  • the number of carbon atoms of the aryl group R X represents is preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12.
  • Aryl group R X represents may further have a substituent. Examples of the substituent include a substituent T described later.
  • the n-valent group represented by X 1 is preferably a group represented by any of the formulas (X-1) to (X-4).
  • L 3 represents a trivalent group
  • T 3 represents a single bond or a divalent linking group
  • the three existing T 3s may be the same or different from each other.
  • L 4 represents a tetravalent group
  • T 4 represents a single bond or a divalent linking group
  • T 4 present four may be the being the same or different .
  • L 5 represents a pentavalent group
  • T 5 represents a single bond or a divalent linking group
  • the five existing T 5s may be the same or different from each other.
  • L 6 represents a hexavalent group
  • T 6 represents a single bond or a divalent linking group
  • the six T 6s may be the same or different from each other. ..
  • * represents a bond.
  • the divalent linking groups represented by T 3 to T 6 include an alkylene group, an arylene group, a heterocyclic group, -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, Examples thereof include -OCO-, -S-, -NHCO-, -CONH-, and a group consisting of a combination of two or more of these.
  • the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
  • the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the alkylene group, arylene group and heterocyclic group may further have a substituent. Examples of the substituent include the substituent T described later.
  • Examples of the trivalent group represented by L 3 include a group obtained by removing one hydrogen atom from the above divalent linking group.
  • Examples of the tetravalent group represented by L 4 include a group obtained by removing two hydrogen atoms from the above-mentioned divalent linking group.
  • Examples of the pentavalent group represented by L 5 include a group obtained by removing three hydrogen atoms from the above divalent linking group.
  • Examples of the hexavalent group represented by L 6 include a group obtained by removing four hydrogen atoms from the above divalent linking group.
  • the 3- hexavalent group represented by L 3 to L 6 may further have a substituent. Examples of the substituent include a substituent T described later.
  • m represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 1 or 2. preferable.
  • N in the formula (AO-1) represents an integer of 1 to 10, and the lower limit of n is preferably 2 or more, and more preferably 3 or more.
  • the upper limit of n is preferably 6 or less, and more preferably 4 or less.
  • substituent T a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NRt 3 CORT 1 , -CONRT 1 Rt 2 , -NRt 3 CONRT 1 Rt 2 , -NRt 3 COORt 1 , -SRt 1 , -SO 2 Rt 1 , -SO 2 ORt 1 , -NRt 3 SO 2 Rt 1 or -SO 2 NRt 1 Rt 2 can be mentioned.
  • Rt 1 to Rt 3 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, respectively.
  • Rt 1 and Rt 2 may be combined to form a ring.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic.
  • the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 2 to 8 carbon atoms.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the heterocyclic group may be a monocyclic ring or a fused ring.
  • the heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers.
  • the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include a group selected from the above-mentioned group of substituents T.
  • Specific compounds include, for example, JP-A-57-11375, JP-A-03-173843, JP-A-06-128195, JP-A-07-206771, JP-A-07-252191, JP-A-2004, JP-A-2004.
  • Specific examples of the specific compound include compounds 1 to 6 described in Examples described later, compounds described in paragraph numbers 0106 to 0109 of JP-A-2015-131937, and paragraph numbers 0028 to JP-A-2015-132791. Examples thereof include the compounds described in 0049, the compounds described in 0043 to 0044 of International Publication No. 2017/170183, and the like.
  • the content of the above-mentioned compound A in the total solid content of the coloring composition is preferably 1 to 10% by mass.
  • the lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more.
  • the upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. Further, it is preferable that the compound A is contained in an amount of 2 to 25 parts by mass with respect to 100 parts by mass of the organic pigment.
  • the lower limit is preferably 5.5 parts by mass or more, and more preferably 7 parts by mass or more.
  • the upper limit is preferably 18 parts by mass or less, and more preferably 13 parts by mass or less.
  • only one compound A may be used, or two or more compounds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the content of the compound represented by the formula (AO-1) in the total solid content of the coloring composition is preferably 1 to 10% by mass.
  • the lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more.
  • the upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less.
  • the lower limit is preferably 5.5 parts by mass or more, and more preferably 7 parts by mass or more.
  • the upper limit is preferably 18 parts by mass or less, and more preferably 13 parts by mass or less.
  • the coloring composition of the present invention only one specific compound may be used, or two or more specific compounds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention can contain an antioxidant.
  • the antioxidant include a phenol-based antioxidant, a phosphite ester-based antioxidant, an amine-based antioxidant, a thiotel-based antioxidant, and the like, and a phenol-based antioxidant is preferable.
  • the phenolic antioxidant include hindered phenol compounds.
  • the phenolic antioxidant is preferably a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • Commercially available phenolic 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 (above, manufactured by ADEKA Corporation) and the like.
  • the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
  • the content of the antioxidant in the total solid content of the coloring composition is preferably 0.001 to 3% by mass.
  • the lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more.
  • the upper limit is preferably 1.5% by mass or less, and more preferably 1% by mass or less.
  • the content of the phenolic antioxidant in the total solid content of the coloring composition is preferably 0.001 to 2% by mass.
  • the lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more.
  • the upper limit is preferably 1.5% by mass or less, and more preferably 1% by mass or less.
  • the total content of the above-mentioned specific compound and the antioxidant in the total solid content of the coloring composition is preferably 1 to 10% by mass.
  • the lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more.
  • the upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less.
  • the total content of the above-mentioned specific compound and the phenolic antioxidant in the total solid content of the coloring composition is preferably 1 to 10% by mass.
  • the lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more.
  • the upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less.
  • the content of the antioxidant is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned specific compound. Is more preferable.
  • the content of the phenolic antioxidant is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned specific compound. It is more preferably by mass. If the ratio of the above-mentioned specific compound to the phenolic antioxidant is in the above range, the effect of improving the storage stability of the coloring composition can be expected. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.
  • the coloring composition of the present invention can contain a polymerizable compound.
  • a polymerizable compound a known compound that can be crosslinked by radicals, acids or heat can be used.
  • the polymerizable compound used in the present invention is preferably a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, and even more preferably 250 or more.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
  • polymerizable compound examples include paragraph numbers 0995 to 0108 of JP2009-288705, paragraph numbers 0227 of JP2013-029760, paragraph numbers 0254 to 0257 of JP2008-292970, and the present invention.
  • dipentaerythritol tri (meth) acrylate commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol tetra (meth) acrylate commercially available KAYARAD D-320.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A) -TMMT
  • 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
  • RP-1040 manufactured by Nihon Kayaku Co., Ltd.
  • Aronix TO-2349 manufactured by Toa Synthetic Co., Ltd.
  • NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • 8UH-1006, 8UH-1012 manufactured by Taisei Fine Chemical Co., Ltd.
  • light acrylate POB-A0 manufactured by Kyoeisha Chemical
  • Examples of the polymerizable compound 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. It is also preferable to use a trifunctional (meth) acrylate compound such as tri (meth) acrylate.
  • Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 manufactured by Toa Synthetic Co., Ltd.
  • NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
  • a polymerizable compound having an acid group can also be used.
  • the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable.
  • examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
  • a polymerizable compound having a caprolactone structure can also be used.
  • the polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • a polymerizable compound having an alkyleneoxy group can also be used.
  • a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups.
  • a hexafunctional (meth) acrylate compound is more preferred.
  • Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene.
  • an environmentally regulatory substance such as toluene.
  • commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the polymerizable compound include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-0322293, and Japanese Patent Application Laid-Open No. 02-016765, and Japanese Patent Application Laid-Open No. 58- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418, Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No.
  • a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-260909 and JP-A No. 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, and AH-600. , T-600, AI-600, LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can also be used.
  • the content of the polymerizable compound in the total solid content of the coloring composition is preferably 0.1 to 50% by mass.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more.
  • the upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less.
  • only one type of polymerizable compound may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention can contain a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible light region is preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
  • It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an ⁇ -hydroxyketone compound.
  • ⁇ -Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable.
  • the photopolymerization initiator the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on.
  • acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
  • Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385.
  • oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) and the like can be mentioned.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).
  • an oxime compound having a benzofuran skeleton can also be used.
  • Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
  • the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
  • the benzoyl group may have a substituent.
  • the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
  • an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
  • RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
  • RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
  • R X3 ⁇ R X14 represents a hydrogen atom or a substituent independently; Provided that at least one of R X10 ⁇ R X14 is an electron withdrawing group.
  • R X12 is an electron withdrawing group, it is preferred that R X10, R X11, R X13 , R X14 is a hydrogen atom.
  • oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photopolymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the colored composition with time can be improved.
  • Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
  • only one kind of photopolymerization initiator may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention can contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0083 to 0092 of JP2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated in the present specification.
  • the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). But it may be.
  • the weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
  • an epoxy resin can be preferably used as the epoxy compound.
  • the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type.
  • Epoxy resin, glycidylamine-based epoxy resin, glycidylated epoxy resin of halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other Examples thereof include a copolymer with another polymerizable unsaturated compound.
  • the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.
  • EHPE3150 manufactured by Dicelle Co., Ltd.
  • EPICLON N-695 manufactured by DIC Corporation
  • Marproof G-0150M Marproof G-0150M, G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by Nichiyu Co., Ltd., epoxy group-containing polymer) and the like can be mentioned.
  • the content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the compound having a cyclic ether group may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention preferably contains a pigment derivative.
  • the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrole pigment.
  • it is more preferably a diketopyrrolopyrrole pigment skeleton.
  • the pigment derivative is preferably a phthalocyanine compound or a diketopyrrolopyrrole compound.
  • Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group and salts thereof.
  • alkali metal ions Li + , Na + , K +, etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+, etc.
  • ammonium ions imidazolium ions, pyridinium ions, etc.
  • Examples include phosphonium ion.
  • Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
  • Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be contained.
  • the maximum value of the molar extinction coefficient in the wavelength region of 400 ⁇ 700 nm of the transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ⁇ mol -1 ⁇ cm -1 or less is not more than 3000L ⁇ mol -1 ⁇ cm -1 Is more preferable, and 100 L ⁇ mol -1 ⁇ cm -1 or less is further preferable.
  • 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 derivative examples include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961.
  • Japanese Patent Laid-Open No. 03-026767 Japanese Patent Application Laid-Open No. 03-153780
  • Japanese Patent Application Laid-Open No. 03-045662 Japanese Patent Application Laid-Open No. 04-285669
  • Japanese Patent Application Laid-Open No. 06-145546 Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158
  • Japanese Patent Laid-Open No. 10-030063 Japanese Patent Application Laid-Open No.
  • the content of the pigment derivative in the total solid content of the coloring composition is preferably 0.3 to 20% by mass.
  • the lower limit is preferably 0.6% by mass or more, and more preferably 0.9% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and further preferably 10% by mass or less.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic pigment.
  • the lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less.
  • only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably in the above range.
  • the coloring composition of the present invention contains a compound having three or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more (hereinafter, also referred to as a specific amine compound). You can also.
  • the molecular weight of the specific amine compound 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, further preferably 10,000 or less, and particularly preferably 2000 or less.
  • the molecular weight of the specific amine compound is the value calculated from the structural formula.
  • the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the 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.
  • the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.
  • the amine value of the specific amine compound is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.
  • the number of basic groups contained in the specific amine compound is preferably 4 or more, more preferably 6 or more, and further preferably 10 or more.
  • the basic group of the specific amine compound is preferably an amino group.
  • the specific amine compound is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino. It is more preferable that the compound contains a group and a tertiary amino group, respectively.
  • the amino group contained in the specific amine compound may be a cyclic amino group.
  • the cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group.
  • the cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group.
  • the cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure.
  • the hindered amine structure it is preferable that the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group.
  • the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl.
  • 2,6-dimethylpiperidyl group 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group.
  • 1,2,2,6,6-pentamethylpiperidyl group or 2,2,6,6-tetramethylpiperidyl group is preferable, and 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.
  • the specific amine compound is preferably polyalkyleneimine because it can further improve the storage stability of the coloring composition.
  • the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively.
  • the number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
  • Specific examples of the alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine.
  • the polyalkyleneimine is particularly preferably polyethyleneimine. Further, polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable. Examples of commercially available polyethyleneimine products 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 the specific amine compound 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 further 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 further preferably 3% by mass or less.
  • the content of the specific amine compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more.
  • the upper limit is preferably 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.
  • the content of the specific amine compound is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the graft resin having an acid group.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more.
  • the upper limit is preferably 45 parts by mass or less, more preferably 40% by mass or less, and further preferably 30 parts by mass or less.
  • the coloring composition of the present invention preferably contains a solvent.
  • the solvent is preferably an organic solvent.
  • the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like.
  • paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein by reference.
  • an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-di
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • the content of the solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
  • the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
  • substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evolution Analysis and Restriction of Chemicals
  • PRTR Policy Release and Transfer Register
  • VOC Volatile and Transfer Registor
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • a method for reducing the environmentally regulated substance there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to improve efficiency.
  • a polymerization inhibitor or the like is added and distilled under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be.
  • These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a colored composition stage prepared by mixing these compounds. It is possible at any stage of.
  • the coloring composition of the present invention may contain a curing accelerator.
  • the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidin salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
  • Specific examples of the curing accelerator include the compound described in paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compound described in paragraph numbers 0246 to 0253 of JP-A-2015-034963, and JP-A-2013-041165. Compounds described in Japanese Patent Laid-Open No.
  • the curing accelerator when the curing accelerator is contained, the content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the coloring composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. Details thereof are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. These compounds are incorporated herein by reference.
  • Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
  • Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
  • the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like.
  • examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.
  • the polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
  • the coloring composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group.
  • a phenyl group and the like preferably an amino group, a (meth) acryloyl group and an epoxy group.
  • silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino.
  • Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy There are propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co
  • the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. , These contents 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. preferable.
  • the silane coupling agent may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
  • the coloring composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
  • the surfactant the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
  • the surfactant is preferably a fluorine-based surfactant.
  • the liquid characteristics particularly, fluidity
  • the liquid saving property is further improved.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in a coloring composition.
  • fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
  • the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
  • fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • 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.
  • a fluorine-based surfactant the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.
  • the fluorine-based surfactant a block polymer can also be used.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000.
  • % indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all of which are Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shinetsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.
  • 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 coloring composition of the present invention only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the coloring composition of the present invention may be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, etc.), if necessary. It may contain a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification.
  • the coloring composition of the present invention may contain a light resistance improving agent.
  • the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774.
  • the coloring composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, which is not bound or coordinated with a pigment or the like. , It is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuation due to elution of metal atoms / metal ions, Effects such as improvement of display characteristics can be expected.
  • Examples of the types of free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, and the like. Examples thereof include Cs, Ni, Cd, Pb and Bi.
  • the content of free halogen not bonded or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is not substantially contained.
  • Examples of the halogen include F, Cl, Br, I and their anions.
  • Examples of the method for reducing free metals and halogens in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the coloring composition of the present invention does not substantially contain terephthalic acid ester.
  • substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
  • the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be restricted.
  • the perfluoroalkyl sulfonic acid particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • a salt thereof and a par
  • the content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition.
  • the coloring composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof.
  • perfluoroalkyl sulfonic acid and its salt by using a compound that can substitute for perfluoroalkyl sulfonic acid and its salt, and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid can be used.
  • a coloring composition that is substantially free of salts thereof may be selected.
  • Examples of compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt.
  • the coloring composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
  • the container for containing the coloring composition is not particularly limited, and a known container can be used.
  • a storage container for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the coloring composition, and suppressing the deterioration of the components.
  • the coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the coloring composition, all the components may be dissolved and / or dispersed in a solvent at the same time to prepare the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to prepare a coloring composition.
  • the mechanical force used for dispersing the organic pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
  • the process and disperser for dispersing organic pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industry centered on suspension (solid / liquid dispersion system)". Practical application The process and disperser described in Paragraph No.
  • the particles may be miniaturized in the salt milling step.
  • the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
  • any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP).
  • filters using materials such as (including high-density, ultra-high molecular weight polyolefin resin).
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore diameter of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.
  • Advantech Toyo Co., Ltd. Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc.
  • KITZ Microfilter Co., Ltd. etc.
  • a fiber-like filter medium As the filter.
  • the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
  • filters for example, a first filter and a second filter
  • the filtration with each filter may be performed only once or twice or more.
  • filters having different pore diameters may be combined within the above-mentioned range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
  • the film of the present invention is a film obtained from the above-mentioned coloring composition of the present invention.
  • the film of the present invention can be used as a color filter or the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, and a yellow pixel.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the intended purpose. For example, the film thickness is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the film of the present invention can be produced through a step of applying the coloring composition of the present invention.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
  • the pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and a step of exposing the colored composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
  • the coloring composition layer of the present invention is used to form the coloring composition layer on the support.
  • the support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.
  • the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • a known method can be used as a method for applying the coloring composition.
  • a drop method drop cast
  • a slit coat method for example, a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
  • Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned.
  • the method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
  • the colored composition layer formed on the support may be dried (prebaked).
  • prebaking may not be performed.
  • the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.
  • the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.
  • the colored composition layer is exposed in a pattern (exposure step).
  • the colored composition layer can be exposed in a pattern by exposing the colored composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
  • pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume.
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2). Can be done.
  • the oxygen concentration and the exposure illuminance may be appropriately combined with each other.
  • the oxygen concentration may be 10% by volume and the illuminance may be 10,000 W / m 2
  • the oxygen concentration may be 35% by volume and the illuminance may be 20000 W / m 2 .
  • the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel).
  • the development and removal of the unexposed portion of the coloring composition layer can be performed using a developing solution.
  • the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
  • the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc.
  • examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed.
  • the nozzle for discharging the rinse liquid from the central portion of the support it is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support.
  • the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.
  • Additional exposure processing and post-baking are post-development curing treatments to complete the curing.
  • the heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. ..
  • the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • the pattern formation by the dry etching method includes a step of forming a colored composition layer on a support using the colored composition of the present invention and curing the entire colored composition layer to form a cured product layer.
  • the color filter of the present invention has the above-mentioned film of the present invention.
  • the film of the present invention is provided as a colored pixel of a color filter, more preferably as a green pixel.
  • the color filter is a color filter having at least a red pixel, a green pixel, and a blue pixel, and a colored pixel having at least one color of the red pixel, the green pixel, and the blue pixel formed of the film of the present invention. Be done.
  • the color filter it has at least a cyan color pixel, a magenta color pixel and a yellow pixel, and at least one color pixel of the cyan color pixel, the magenta color pixel and the yellow pixel is composed of the film of the present invention.
  • the color filter can be used for solid-state image pickup devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the width of the pixels included in the color 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 further preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, further 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 color filter has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less.
  • the lower limit is not specified, but it is preferably 0.1 nm or more, for example.
  • the surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be appropriately set to a preferable 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, it is preferred that the volume resistivity value of the pixel is 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more. The upper limit is not specified, but it is preferably 10 14 ⁇ ⁇ cm or less, for example.
  • the volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the film (pixel) of the present invention.
  • various functions such as oxygen blocking, low reflection, prohydrophobicization, 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 resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
  • the components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and 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 thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, 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 for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4. Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.
  • the resin composition When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as the application method of the resin composition.
  • a known organic solvent for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.
  • the protective layer is formed by the chemical vapor deposition method, the known chemical vapor deposition method (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) is used as the chemical vapor deposition method. Can be used.
  • the protective layer contains organic / inorganic fine particles, an absorbent for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an adhesive, a surfactant, and other additives, if necessary. Is also good.
  • organic / inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like.
  • a known absorber can be used as the absorber of light having a specific wavelength.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
  • the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
  • the color filter may have a base layer.
  • the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • the color filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the solid-state image sensor of the present invention has the above-mentioned film of the present invention.
  • the configuration of the solid-state image sensor is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, and examples thereof include the following configurations.
  • a solid-state image pickup device CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.
  • a transfer electrode made of polysilicon or the like.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall preferably has a lower refractive index than each colored pixel. Examples of the image pickup apparatus having such a structure are described in JP-A-2012-227478, JP-A-2014-179757, International Publication No. 2018/043654, and US Patent Application Publication No.
  • the image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.
  • the image display device of the present invention has the above-mentioned film of the present invention.
  • the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • the liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
  • ⁇ Manufacturing of dispersion> After mixing the raw materials shown in the table below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm was added, and dispersion treatment was performed for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion liquid. ..
  • the numerical value of the blending amount of each raw material in the table below is a part by mass.
  • the value of the blending amount of the resin (dispersant) is the value of the blending amount in the resin solution having a solid content of 20% by mass.
  • PR122 C.I. I. Pigment Red 122 (red pigment)
  • PR177 C.I. I. Pigment Red 177 (red pigment)
  • PR254 C.I. I. Pigment Red 254 (red pigment)
  • PR264 C.I. I. Pigment Red 264 (red pigment)
  • PR269 C.I. I. Pigment Red 269 (red pigment)
  • PR272 C.I. I. Pigment Red 272 (red pigment)
  • PY129 C.I. I. Pigment Yellow 129 (yellow pigment)
  • PY139 C.I. I. Pigment Yellow 139 (yellow pigment)
  • PY150 C.I. I. Pigment Yellow 150 (yellow pigment)
  • PY185 C.I.
  • [dye] AR289 C.I. I. Acid Red 289
  • Dye 1 A compound having the following structure (xanthene dye, iPr is an isopropyl group in the following structural formula)
  • Dye 2 A polymer having the following structure (weight average molecular weight 7000) and C.I. I. Acid Red 52 salt-forming compound (xanthene dye)
  • Dye 3 A compound with the following structure (xanthene dye)
  • Dispersion aid Polyethyleneimine (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd., molecular weight 300, resin content 98% by mass or more, viscosity 200-500 mPa ⁇ s)
  • Dispersion aid 2 Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd., molecular weight 600, resin content 98% by mass or more, viscosity 500-2500 mPa ⁇ s)
  • Dispersion aid 3 Polyethyleneimine (Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd., molecular weight 1800, resin content 98% by mass or more, viscosity 8500 to 15000 mPa ⁇ s)
  • Dispersion aid 4 Polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd., molecular weight 10,000, resin content 98% by mass or more, viscosity 40,000 to 150,000 mP
  • ⁇ Resin> B-1 A resin solution of resin B-1 synthesized by the following method (solid content concentration 20% by mass). 50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted.
  • AIBN azobisisobutyronitrile
  • a resin solution of the resin B-2 synthesized by the following method (solid content concentration 20% by mass). 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate and 45.4 parts by mass of PGMEA were charged in the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted.
  • AIBN azobisisobutyronitrile
  • a resin solution of the resin B-3 synthesized by the following method solid content concentration 20% by mass.
  • the acid value was 43 mgKOH / g and the weight average molecular weight was the same except that 20 parts by mass of t-butyl methacrylate was changed to 20 parts by mass of (3-ethyloxetane-3-yl) methyl methacrylate.
  • a resin solution of 9000 resin B-3 (graft resin having an acid group) having the following structure was obtained.
  • Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units.
  • Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units.
  • B-6 Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the mass ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 13000, acid 20 mass% PGMEA solution with a value of 65 mgKOH / g)
  • B-7 20 mass of a resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 10000). % PGMEA solution
  • B-8 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the mass ratio. Weight average molecular weight 13000, acid value 74 mgKOH / g)
  • B-9 A 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000, acid value 69 mgKOH / g).
  • B-10 A 20 mass% PGMEA solution of a resin having the following structure (block copolymer, the numerical value added to the main chain is a mass ratio. Weight average molecular weight 74000, acid value 8 mgKOH / g, amine value 95 mgKOH / g).
  • B-11 20 mass% PGMEA solution of a resin having the following structure (block copolymer, the numerical value added to the main chain is the molar ratio. Weight average molecular weight 6000).
  • B-12 Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the mass ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 13000, acid 20 mass% PGMEA solution with a value of 19 mgKOH / g)
  • ⁇ Manufacturing of coloring composition The raw materials listed in the table below were mixed to prepare a colored composition.
  • the value of the blending amount of the resin is the value of the blending amount in the resin solution having a solid content of 20% by mass.
  • the content of the coloring material in the total solid content of the coloring composition is shown in the column of "coloring material content”.
  • the content of the specific compound in the total solid content of the coloring composition is shown in the column of "Specific compound content”.
  • the raw materials other than the dispersion liquid and the resin are as follows.
  • G-1, G-2 Compounds with the following structure
  • G-3 Irgure OXE01 (Oxime compound manufactured by BASF)
  • G-4 Irgure OXE02 (Oxime compound manufactured by BASF)
  • G-5 Omnirad 379 ( ⁇ -aminoketone compound manufactured by IGM Resins B.V.)
  • (Surfactant) I-1 A 1% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000). In the following formula,% indicating the ratio of the repeating unit is mol%.
  • A-1 EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol)
  • Antioxidant 1 Compound with the following structure (phenolic antioxidant, t-Bu in the structural formula is tert-butyl group)
  • Antioxidant 2 A compound having the following structure (phenolic antioxidant, t-Bu in the structural formula is a tert-butyl group)
  • Antioxidant 3 Compound with the following structure (phosphorus antioxidant)
  • the transmittance of light with a wavelength of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the maximum value ( ⁇ Tmax) of the amount of change in transmittance was obtained.
  • the spectral variation after the heat resistance test was evaluated in.
  • the amount of change in the transmittance is the difference in the transmittance of the film before and after the heat resistance test (
  • the maximum value ( ⁇ Tmax) of the change amount of the transmittance is the change amount of the transmittance at the wavelength where the change amount of the transmittance is the largest before and after the heat resistance test.
  • a composition for forming a base layer (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a glass wafer by a spin coating method so that the film thickness is 0.1 ⁇ m, and 220 using a hot plate.
  • the underlayer was formed by heating at ° C. for 1 hour.
  • Each coloring composition was applied onto the glass wafer with a base layer by a spin coating method so that the film thickness after post-baking would be the film thickness shown in the table. Then, using a hot plate, the composition layer was formed by heating at 100 ° C. for 2 minutes.
  • the composition layer was exposed to light having a wavelength of 365 nm at an exposure amount of 500 mJ / cm 2 using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.).
  • the composition layer after exposure was paddle-developed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was rinsed with water in a spin shower and then washed with pure water. Then, the water droplets were blown off with high-pressure air, the glass wafer was naturally dried, and then post-baked at 220 ° C. for 300 seconds using a hot plate to form a film having the film thickness shown in the table.
  • the obtained film was stored in a high temperature chamber set at 120 ° C. for 1000 hours, and a heat resistance test was carried out.
  • the luminance distribution is analyzed by the following method using a glass wafer (evaluation substrate) on which a film is formed before and after the heat resistance test, and color unevenness is evaluated based on the number of pixels whose deviation from the average is ⁇ 10% or more. Was done. The method of measuring the luminance distribution will be described.
  • An evaluation substrate is installed between the observation lens of the optical microscope and the light source to irradiate the observation lens with light, and the transmitted light state is measured by the optical microscope MX-50 (manufactured by Olympus) equipped with a digital camera. Observed using.
  • Imaging of the film surface was performed on five arbitrarily selected regions.
  • the brightness of the captured image was quantified and saved as a density distribution of 256 gradations from 0 to 255.
  • the luminance distribution was analyzed from this image, and the color unevenness was evaluated with the number of pixels whose deviation from the average exceeded ⁇ 10%.
  • the evaluation criteria are as follows. If the evaluation is A to C, it is judged that there is no practical problem.
  • A The number of pixels whose deviation from the average exceeds ⁇ 10% is 1000 or less.
  • B The number of pixels whose deviation from the average exceeds ⁇ 10% is more than 1000 and 3000 or less.
  • C The deviation from the average is ⁇ 10.
  • the number of pixels exceeding% exceeds 3000 and is 5000 or less.
  • D The deviation from the average exceeds ⁇ 10%.
  • the number of pixels exceeds 5000.
  • a to C are in the range where there is no problem in use.
  • a composition for forming a base layer (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a crow wafer by a spin coating method so that the film thickness is 0.1 ⁇ m, and the temperature is 220 ° C. using a hot plate.
  • the underlayer was formed by heating for 1 hour.
  • Each coloring composition was applied onto the glass wafer with a base layer by a spin coating method so that the film thickness after post-baking would be the film thickness shown in the table. Then, using a hot plate, the composition layer was formed by heating at 100 ° C. for 2 minutes.
  • the composition layer was exposed to light having a wavelength of 365 nm at an exposure amount of 1000 mJ / cm 2 using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.).
  • the glass wafer on which the composition layer after exposure was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM) was placed. Paddle development was performed at 23 ° C. for 60 seconds using a 60% diluted solution manufactured by Electronics Materials Co., Ltd.
  • the glass wafer is fixed to a horizontal rotary table by a vacuum chuck method, and while the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in a shower shape from a ejection nozzle to perform a rinse treatment. And then spray dried. Further, heat treatment (post-baking) was performed for 480 seconds using a hot plate at 200 ° C. to obtain a first-layer colored film. A coloring composition for color mixing evaluation was applied onto the obtained first colored film using a spin coater so that the film thickness after prebaking was 0.6 ⁇ m, and 120 using a hot plate at 100 ° C.
  • Heat treatment was performed for seconds to obtain a laminated color filter in which a coloring composition layer (second layer) for color mixing evaluation was formed on the first coloring film.
  • the obtained laminated color filter was developed, rinsed and spray-dried in the same manner as in the formation of the first colored pixel, and the colored composition layer for color mixing evaluation was developed and removed.
  • the spectral variation ( ⁇ T% max) of the maximum transmittance of the first colored film immediately after the preparation of the first colored film and after the development and removal of the colored composition layer for color mixing evaluation was measured by MCPD-3000 (Otsuka Electronics (Otsuka Electronics Co., Ltd.). The color mixture of the residue of the second layer coloring composition remaining on the first layer coloring film was evaluated.
  • the maximum transmittance is the amount of change in the transmittance of the first colored film immediately after the production of the first colored film and after the development and removal of the colored composition layer for color mixing evaluation, and is the change in the transmittance. It is the amount of change in transmittance at the wavelength with the largest amount. The smaller the spectral variation ( ⁇ T% max) of the maximum transmittance, the less likely it is that residual color mixing will occur, which is more desirable.
  • a to C are in the range where there is no problem in use. Except for Examples B1 to B9, the coloring composition for color mixture evaluation includes 65 parts by mass of the dispersion liquid B9, 6 parts by mass of the resin B-9, and 2.8 parts by mass of the polymerizable monomer M-2.
  • a coloring composition prepared by mixing 0.8 parts by mass of a photopolymerization initiator G-3, 5 parts by mass of a surfactant I-1, and 20.4 parts by mass of a solvent K-1. was used. Further, for Examples B1 to B9, the coloring composition of Example R1 was used as the coloring composition for color mixing evaluation.
  • the composition for forming a base layer was changed from CT-4000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) to the compositions for forming a base layer 1 to 11 prepared below, and these base layers were changed.
  • a silicon wafer with a base layer obtained by applying a forming composition to a film thickness of 3 nm by a spin coating method and heating at 220 ° C. for 5 minutes using a hot plate to form a base layer. Even when the adhesion was evaluated by the same procedure using the coloring composition of each example above, the same effect as that of each example was obtained.
  • Resin C-1 PGMEA 30% by mass solution of resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 20000)
  • Resin C-2 Resin having the following structure (the numerical value added to the main chain is molar) Ratio.
  • Resin C-3 PGMEA 30% by mass solution with a resin having the following structure (the numerical value attached to the main chain is a molar ratio. Weight average molecular weight of 20000).
  • PGMEA 30% by mass solution of resin having the following structure is the numerical value added to the main chain is the molar ratio.
  • Resin C-5 Resin having the following structure (the numerical value added to the main chain is the molar ratio.
  • Resin C-6 PGMEA 30% by mass solution having the following structure (the numerical value added to the main chain is the molar ratio.
  • Resin C-7 of the following structure PGMEA 30% by mass solution of resin (value added to the main chain is the molar ratio.
  • Resin C-8 Resin having the following structure (value added to the main chain is the molar ratio.
  • Surfactant 1 A compound having the following structure (weight average molecular weight 14000,% indicating the ratio of repeating units is mol%).
  • Surfactant 2 KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., siloxane-based surfactant)
  • solvent 1 Propylene glycol monomethyl ether acetate (PGMEA)
  • Example 1001 The green coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 ⁇ m square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water.
  • TMAH tetramethylammonium hydroxide
  • the green coloring composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate.
  • the red coloring composition and the blue coloring composition were also patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having green pixels, red pixels and blue pixels.
  • green pixels are formed by a Bayer pattern
  • red pixels and blue pixels are formed by an island pattern in an adjacent region thereof.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • the coloring composition of Example G1 was used.
  • the red coloring composition the coloring composition of Example R1 was used.
  • the blue coloring composition the coloring composition of Example B1 was used.
  • Example 1002 A cyan-colored composition was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 ⁇ m square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the cyan-colored composition was patterned to form cyan-colored pixels.
  • the yellow coloring composition and the magenta coloring composition were also patterned by the same process to sequentially form yellow pixels and magenta color pixels to form a color filter having cyan color pixels, yellow pixels and magenta color pixels.
  • cyan pixels are formed by a Bayer pattern, and yellow pixels and magenta pixels are formed by an island pattern in an adjacent region thereof.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • the coloring composition of Example C1 was used.
  • the coloring composition of Example Y1 was used.
  • the magenta coloring composition the coloring composition of Example M1 was used.

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Abstract

This coloring composition contains: a coloring material including an organic pigment; a resin; and a compound A protected with a protecting group that is capable of detaching, through application of heat, a phenolic hydroxy group of a phenol-based antioxidant. In the total solid content of the coloring composition, the coloring material is contained in an amount of 40 mass% or more. This film is obtained by using said coloring composition. This color filter, this solid-state imaging element, and this image display device include said film.

Description

着色組成物、膜、カラーフィルタ、固体撮像素子および画像表示装置Coloring compositions, films, color filters, solid-state image sensors and image display devices
　本発明は、有機顔料を含む着色組成物に関する。また、本発明は、着色組成物を用いた膜、カラーフィルタ、固体撮像素子および画像表示装置に関する。 The present invention relates to a coloring composition containing an organic pigment. The present invention also relates to a film, a color filter, a solid-state image pickup device, and an image display device using a coloring composition.
　近年、デジタルカメラ、カメラ付き携帯電話等の普及から、電荷結合素子（ＣＣＤ）イメージセンサなどの固体撮像素子の需要が大きく伸びている。ディスプレイや光学素子のキーデバイスとしてカラーフィルタが使用されている。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 widespread use 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 the three primary colors of red, green, and blue, and plays a role of decomposing transmitted light into the three primary colors.
　カラーフィルタの各色の着色画素は、顔料などの色材を含む着色組成物を用いて製造されている。 The colored pixels of each color of the color filter are manufactured by using a coloring composition containing a coloring material such as a pigment.
　また、特許文献１には、潜在性酸化防止剤（Ａ）及び着色剤（Ｂ）を含有する着色組成物に関する発明が記載されている。 Further, Patent Document 1 describes an invention relating to a coloring composition containing a latent antioxidant (A) and a coloring agent (B).
特開２０１５－１３１９３７号公報Japanese Unexamined Patent Publication No. 2015-131937
　本発明者が、有機顔料を含む着色組成物を用いて得られる膜について鋭意検討を進めたところ、長期間の加熱処理（例えば、１３０℃で１０００時間の加熱処理）後の膜の分光変動や色ムラについて、更なる改善の余地があることが分かった。特に、膜中の色材の含有量が多くなるほど、長期の耐熱試験後の膜の分光変動や色ムラが大きくなる傾向にあった。 As a result of diligent studies on a film obtained by using a coloring composition containing an organic pigment, the present inventor found that the spectral fluctuation of the film after a long-term heat treatment (for example, heat treatment at 130 ° C. for 1000 hours) was observed. It was found that there is room for further improvement in color unevenness. In particular, as the content of the coloring material in the film increases, the spectral fluctuation and color unevenness of the film after a long-term heat resistance test tend to increase.
　よって、本発明の目的は、長期間の加熱処理後も分光変動が小さく、色ムラの発生が抑制された膜を得ることのできる着色組成物、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 a coloring composition, a film, a color filter, a solid-state image pickup device, and an image display device capable of obtaining a film in which spectral fluctuation is small even after a long-term heat treatment and the occurrence of color unevenness is suppressed. Is to provide.
　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。
　＜１＞　有機顔料を含む色材と、樹脂と、フェノール系酸化防止剤のフェノール性ヒドロキシ基を加熱により脱離可能な保護基で保護した化合物Ａと、を含む着色組成物であり、
　上記着色組成物の全固形分中に上記色材を４０質量％以上含む、着色組成物。
　＜２＞　上記着色組成物の全固形分中に上記化合物Ａを１～１０質量％含む、＜１＞に記載の着色組成物。
　＜３＞　上記有機顔料の１００質量部に対して上記化合物Ａを２～２５質量部含む、＜１＞または＜２＞に記載の着色組成物。
　＜４＞　有機顔料を含む色材と、樹脂と、式（ＡＯ－１）で表される化合物と、を含む着色組成物であり、
　上記着色組成物の全固形分中に上記色材を４０質量％以上含む、着色組成物；
Figure JPOXMLDOC01-appb-C000002
 　式中、Ｒ１は、置換基を表し、
　Ｒ２は、－ＣＯＯＲ１１、－ＣＨ２－ＣＨ＝ＣＲ１２Ｒ１３、－ＣＨ２（－Ｏ－ＬＲ１）ｑ－Ｏ－Ｒ１４またはＳｉＲ１５Ｒ１６Ｒ１７を表し、
　Ｒ１１、Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７はそれぞれ独立してアルキル基を表し、
　Ｒ１２およびＲ１３はそれぞれ独立して水素原子またはアルキル基を表し、
　ＬＲ１はアルキレン基を表し、
　ｑは０または１を表し、
　ｑが１の場合、ＬＲ１とＲ１４は結合して環を形成していてもよく、
　ｍは０～４の整数を表し、
　ｎは１～１０の整数を表し、
　Ｘ１はｎ価の基を表す。
　＜５＞　上記着色組成物の全固形分中に上記式（ＡＯ－１）で表される化合物を１～１０質量％含む、＜４＞に記載の着色組成物。
　＜６＞　上記有機顔料の１００質量部に対して上記式（ＡＯ－１）で表される化合物を２～２５質量部含む、＜４＞または＜５＞に記載の着色組成物。
　＜７＞　上記有機顔料は緑色顔料、黄色顔料および赤色顔料から選ばれる少なくとも１種を含む、＜１＞～＜６＞のいずれか１つに記載の着色組成物。
　＜８＞　上記有機顔料は緑色顔料を含み、上記緑色顔料はフタロシアニン化合物を含む、＜１＞～＜６＞のいずれか１つに記載の着色組成物。
　＜９＞　上記樹脂は酸基を有するグラフト樹脂を含む、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
　＜１０＞　上記グラフト樹脂の酸価が２０～１５０ｍｇＫＯＨ／ｇである、＜９＞に記載の着色組成物。
　＜１１＞　上記グラフト樹脂の重量平均分子量が３０００～３５０００である、＜９＞または＜１０＞に記載の着色組成物。
　＜１２＞　更に、光重合開始剤と重合性化合物とを含む、＜１＞～＜１１＞のいずれか１つに記載の着色組成物。
　＜１３＞　上記光重合開始剤は、芳香族環に電子求引性基が導入された芳香族環基を有するオキシム化合物を含む、＜１２＞に記載の着色組成物。
　＜１４＞　更にフェノール系酸化防止剤を含む、＜１＞～＜１３＞のいずれか１つに記載の着色組成物。
　＜１５＞　＜１＞～＜１４＞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。
　＜１６＞　＜１５＞に記載の膜を含むカラーフィルタ。
　＜１７＞　＜１５＞に記載の膜を含む固体撮像素子。
　＜１８＞　＜１５＞に記載の膜を含む画像表示装置。 According to the study of the present inventor, it has been found that the above-mentioned object can be achieved by the coloring composition described later, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A coloring composition containing a coloring material containing an organic pigment, a resin, and a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protecting group that can be desorbed by heating.
A coloring composition containing 40% by mass or more of the coloring material in the total solid content of the coloring composition.
<2> The coloring composition according to <1>, which contains 1 to 10% by mass of the compound A in the total solid content of the coloring composition.
<3> The coloring composition according to <1> or <2>, which contains 2 to 25 parts by mass of the compound A with respect to 100 parts by mass of the organic pigment.
<4> A coloring composition containing a coloring material containing an organic pigment, a resin, and a compound represented by the formula (AO-1).
A coloring composition containing 40% by mass or more of the coloring material in the total solid content of the coloring composition;
Figure JPOXMLDOC01-appb-C000002
 In the formula, R 1 represents a substituent and represents
R 2 represents -COOR 11 , -CH 2- CH = CR 12 R 13 , -CH 2 (-OL R1 ) q- O-R 14 or SiR 15 R 16 R 17 .
R 11 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group.
R 12 and R 13 independently represent a hydrogen atom or an alkyl group, respectively.
LR1 represents an alkylene group
q represents 0 or 1 and represents
When q is 1, L R1 and R 14 may be combined to form a ring.
m represents an integer from 0 to 4 and represents
n represents an integer from 1 to 10 and represents
X 1 represents an n-valent group.
<5> The coloring composition according to <4>, wherein the total solid content of the coloring composition contains 1 to 10% by mass of the compound represented by the above formula (AO-1).
<6> The coloring composition according to <4> or <5>, which contains 2 to 25 parts by mass of the compound represented by the above formula (AO-1) with respect to 100 parts by mass of the organic pigment.
<7> The coloring composition according to any one of <1> to <6>, wherein the organic pigment contains at least one selected from a green pigment, a yellow pigment and a red pigment.
<8> The coloring composition according to any one of <1> to <6>, wherein the organic pigment contains a green pigment, and the green pigment contains a phthalocyanine compound.
<9> The coloring composition according to any one of <1> to <8>, wherein the resin contains a graft resin having an acid group.
<10> The coloring composition according to <9>, wherein the acid value of the graft resin is 20 to 150 mgKOH / g.
<11> The coloring composition according to <9> or <10>, wherein the graft resin has a weight average molecular weight of 3000 to 35000.
<12> The coloring composition according to any one of <1> to <11>, further comprising a photopolymerization initiator and a polymerizable compound.
<13> The coloring composition according to <12>, wherein the photopolymerization initiator contains an oxime compound having an aromatic ring group in which an electron-attracting group is introduced into the aromatic ring.
<14> The coloring composition according to any one of <1> to <13>, further containing a phenolic antioxidant.
<15> A film obtained by using the coloring composition according to any one of <1> to <14>.
<16> A color filter containing the film according to <15>.
<17> A solid-state image sensor including the film according to <15>.
<18> An image display device including the film according to <15>.
　本発明によれば、長期間の加熱処理後も分光変動が小さく、色ムラの発生が抑制された膜を得ることのできる着色組成物、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。 INDUSTRIAL APPLICABILITY According to the present invention, there are provided a coloring composition, a film, a color filter, a solid-state image pickup device, and an image display device capable of obtaining a film in which spectral fluctuation is small even after a long-term heat treatment and the occurrence of color unevenness is suppressed. can do.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、構造式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、重量平均分子量および数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）法により測定したポリスチレン換算値である。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において「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。 Hereinafter, the contents of the present invention will be described in detail.
In the present specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl ”represents both acryloyl and / or methacryloyl.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
＜着色組成物＞
　本発明の着色組成物の第１の態様は、有機顔料を含む色材と、樹脂と、フェノール系酸化防止剤のフェノール性ヒドロキシ基を加熱により脱離可能な保護基で保護した化合物Ａと、を含む着色組成物であり、着色組成物の全固形分中に色材を４０質量％以上含むことを特徴とする。
　また、本発明の着色組成物の第２の態様は、有機顔料を含む色材と、樹脂と、式（ＡＯ－１）で表される化合物と、を含む着色組成物であり、着色組成物の全固形分中に色材を４０質量％以上含むことを特徴とする。
　以下、上述した化合物Ａと式（ＡＯ－１）で表される化合物とを合わせて特定化合物ともいう。 <Coloring composition>
A first aspect of the coloring composition of the present invention comprises a coloring material containing an organic pigment, a resin, and a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protective group that can be desorbed by heating. It is a coloring composition containing 40% by mass or more of a coloring material in the total solid content of the coloring composition.
The second aspect of the coloring composition of the present invention is a coloring composition containing a coloring material containing an organic pigment, a resin, and a compound represented by the formula (AO-1). It is characterized by containing 40% by mass or more of a coloring material in the total solid content of the above.
Hereinafter, the compound A described above and the compound represented by the formula (AO-1) are collectively referred to as a specific compound.
　本発明の着色組成物は、着色組成物の全固形分中に有機顔料を含む色材を４０質量％以上含有しているにもかかわらず、上述した特定化合物を含むことにより、長期間の加熱処理後も分光変動が小さく、色ムラの発生が抑制された膜を形成することができる。このような効果が得られる詳細な理由は不明であるが、以下によるものであると推測される。 Although the coloring composition of the present invention contains 40% by mass or more of a coloring material containing an organic pigment in the total solid content of the coloring composition, it is heated for a long period of time by containing the above-mentioned specific compound. Even after the treatment, the spectral fluctuation is small, and it is possible to form a film in which the occurrence of color unevenness is suppressed. The detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following.
　本発明の着色組成物に含まれる上述した特定化合物は、製膜時（例えばポストベーク時など）に保護基が脱離してフェノール性ヒドロキシ基が生成され、酸化防止剤としての機能が発揮されると推測される。そして、特定化合物から生成される酸化防止剤として機能する成分の作用により、高温下での有機顔料の劣化や凝集を抑制することができたと推測される。このため、本発明の着色組成物は、長期間の加熱処理後も分光変動が小さく、色ムラの発生が抑制された膜を形成することができると推測される。 The above-mentioned specific compound contained in the coloring composition of the present invention has a protective group desorbed at the time of film formation (for example, at the time of post-baking) to generate a phenolic hydroxy group, and exhibits a function as an antioxidant. It is presumed. It is presumed that the action of the component that functions as an antioxidant produced from the specific compound could suppress the deterioration and aggregation of the organic pigment at high temperatures. Therefore, it is presumed that the coloring composition of the present invention can form a film in which spectral fluctuation is small and the occurrence of color unevenness is suppressed even after a long-term heat treatment.
　また、酸化防止剤を含む着色組成物を用いて膜を形成する場合、製膜時の加熱や露光などによって酸化防止剤が分解や変性して、膜中に十分な量の酸化防止剤が残存していないことがある。これに対し、上述した特定化合物は、製膜時に保護基が脱離してフェノール性ヒドロキシ基が生成されて、酸化防止剤としての機能が発揮されるものであるため、特定化合物の含有量が少量であっても膜中に十分な量の酸化防止剤として機能する成分を含有させることができる。このため、本発明の着色組成物は処方設計の自由度をより高めることもできる。 Further, when a film is formed using a coloring composition containing an antioxidant, the antioxidant is decomposed or denatured by heating or exposure during film formation, and a sufficient amount of the antioxidant remains in the film. I may not have done it. On the other hand, the above-mentioned specific compound has a small content of the specific compound because the protecting group is desorbed at the time of film formation to generate a phenolic hydroxy group and the specific compound exhibits a function as an antioxidant. Even so, the membrane can contain a sufficient amount of a component that functions as an antioxidant. Therefore, the coloring composition of the present invention can further increase the degree of freedom in formulation design.
　本発明の着色組成物は、カラーフィルタ用の着色組成物として好ましく用いられる。
具体的には、カラーフィルタの着色画素形成用の着色組成物として好ましく用いることができる。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、シアン色画素および黄色画素などが挙げられ、緑色画素またはシアン色画素であることが好ましい。また、本発明の着色組成物は、固体撮像素子用の着色組成物として好ましく用いることができ、固体撮像素子に用いられるカラーフィルタの着色画素形成用の着色組成物としてより好ましく用いることができる。 The coloring composition of the present invention is preferably used as a coloring composition for a color filter.
Specifically, it can be preferably used as a coloring composition for forming colored pixels of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, a yellow pixel, and the like, and a green pixel or a cyan color pixel is preferable. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a solid-state image sensor, and more preferably as a coloring composition for forming colored pixels of a color filter used for a solid-state image sensor.
　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 coloring composition of the present invention will be described.
＜＜色材＞＞
　本発明の着色組成物は色材を含有する。本発明の着色組成物に含まれる色材は、有機顔料を含む。なお、本明細書において、有機顔料とは有機化合物で構成された顔料のことである。また、本明細書において、顔料とは溶剤に対して溶解しにくい色材を意味する。顔料は、２３℃の水１００ｇおよび２３℃のプロピレングリコールモノメチルエーテルアセテート１００ｇに対する溶解度がいずれも０．１ｇ以下であることが好ましく、０．０１ｇ以下であることがより好ましい。 << Color material >>
The coloring composition of the present invention contains a coloring material. The coloring material contained in the coloring composition of the present invention contains an organic pigment. In the present specification, the organic pigment is a pigment composed of an organic compound. Further, in the present specification, the pigment means a coloring material that is difficult to dissolve in a solvent. The solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
　有機顔料の平均一次粒子径は、１～２００ｎｍが好ましい。下限は５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。上限は、１８０ｎｍ以下が好ましく、１５０ｎｍ以下がより好ましく、１００ｎｍ以下が更に好ましい。有機顔料の平均一次粒子径が上記範囲であれば、着色組成物中における有機顔料の分散安定性が良好である。なお、本発明において、有機顔料の一次粒子径は、有機顔料の一次粒子を透過型電子顕微鏡により観察し、得られた画像写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本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 size of the organic pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less. When the average primary particle size of the organic pigment is in the above range, the dispersion stability of the organic pigment in the coloring composition is good. In the present invention, the primary particle size of the organic pigment can be obtained from an image photograph obtained by observing the primary particles of the organic pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without aggregation.
　有機顔料は有彩色有機顔料であることが好ましい。有彩色有機顔料としては、例えば、黄色顔料、オレンジ色顔料、赤色顔料、緑色顔料、紫色顔料、青色顔料などが挙げられる。本発明で用いられる有機顔料は、緑色顔料、黄色顔料および赤色顔料から選ばれる少なくとも１種を含むものであることが好ましく、緑色顔料を含むものであることがより好ましい。 The organic pigment is preferably a chromatic organic pigment. Examples of the chromatic organic pigment include a yellow pigment, an orange pigment, a red pigment, a green pigment, a purple pigment, and a blue pigment. The organic pigment used in the present invention preferably contains at least one selected from a green pigment, a yellow pigment and a red pigment, and more preferably contains a green pigment.
　緑色顔料としては、フタロシアニン化合物、スクアリリウム化合物などが挙げられる。ここで、緑色顔料であるフタロシアニン化合物（フタロシアニン緑色顔料ともいう）は、膜中で熱拡散し易い傾向にあり、加熱後の膜中においてフタロシアニン緑色顔料が凝集して加熱後の膜の分光特性が変動したり、色ムラが生じ易い傾向にあるが、本発明の着色組成物によれば、フタロシアニン緑色顔料を用いた場合であっても、分光特性の変動や色ムラの発生を効果的に抑制することができる。このため、緑色顔料としてフタロシアニン化合物（フタロシアニン緑色顔料）を用いた場合において特に顕著な効果が得られる。 Examples of the green pigment include phthalocyanine compounds and squarylium compounds. Here, the phthalocyanine compound (also referred to as phthalocyanine green pigment), which is a green pigment, tends to be easily heat-diffused in the film, and the phthalocyanine green pigment aggregates in the heated film to improve the spectral characteristics of the heated film. Although it tends to fluctuate and cause color unevenness, according to the coloring composition of the present invention, fluctuations in spectral characteristics and occurrence of color unevenness are effectively suppressed even when a phthalocyanine green pigment is used. can do. Therefore, a particularly remarkable effect can be obtained when a phthalocyanine compound (phthalocyanine green pigment) is used as the green pigment.
　フタロシアニン緑色顔料としては、Ｃｕ、Ａｌ、Ｃｏ、Ｎｉ、ＴｉまたはＺｎを中心金属として有するフタロシアニン化合物が挙げられ、本発明の効果がより顕著に奏されるという理由から、フタロシアニン緑色顔料は、Ｃｕ、ＺｎまたはＡｌを中心金属として有するフタロシアニン化合物であることが更に好ましく、ＣｕまたはＺｎを中心金属として有するフタロシアニン化合物であることがより一層好ましい。上記中心金属にはさらに配位子が配位していてもよい。また、上記フタロシアニン化合物はハロゲン化フタロシアニン化合物であることが好ましい。ここで、ハロゲン化フタロシアニン化合物とは、ハロゲン原子を置換基として有するフタロシアニン化合物のことである。 Examples of the phthalocyanine green pigment include a phthalocyanine compound having Cu, Al, Co, Ni, Ti or Zn as a central metal, and the phthalocyanine green pigment is described as Cu, because the effect of the present invention is more prominently exhibited. It is more preferably a phthalocyanine compound having Zn or Al as a central metal, and even more preferably a phthalocyanine compound having Cu or Zn as a central metal. A ligand may be further coordinated to the central metal. Further, the phthalocyanine compound is preferably a halogenated phthalocyanine compound. Here, the halogenated phthalocyanine compound is a phthalocyanine compound having a halogen atom as a substituent.
　緑色顔料の具体例としては、カラーインデックス（Ｃ．Ｉ．）ピグメントグリーン７，１０，３６，３７，５８，５９，６２，６３，６４，６５，６６等が挙げられる。また、緑色顔料として、１分子中のハロゲン原子の平均個数が１０～１４個であり、かつ、臭素原子の平均個数が８～１２個で、塩素原子の平均個数が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号に記載されたフタロシアニン顔料が挙げられる。また、緑色顔料として中国特許出願第１０６９０９０２７号明細書に記載の化合物、国際公開第２０１２／１０２３９５号に記載のリン酸エステルを配位子として有するフタロシアニン化合物、特開２０１９－００８０１４号公報に記載のフタロシアニン化合物、特開２０１８－１８００２３号公報に記載のフタロシアニン化合物、特開２０１９－０３８９５８号公報に記載の化合物などを用いることもできる。 Specific examples of the green pigment include Color Index (CI) Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66 and the like. Further, as a green pigment, a halogen having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5. Halogenated zinc phthalocyanine pigments can also be used. Specific examples include the phthalocyanine pigment described in International Publication No. 2015/118720. Further, as a green pigment, the compound described in Chinese Patent Application No. 106900927, the phthalocyanine compound having a phosphate ester described in International Publication No. 2012/102395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, and the like can also be used.
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン７，３６，５８，５９，６２，６３が好ましい。 As a green pigment, C.I. I. Pigment greens 7, 36, 58, 59, 62, 63 are preferred.
　黄色顔料としては、アゾ化合物、アゾメチン化合物、キノフタロン化合物、イソインドリノン化合物、イソインドリン化合物、プテリジン化合物、アントラキノン化合物等が挙げられる。 Examples of the yellow pigment include azo compounds, azomethine compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, pteridine compounds, anthraquinone compounds and the like.
　黄色顔料の具体例としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４，２１５，２２８，２３１，２３２，２３３，２３４，２３５，２３６等が挙げられる。 Specific examples of yellow pigments include C.I. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1,36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179, 180,181,182,185,187,188,193,194,199,213,214,215,228,231,232,233,234,235,236 and the like can be mentioned.
　また、黄色顔料としては、下記構造のアゾバルビツール酸ニッケル錯体を用いることもできる。
Figure JPOXMLDOC01-appb-C000003
 Further, as the yellow pigment, a nickel azobarbituric acid complex having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000003
　また、黄色顔料として、特開２０１３－０５４３３９号公報の段落番号００１１～００３４に記載のキノフタロン化合物、特開２０１４－０２６２２８号公報の段落番号００１３～００５８に記載のキノフタロン化合物、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、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。 Further, as the yellow pigment, the quinophthalone compound described in paragraphs 0011 to 0034 of JP2013-054339, the quinophthalone compound described in paragraphs 0013 to 0058 of JP2014-026228, and JP-A-2018-0626444. The isoindrin compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, the quinophthalone compound described in JP-A-6432076, JP-A-2018-155881 The quinophthalone compound described in JP-A-2018-11757, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2017-197640, JP-A-2016 The quinophthalone compound described in JP-A-145282, the quinophthalone compound described in JP-A-2014-0855565, the quinophthalone compound described in JP-A-2014-0211139, the quinophthalone compound described in JP-A-2013-209614, and the present invention. The quinophthalone compound described in JP2013-209435, the quinophthalone compound described in JP2013-181015, the quinophthalone compound described in JP2013-061622, and the quinophthalone compound described in JP2013-032486. , A quinophthalone compound described in JP-A-2012-226110, a quinophthalone compound described in JP-A-2008-074987, a quinophthalone compound described in JP-A-2008-081565, and a quinophthalone compound described in JP-A-2008-074986. Kinophthalone compound, quinophthalone compound described in JP-A-2008-074985, quinophthalone compound described in JP-A-2008-054202, quinophthalone compound described in JP-A-2008-031281, JP-A-48-032765. The quinophthalone compound described, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in JP-A-6607427, the compound described in JP-A-2020-033525, and the compound described in JP-A-2020-033524. , The compound described in JP-A-2020-033523, the compound described in JP-A-2020-033522, the compound described in JP-A-2020-033521, International Publication No. 2 The compound described in 020/045200, the compound described in International Publication No. 2020/045199, and the compound described in International Publication No. 2020/045197 can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value.
　また、黄色顔料として、下記式（ＱＰ１）で表される化合物、および、下記式（ＱＰ２）で表される化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000004
 Further, as the yellow pigment, a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.
Figure JPOXMLDOC01-appb-C000004
　式（ＱＰ１）中、Ｘ１～Ｘ１６は各々独立に水素原子又はハロゲン原子を表し、Ｚ１は炭素数１～３のアルキレン基を表す。式（ＱＰ１）で表される化合物の具体例としては、特許第６４４３７１１号公報の段落番号００１６に記載されている化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000005
 In the formula (QP1), X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compound described in paragraph No. 0016 of Japanese Patent No. 6443711.
Figure JPOXMLDOC01-appb-C000005
　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。 Wherein (QP2), Y 1 ~ Y 3 represents a halogen atom independently. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (N + m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１２９，１３８，１３９，１５０，１８５，２１５が好ましく、Ｃ．Ｉ．ピグメントイエロー１３９，１５０，１８５がより好ましい。 As a yellow pigment, C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 215 is preferred, and C.I. I. Pigment Yellow 139, 150, 185 is more preferred.
　赤色顔料としては、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、ペリレン化合物およびチオインジゴ化合物などが挙げられる。 Examples of the red pigment include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds and thioindigo compounds.
　赤色顔料の具体例としては、Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２６９，２７０，２７２，２７９，２９１，２９４，２９５，２９６，２９７等が挙げられる。また、赤色顔料として、特開２０１７－２０１３８４号公報に記載の構造中に少なくとも１つの臭素原子が置換したジケトピロロピロール化合物、特許第６２４８８３８号の段落番号００１６～００２２に記載のジケトピロロピロール化合物、国際公開第２０１２／１０２３９９号に記載のジケトピロロピロール化合物、国際公開第２０１２／１１７９６５号に記載のジケトピロロピロール化合物、特開２０１２－２２９３４４号公報に記載のナフトールアゾ化合物、特許第６５１６１１９号公報に記載の赤色顔料、特許第６５２５１０１号公報に記載の赤色顔料などを用いることもできる。また、赤色顔料として、芳香族環に対して酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 Specific examples of red pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48: 2,48:3,48:4 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 294, 295, 296, 297 and the like can be mentioned. Further, as a red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole described in paragraphs 0016 to 0022 of Patent No. 6248838. Compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117956, naphthol azo compounds described in JP-A-2012-229344, Patent No. The red pigment described in Japanese Patent No. 6516119, the red pigment described in Japanese Patent No. 6525101, and the like can also be used. Further, as the red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. ..
　オレンジ色顔料としては、Ｃ．Ｉ．ピグメントオレンジ２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等が挙げられる。 As an orange pigment, C.I. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. Can be mentioned.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１，１９，２３，２７，３２，３７，４２，６０，６１等が挙げられる。 As a purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 and the like.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，２９，６０，６４，６６，７９，８０，８７，８８等が挙げられる。 As a blue pigment, C.I. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87,88 etc. Be done.
　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。 Regarding the diffraction angles preferably possessed by various pigments, Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Laid-Open No. 2020-026553, and Japanese Patent Application Laid-Open No. 2020-033526 are described. These contents are incorporated herein by reference.
　有彩色有機顔料は、２種以上組み合わせて用いてもよい。例えば、本発明の着色組成物をカラーフィルタの緑色画素形成用として用いる場合には、緑色顔料と黄色顔料とを併用することが好ましい。また、緑色顔料と黄色顔料との割合は、緑色顔料１００質量部に対して、黄色顔料が１０～１２０質量部であることが好ましく、２０～１００質量部であることがより好ましく、２５～７５質量部であることが更に好ましい。 Two or more kinds of chromatic organic pigments may be used in combination. For example, when the coloring composition of the present invention is used for forming green pixels of a color filter, it is preferable to use a green pigment and a yellow pigment in combination. The ratio of the green pigment to the yellow pigment is preferably 10 to 120 parts by mass, more preferably 20 to 100 parts by mass, and 25 to 75 parts by mass with respect to 100 parts by mass of the green pigment. It is more preferably by mass.
　本発明の着色組成物に用いられる色材には、有機顔料に加えて更に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、ピラゾールアゾ化合物、アニリノアゾ化合物、トリアリールメタン化合物、アントラキノン化合物、アントラピリドン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物、キサンテン化合物、フタロシアニン化合物、ベンゾピラン化合物、インジゴ化合物、ピロメテン化合物が挙げられる。また、特開２０１２－１５８６４９号公報に記載のチアゾール化合物、特開２０１１－１８４４９３号公報に記載のアゾ化合物、特開２０１１－１４５５４０号公報に記載のアゾ化合物を用いることもできる。また、染料としては、色素多量体を用いることもできる。色素多量体は、一分子中に、色素構造を２以上有するものであり、色素構造を３以上有することが好ましい。上限は、特に限定はないが、１００以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量（Ｍｗ）は、２０００～５００００が好ましい。下限は、３０００以上がより好ましく、６０００以上がさらに好ましい。上限は、３００００以下がより好ましく、２００００以下がさらに好ましい。色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報、特開２０１６－１０２１９１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。 As the coloring material used in the coloring composition of the present invention, a dye may be further used in addition to the organic pigment. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound, xanthene compound, Examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds. Further, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and the azo compound described in JP-A-2011-145540 can also be used. Further, as the dye, a dye multimer can also be used. 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 have the same dye structure or may have different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. For dye multimers, JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, JP-A-2016-102191, International Publication No. 2016 / The compounds described in 031442 and the like can also be used.
　着色組成物の全固形分中における色材の含有量は、４０質量％以上であり、４５質量％以上であることが好ましく、５０質量％以上であることがより好ましい。また、着色組成物の全固形分中における色材の含有量の上限は、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。
　また、着色組成物の全固形分中における有機顔料の含有量は、２０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、４５質量％以上であることが更に好ましく、４５質量％以上であることが特に好ましい。また、着色組成物の全固形分中における有機顔料の含有量の上限は、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。
　また、色材中における有機顔料の含有量は、５０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、８０質量％以上であることが更に好ましく、９０質量％以上であることが特に好ましい。上限は１００質量％以下であってもよい。 The content of the coloring material in the total solid content of the coloring composition is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more. Further, the upper limit of the content of the coloring material in the total solid content of the coloring composition is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. preferable.
The content of the organic pigment in the total solid content of the coloring composition is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more. It is particularly preferable that it is 45% by mass or more. Further, the upper limit of the content of the organic pigment in the total solid content of the coloring composition is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. preferable.
The content of the organic pigment in the coloring material is preferably 50% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. It is particularly preferable to have. The upper limit may be 100% by mass or less.
＜＜樹脂＞＞
　本発明の着色組成物は、樹脂を含有する。樹脂は、例えば、顔料を着色組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料を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の目的で使用することもできる。 << Resin >>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing the pigment in the coloring composition or for the purpose of a binder. The resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such use of the resin is an example, and it can be used for purposes other than such use.
　樹脂の重量平均分子量（Ｍｗ）は、３０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、４０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.
　樹脂としては、（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、ポリイミン樹脂、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、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。また、特開２０１７－２０６６８９号公報の段落番号００４１～００６０に記載の樹脂、特開２０１８－０１０８５６号公報の段落番号００２２～００７１に記載の樹脂を用いることもできる。 Examples of the resin include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyimine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resin described in paragraph numbers 0041 to 0060 of JP-A-2017-206689 and the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856 can also be used.
　本発明において、樹脂として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、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。酸基を有する樹脂は、例えば、アルカリ可溶性樹脂として用いることができる。 In the present invention, it is preferable to use a resin having an acid group as the resin. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. The resin having an acid group can be used, for example, as an alkali-soluble resin.
　酸基を有する樹脂は、酸基を側鎖に有する繰り返し単位を含むことが好ましく、酸基を側鎖に有する繰り返し単位を樹脂の全繰り返し単位中５～７０モル％含むことがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の上限は、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましい。酸基を側鎖に有する繰り返し単位の含有量の下限は、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましい。 The resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
　酸基を有する樹脂は、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ことも好ましい。 The resin having an acid group is a monomer 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 include repeating units derived from the components.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（ＥＤ１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
Figure JPOXMLDOC01-appb-C000007
 　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 hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
Figure JPOXMLDOC01-appb-C000007
 In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For the details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, and the contents thereof are incorporated in the present specification.
　エーテルダイマーの具体例としては、例えば、特開２０１３－０２９７６０号公報の段落番号０３１７の記載を参酌することができ、この内容は本明細書に組み込まれる。 As a specific example of the ether dimer, for example, the description in paragraph No. 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.
　本発明で用いられる樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含むことも好ましい。
Figure JPOXMLDOC01-appb-C000008
 　式（Ｘ）中、Ｒ１は、水素原子またはメチル基を表し、Ｒ２は炭素数２～１０のアルキレン基を表し、Ｒ３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin used in the present invention preferably contains a repeating unit derived from the compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000008
 In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer from 1 to 15.
　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。 Regarding the resin having an acid group, the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 0999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can also be used.
　酸基を有する樹脂の酸価は、５～２００ｍｇＫＯＨ／ｇが好ましい。上限は１５０ｍｇＫＯＨ／ｇ以下であることが好ましく、１００ｍｇＫＯＨ／ｇ以下であることがより好ましく、８０ｍｇＫＯＨ／ｇ以下であることが更に好ましい。下限は１０ｍｇＫＯＨ／ｇ以上であることが好ましく、１５ｍｇＫＯＨ／ｇ以上であることがより好ましく、２０ｍｇＫＯＨ／ｇ以上であることが更に好ましい。酸基を有する樹脂の重量平均分子量（Ｍｗ）は、３０００～３５０００であることが好ましい。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。下限は、４０００以上であることが好ましく、６０００以上であることがより好ましく、７０００以上であることが更に好ましい。 The acid value of the resin having an acid group is preferably 5 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more. The weight average molecular weight (Mw) of the resin having an acid group is preferably 3000 to 35000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
　本発明の着色組成物は、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。塩基性基を有する樹脂としては、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が挙げられる。 The coloring composition of the present invention can also use a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, and has both a repeating unit having a basic group in the 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 the side chain and a repeating unit not containing a basic group is further 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, and more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less. Examples of the resin having a basic group are described in the block copolymers (B) described in paragraphs 0063 to 0112 of JP2014-219665A and paragraphs 0046 to 0076 of JP-A-2018-156021. The block copolymer A1 can be mentioned.
　本発明の着色組成物は、酸基を有するグラフト樹脂（以下、酸性グラフト樹脂ともいう）を含むことが好ましい。この態様によれば、長期間の加熱処理後の膜の分光変動や、色ムラの発生をより効果的に抑制することができる。このような効果が得られる詳細な理由は不明であるが、次によるものであると推測される。すなわち、製膜時に酸性グラフト樹脂の酸基の作用によって、上述した特定化合物からの保護基の脱離反応が促進されて、膜中に特定化合物から生成される酸化防止剤として機能する成分の含有量を高めることができると推測される。そして、酸性グラフト樹脂のグラフト鎖によって有機顔料の凝集を抑制でき、更には、特定化合物から生成される酸化防止剤として機能する成分の作用により、高温下での有機顔料の劣化や凝集を抑制することができると推測される。このような理由により、長期間の加熱処理後の膜の分光変動や、色ムラの発生をより抑制することができると推測される。 The coloring composition of the present invention preferably contains a graft resin having an acid group (hereinafter, also referred to as an acidic graft resin). According to this aspect, it is possible to more effectively suppress the spectral fluctuation of the film and the occurrence of color unevenness after a long-term heat treatment. The detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following. That is, the action of the acid group of the acidic graft resin during film formation promotes the elimination reaction of the protecting group from the above-mentioned specific compound, and the film contains a component that functions as an antioxidant produced from the specific compound. It is presumed that the amount can be increased. Then, the aggregation of the organic pigment can be suppressed by the graft chain of the acidic graft resin, and further, the deterioration and aggregation of the organic pigment at high temperature are suppressed by the action of the component which functions as an antioxidant produced from the specific compound. It is speculated that it can be done. For this reason, it is presumed that the spectral fluctuation of the film after a long-term heat treatment and the occurrence of color unevenness can be further suppressed.
　酸性グラフト樹脂は分散剤として好ましく用いることができる。ここで、グラフト樹脂とは、グラフト鎖を有する繰り返し単位を含む樹脂を意味する。また、グラフト鎖とは、繰り返し単位の主鎖から枝分かれして伸びるポリマー鎖のことを意味する。 The acidic graft resin can be preferably used as a dispersant. Here, the graft resin means a resin containing a repeating unit having a graft chain. Further, the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit.
　グラフト鎖は、ポリエステル構造、ポリエーテル構造、ポリ（メタ）アクリル構造、ポリスチレン構造、ポリウレタン構造、ポリウレア構造およびポリアミド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であることが好ましく、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であることがより好ましい。 The graft chain is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure, and the polyester structure, More preferably, it is a polymer chain containing at least one structure selected from a polyether structure and a poly (meth) acrylic structure.
　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、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、ヒドロキシ基、アミノ基等が挙げられる。なかでも、顔料など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５～２４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、分岐、及び、環状のいずれでもよく、直鎖または分岐が好ましい。 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 aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, an amino group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferable.
　グラフト鎖の重量平均分子量は、５００～１００００であることが好ましい。上限は、５０００以下であることが好ましく、３０００以下であることがより好ましい。下限は８００以上であることが好ましく、１０００以上であることがより好ましい。なお、本明細書において、グラフト鎖の重量平均分子量は、グラフト鎖を有する繰り返し単位の重合に用いた原料モノマーの重量平均分子量から算出した値である。例えば、グラフト鎖を有する繰り返し単位は、マクロモノマーを重合することで形成できる。ここで、マクロモノマーとは、ポリマー末端に重合性基が導入された高分子化合物を意味する。また、原料モノマーの重量平均分子量の値は、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を用いる。 The weight average molecular weight of the graft chain is preferably 500 to 10000. The upper limit is preferably 5000 or less, and more preferably 3000 or less. The lower limit is preferably 800 or more, and more preferably 1000 or more. In the present specification, the weight average molecular weight of the graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit having the graft chain. For example, repeating units with graft chains can be formed by polymerizing macromonomers. Here, the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer. Further, as the value of the weight average molecular weight of the raw material monomer, the polystyrene-equivalent value measured by the GPC (gel permeation chromatography) method is used.
　酸性グラフト樹脂が有する酸基としては、カルボキシル基、スルホ基、リン酸基が挙げられ、カルボキシル基が好ましい。酸性グラフト樹脂の酸価は、２０～１５０ｍｇＫＯＨ／ｇが好ましい。上限は１２０ｍｇＫＯＨ／ｇ以下であることが好ましく、１００ｍｇＫＯＨ／ｇ以下であることがより好ましく、８０ｍｇＫＯＨ／ｇ以下であることが更に好ましい。下限は２５ｍｇＫＯＨ／ｇ以上であることが好ましく、３０ｍｇＫＯＨ／ｇ以上であることがより好ましく、３５ｍｇＫＯＨ／ｇ以上であることが更に好ましい。 Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. The acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g. The upper limit is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 35 mgKOH / g or more.
　酸性グラフト樹脂の重量平均分子量は、３０００～３５０００であることが好ましい。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。下限は、４０００以上であることが好ましく、６０００以上であることがより好ましく、７０００以上であることが更に好ましい。 The weight average molecular weight of the acidic graft resin is preferably 3000 to 35000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
　酸性グラフト樹脂としては、グラフト鎖を有する繰り返し単位と酸基を有する繰り返し単位とを含む樹脂、下記の式（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。酸性グラフト樹脂は、さらに重合性基を有する繰り返し単位などの他の繰り返し単位を含んでいてもよい。重合性基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などエチレン性不飽和結合含有基が挙げられる。 Examples of the acidic graft resin include a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, a resin having a repeating unit represented by the following formula (Ac-2), and the like. The acidic graft resin may further contain other repeating units such as repeating units having a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
　酸性グラフト樹脂が、グラフト鎖を有する繰り返し単位と、酸基を有する繰り返し単位とを含む樹脂である場合、酸性グラフト樹脂は、酸性グラフト樹脂の全繰り返し単位中にグラフト鎖を有する繰り返し単位を１モル％以上含むことが好ましく、２モル％以上含有することがより好ましく、３モル％以上含有することが更に好ましい。上限は、９０モル％とすることもでき、８０モル％以下とすることもでき、７０モル％以下とすることもでき、６０モル％以下とすることもでき、５０モル％以下とすることもできる。また、酸性グラフト樹脂は、酸性グラフト樹脂の全繰り返し単位中に酸基を有する繰り返し単位を１モル％以上含むことが好ましく、２モル％以上含有することがより好ましく、３モル％以上含有することが更に好ましい。上限は、９０モル％とすることもでき、８０モル％以下とすることもでき、７０モル％以下とすることもでき、６０モル％以下とすることもでき、５０モル％以下とすることもできる。 When the acidic graft resin is a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, the acidic graft resin contains 1 mol of the repeating unit having a graft chain in all the repeating units of the acidic graft resin. % Or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more is further preferable. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can. Further, the acidic graft resin preferably contains 1 mol% or more of the repeating units having an acid group in all the repeating units of the acidic graft resin, more preferably 2 mol% or more, and 3 mol% or more. Is more preferable. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
　次に、式（Ａｃ－２）で表される繰り返し単位について説明する。
Figure JPOXMLDOC01-appb-C000009
 　式（Ａｃ－２）中、Ａｒ１０は芳香族カルボキシル基を含む基を表し、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。 Next, the repeating unit represented by the equation (Ac-2) will be described.
Figure JPOXMLDOC01-appb-C000009
 In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 represents -COO- or -CONH-, L 12 represents a trivalent linking group, and P 10 represents a polymer. Represents a chain.
　式（Ａｃ－２）においてＡｒ１０が表す芳香族カルボキシル基を含む基としては、芳香族トリカルボン酸無水物から由来する構造、芳香族テトラカルボン酸無水物から由来する構造などが挙げられる。芳香族トリカルボン酸無水物および芳香族テトラカルボン酸無水物としては、下記構造の化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000010
 Examples of the group containing an aromatic carboxyl group represented by Ar 10 in the formula (Ac-2) 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 acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.
Figure JPOXMLDOC01-appb-C000010
　上記式中、Ｑ１は、単結合、－Ｏ－、－ＣＯ－、－ＣＯＯＣＨ２ＣＨ２ＯＣＯ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、下記式（Ｑ－１）で表される基または下記式（Ｑ－２）で表される基を表す。
Figure JPOXMLDOC01-appb-C000011
 In the above formula, Q 1 is represented by a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).
Figure JPOXMLDOC01-appb-C000011
　Ａｒ１０が表す芳香族カルボキシル基を含む基は、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。Ａｒ１０が表す芳香族カルボキシル基を含む基の具体例としては、式（Ａｒ－１１）で表される基、式（Ａｒ－１２）で表される基、式（Ａｒ－１３）で表される基などが挙げられる。
Figure JPOXMLDOC01-appb-C000012
 The group containing an aromatic carboxyl group represented by Ar 10 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 carboxyl group represented by Ar 10 include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13). Examples include the base.
Figure JPOXMLDOC01-appb-C000012
　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Ｌ１１との結合位置を表す。 In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In the 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 the 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 the 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-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
In the formulas (Ar-11) to (Ar-13), * 1 represents the bonding position with L 11.
　式（Ａｃ－２）においてＬ１１は、－ＣＯＯ－であることが好ましい。 In the formula (Ac-2), L 11 is preferably —COO−.
　式（Ａｃ－２）においてＬ１２が表す３価の連結基としては、炭化水素基、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－Ｓ－およびこれらの２種以上を組み合わせた基が挙げられる。炭化水素基は、脂肪族炭化水素基、芳香族炭化水素基が挙げられる。脂肪族炭化水素基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１５が更に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよい。芳香族炭化水素基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１０が更に好ましい。炭化水素基は置換基を有していてもよい。置換基としては、ヒドロキシ基などが挙げられる。Ｌ１２が表す３価の連結基は、式（Ｌ１２－１）で表される基であることが好ましく、式（Ｌ１２－２）で表される基であることがより好ましい。
Figure JPOXMLDOC01-appb-C000013
 The trivalent linking group represented by L 12 in the formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these. A group that combines species or more can be mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of 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 number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and the like. The trivalent linking group represented by L 12 is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).
Figure JPOXMLDOC01-appb-C000013
　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 the formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, * 1 represents the bonding position with L 11 in the formula (Ac-2), and * 2 represents the bonding position with L 11 in the formula (Ac-2). It represents a bonding position to P 10 of the Ac-2). The trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined with, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined 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 the formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, * 1 represents the bonding position with L 11 of the formula (Ac-2), and * 2 represents the bonding position of the formula (Ac-2). It represents a bonding position to P 10 of the Ac-2). The trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.
　式（Ａｃ－２）の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（メタ）アクリル構造、ポリスチレン構造、ポリウレタン構造、ポリウレア構造およびポリアミド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が挙げられ、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であることが好ましい。Ｐ１０が表すポリマー鎖の重量平均分子量は、５００～１００００であることが好ましい。上限は、５０００以下であることが好ましく、３０００以下であることがより好ましい。下限は８００以上であることが好ましく、１０００以上であることがより好ましい。 Polymer chains represented by P 10 of the formula (Ac-2) comprises a polyester structure, a polyether structure, poly (meth) acrylic structure, polystyrene structure, polyurethane structure, at least one structure selected from a polyurea structure and polyamide structure The polymer chain is mentioned, and is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly (meth) acrylic structure. The weight average molecular weight of the polymer chain represented by P 10 is preferably 500 to 10000. The upper limit is preferably 5000 or less, and more preferably 3000 or less. The lower limit is preferably 800 or more, and more preferably 1000 or more.
　Ｐ１０が表すポリマー鎖は、側鎖にエチレン性不飽和結合含有基を含む繰り返し単位を含むことも好ましい。また、Ｐ１０を構成する全繰り返し単位中におけるエチレン性不飽和結合含有基を側鎖に含む繰り返し単位の割合は、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることが更に好ましい。上限は、１００質量％とすることができ、９０質量％以下であることが好ましく、６０質量％以下であることが更に好ましい。 The polymer chain represented by P 10 preferably contains a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. The proportion of the repeating units containing an ethylenically unsaturated bond-containing group in the total repeating units constituting the P 10 in a side chain is preferably 5 mass% or more, more preferably 10 mass% or more , 20% by mass or more is more preferable. The upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.
　Ｐ１０が表すポリマー鎖は、酸基を含む繰り返し単位を含むことも好ましい。酸基としては、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられる。Ｐ１０を構成する全繰り返し単位中における酸基を含む繰り返し単位の割合は、１～３０質量％であることが好ましく、２～２０質量％であることがより好ましく、３～１０質量％であることが更に好ましい。 It is also preferable that the polymer chain represented by P 10 contains a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The ratio of the repeating unit containing an acid group in all the repeating units constituting P 10 is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 10% by mass. Is even more preferable.
　酸性グラフト樹脂の具体例としては、後述する実施例に記載の樹脂Ｂ－１～Ｂ－７などが挙げられる。また、酸性グラフト樹脂としては、特開２０１２－２５５１２８号公報の段落番号００２５～００９４に記載された樹脂、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６に記載されたポリイミン樹脂を用いることもできる。 Specific examples of the acidic graft resin include resins B-1 to B-7 described in Examples described later. Further, as the acidic graft resin, the resin described in paragraphs 0025 to 0094 of JP2012-255128 and the polyimine resin described in paragraphs 0102 to 0166 of JP2012-255128 may be used. can.
　本発明の着色組成物は、分散剤としての樹脂を含むことが好ましい。分散剤としては、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。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）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、アミノ基であることが好ましい。 The coloring composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、コア部に複数個のポリマー鎖が結合した構造の樹脂であることも好ましい。このような樹脂としては、例えばデンドリマー（星型ポリマーを含む）が挙げられる。また、デンドリマーの具体例としては、特開２０１３－０４３９６２号公報の段落番号０１９６～０２０９に記載された高分子化合物Ｃ－１～Ｃ－３１などが挙げられる。 It is also preferable that the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
　また、上述した酸性グラフト樹脂などの樹脂を分散剤として用いることもできる。 Further, a resin such as the above-mentioned acidic graft resin can also be used as a dispersant.
　また、分散剤として用いる樹脂は、エチレン性不飽和結合含有基を側鎖に有する繰り返し単位を含む樹脂であることも好ましい。エチレン性不飽和結合含有基を側鎖に有する繰り返し単位の含有量は、樹脂の全繰り返し単位中１０モル％以上であることが好ましく、１０～８０モル％であることがより好ましく、２０～７０モル％であることが更に好ましい。 Further, the resin used as the dispersant is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.
　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、ＢＹＫＣｈｅｍｉｅ社製のＤＩＳＰＥＲＢＹＫシリーズ（例えば、ＤＩＳＰＥＲＢＹＫ－１１１、１６１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７６５００など）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。なお、上記分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。 Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.
　着色組成物の全固形分中における樹脂の含有量は、１～４５質量％が好ましい。下限は、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、４０質量％以下が好ましく、３０質量％以下がより好ましい。
　また、着色組成物の全固形分中における酸性グラフト樹脂の含有量は、１～４５質量％が好ましい。下限は、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、４０質量％以下が好ましく、３０質量％以下がより好ましい。
　また、酸性グラフト樹脂の含有量は、特定化合物１００質量部に対して１００～３０００質量部が好ましい。下限は、２００質量部以上が好ましく、３００質量部以上がより好ましい。上限は、２５００質量部以下が好ましく、２０００質量部以下がより好ましい。 The content of the resin in the total solid content of the coloring composition is preferably 1 to 45% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
The content of the acidic graft resin in the total solid content of the coloring composition is preferably 1 to 45% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
The content of the acidic graft resin is preferably 100 to 3000 parts by mass with respect to 100 parts by mass of the specific compound. The lower limit is preferably 200 parts by mass or more, and more preferably 300 parts by mass or more. The upper limit is preferably 2500 parts by mass or less, more preferably 2000 parts by mass or less.
＜＜特定化合物＞＞
　本発明の着色組成物は、フェノール系酸化防止剤のフェノール性ヒドロキシ基を加熱により脱離可能な保護基で保護した化合物Ａ、または、式（ＡＯ－１）で表される化合物を含む。以下、上述した化合物Ａと式（ＡＯ－１）で表される化合物とを合わせて特定化合物ともいう。 << Specific compound >>
The coloring composition of the present invention contains a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protective group that can be desorbed by heating, or a compound represented by the formula (AO-1). Hereinafter, the compound A described above and the compound represented by the formula (AO-1) are collectively referred to as a specific compound.
　化合物Ａは、１８０℃以上に加熱されることで保護基が脱離してフェノール性ヒドロキシ基が生成される化合物であることが好ましい。化合物Ａにおける上記保護基としては、酸無水物、酸塩化物、ｔｅｒｔ－ブトキシカルボニル化剤、アルキルハライド化合物、シリルクロライド化合物、アリルエーテル化合物またはメタリルエーテル化合物の反応残基などが挙げられる。保護基の具体例としては、式（ＡＯ－１）のＲ２が表す構造の基が挙げられる。また、保護基の式量はベーク時に揮発して残存しない方が好ましいという理由から３０～２００であることが好ましく、３５～１００であることがより好ましく、４０～７０であることが更に好ましい。 The compound A is preferably a compound in which the protecting group is removed by heating to 180 ° C. or higher to generate a phenolic hydroxy group. Examples of the protecting group in compound A include acid anhydrides, acid acid compounds, tert-butoxycarbonylating agents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, reaction residues of metalyl ether compounds and the like. Specific examples of the protecting group include a group having a structure represented by R 2 of the formula (AO-1). The formula amount of the protecting group is preferably 30 to 200, more preferably 35 to 100, and even more preferably 40 to 70 because it is preferable that the protecting group volatilizes and does not remain at the time of baking.
　化合物Ａは、上記保護基で保護されたフェノール性ヒドロキシ基（以下、保護ヒドロキシ基ともいう）を１分子中に１～１０個含む化合物であることが好ましい。下限は２個以上であることが好ましく、３個以上であることがより好ましい。上限は６個以下であることが好ましく、４個以下であることがより好ましい。 Compound A is preferably a compound containing 1 to 10 phenolic hydroxy groups (hereinafter, also referred to as protected hydroxy groups) protected by the protecting group in one molecule. The lower limit is preferably 2 or more, and more preferably 3 or more. The upper limit is preferably 6 or less, and more preferably 4 or less.
　化合物Ａは、式（ＡＯ－１）で表される化合物であることが好ましい。 Compound A is preferably a compound represented by the formula (AO-1).
Figure JPOXMLDOC01-appb-C000014
 　式中、Ｒ１は、置換基を表し、
　Ｒ２は、－ＣＯＯＲ１１、－ＣＨ２－ＣＨ＝ＣＲ１２Ｒ１３、－ＣＨ２（－Ｏ－ＬＲ１）ｑ－Ｏ－Ｒ１４またはＳｉＲ１５Ｒ１６Ｒ１７を表し、
　Ｒ１１、Ｒ１２、Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７はそれぞれ独立してアルキル基を表し、
　Ｒ１３は水素原子またはアルキル基を表し、
　ＬＲ１はアルキレン基を表し、
　ｑは０または１を表し、
　ｑが１の場合、ＬＲ１とＲ１４は結合して環を形成していてもよく、
　ｍは０～４の整数を表し、
　ｎは１～１０の整数を表し、
　Ｘ１はｎ価の基を表す。
Figure JPOXMLDOC01-appb-C000014
 In the formula, R 1 represents a substituent and represents
R 2 represents -COOR 11 , -CH 2- CH = CR 12 R 13 , -CH 2 (-OL R1 ) q- O-R 14 or SiR 15 R 16 R 17 .
R 11 , R 12 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group.
R 13 represents a hydrogen atom or an alkyl group.
LR1 represents an alkylene group
q represents 0 or 1 and represents
When q is 1, L R1 and R 14 may be combined to form a ring.
m represents an integer from 0 to 4 and represents
n represents an integer from 1 to 10 and represents
X 1 represents an n-valent group.
　式（ＡＯ－１）のＲ１が表す置換基としては、後述する置換基Ｔが挙げられ、アルキル基、アリール基、複素環基であることが好ましく、アルキル基であることがより好ましい。アルキル基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれでもよいが、脱離後にフェノール系酸化防止剤としての機能が良好であるという理由から分岐または環状であることが好ましく、分岐であることがより好ましい。 Examples of the substituent represented by R 1 in the formula (AO-1) include a substituent T described later, which is preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched or cyclic, but is preferably branched or cyclic because of its good function as a phenolic antioxidant after desorption, and more preferably branched. ..
　式（ＡＯ－１）のＲ２は、－ＣＯＯＲ１１、－ＣＨ２－ＣＨ＝ＣＲ１２Ｒ１３、－ＣＨ２（－Ｏ－ＬＲ１）ｑ－Ｏ－Ｒ１４またはＳｉＲ１５Ｒ１６Ｒ１７を表す。Ｒ１１、Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７はそれぞれ独立してアルキル基を表し、Ｒ１２およびＲ１３はそれぞれ独立して水素原子またはアルキル基を表し、ＬＲ１はアルキレン基を表し、ｑは０または１を表し、ｑが１の場合、ＬＲ１とＲ１４は結合して環を形成していてもよい。 R 2 of the formula (AO-1) is -COOR 11 , -CH 2- CH = CR 12 R 13 , -CH 2 (-OL R1 ) q - OR 14 or SiR 15 R 16 R 17 show. R 11 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group, R 12 and R 13 independently represent a hydrogen atom or an alkyl group, and L R 1 represents an alkylene group. q represents 0 or 1, and when q is 1, L R1 and R 14 may be combined to form a ring.
　Ｒ１１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が更に好ましい。アルキル基は直鎖、分岐または環状のいずれでもよいが、脱離する温度が適切であるという理由から分岐のアルキル基であることが好ましい。Ｒ１１が表すアルキル基は置換基を有していてもよい。置換基としては後述する置換基Ｔが挙げられ、アリール基であることが好ましい。Ｒ１１の具体例としては、ｔｅｒｔ－ブチル基、ベンジル基などが挙げられる。 The number of carbon atoms of the alkyl group represented by R 11 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched or cyclic, but is preferably a branched alkyl group because the desorption temperature is appropriate. The alkyl group represented by R 11 may have a substituent. Examples of the substituent include a substituent T described later, and an aryl group is preferable. Specific examples of R 11 include a tert-butyl group and a benzyl group.
　Ｒ１２およびＲ１３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が更に好ましい。Ｒ１１およびＲ１２が表すアルキル基は直鎖、分岐または環状のいずれでもよいが、より低コストでの製造が可能という理由から直鎖または分岐のアルキル基であることが好ましく、直鎖のアルキル基であることがより好ましい。なかでも、Ｒ１２およびＲ１３はそれぞれ独立してアルキ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 of the alkyl group represented by R 12 and R 13 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group represented by R 11 and R 12 may be linear, branched or cyclic, but is preferably a linear or branched alkyl group because it can be produced at a lower cost, and is preferably a linear alkyl. It is more preferable that it is a group. Among them, R 12 and R 13 are preferably independent alkyl groups, and more preferably methyl groups.
　Ｒ１４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。アルキル基は直鎖、分岐または環状のいずれでもよいが、より低コストでの製造が可能という理由から直鎖のアルキル基であることが好ましい。 The number of carbon atoms of the alkyl group represented by R 14 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group because it can be produced at a lower cost.
　Ｒ１５～Ｒ１７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。アルキル基は直鎖、分岐または環状のいずれでもよいが、より低コストでの製造が可能という理由から直鎖のアルキル基であることが好ましい。 The number of carbon atoms of the alkyl group represented by R 15 to R 17 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group because it can be produced at a lower cost.
　ＬＲ１が表すアルキレン基の炭素数は、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。アルキレン基は直鎖、分岐または環状のいずれでもよいが、より低コストでの製造が可能という理由から直鎖または分岐のアルキレン基であることが好ましい。また、ＬＲ１とＲ１４は結合して環を形成していてもよい。なお、「－ＣＨ２（－Ｏ－ＬＲ１）ｑ－Ｏ－Ｒ１４」で表される基において、ｑが０である場合は、－ＣＨ２－Ｏ－Ｒ１４で表される構造の基である。 The alkylene group L R1 represents is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, 1 to 3 particularly preferred. The alkylene group may be linear, branched or cyclic, but is preferably a linear or branched alkylene group because it can be produced at a lower cost. Further, L R1 and R 14 may form a ring. In addition, in the group represented by "-CH 2 (-OL R1 ) q- OR 14 ", when q is 0, the group of the structure represented by -CH 2- OR 14 Is.
　Ｒ２が表す基の具体例としては、ｔｅｒｔ－ブトキシカルボニル基、ベンジルオキシカルボニル基、テトラヒドロピラニル基、メトキシメチル基、２－メトキシエトキシメチル基、トリメチルシリル基、－ＣＨ２－ＣＨ＝Ｃ（ＣＨ３）２、－ＣＨ２－ＣＨ＝ＣＨ２などが挙げられ、ｔｅｒｔ－ブトキシカルボニル基および－ＣＨ２－ＣＨ＝Ｃ（ＣＨ３）２が好ましい。 Specific examples of the group represented by R 2 include tert-butoxycarbonyl group, benzyloxycarbonyl group, tetrahydropyranyl group, methoxymethyl group, 2-methoxyethoxymethyl group, trimethylsilyl group, -CH 2- CH = C (CH). 3 ) 2 , -CH 2 -CH = CH 2, and the like, and tert-butoxycarbonyl group and -CH 2- CH = C (CH 3 ) 2 are preferable.
　式（ＡＯ－１）のＸ１が表すｎ価の基としては、脂肪族炭化水素基、芳香族炭化水素基、複素環基、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－、－ＮＲＸ－、－ＮＲＸＣＯ－、－ＣＯＮＲＸ－、－ＮＲＸＳＯ２－、－ＳＯ２ＮＲＸ－およびこれらの組み合わせからなる基が挙げられ、ＲＸは水素原子、アルキル基またはアリール基を表す。脂肪族炭化水素基の炭素数は、１～２０が好ましく、２～２０がより好ましく、２～１０がさらに好ましく、２～５が特に好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれであってもよい。また、環状の脂肪族炭化水素基は、単環、多環のいずれであってもよい。芳香族炭化水素基の炭素数は、６～１８が好ましく、６～１４がより好ましく、６～１０がさらに好ましい。芳香族炭化水素基は、単環または縮合数が２～４の縮合環の芳香族炭化水素基であることが好ましい。芳香族炭化水素基としては、ベンゼン環基であることが好ましい。複素環基は、単環または縮合数が２～４の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は１～３が好ましい。複素環基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。複素環基の環を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。脂肪族炭化水素基、芳香族炭化水素基および複素環基は置換基を有していてもよい。置換基としては、後述する置換基Ｔで挙げた基が挙げられる。また、ＲＸが表すアルキル基の炭素数は１～２０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましく、直鎖がより好ましい。ＲＸが表すアルキル基はさらに置換基を有していてもよい。置換基としては後述する置換基Ｔが挙げられる。ＲＸが表すアリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。ＲＸが表すアリール基はさらに置換基を有していてもよい。置換基としては後述する置換基Ｔが挙げられる。 The n-valent group represented by X 1 in the formula (AO-1) includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, —O—, —S—, —CO—, —COO—, -OCO-, -SO 2- , -NR X- , -NR X CO-, -CONR X- , -NR X SO 2- , -SO 2 NR X- and a group consisting of a combination thereof can be mentioned. X represents a hydrogen atom, an alkyl group or an aryl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, further preferably 2 to 10, and particularly preferably 2 to 5. The aliphatic hydrocarbon group may be linear, branched or cyclic. Further, the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a monocyclic or an aromatic hydrocarbon group having a condensed ring having 2 to 4 condensation numbers. The aromatic hydrocarbon group is preferably a benzene ring group. The heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. Aliphatic hydrocarbon groups, aromatic hydrocarbon groups and heterocyclic groups may have substituents. Examples of the substituent include the groups listed in Substituent T described later. The number of carbon atoms of the alkyl group represented by R X is preferably 1-20, more preferably 1-15, 1-8 is more preferable. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. Alkyl group R X represents may further have a substituent. Examples of the substituent include a substituent T described later. The number of carbon atoms of the aryl group R X represents is preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 12. Aryl group R X represents may further have a substituent. Examples of the substituent include a substituent T described later.
　Ｘ１が表すｎ価の基は、式（Ｘ－１）～（Ｘ－４）のいずれかで表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000015
 　式（Ｘ－１）中、Ｌ３は３価の基を表し、Ｔ３は単結合又は２価の連結基を表し、３個存在するＴ３は互いに同一であっても異なっていてもよい。
　式（Ｘ－２）中、Ｌ４は４価の基を表し、Ｔ４は単結合又は２価の連結基を表し、４個存在するＴ４は互いに同一であっても異なっていてもよい。
　式（Ｘ－３）中、Ｌ５は５価の基を表し、Ｔ５は単結合又は２価の連結基を表し、５個存在するＴ５は互いに同一であっても異なっていてもよい。
　式（Ｘ－４）中、Ｌ６は６価の基を表し、Ｔ６は単結合又は２価の連結基を表し、６個存在するＴ６は互いに同一であっても異なっていてもよい。
　上記式中、＊は結合手を表す。 The n-valent group represented by X 1 is preferably a group represented by any of the formulas (X-1) to (X-4).
Figure JPOXMLDOC01-appb-C000015
 In formula (X-1), L 3 represents a trivalent group, T 3 represents a single bond or a divalent linking group, and the three existing T 3s may be the same or different from each other. ..
Wherein (X-2), L 4 represents a tetravalent group, T 4 represents a single bond or a divalent linking group, T 4 present four may be the being the same or different ..
In formula (X-3), L 5 represents a pentavalent group, T 5 represents a single bond or a divalent linking group, and the five existing T 5s may be the same or different from each other. ..
In formula (X-4), L 6 represents a hexavalent group, T 6 represents a single bond or a divalent linking group, and the six T 6s may be the same or different from each other. ..
In the above formula, * represents a bond.
　Ｔ３～Ｔ６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、複素環基、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－、－ＮＨＣＯ－、－ＣＯＮＨ－、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。
　アルキレン基の炭素数は１～２０が好ましく、１～１０がより好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよく、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。
　アリーレン基の炭素数は、６～２０が好ましく、６～１２がより好ましい。
　アルキレン基、アリーレン基および複素環基は、更に置換基を有していてもよい。置換基としては後述する置換基Ｔが挙げられる。 The divalent linking groups represented by T 3 to T 6 include an alkylene group, an arylene group, a heterocyclic group, -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, Examples thereof include -OCO-, -S-, -NHCO-, -CONH-, and a group consisting of a combination of two or more of these.
The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
The alkylene group, arylene group and heterocyclic group may further have a substituent. Examples of the substituent include the substituent T described later.
　Ｌ３が表す３価の基としては、上記の２価の連結基から水素原子を１個除いた基が挙げられる。Ｌ４が表す４価の基としては、上記の２価の連結基から水素原子を２個除いた基が挙げられる。Ｌ５が表す５価の基としては、上記の２価の連結基から水素原子を３個除いた基が挙げられる。Ｌ６が表す６価の基としては、上記の２価の連結基から水素原子を４個除いた基が挙げられる。Ｌ３～Ｌ６が表す３～６価の基は、更に置換基を有していてもよい。置換基としては後述する置換基Ｔが挙げられる。 Examples of the trivalent group represented by L 3 include a group obtained by removing one hydrogen atom from the above divalent linking group. Examples of the tetravalent group represented by L 4 include a group obtained by removing two hydrogen atoms from the above-mentioned divalent linking group. Examples of the pentavalent group represented by L 5 include a group obtained by removing three hydrogen atoms from the above divalent linking group. Examples of the hexavalent group represented by L 6 include a group obtained by removing four hydrogen atoms from the above divalent linking group. The 3- hexavalent group represented by L 3 to L 6 may further have a substituent. Examples of the substituent include a substituent T described later.
　式（ＡＯ－１）のｍは０～４の整数を表し、ｍは０～３の整数であることが好ましく、０～２の整数であることがより好ましく、１または２であることが特に好ましい。 In the formula (AO-1), m represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 1 or 2. preferable.
　式（ＡＯ－１）のｎは１～１０の整数を表し、ｎの下限は２以上であることが好ましく、３以上であることがより好ましい。ｎの上限は６以下であることが好ましく、４以下であることがより好ましい。 N in the formula (AO-1) represents an integer of 1 to 10, and the lower limit of n is preferably 2 or more, and more preferably 3 or more. The upper limit of n is preferably 6 or less, and more preferably 4 or less.
（置換基Ｔ）
　置換基Ｔとしては、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アリール基、複素環基、－ＯＲｔ１、－ＣＯＲｔ１、－ＣＯＯＲｔ１、－ＯＣＯＲｔ１、－ＮＲｔ１Ｒｔ２、－ＮＲｔ３ＣＯＲｔ１、－ＣＯＮＲｔ１Ｒｔ２、－ＮＲｔ３ＣＯＮＲｔ１Ｒｔ２、－ＮＲｔ３ＣＯＯＲｔ１、－ＳＲｔ１、－ＳＯ２Ｒｔ１、－ＳＯ２ＯＲｔ１、－ＮＲｔ３ＳＯ２Ｒｔ１または－ＳＯ２ＮＲｔ１Ｒｔ２が挙げられる。Ｒｔ１～Ｒｔ３は、それぞれ独立して水素原子、アルキル基、アリール基または複素環基を表す。Ｒｔ１とＲｔ２が結合して環を形成してもよい。 (Substituent T)
As the substituent T, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NRt 3 CORT 1 , -CONRT 1 Rt 2 , -NRt 3 CONRT 1 Rt 2 , -NRt 3 COORt 1 , -SRt 1 , -SO 2 Rt 1 , -SO 2 ORt 1 , -NRt 3 SO 2 Rt 1 or -SO 2 NRt 1 Rt 2 can be mentioned. Rt 1 to Rt 3 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, respectively. Rt 1 and Rt 2 may be combined to form a ring.
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　アルキル基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～８が更に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよい。
　アルケニル基の炭素数は、２～３０が好ましく、２～１５がより好ましく、２～８が更に好ましい。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。
　複素環基は、単環であってもよく、縮合環であってもよい。複素環基は、単環または縮合数が２～４の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は１～３が好ましい。複素環基の環を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。複素環基の環を構成する炭素原子の数は３～３０が好ましく、３～１８がより好ましく、３～１２がより好ましい。
　アルキル基、アリール基および複素環基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基Ｔの群から選ばれる基が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched or cyclic.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 2 to 8 carbon atoms.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
The heterocyclic group may be a monocyclic ring or a fused ring. The heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
The alkyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include a group selected from the above-mentioned group of substituents T.
　特定化合物は、例えば、特開昭５７－１１１３７５号公報、特開平０３－１７３８４３号公報、特開平０６－１２８１９５号公報、特開平０７－２０６７７１号公報、特開平０７－２５２１９１号公報、特表２００４－５０１１２８号公報に記載された方法により製造されたフェノール化合物と、酸無水物、酸塩化物、ｔｅｒｔ－ブトキシカルボニル化試薬、アルキルハライド化合物、シリルクロライド化合物、アリルエーテル化合物、１－クロロ－３－メチル－２－ブテン等を反応させて得ることができる。特定化合物の具体例としては、後述する実施例に記載の化合物１～６、特開２０１５－１３１９３７号公報の段落番号０１０６～０１０９に記載の化合物、特開２０１５－１３２７９１号公報の段落番号００２８～００４９に記載の化合物、国際公開第２０１７／１７０１８３号の００４３～００４４に記載の化合物などが挙げられる。 Specific compounds include, for example, JP-A-57-11375, JP-A-03-173843, JP-A-06-128195, JP-A-07-206771, JP-A-07-252191, JP-A-2004, JP-A-2004. -The phenol compound produced by the method described in JP-501128, acid anhydride, acid anhydride, tert-butoxycarbonylation reagent, alkyl halide compound, silyl chloride compound, allyl ether compound, 1-chloro-3-. It can be obtained by reacting with methyl-2-butene or the like. Specific examples of the specific compound include compounds 1 to 6 described in Examples described later, compounds described in paragraph numbers 0106 to 0109 of JP-A-2015-131937, and paragraph numbers 0028 to JP-A-2015-132791. Examples thereof include the compounds described in 0049, the compounds described in 0043 to 0044 of International Publication No. 2017/170183, and the like.
　着色組成物の全固形分中における上述した化合物Ａの含有量は１～１０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、３質量％以上であることがより好ましい。上限は、８質量％以下であることが好ましく、６質量％以下であることがより好ましい。また、有機顔料の１００質量部に対して化合物Ａを２～２５質量部含むことが好ましい。下限は、５．５質量部以上であることが好ましく、７質量部以上であることがより好ましい。上限は、１８質量部以下であることが好ましく、１３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において、化合物Ａは１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the above-mentioned compound A in the total solid content of the coloring composition is preferably 1 to 10% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. Further, it is preferable that the compound A is contained in an amount of 2 to 25 parts by mass with respect to 100 parts by mass of the organic pigment. The lower limit is preferably 5.5 parts by mass or more, and more preferably 7 parts by mass or more. The upper limit is preferably 18 parts by mass or less, and more preferably 13 parts by mass or less. In the coloring composition of the present invention, only one compound A may be used, or two or more compounds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
　また、着色組成物の全固形分中における式（ＡＯ－１）で表される化合物の含有量は１～１０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、３質量％以上であることがより好ましい。上限は、８質量％以下であることが好ましく、６質量％以下であることがより好ましい。また、有機顔料の１００質量部に対して式（ＡＯ－１）で表される化合物を２～２５質量部含むことが好ましい。下限は、５．５質量部以上であることが好ましく、７質量部以上であることがより好ましい。上限は、１８質量部以下であることが好ましく、１３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において、特定化合物は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。 Further, the content of the compound represented by the formula (AO-1) in the total solid content of the coloring composition is preferably 1 to 10% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. Further, it is preferable to contain 2 to 25 parts by mass of the compound represented by the formula (AO-1) with respect to 100 parts by mass of the organic pigment. The lower limit is preferably 5.5 parts by mass or more, and more preferably 7 parts by mass or more. The upper limit is preferably 18 parts by mass or less, and more preferably 13 parts by mass or less. In the coloring composition of the present invention, only one specific compound may be used, or two or more specific compounds may be used. When two or more kinds are used, 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、亜リン酸エステル系酸化防止剤、アミン系酸化防止剤、チオ―テル系酸化防止剤などが挙げられ、フェノール系酸化防止剤であることが好ましい。上述した特定化合物とフェノール系酸化防止剤とを併用することで、着色組成物の保存安定性が良化するという効果が期待できる。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。フェノール系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を使用することもできる。 << Antioxidant >>
The coloring composition of the present invention can contain an antioxidant. Examples of the antioxidant include a phenol-based antioxidant, a phosphite ester-based antioxidant, an amine-based antioxidant, a thiotel-based antioxidant, and the like, and a phenol-based antioxidant is preferable. By using the above-mentioned specific compound in combination with a phenolic antioxidant, the effect of improving the storage stability of the coloring composition can be expected. Examples of the phenolic antioxidant include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Commercially available phenolic 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 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
　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、０．００１～３質量％であることが好ましい。下限は、０．００５質量％以上であることが好ましく、０．０１質量％以上であることがより好ましい。上限は、１．５質量％以下であることが好ましく、１質量％以下であることがより好ましい。また、着色組成物の全固形分中におけるフェノール系酸化防止剤の含有量は、０．００１～２質量％であることが好ましい。下限は、０．００５質量％以上であることが好ましく、０．０１質量％以上であることがより好ましい。上限は、１．５質量％以下であることが好ましく、１質量％以下であることがより好ましい。 The content of the antioxidant in the total solid content of the coloring composition is preferably 0.001 to 3% by mass. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 1.5% by mass or less, and more preferably 1% by mass or less. Further, the content of the phenolic antioxidant in the total solid content of the coloring composition is preferably 0.001 to 2% by mass. The lower limit is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. The upper limit is preferably 1.5% by mass or less, and more preferably 1% by mass or less.
　また、着色組成物の全固形分中における上述した特定化合物と酸化防止剤との合計の含有量は１～１０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、３質量％以上であることがより好ましい。上限は、８質量％以下であることが好ましく、６質量％以下であることがより好ましい。また、着色組成物の全固形分中における上述した特定化合物とフェノール系酸化防止剤との合計の含有量は１～１０質量％であることが好ましい。下限は、２．５質量％以上であることが好ましく、３質量％以上であることがより好ましい。上限は、８質量％以下であることが好ましく、６質量％以下であることがより好ましい。 Further, the total content of the above-mentioned specific compound and the antioxidant in the total solid content of the coloring composition is preferably 1 to 10% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. Further, the total content of the above-mentioned specific compound and the phenolic antioxidant in the total solid content of the coloring composition is preferably 1 to 10% by mass. The lower limit is preferably 2.5% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less.
　また、酸化防止剤の含有量は、上述した特定化合物１００質量部に対して０．１～２００質量部であることが好ましく、１～１００質量部であることがより好ましく、２～５０質量部であることが更に好ましい。また、フェノール系酸化防止剤の含有量は、上述した特定化合物１００質量部に対して０．１～２００質量部であることが好ましく、１～１００質量部であることがより好ましく、２～５０質量部であることが更に好ましい。上述した特定化合物とフェノール系酸化防止剤との割合が上記範囲であれば着色組成物の保存安定性が良化するという効果が期待できる。
　酸化防止剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the antioxidant is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned specific compound. Is more preferable. The content of the phenolic antioxidant is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned specific compound. It is more preferably by mass. If the ratio of the above-mentioned specific compound to the phenolic antioxidant is in the above range, the effect of improving the storage stability of the coloring composition can be expected.
Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.
＜＜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ことができる。重合性化合物としては、ラジカル、酸または熱により架橋可能な公知の化合物を用いることができる。本発明で用いられる重合性化合物は、エチレン性不飽和結合含有基を有する化合物であることが好ましい。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 can contain a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by radicals, acids or heat can be used. The polymerizable compound used in the present invention is preferably a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.
　重合性化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。重合性化合物の分子量は、１００～３０００が好ましい。上限は、２０００以下がより好ましく、１５００以下が更に好ましい。下限は、１５０以上がより好ましく、２５０以上が更に好ましい。 The polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.
　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３～１５個含む化合物であることがより好ましく、エチレン性不飽和結合含有基を３～６個含む化合物であることが更に好ましい。また、重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。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号公報の段落番号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 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples of the polymerizable compound include paragraph numbers 0995 to 0108 of JP2009-288705, paragraph numbers 0227 of JP2013-029760, paragraph numbers 0254 to 0257 of JP2008-292970, and the present invention. Compounds described in paragraphs 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048637, Japanese Patent No. 6057891 and Japanese Patent Application Laid-Open No. 6031807. These contents are incorporated in the present specification.
　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）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。また、重合性化合物としては、ジグリセリンＥＯ（エチレンオキシド）変性（メタ）アクリレート（市販品としてはＭ－４６０；東亞合成製）、ペンタエリスリトールテトラアクリレート（新中村化学工業（株）製、ＮＫエステルＡ－ＴＭＭＴ）、１，６－ヘキサンジオールジアクリレート（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＤＤＡ）、ＲＰ－１０４０（日本化薬（株）製）、アロニックスＴＯ－２３４９（東亞合成（株）製）、ＮＫオリゴＵＡ－７２００（新中村化学工業（株）製）、８ＵＨ－１００６、８ＵＨ－１０１２（大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることもできる。 As the polymerizable compound, dipentaerythritol tri (meth) acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetra (meth) acrylate (commercially available KAYARAD D-320). ; Nippon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (commercially available) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups via ethylene glycol and / or propylene glycol residues. Compounds with a bound structure (eg, SR454, SR499 commercially available from Sartmer) are preferred. As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A) -TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nihon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toa Synthetic Co., Ltd.) , NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. You can also.
　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好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）などが挙げられる。 Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, and pentaerythritol. It is also preferable to use a trifunctional (meth) acrylate compound such as tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toa Synthetic Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
　重合性化合物としては、酸基を有する重合性化合物を用いることもできる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性化合物の市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。酸基を有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。 As the polymerizable compound, a polymerizable compound having an acid group can also be used. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
　重合性化合物としては、カプロラクトン構造を有する重合性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重合性化合物は、例えば、日本化薬（株）からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０、ＤＰＣＡ－３０、ＤＰＣＡ－６０、ＤＰＣＡ－１２０等が挙げられる。 As the polymerizable compound, a polymerizable compound having a caprolactone structure can also be used. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
　重合性化合物としては、アルキレンオキシ基を有する重合性化合物を用いることもできる。アルキレンオキシ基を有する重合性化合物は、エチレンオキシ基および／またはプロピレンオキシ基を有する重合性化合物が好ましく、エチレンオキシ基を有する重合性化合物がより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物がさらに好ましい。アルキレンオキシ基を有する重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. As the polymerizable compound having an alkyleneoxy group, a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferred. Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.
　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。フルオレン骨格を有する重合性化合物の市販品としては、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. Examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (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 an environmentally regulatory substance such as toluene. Examples of commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
　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号公報に記載されたウレタンアクリレート類、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、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、重合性化合物としては、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 described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-0322293, and Japanese Patent Application Laid-Open No. 02-016765, and Japanese Patent Application Laid-Open No. 58- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418, Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-260909 and JP-A No. 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, and AH-600. , T-600, AI-600, LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) and the like 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０．１～５０質量％であることが好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、４０質量％以下がより好ましく、３０質量％以下が更に好ましい。本発明の着色組成物において、重合性化合物は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the polymerizable compound in the total solid content of the coloring composition is preferably 0.1 to 50% by mass. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less. In the coloring composition of the present invention, only one type of polymerizable compound may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
＜＜光重合開始剤＞＞
　本発明の着色組成物は光重合開始剤を含むことができる。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視光領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。 << Photopolymerization Initiator >>
The coloring composition of the present invention can contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible light region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.
　光重合開始剤としては、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物であることが好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光重合開始剤としては、特開２０１４－１３０１７３号公報の段落００６５～０１１１、特許第６３０１４８９号公報に記載された化合物、ＭＡＴＥＲＩＡＬ　ＳＴＡＧＥ　３７～６０ｐ，ｖｏｌ．１９，Ｎｏ．３，２０１９に記載されたパーオキサイド系光重合開始剤、国際公開第２０１８／２２１１７７号に記載の光重合開始剤、国際公開第２０１８／１１０１７９号に記載の光重合開始剤、特開２０１９－０４３８６４号公報に記載の光重合開始剤、特開２０１９－０４４０３０号公報に記載の光重合開始剤、特開２０１９－１６７３１３号公報に記載の過酸化物系開始剤が挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an α-hydroxyketone compound. , Α-Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable. Further, as the photopolymerization initiator, the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.
　α－ヒドロキシケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　１８４、Ｏｍｎｉｒａｄ　１１７３、Ｏｍｎｉｒａｄ　２９５９、Ｏｍｎｉｒａｄ　１２７（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　１８４、Ｉｒｇａｃｕｒｅ　１１７３、Ｉｒｇａｃｕｒｅ　２９５９、Ｉｒｇａｃｕｒｅ　１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、Ｏｍｎｉｒａｄ　９０７、Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３６９Ｅ、Ｏｍｎｉｒａｄ　３７９ＥＧ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　９０７、Ｉｒｇａｃｕｒｅ　３６９、Ｉｒｇａｃｕｒｅ　３６９Ｅ、Ｉｒｇａｃｕｒｅ　３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、Ｏｍｎｉｒａｄ　８１９、Ｏｍｎｉｒａｄ　ＴＰＯ（以上、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製）、Ｉｒｇａｃｕｒｅ　８１９、Ｉｒｇａｃｕｒｅ　ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
　オキシム化合物としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－０６６３８５号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－０１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開第２０１５／１５２１５３号に記載の化合物、国際公開第２０１７／０５１６８０号に記載の化合物、特開２０１７－１９８８６５号公報に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３８に記載の化合物、国際公開第２０１３／１６７５１５号に記載の化合物などが挙げられる。オキシム化合物の具体例としては、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。市販品としては、Ｉｒｇａｃｕｒｅ　ＯＸＥ０１、Ｉｒｇａｃｕｒｅ　ＯＸＥ０２、Ｉｒｇａｃｕｒｅ　ＯＸＥ０３、Ｉｒｇａｃｕｒｅ　ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光重合開始剤２）が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズＮＣＩ－７３０、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-109766, compounds described in Japanese Patent Application Laid-Open No. 6065596, International Publication No. 2015. The compound described in / 152153, the compound described in International Publication No. 2017/051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, Examples thereof include the compounds described in International Publication No. 2013/167515. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA PTOMER N-1919 (Co., Ltd.). Examples thereof include a photopolymerization initiator 2) manufactured by ADEKA and described in JP2012-014552A. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and hardly discoloring. Examples of commercially available products include ADEKA ARCLUS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
　光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物、特許０６６３６０８１号に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
　光重合開始剤としては、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第２０１３／０８３５０５号に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
　光重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like can be mentioned.
　光重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載されている化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載されている化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）が挙げられる。 As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).
　光重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第２０１５／０３６９１０号に記載されているＯＥ－０１～ＯＥ－７５が挙げられる。 As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
　光重合開始剤としては、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。このような光重合開始剤としては国際公開第２０１９／０８８０５５号に記載された化合物などが挙げられる。 As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
　光重合開始剤としては、芳香族環に電子求引性基が導入された芳香族環基ＡｒＯＸ１を有するオキシム化合物（以下、オキシム化合物ＯＸともいう）を用いることもできる。上記芳香族環基ＡｒＯＸ１が有する電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。ベンゾイル基は、置換基を有していてもよい。置換基としては、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルケニル基、アルキルスルファニル基、アリールスルファニル基、アシル基またはアミノ基であることが好ましく、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基またはアミノ基であることがより好ましく、アルコキシ基、アルキルスルファニル基またはアミノ基であることが更に好ましい。 As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. Examples of the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group. An acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzoyl group is further preferable, because it is easy to form a film having excellent light resistance. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group. It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
　オキシム化合物ＯＸは、式（ＯＸ１）で表される化合物および式（ＯＸ２）で表される化合物から選ばれる少なくとも１種であることが好ましく、式（ＯＸ２）で表される化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000016
 　式中、ＲＸ１は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
　ＲＸ２は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
　ＲＸ３～ＲＸ１４は、それぞれ独立して水素原子または置換基を表す；
　ただし、ＲＸ１０～ＲＸ１４のうち少なくとも一つは、電子求引性基である。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
Figure JPOXMLDOC01-appb-C000016
 In the formula, RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. Represents a group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group.
RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
R X3 ~ R X14 represents a hydrogen atom or a substituent independently;
Provided that at least one of R X10 ~ R X14 is an electron withdrawing group.
　上記式において、ＲＸ１２が電子求引性基であり、ＲＸ１０、ＲＸ１１、ＲＸ１３、ＲＸ１４は水素原子であることが好ましい。 In the above formulas, R X12 is an electron withdrawing group, it is preferred that R X10, R X11, R X13 , R X14 is a hydrogen atom.
　オキシム化合物ＯＸの具体例としては、特許第４６００６００号公報の段落番号００８３～０１０５に記載の化合物が挙げられる。 Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　オキシム化合物は、波長３５０～５００ｎｍの範囲に極大吸収波長を有する化合物が好ましく、波長３６０～４８０ｎｍの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長３６５ｎｍ又は波長４０５ｎｍにおけるモル吸光係数は、感度の観点から、高いことが好ましく、１０００～３０００００であることがより好ましく、２０００～３０００００であることが更に好ましく、５０００～２０００００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
　光重合開始剤としては、２官能あるいは３官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、着色組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光ラジカル重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開第２０１５／００４５６５号、特表２０１６－５３２６７５号公報の段落番号０４０７～０４１２、国際公開第２０１７／０３３６８０号の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開第２０１６／０３４９６３号に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）、特許第６４６９６６９号公報に記載されているオキシムエステル光開始剤などが挙げられる。 As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the colored composition with time can be improved. .. Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Dimerics of oxime compounds described in paragraphs 0407 to 0412, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP-A-2013-522445. G), Cmpd1-7 described in International Publication No. 2016/034943, Oxime Esters Photoinitiator described in paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, is described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators.
　着色組成物の全固形分中における光重合開始剤の含有量は０．１～３０質量％が好ましい。下限は、０．５質量％以上が好ましく、１質量％以上がより好ましい。上限は、２０質量％以下が好ましく、１５質量％以下がより好ましい。本発明の着色組成物において、光重合開始剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. In the coloring composition of the present invention, only one kind of photopolymerization initiator may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
＜＜環状エーテル基を有する化合物＞＞
　本発明の着色組成物は、環状エーテル基を有する化合物を含有することができる。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。環状エーテル基を有する化合物は、エポキシ基を有する化合物（以下、エポキシ化合物ともいう）であることが好ましい。エポキシ化合物としては、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物、特開２０１７－１７９１７２号公報に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。 << Compound with cyclic ether group >>
The coloring composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0083 to 0092 of JP2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated in the present specification.
　エポキシ化合物は、低分子化合物（例えば、分子量２０００未満、さらには、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）でもよい。エポキシ化合物の重量平均分子量は、２００～１０００００が好ましく、５００～５００００がより好ましい。重量平均分子量の上限は、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。 The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). But it may be. The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
　エポキシ化合物としては、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、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂、複素環式エポキシ樹脂、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。エポキシ樹脂のエポキシ当量は、３１０～３３００ｇ／ｅｑであることが好ましく、３１０～１７００ｇ／ｅｑであることがより好ましく、３１０～１０００ｇ／ｅｑであることが更に好ましい。 As the epoxy compound, an epoxy resin can be preferably used. Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type. Epoxy resin, glycidylamine-based epoxy resin, glycidylated epoxy resin of halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other Examples thereof include a copolymer with another polymerizable unsaturated compound. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.
　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、ＥＨＰＥ３１５０（（株）ダイセル製）、ＥＰＩＣＬＯＮ　Ｎ－６９５（ＤＩＣ（株）製）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（以上、日油（株）製、エポキシ基含有ポリマー）等が挙げられる。 Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Dicelle Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by Nichiyu Co., Ltd., epoxy group-containing polymer) and the like can be mentioned.
　着色組成物の全固形分中における環状エーテル基を有する化合物の含有量は、０．１～２０質量％が好ましい。下限は、例えば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、例えば、１５質量％以下が好ましく、１０質量％以下が更に好ましい。環状エーテル基を有する化合物は１種のみでもよく、２種以上でもよい。２種以上の場合は、それらの合計量が上記範囲となることが好ましい。 The content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is within the above range.
＜＜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好ましい。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。顔料誘導体を構成する色素骨格としては、キノリン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾイソインドール色素骨格、ベンゾチアゾール色素骨格、イミニウム色素骨格、スクアリリウム色素骨格、クロコニウム色素骨格、オキソノール色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、アゾ色素骨格、アゾメチン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、キナクリドン色素骨格、ジオキサジン色素骨格、ペリノン色素骨格、ペリレン色素骨格、チアジンインジゴ色素骨格、チオインジゴ色素骨格、イソインドリン色素骨格、イソインドリノン色素骨格、キノフタロン色素骨格、イミニウム色素骨格、ジチオール色素骨格、トリアリールメタン色素骨格、ピロメテン色素骨格等が挙げられ、フタロシアニン色素骨格、ジケトピロロピロール色素骨格、ベンゾイソインドール色素骨格、アントラキノン色素骨格、ジアントラキノン色素骨格、チアジンインジゴ色素骨格、アゾ色素骨格、キノフタロン色素骨格またはキナクリドン色素骨格であることが好ましく、フタロシアニン色素骨格またはジケトピロロピロール色素骨格であることがより好ましい。すなわち、顔料誘導体はフタロシアニン化合物またはジケトピロロピロール化合物であることが好ましい。酸基としては、スルホ基、カルボキシル基、リン酸基及びこれらの塩が挙げられる。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。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。 << Pigment derivative >>
The coloring composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton. The pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrole pigment. Skeleton, diketopyrrolopyrrole pigment skeleton, azo pigment skeleton, azomethine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton , Thiadine indigo pigment skeleton, thioindigo pigment skeleton, isoindolin pigment skeleton, isoindolinone pigment skeleton, quinophthalone pigment skeleton, iminium pigment skeleton, dithiol pigment skeleton, triarylmethane pigment skeleton, pyrromethene pigment skeleton, etc. Skeleton, diketopyrrolopyrrole pigment skeleton, benzoisoindole pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, thiazine indigo pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton or quinacridone pigment skeleton, preferably phthalocyanine pigment skeleton. Alternatively, it is more preferably a diketopyrrolopyrrole pigment skeleton. That is, the pigment derivative is preferably a phthalocyanine compound or a diketopyrrolopyrrole compound. Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group and salts thereof. As the atoms or atomic groups constituting the salt, alkali metal ions (Li + , Na + , K +, etc.), alkaline earth metal ions (Ca 2+ , Mg 2+, etc.), ammonium ions, imidazolium ions, pyridinium ions, etc. Examples include phosphonium ion. Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group. Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
　顔料誘導体としては、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）を含有することもできる。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 be contained. The maximum value of the molar extinction coefficient in the wavelength region of 400 ~ 700 nm of the transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L · mol -1 · cm -1 or less is not more than 3000L · mol -1 · cm -1 Is more preferable, and 100 L · mol -1 · cm -1 or less is further preferable. 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、後述する実施例に記載の化合物、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平０１－２１７０７７号公報、特開平０３－００９９６１号公報、特開平０３－０２６７６７号公報、特開平０３－１５３７８０号公報、特開平０３－０４５６６２号公報、特開平０４－２８５６６９号公報、特開平０６－１４５５４６号公報、特開平０６－２１２０８８号公報、特開平０６－２４０１５８号公報、特開平１０－０３００６３号公報、特開平１０－１９５３２６号公報、国際公開第２０１１／０２４８９６号の段落番号００８６～００９８、国際公開第２０１２／１０２３９９号の段落番号００６３～００９４、国際公開第２０１７／０３８２５２号の段落番号００８２、特開２０１５－１５１５３０号公報の段落番号０１７１、特開２０１１－２５２０６５号公報の段落番号０１６２～０１８３、特開２００３－０８１９７２号公報、特許第５２９９１５１号公報、特開２０１５－１７２７３２号公報、特開２０１４－１９９３０８号公報、特開２０１４－０８５５６２号公報、特開２０１４－０３５３５１号公報、特開２００８－０８１５６５号公報に記載の化合物が挙げられる。 Specific examples of the pigment derivative include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961. , Japanese Patent Laid-Open No. 03-026767, Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-045662, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158, Japanese Patent Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, paragraph numbers 0086 to 0998 of International Publication No. 2011/024896, paragraph numbers 0063 to 0094 of International Publication No. 2012/102399. , International Publication No. 2017/038252, paragraph No. 802, JP-A-2015-151530, paragraph No. 0171, JP-A-2011-52065, paragraph numbers 0162 to 0183, JP-A-2003-081972, Patent No. 5299151. Examples thereof include the compounds described in JP-A-2015-172732, JP-A-2014-199308, JP-A-2014-0855662, JP-A-2014-055351, and JP-A-2008-081565.
　着色組成物の全固形分中における顔料誘導体の含有量は０．３～２０質量％であることが好ましい。下限は０．６質量％以上であることが好ましく、０．９質量％以上であることがより好ましい。上限は１５質量％以下であることが好ましく、１２．５質量％以下であることがより好ましく、１０質量％以下であることが更に好ましい。また、顔料誘導体の含有量は有機顔料１００質量部に対して１～３０質量部であることが好ましい。下限は２質量部以上であることが好ましく、３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く、１５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において、顔料誘導体は１種のみを用いてもよいし、２種以上を併用してもよい。２種以上併用す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 the pigment derivative in the total solid content of the coloring composition is preferably 0.3 to 20% by mass. The lower limit is preferably 0.6% by mass or more, and more preferably 0.9% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and further preferably 10% by mass or less. The content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less. In the coloring composition of the present invention, only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably in the above range.
＜＜特定アミン化合物＞＞
　本発明の着色組成物は、１分子中に塩基性基を３個以上含み、アミン価が２．７ｍｍｏｌ／ｇ以上で、分子量が１００以上の化合物（以下特定アミン化合物ともいう）を含有することもできる。 << Specific amine compound >>
The coloring composition of the present invention contains a compound having three or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more (hereinafter, also referred to as a specific amine compound). You can also.
　特定アミン化合物の分子量は、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、特定アミン化合物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、特定アミン化合物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 specific amine compound 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, further preferably 10,000 or less, and particularly preferably 2000 or less. When the molecular weight of the specific amine compound can be calculated from the structural formula, the molecular weight of the specific amine compound is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the 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 it cannot be measured by the viscosity method or it is difficult to measure by the viscosity method, the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.
　特定アミン化合物のアミン価は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 specific amine compound is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.
　特定アミン化合物に含まれる塩基性基の数は４個以上であることが好ましく、６個以上であることがより好ましく、１０個以上であることが更に好ましい。 The number of basic groups contained in the specific amine compound is preferably 4 or more, more preferably 6 or more, and further preferably 10 or more.
　特定アミン化合物が有する塩基性基は、アミノ基であることが好ましい。また、特定アミン化合物は、１級アミノ基を有する化合物であることが好ましく、１級アミノ基と、３級アミノ基とをそれぞれ含む化合物であることがより好ましく、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化合物であることが更に好ましい。 The basic group of the specific amine compound is preferably an amino group. Further, the specific amine compound is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino. It is more preferable that the compound contains a group and a tertiary amino group, respectively.
　また、特定アミン化合物が有するアミノ基は、環状アミノ基であってもよい。環状アミノ基は、ピペリジノ基等のような脂肪族環状アミノ基であってもよく、ピリジル基等のような芳香族環状アミノ基であってもよい。環状アミノ基は、５員環又は６員環構造を有する環状アミノ基であることが好ましく、６員環構造を有する環状アミノ基であることがより好ましく、６員環構造を有する脂肪族環状アミノ基であることが更に好ましい。環状アミノ基は、ヒンダードアミン構造を有することが好ましく、６員環のヒンダードアミン構造を有することが特に好ましい。ヒンダードアミン構造としては、環状アミノ基の窒素原子に隣接する環構造における２つの炭素原子にアルキル基等の置換基を有することが好ましい。ヒンダードアミン構造を有する環状アミノ基としては、例えば、１，２，２，６，６－ペンタメチルピペリジル基、２，２，６，６－テトラメチルピペリジル基、１，２，６，６－トリメチルピペリジル基、２，６－ジメチルピペリジル基、１－メチル－２，６－ジ（ｔ－ブチル）ピペリジル基、２，６－ジ（ｔ－ブチル）ピペリジル基、１，２，２，５，５－ペンタメチルピロリジル基、２，２，５，５－テトラメチルピロリジル基等が挙げられる。なかでも、１，２，２，６，６－ペンタメチルピペリジル基、又は、２，２，６，６－テトラメチルピペリジル基が好ましく、１，２，２，６，６－ペンタメチルピペリジル基がより好ましい。 Further, the amino group contained in the specific amine compound may be a cyclic amino group. The cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group. The cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group. The cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure. As the hindered amine structure, it is preferable that the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group. Examples of the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl. Group, 2,6-dimethylpiperidyl group, 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group. Of these, 1,2,2,6,6-pentamethylpiperidyl group or 2,2,6,6-tetramethylpiperidyl group is preferable, and 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.
　特定アミン化合物としては、着色組成物の保存安定性をより向上できるという理由から、ポリアルキレンイミンであることが好ましい。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーであって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。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。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。 The specific amine compound is preferably polyalkyleneimine because it can further improve the storage stability of the coloring composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively. The number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2. Specific examples of the alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. preferable. The polyalkyleneimine is particularly preferably polyethyleneimine. Further, polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable. Examples of commercially available polyethyleneimine products 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特定アミン化合物の含有量は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。 The content of the specific amine compound 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 further 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 further preferably 3% by mass or less.
　また、特定アミン化合物の含有量は、顔料１００質量部に対して０．５～１０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８質量部以下であることが好ましく、７質量％以下であることがより好ましく、５質量部以下であることが更に好ましい。 Further, the content of the specific amine compound is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. The upper limit is preferably 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.
　また、特定アミン化合物の含有量は、酸基を有するグラフト樹脂の１００質量部に対して０．５～５０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、３質量部以上であることが更に好ましい。上限は４５質量部以下であることが好ましく、４０質量％以下であることがより好ましく、３０質量部以下であることが更に好ましい。 Further, the content of the specific amine compound is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the graft resin having an acid group. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more. The upper limit is preferably 45 parts by mass or less, more preferably 40% by mass or less, and further preferably 30 parts by mass or less.
＜＜溶剤＞＞
　本発明の着色組成物は、溶剤を含有することが好ましい。溶剤は、有機溶剤であることが好ましい。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、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などが挙げられる。ただし有機溶剤としての芳香族炭化水素類（ベンゼン、トルエン、キシレン、エチルベンゼン等）は、環境面等の理由により低減したほうがよい場合がある（例えば、有機溶剤全量に対して、５０質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）以下とすることもでき、１０質量ｐｐｍ以下とすることもでき、１質量ｐｐｍ以下とすることもできる）。 << Solvent >>
The coloring composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. For these details, paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methylethylketone, Gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane diacetate-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol and the like can be mentioned. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).
　本発明においては、金属含有量の少ない有機溶剤を用いることが好ましく、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 having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, 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、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
　有機溶剤には、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 having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
　有機溶剤中の過酸化物の含有率は０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
　着色組成物中における溶剤の含有量は、１０～９５質量％であることが好ましく、２０～９０質量％であることがより好ましく、３０～９０質量％であることが更に好ましい。 The content of the solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
　また、本発明の着色組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、着色組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、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。 Further, it is preferable that the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations. In the present invention, substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evolution Analysis and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) method, VOC (Volatile and Transfer Registor) method, VOC (Volatile Organic Compounds), and VOC (Volatile Organic Compounds). The method is strictly regulated. These compounds may be used as a solvent in producing each component used in the coloring composition, and may be mixed in the coloring composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally regulated substance, there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to improve efficiency. When a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added and distilled under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be. These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a colored composition stage prepared by mixing these compounds. It is possible at any stage of.
＜＜硬化促進剤＞＞
　本発明の着色組成物は、硬化促進剤を含んでもよい。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ル基含有エポキシ硬化剤などが挙げられる。硬化促進剤を含有する場合、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％が好ましく、０．８～６．４質量％がより好ましい。 << Curing Accelerator >>
The coloring composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidin salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like. Specific examples of the curing accelerator include the compound described in paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compound described in paragraph numbers 0246 to 0253 of JP-A-2015-034963, and JP-A-2013-041165. Compounds described in Japanese Patent Laid-Open No. 0186-0251, ionic compounds described in JP-A-2014-0551114, compounds described in paragraphs 0071-0080 of JP-A-2012-150180, JP-A-2011-253504. Examples thereof include an alkoxysilane compound having an epoxy group described in Japanese Patent No. 5, a compound described in paragraphs 805 to 0092 of Japanese Patent No. 5765059, and a carboxyl group-containing epoxy curing agent described in JP-A-2017-036379. When the curing accelerator is contained, the content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
＜＜紫外線吸収剤＞＞
　本発明の着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－０６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。また、紫外線吸収剤は、特許第６２６８９６７号公報の段落番号００４９～００５９に記載された化合物を用いることもできる。着色組成物の全固形分中における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。本発明の着色組成物において、紫外線吸収剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 << UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. Details thereof are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. These compounds are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. 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. In the coloring composition of the present invention, only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
＜＜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。重合禁止剤を含有する場合、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％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、合計量が上記範囲となることが好ましい。 << Polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable. When the polymerization inhibitor is contained, the content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass. The polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
＜＜シランカップリング剤＞＞
　本発明の着色組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アリル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、Ｎ－β－アミノエチル－γ－アミノプロピルメチルジメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－６０２）、Ｎ－β－アミノエチル－γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－６０３）、Ｎ－β－アミノエチル－γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－６０２）、γ－アミノプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－９０３）、γ－アミノプロピルトリエトキシシラン（信越化学工業（株）製、商品名　ＫＢＥ－９０３）、３－メタクリロキシプロピルメチルジメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－５０２）、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製、商品名　ＫＢＭ－５０３）等がある。また、シランカップリング剤の具体例については、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。シランカップリング剤を含有する場合、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％が好ましく、０．０５～１０．０質量％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、合計量が上記範囲となることが好ましい。 << Silane Coupling Agent >>
The coloring composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by 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 the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group. , A phenyl group and the like, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino. Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy There are 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 the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. , These contents are incorporated herein. When a silane coupling agent is contained, 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. preferable. The silane coupling agent may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
＜＜界面活性剤＞＞
　本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開第２０１５／１６６７７９号の段落番号０２３８～０２４５に記載された界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 << Surfactant >>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. As for the surfactant, the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
　本発明において、界面活性剤はフッ素系界面活性剤であることが好ましい着色組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。 In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the coloring composition, the liquid characteristics (particularly, fluidity) are further improved, and the liquid saving property is further improved. Can be improved. It is also possible to form a film having a small thickness unevenness.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、より好ましくは５～３０質量％であり、特に好ましくは７～２５質量％である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、着色組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in a coloring composition.
　フッ素系界面活性剤としては、特開２０１４－０４１３１８号公報の段落番号００６０～００６４（対応する国際公開第２０１４／０１７６６９号の段落番号００６０～００６４）等に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤、特開２０２０－００８６３４号公報に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックＦ－１７１、Ｆ－１７２、Ｆ－１７３、Ｆ－１７６、Ｆ－１７７、Ｆ－１４１、Ｆ－１４２、Ｆ－１４３、Ｆ－１４４、Ｆ－４３７、Ｆ－４７５、Ｆ－４７７、Ｆ－４７９、Ｆ－４８２、Ｆ－５５４、Ｆ－５５５－Ａ、Ｆ－５５６、Ｆ－５５７、Ｆ－５５８、Ｆ－５５９、Ｆ－５６０、Ｆ－５６１、Ｆ－５６５、Ｆ－５６３、Ｆ－５６８、Ｆ－５７５、Ｆ－７８０、ＥＸＰ、ＭＦＳ－３３０、Ｒ－４１、Ｒ－４１－ＬＭ、Ｒ－０１、Ｒ－４０、Ｒ－４０－ＬＭ、ＲＳ－４３、ＴＦ－１９５６、ＲＳ－９０、Ｒ－９４、ＲＳ－７２－Ｋ、ＤＳ－２１（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、ＡＧＣ（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）、フタージェント７１０ＦＭ、６１０ＦＭ、６０１ＡＤ、６０１ＡＤＨ２、６０２Ａ、２１５Ｍ、２４５Ｆ（以上、株）ＮＥＯＳ製）等が挙げられる。 Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafuck 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-41, R-41-LM, R-01, R-40, R -40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo) 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Surfactant 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by NEOS), etc. Can be mentioned.
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（化学工業日報（２０１６年２月２２日）、日経産業新聞（２０１６年２月２３日））、例えばメガファックＤＳ－２１が挙げられる。 Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied. Can be suitably used. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Further, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.
　フッ素系界面活性剤は、ブロックポリマーを用いることもできる。例えば特開２０１１－０８９０９０号公報に記載された化合物が挙げられる。フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。また、特開２０１０－０３２６９８号公報の段落番号００１６～００３７に記載されたフッ素含有界面活性剤や、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000019
 　上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in JP-A-2011-089090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
Figure JPOXMLDOC01-appb-C000019
 The weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、例えばＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。また、フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（富士フイルム和光純薬工業製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm sum) Kojunyaku Kogyo), Pionin D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.), etc. Can be mentioned.
　シリコン系界面活性剤としては、例えば、トーレシリコーンＤＣ３ＰＡ、トーレシリコーンＳＨ７ＰＡ、トーレシリコーンＤＣ１１ＰＡ、トーレシリコーンＳＨ２１ＰＡ、トーレシリコーンＳＨ２８ＰＡ、トーレシリコーンＳＨ２９ＰＡ、トーレシリコーンＳＨ３０ＰＡ、トーレシリコーンＳＨ８４００（以上、東レ・ダウコーニング（株）製）、ＴＳＦ－４４４０、ＴＳＦ－４３００、ＴＳＦ－４４４５、ＴＳＦ－４４６０、ＴＳＦ－４４５２（以上、モメンティブ・パフォーマンス・マテリアルズ社製）、ＫＰ－３４１、ＫＦ－６００１、ＫＦ－６００２（以上、信越シリコーン株式会社製）、ＢＹＫ３０７、ＢＹＫ３２３、ＢＹＫ３３０（以上、ビックケミー社製）等が挙げられる。 Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all of which are Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shinetsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.
　着色組成物の全固形分中における界面活性剤の含有量は、０．００１質量％～５．０質量％が好ましく、０．００５～３．０質量％がより好ましい。本発明の着色組成物において、界面活性剤は１種のみを用いてもよく、２種以上を用いてもよい。２種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 The content of the 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. In the coloring composition of the present invention, only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
＜＜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、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など）を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開２０１２－００３２２５号公報の段落番号０１８３以降（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。 << Other ingredients >>
The coloring composition of the present invention may be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent, etc.), if necessary. It may contain a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification.
　本発明の着色組成物は、耐光性改良剤を含んでもよい。耐光性改良剤としては、特開２０１７－１９８７８７号公報の段落番号００３６～００３７に記載の化合物、特開２０１７－１４６３５０号公報の段落番号００２９～００３４に記載の化合物、特開２０１７－１２９７７４号公報の段落番号００３６～００３７、００４９～００５２に記載の化合物、特開２０１７－１２９６７４号公報の段落番号００３１～００３４、００５８～００５９に記載の化合物、特開２０１７－１２２８０３号公報の段落番号００３６～００３７、００５１～００５４に記載の化合物、国際公開第２０１７／１６４１２７号の段落番号００２５～００３９に記載の化合物、特開２０１７－１８６５４６号公報の段落番号００３４～００４７に記載の化合物、特開２０１５－０２５１１６号公報の段落番号００１９～００４１に記載の化合物、特開２０１２－１４５６０４号公報の段落番号０１０１～０１２５に記載の化合物、特開２０１２－１０３４７５号公報の段落番号００１８～００２１に記載の化合物、特開２０１１－２５７５９１号公報の段落番号００１５～００１８に記載の化合物、特開２０１１－１９１４８３号公報の段落番号００１７～００２１に記載の化合物、特開２０１１－１４５６６８号公報の段落番号０１０８～０１１６に記載の化合物、特開２０１１－２５３１７４号公報の段落番号０１０３～０１５３に記載の化合物などが挙げられる。 The coloring composition of the present invention may contain a light resistance improving agent. Examples of the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774. The compounds described in paragraphs 0036 to 0037 and 0049 to 0052, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, paragraph numbers 0036 to 0037 of JP-A-2017-122803. , 0051 to 0054, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017/164127, the compounds described in paragraphs 0034 to 0047 of JP-A-2017-186546, the compounds of JP-A-2015-025116. The compounds described in paragraph numbers 0019 to 0041 of JP-A, the compounds described in paragraph numbers 0101 to 0125 of JP2012-145604, the compounds described in paragraph numbers 0018 to 0021 of JP-A-2012-103475, the present invention. The compounds described in paragraphs 0015 to 0018 of JP-A-2011-257591, the compounds described in paragraph numbers 0017 to 0021 of JP-A-2011-191483, and paragraph numbers 0108 to 0116 of JP-A-2011-145668. , And the compounds described in paragraphs 0103 to 0153 of JP-A-2011-253174.
　本発明の着色組成物は、顔料などと結合または配位していない遊離の金属の含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。この態様によれば、顔料分散性の安定化（凝集抑止）、分散性良化に伴う分光特性の向上、硬化性成分の安定化、金属原子・金属イオンの溶出に伴う導電性変動の抑止、表示特性の向上などの効果が期待できる。また、特開２０１２－１５３７９６号公報、特開２０００－３４５０８５号公報、特開２００５－２００５６０号公報、特開平０８－０４３６２０号公報、特開２００４－１４５０７８号公報、特開２０１４－１１９４８７号公報、特開２０１０－０８３９９７号公報、特開２０１７－０９０９３０号公報、特開２０１８－０２５６１２号公報、特開２０１８－０２５７９７号公報、特開２０１７－１５５２２８号公報、特開２０１８－０３６５２１号公報などに記載された効果も得られる。上記の遊離の金属の種類としては、Ｎａ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｒ、Ｃｏ、Ｍｇ、Ａｌ、Ｓｎ、Ｚｒ、Ｇａ、Ｇｅ、Ａｇ、Ａｕ、Ｐｔ、Ｃｓ、Ｎi、Ｃｄ、Ｐｂ、Ｂｉ等が挙げられる。また、本発明の着色組成物は、顔料などと結合または配位していない遊離のハロゲンの含有量が１００ｐｐｍ以下であることが好ましく、５０ｐｐｍ以下であることがより好ましく、１０ｐｐｍ以下であることが更に好ましく、実質的に含有しないことが特に好ましい。ハロゲンとしては、Ｆ、Ｃｌ、Ｂｒ、Ｉ及びそれらの陰イオンが挙げられる。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、イオン交換樹脂による精製等の方法が挙げられる。 The coloring composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, which is not bound or coordinated with a pigment or the like. , It is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuation due to elution of metal atoms / metal ions, Effects such as improvement of display characteristics can be expected. Further, JP-A-2012-153796, JP-A-2000-34585, JP-A-2005-2005, JP-A-08-043620, JP-A-2004-145878, JP-A-2014-119487, Described in JP-A-2010-083979, JP-A-2017-090930, JP-A-2018-025612, JP-A-2018-025797, JP-A-2017-155228, JP-A-2018-036521 and the like. The effect that was done is also obtained. Examples of the types of free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, and the like. Examples thereof include Cs, Ni, Cd, Pb and Bi. Further, in the coloring composition of the present invention, the content of free halogen not bonded or coordinated with a pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is not substantially contained. Examples of the halogen include F, Cl, Br, I and their anions. Examples of the method for reducing free metals and halogens in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
　本発明の着色組成物は、テレフタル酸エステルを実質的に含まないことも好ましい。ここで、「実質的に含まない」とは、テレフタル酸エステルの含有量が、着色組成物の全量中、１０００質量ｐｐｂ以下であることを意味し、１００質量ｐｐｂ以下であることがより好ましく、ゼロであることが特に好ましい。 It is also preferable that the coloring composition of the present invention does not substantially contain terephthalic acid ester. Here, "substantially free" means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
　環境規制の観点から、パーフルオロアルキルスルホン酸及びその塩、並びにパーフルオロアルキルカルボン酸及びその塩の使用が規制されることがある。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 viewpoint of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be restricted. In the coloring composition of the present invention, when the content of the above-mentioned compound is reduced, the perfluoroalkyl sulfonic acid (particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group), a salt thereof, and a par The content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof. For example, by using a compound that can substitute for perfluoroalkyl sulfonic acid and its salt, and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid can be used. And a coloring composition that is substantially free of salts thereof may be selected. Examples of compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The coloring composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
＜＜収容容器＞＞
　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 containing the coloring composition is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the coloring composition, and suppressing the deterioration of the components.
＜着色組成物の調製方法＞
　本発明の着色組成物は、前述の成分を混合して調製できる。着色組成物の調製に際しては、全成分を同時に溶剤に溶解および／または分散して着色組成物を調製してもよいし、必要に応じて、各成分を適宜２つ以上の溶液または分散液としておいて、使用時（塗布時）にこれらを混合して着色組成物を調製してもよい。 <Preparation method of coloring composition>
The coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the coloring composition, all the components may be dissolved and / or dispersed in a solvent at the same time to prepare the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to prepare a coloring composition.
　また、着色組成物の調製に際して、有機顔料を分散させるプロセスを含むことが好ましい。有機顔料を分散させるプロセスにおいて、有機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）における有機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、有機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。また有機顔料を分散させるプロセスにおいては、ソルトミリング工程にて粒子の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 Further, it is preferable to include a process of dispersing the organic pigment in the preparation of the coloring composition. In the process of dispersing the organic pigment, the mechanical force used for dispersing the organic pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverization of the organic pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to process under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove the coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing organic pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industry centered on suspension (solid / liquid dispersion system)". Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the organic pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
　着色組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、着色組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 In preparing the coloring composition, it is preferable to filter the coloring composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Examples thereof include filters using materials such as (including high-density, ultra-high molecular weight polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＸＥＹ、ＤＦＡ４２０１ＮＡＥＹ、ＤＦＡ４２０１Ｊ００６Ｐなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the hole diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used. ..
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 It is also preferable to use a fiber-like filter medium as the filter. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using a filter, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
＜膜＞
　本発明の膜は、上述した本発明の着色組成物から得られる膜である。本発明の膜は、カラーフィルタなどに用いることができる。具体的には、カラーフィルタの着色層（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。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、５μｍ以下が好ましく、１μｍ以下がより好ましく、０．６μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 <Membrane>
The film of the present invention is a film obtained from the above-mentioned coloring composition of the present invention. The film of the present invention can be used as a color filter or the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, and a yellow pixel. The film thickness of the film of the present invention can be appropriately adjusted according to the intended purpose. For example, the film thickness is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.
＜膜の製造方法＞
　次に、本発明の膜の製造方法について説明する。本発明の膜は、本発明の着色組成物を塗布する工程を経て製造できる。膜の製造方法においては、更にパターン（画素）を形成する工程を含むことが好ましい。パターン（画素）の形成方法としては、フォトリソグラフィ法、ドライエッチング法が挙げられ、フォトリソグラフィ法が好ましい。 <Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the coloring composition of the present invention. The film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
　フォトリソグラフィ法によるパターン形成は、本発明の着色組成物を用いて支持体上に着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、着色組成物層の未露光部を現像除去してパターン（画素）を形成する工程と、を含むことが好ましい。必要に応じて、着色組成物層をベークする工程（プリベーク工程）、および、現像されたパターン（画素）をベークする工程（ポストベーク工程）を設けてもよい。 The pattern formation by the photolithography method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer in a pattern, and a step of exposing the colored composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
　着色組成物層を形成する工程では、本発明の着色組成物を用いて、支持体上に着色組成物層を形成する。支持体としては、特に限定は無く、用途に応じて適宜選択できる。例えば、ガラス基板、シリコン基板などが挙げられ、シリコン基板であることが好ましい。また、シリコン基板には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、シリコン基板には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、シリコン基板には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下地層が設けられていてもよい。下地層の表面接触角は、ジヨードメタンで測定した際に２０～７０°であることが好ましい。また、水で測定した際に３０～８０°であることが好ましい。下地層の表面接触角が上記範囲であれば、着色組成物の塗れ性が良好である。下地層の表面接触角の調整は、例えば、界面活性剤の添加などの方法で行うことができる。 In the step of forming the coloring composition layer, the coloring composition layer of the present invention is used to form the coloring composition layer on the support. The support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
　着色組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコーティング）；流延塗布法；スリットアンドスピン法；プリウェット法（例えば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えば、オンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５ページ～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、着色組成物の塗布方法については、国際公開第２０１７／０３０１７４号、国際公開第２０１７／０１８４１９号の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As a method for applying the coloring composition, a known method can be used. For example, a drop method (drop cast); a slit coat method; a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned. The method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
　支持体上に形成した着色組成物層は、乾燥（プリベーク）してもよい。低温プロセスにより膜を製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０～３００秒が好ましく、４０～２５０秒がより好ましく、８０～２２０秒がさらに好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。 The colored composition layer formed on the support may be dried (prebaked). When the membrane is manufactured by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.
　次に、着色組成物層をパターン状に露光する（露光工程）。例えば、着色組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン状に露光することができる。これにより、露光部分を硬化することができる。 Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by exposing the colored composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
　露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。また、３００ｎｍ以上の長波な光源も利用できる。 Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
　また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光（パルス露光）してもよい。なお、パルス露光とは、短時間（例えば、ミリ秒レベル以下）のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。 Further, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be performed for exposure (pulse exposure). The pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).
　照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば、酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、または、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、または、５０体積％）で露光してもよい。また、露光照度は適宜設定することが可能であり、通常１０００Ｗ／ｍ２～１０００００Ｗ／ｍ２（例えば、５０００Ｗ／ｍ２、１５０００Ｗ／ｍ２、または、３５０００Ｗ／ｍ２）の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume. The exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other. For example, the oxygen concentration may be 10% by volume and the illuminance may be 10,000 W / m 2 , and the oxygen concentration may be 35% by volume and the illuminance may be 20000 W / m 2 .
　次に、着色組成物層の未露光部を現像除去してパターン（画素）を形成する。着色組成物層の未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の着色組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上するため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 Next, the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed portion of the coloring composition layer can be performed using a developing solution. As a result, the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
　現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液（アルカリ現像液）が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。また、現像後純水で洗浄（リンス）することも好ましい。また、リンスは、現像後の着色組成物層が形成された支持体を回転させつつ、現像後の着色組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルを支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc. Examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.
　現像後、乾燥を施した後に追加露光処理や加熱処理（ポストベーク）を行うことが好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。ポストベークにおける加熱温度は、例えば、１００～２４０℃が好ましく、２００～２４０℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長４００ｎｍ以下の光であることが好ましい。また、追加露光処理は、韓国公開特許第１０－２０１７－０１２２１３０号公報に記載された方法で行ってもよい。 It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure processing and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
　ドライエッチング法でのパターン形成は、本発明の着色組成物を用いて支持体上に着色組成物層を形成し、この着色組成物層の全体を硬化させて硬化物層を形成する工程と、この硬化物層上にフォトレジスト層を形成する工程と、フォトレジスト層をパターン状に露光したのち、現像してレジストパターンを形成する工程と、このレジストパターンをマスクとして硬化物層に対してエッチングガスを用いてドライエッチングする工程と、を含むことが好ましい。フォトレジスト層の形成においては、更にプリベーク処理を施すことが好ましい。特に、フォトレジスト層の形成プロセスとしては、露光後の加熱処理、現像後の加熱処理（ポストベーク処理）を実施する形態が望ましい。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 The pattern formation by the dry etching method includes a step of forming a colored composition layer on a support using the colored composition of the present invention and curing the entire colored composition layer to form a cured product layer. A step of forming a photoresist layer on the cured product layer, a step of exposing the photoresist layer in a pattern and then developing to form a resist pattern, and a step of etching the cured product layer using this resist pattern as a mask. It is preferable to include a step of dry etching with a gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as a process for forming the photoresist layer, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993 can be referred to, and this content is incorporated in the present specification.
＜カラーフィルタ＞
　次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の膜を有する。好ましくは、カラーフィルタの着色画素として、より好ましくは緑色画素として本発明の膜を有する。 <Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. Preferably, the film of the present invention is provided as a colored pixel of a color filter, more preferably as a green pixel.
　カラーフィルタの一態様としては、赤色画素、緑色画素及び青色画素を少なくとも有し、赤色画素、緑色画素及び青色画素の少なくとも１色の着色画素が本発明の膜で構成されているカラーフィルタが挙げられる。カラーフィルタの他の態様としては、シアン色画素、マゼンタ色画素及び黄色画素を少なくとも有し、シアン色画素、マゼンタ色画素及び黄色画素の少なくとも１色の着色画素が本発明の膜で構成されているカラーフィルタが挙げられる。 One aspect of the color filter is a color filter having at least a red pixel, a green pixel, and a blue pixel, and a colored pixel having at least one color of the red pixel, the green pixel, and the blue pixel formed of the film of the present invention. Be done. As another aspect of the color filter, it has at least a cyan color pixel, a magenta color pixel and a yellow pixel, and at least one color pixel of the cyan color pixel, the magenta color pixel and the yellow pixel is composed of the film of the present invention. There are color filters.
　カラーフィルタは、ＣＣＤ（電荷結合素子）やＣＭＯＳ（相補型金属酸化膜半導体）などの固体撮像素子や画像表示装置などに用いることができる。 The color filter can be used for solid-state image pickup devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.
　カラーフィルタにおいて本発明の膜の膜厚は、目的に応じて適宜調整できる。膜厚は、５μｍ以下が好ましく、１μｍ以下がより好ましく、０．６μｍ以下がさらに好ましい。膜厚の下限は、０．１μｍ以上が好ましく、０．２μｍ以上がより好ましく、０．３μｍ以上がさらに好ましい。 In the color filter, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.
　カラー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 color 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 further preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
　カラー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、例えば超高抵抗計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 color 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 further preferably 15 nm or less. The lower limit is not specified, but it is preferably 0.1 nm or more, for example. The surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco. Further, the contact angle of water on the pixel can be appropriately set to a preferable 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, it is preferred that the volume resistivity value of the pixel is 10 9 Ω · cm or more, and more preferably 10 11 Ω · cm or more. The upper limit is not specified, but it is preferably 10 14 Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).
　カラーフィルタにおいては、本発明の膜（画素）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、有機溶剤に溶解した樹脂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、ポリカーボネート樹脂、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 color filter, a protective layer may be provided on the surface of the film (pixel) of the present invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, prohydrophobicization, 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 resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. The components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and 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 thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, 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 for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4. Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.
　樹脂組成物を塗布して保護層を形成する場合、樹脂組成物の塗布方法としては、スピンコート法、キャスト法、スクリーン印刷法、インクジェット法等の公知の方法を用いることができる。樹脂組成物に含まれる有機溶剤は、公知の有機溶剤（例えば、プロピレングリコール１－モノメチルエーテル２－アセテート、シクロペンタノン、乳酸エチル等）を用いることが出来る。保護層を化学気相蒸着法にて形成する場合、化学気相蒸着法としては、公知の化学気相蒸着法（熱化学気相蒸着法、プラズマ化学気相蒸着法、光化学気相蒸着法）を用いることができる。 When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as the application method of the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by the chemical vapor deposition method, the known chemical vapor deposition method (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) is used as the chemical vapor deposition method. Can be used.
　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、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 contains organic / inorganic fine particles, an absorbent for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an adhesive, a surfactant, and other additives, if necessary. Is also good. Examples of organic / inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like. A known absorber can be used as the absorber of light having a specific wavelength. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass 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。 Further, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
　カラーフィルタは、下地層を有していてもよい。下地層の表面接触角は、ジヨードメタンで測定した際に２０～７０°であることが好ましい。また、水で測定した際に３０～８０°であることが好ましい。下地層の表面接触角の調整は、たとえば、界面活性剤の添加などの方法で行うことができる。 The color filter may have a base layer. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
　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、各画素が埋め込まれた構造を有していてもよい。 The color filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
＜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、本発明の膜を備え、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 image sensor>
The solid-state image sensor of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state image sensor is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, and examples thereof 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、米国特許出願公開第２０１８／００４０６５６号明細書に記載の装置が挙げられる。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。 On the substrate, there are a plurality of photodiodes constituting the light receiving area of a solid-state image pickup device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to have a light-shielding film in which only the light-receiving part of the photodiode is open, and to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. And has a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Examples of the image pickup apparatus having such a structure are described in JP-A-2012-227478, JP-A-2014-179757, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. Equipment is mentioned. The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.
＜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 above-mentioned film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Industrial Books). Co., Ltd. (issued in 1989) ”. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜分散液の製造＞
　下記の表に記載の原料を混合したのち、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて５時間分散処理を行い、ビーズをろ過で分離して分散液を製造した。下記の表の各原料の配合量の数値は質量部である。なお、樹脂（分散剤）の配合量の値は、固形分２０質量％の樹脂溶液での配合量の値である。 <Manufacturing of dispersion>
After mixing the raw materials shown in the table below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm was added, and dispersion treatment was performed for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion liquid. .. The numerical value of the blending amount of each raw material in the table below is a part by mass. The value of the blending amount of the resin (dispersant) is the value of the blending amount in the resin solution having a solid content of 20% by mass.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　上記表の略語で記載した原料は以下の通りである。 The raw materials described by the abbreviations in the above table are as follows.
（色材）
［有機顔料］
　ＰＲ１２２　：　Ｃ．Ｉ．ピグメントレッド１２２（赤色顔料）
　ＰＲ１７７　：　Ｃ．Ｉ．ピグメントレッド１７７（赤色顔料）
　ＰＲ２５４　：　Ｃ．Ｉ．ピグメントレッド２５４（赤色顔料）
　ＰＲ２６４　：　Ｃ．Ｉ．ピグメントレッド２６４（赤色顔料）
　ＰＲ２６９　：　Ｃ．Ｉ．ピグメントレッド２６９（赤色顔料）
　ＰＲ２７２　：　Ｃ．Ｉ．ピグメントレッド２７２（赤色顔料）
　ＰＹ１２９　：　Ｃ．Ｉ．ピグメントイエロー１２９（黄色顔料）
　ＰＹ１３９　：　Ｃ．Ｉ．ピグメントイエロー１３９（黄色顔料）
　ＰＹ１５０　：　Ｃ．Ｉ．ピグメントイエロー１５０（黄色顔料）
　ＰＹ１８５　：　Ｃ．Ｉ．ピグメントイエロー１８５（黄色顔料）
　ＰＹ２１５　：　Ｃ．Ｉ．ピグメントイエロー２１５（黄色顔料）
　Ｙｅｌｌｏｗ１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000025
 　Ｙｅｌｌｏｗ２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000026
 　Ｙｅｌｌｏｗ３：下記構造の化合物
Figure JPOXMLDOC01-appb-C000027
 　ＰＯ７１　：　Ｃ．Ｉ．ピグメントオレンジ７１（オレンジ色顔料）
　ＰＧ７　：　Ｃ．Ｉ．ピグメントグリーン７（緑色顔料）
　ＰＧ３６　：　Ｃ．Ｉ．ピグメントグリーン３６（緑色顔料）
　ＰＧ５８　：　Ｃ．Ｉ．ピグメントグリーン５８（緑色顔料）
　ＰＧ６２　：　Ｃ．Ｉ．ピグメントグリーン６２（緑色顔料）
　ＰＧ６３　：　Ｃ．Ｉ．ピグメントグリーン６３（緑色顔料）
　ＰＢ１５：６　：　Ｃ．Ｉ．ピグメントブルー１５：６（青色顔料）
　ＰＢ６０　：　Ｃ．Ｉ．ピグメントブルー６０（青色顔料）
　ＰＶ２３　：　Ｃ．Ｉ．ピグメントバイオレット２３（紫色顔料）
　ＰＶ２９　：　Ｃ．Ｉ．ピグメントバイオレット２９（紫色顔料）
　Ａｌフタロシアニン：下記構造の化合物
Figure JPOXMLDOC01-appb-C000028
 (Color material)
[Organic pigment]
PR122: C.I. I. Pigment Red 122 (red pigment)
PR177: C.I. I. Pigment Red 177 (red pigment)
PR254: C.I. I. Pigment Red 254 (red pigment)
PR264: C.I. I. Pigment Red 264 (red pigment)
PR269: C.I. I. Pigment Red 269 (red pigment)
PR272: C.I. I. Pigment Red 272 (red pigment)
PY129: C.I. I. Pigment Yellow 129 (yellow pigment)
PY139: C.I. I. Pigment Yellow 139 (yellow pigment)
PY150: C.I. I. Pigment Yellow 150 (yellow pigment)
PY185: C.I. I. Pigment Yellow 185 (yellow pigment)
PY215: C.I. I. Pigment Yellow 215 (yellow pigment)
Yellow1: Compound with the following structure
Figure JPOXMLDOC01-appb-C000025
 Yellow2: Compound with the following structure
Figure JPOXMLDOC01-appb-C000026
 Yellow3: Compound with the following structure
Figure JPOXMLDOC01-appb-C000027
 PO71: C.I. I. Pigment Orange 71 (orange pigment)
PG7: C.I. I. Pigment Green 7 (green pigment)
PG36: C.I. I. Pigment Green 36 (green pigment)
PG58: C.I. I. Pigment Green 58 (green pigment)
PG62: C.I. I. Pigment Green 62 (green pigment)
PG63: C.I. I. Pigment Green 63 (green pigment)
PB15: 6: C.I. I. Pigment Blue 15: 6 (blue pigment)
PB60: C.I. I. Pigment Blue 60 (blue pigment)
PV23: C.I. I. Pigment Violet 23 (purple pigment)
PV29: C.I. I. Pigment Violet 29 (purple pigment)
Al Phthalocyanine: A compound having the following structure
Figure JPOXMLDOC01-appb-C000028
［染料］
　ＡＲ２８９：Ｃ．Ｉ．アシッドレッド２８９
　染料１：下記構造の化合物（キサンテン染料、以下の構造式中、ｉＰｒはイソプロピル基である）
Figure JPOXMLDOC01-appb-C000029
 　染料２：下記構造のポリマー（重量平均分子量７０００）とＣ．Ｉ．アシッドレッド５２の造塩化合物（キサンテン染料）
Figure JPOXMLDOC01-appb-C000030
 　染料３：下記構造の化合物（キサンテン染料）
Figure JPOXMLDOC01-appb-C000031
 [dye]
AR289: C.I. I. Acid Red 289
Dye 1: A compound having the following structure (xanthene dye, iPr is an isopropyl group in the following structural formula)
Figure JPOXMLDOC01-appb-C000029
 Dye 2: A polymer having the following structure (weight average molecular weight 7000) and C.I. I. Acid Red 52 salt-forming compound (xanthene dye)
Figure JPOXMLDOC01-appb-C000030
 Dye 3: A compound with the following structure (xanthene dye)
Figure JPOXMLDOC01-appb-C000031
（顔料誘導体）
　誘導体１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000032
 　誘導体２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000033
 　誘導体３：下記構造の化合物
Figure JPOXMLDOC01-appb-C000034
 　誘導体４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000035
 　誘導体５：下記構造の化合物
Figure JPOXMLDOC01-appb-C000036
 (Pigment derivative)
Derivative 1: Compound with the following structure
Figure JPOXMLDOC01-appb-C000032
 Derivative 2: A compound having the following structure
Figure JPOXMLDOC01-appb-C000033
 Derivative 3: A compound having the following structure
Figure JPOXMLDOC01-appb-C000034
 Derivative 4: Compound with the following structure
Figure JPOXMLDOC01-appb-C000035
 Derivative 5: Compound with the following structure
Figure JPOXMLDOC01-appb-C000036
（分散助剤）
　分散助剤１：　ポリエチレンイミン（エポミンＳＰー００３、（株）日本触媒製、分子量３００、樹脂分９８質量％以上、粘度２００～５００ｍＰａ・ｓ）
　分散助剤２：　ポリエチレンイミン（エポミンＳＰー００６、（株）日本触媒製、分子量６００、樹脂分９８質量％以上、粘度５００～２５００ｍＰａ・ｓ）
　分散助剤３：　ポリエチレンイミン（エポミンＳＰー０１８、（株）日本触媒製、分子量１８００、樹脂分９８質量％以上、粘度８５００～１５０００ｍＰａ・ｓ）
　分散助剤４：　ポリエチレンイミン（エポミンＳＰー２００、（株）日本触媒製、分子量１００００、樹脂分９８質量％以上、粘度４００００～１５００００ｍＰａ・ｓ） (Dispersion aid)
Dispersion aid 1: Polyethyleneimine (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd., molecular weight 300, resin content 98% by mass or more, viscosity 200-500 mPa · s)
Dispersion aid 2: Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd., molecular weight 600, resin content 98% by mass or more, viscosity 500-2500 mPa · s)
Dispersion aid 3: Polyethyleneimine (Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd., molecular weight 1800, resin content 98% by mass or more, viscosity 8500 to 15000 mPa · s)
Dispersion aid 4: Polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd., molecular weight 10,000, resin content 98% by mass or more, viscosity 40,000 to 150,000 mPa · s)
＜樹脂＞
　Ｂ－１：以下の方法で合成した樹脂Ｂ－１の樹脂溶液（固形分濃度２０質量％）。
　メチルメタクリレート５０質量部、ｎ－ブチルメタクリレート５０質量部、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）４５．４質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を７０℃に加熱して、３－メルカプト－１，２－プロパンジオール６質量部を添加して、さらにＡＩＢＮ（アゾビスイソブチロニトリル）０．１２質量部を加え、１２時間反応させた。固形分測定により９５％が反応したことを確認した。次に、ピロメリット酸無水物９．７質量部、ＰＧＭＥＡ７０．３質量部、触媒としてＤＢＵ（１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン）０．２０質量部を追加し、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化していることを確認し反応を終了した。ＰＧＭＥＡを加えて不揮発分（固形分濃度）を２０質量％に調整し、酸価４３ｍｇＫＯＨ／ｇ、重量平均分子量９０００の下記構造の樹脂Ｂ－１（酸基を有するグラフト樹脂）の樹脂溶液を得た。
Figure JPOXMLDOC01-appb-C000037
 <Resin>
B-1: A resin solution of resin B-1 synthesized by the following method (solid content concentration 20% by mass).
50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added. , 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added to adjust the non-volatile content (solid content concentration) to 20% by mass to obtain a resin solution of resin B-1 (graft resin having an acid group) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9000 and having the following structure. rice field.
Figure JPOXMLDOC01-appb-C000037
　Ｂ－２：以下の方法で合成した樹脂Ｂ－２の樹脂溶液（固形分濃度２０質量％）。
　メチルメタクリレート５０質量部、ｎ－ブチルメタクリレート３０質量部、ｔ－ブチルメタクリレート２０質量部、ＰＧＭＥＡ４５．４質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を７０℃に加熱して、３－メルカプト－１，２－プロパンジオール６質量部を添加して、さらにＡＩＢＮ（アゾビスイソブチロニトリル）０．１２質量部を加え、１２時間反応させた。固形分測定により９５％が反応したことを確認した。次に、ピロメリット酸無水物９．７質量部、ＰＧＭＥＡ７０．３質量部、触媒としてＤＢＵ（１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン）０．２０質量部を追加し、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化していることを確認し反応を終了した。ＰＧＭＥＡを加えて不揮発分（固形分濃度）を２０質量％に調整し、酸価４３ｍｇＫＯＨ／ｇ、重量平均分子量９０００の下記構造の樹脂Ｂ－２（酸基を有するグラフト樹脂）の樹脂溶液を得た。
Figure JPOXMLDOC01-appb-C000038
 B-2: A resin solution of the resin B-2 synthesized by the following method (solid content concentration 20% by mass).
50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate and 45.4 parts by mass of PGMEA were charged in the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added. , 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added to adjust the non-volatile content (solid content concentration) to 20% by mass to obtain a resin solution of resin B-2 (graft resin having an acid group) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9000 and having the following structure. rice field.
Figure JPOXMLDOC01-appb-C000038
　Ｂ－３：以下の方法で合成した樹脂Ｂ－３の樹脂溶液（固形分濃度２０質量％）。
　樹脂Ｂ－２の合成において、ｔ－ブチルメタクリレート２０質量部を、（３－エチルオキセタン－３－イル）メチルメタクリレート２０質量部に変更した以外は同様にして、酸価４３ｍｇＫＯＨ／ｇ、重量平均分子量９０００の下記構造の樹脂Ｂ－３（酸基を有するグラフト樹脂）の樹脂溶液を得た。
Figure JPOXMLDOC01-appb-C000039
 B-3: A resin solution of the resin B-3 synthesized by the following method (solid content concentration 20% by mass).
In the synthesis of resin B-2, the acid value was 43 mgKOH / g and the weight average molecular weight was the same except that 20 parts by mass of t-butyl methacrylate was changed to 20 parts by mass of (3-ethyloxetane-3-yl) methyl methacrylate. A resin solution of 9000 resin B-3 (graft resin having an acid group) having the following structure was obtained.
Figure JPOXMLDOC01-appb-C000039
　Ｂ－４：下記構造の樹脂（酸基を有するグラフト樹脂、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量２４０００、酸価４７ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000040
 B-4: Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 47 mgKOH / G) 20% by mass PGMEA solution
Figure JPOXMLDOC01-appb-C000040
　Ｂ－５：下記構造の樹脂（酸基を有するグラフト樹脂、主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。重量平均分子量１６０００、酸価６７ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000041
 B-5: Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH / G) 20% by mass PGMEA solution
Figure JPOXMLDOC01-appb-C000041
　Ｂ－６：下記構造の樹脂（酸基を有するグラフト樹脂、主鎖に付記された数値は質量比であり、側鎖に付記された数値は繰り返し単位の数である。重量平均分子量１３０００、酸価６５ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000042
 B-6: Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the mass ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 13000, acid 20 mass% PGMEA solution with a value of 65 mgKOH / g)
Figure JPOXMLDOC01-appb-C000042
　Ｂ－７：下記構造の樹脂（酸基を有するグラフト樹脂、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１００００）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000043
 B-7: 20 mass of a resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 10000). % PGMEA solution
Figure JPOXMLDOC01-appb-C000043
　Ｂ－８：下記構造の樹脂（主鎖に付記された数値は質量比である。重量平均分子量１３０００、酸価７４ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000044
 B-8: 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the mass ratio. Weight average molecular weight 13000, acid value 74 mgKOH / g)
Figure JPOXMLDOC01-appb-C000044
　Ｂ－９：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、酸価６９ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000045
 B-9: A 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000, acid value 69 mgKOH / g).
Figure JPOXMLDOC01-appb-C000045
　Ｂ－１０：下記構造の樹脂（ブロック共重合体、主鎖に付記された数値は質量比である。重量平均分子量７４０００、酸価８ｍｇＫＯＨ／ｇ、アミン価９５ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000046
 B-10: A 20 mass% PGMEA solution of a resin having the following structure (block copolymer, the numerical value added to the main chain is a mass ratio. Weight average molecular weight 74000, acid value 8 mgKOH / g, amine value 95 mgKOH / g).
Figure JPOXMLDOC01-appb-C000046
　Ｂ－１１：下記構造の樹脂（ブロック共重合体、主鎖に付記した数値はモル比である。重量平均分子量６０００）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000047
 B-11: 20 mass% PGMEA solution of a resin having the following structure (block copolymer, the numerical value added to the main chain is the molar ratio. Weight average molecular weight 6000).
Figure JPOXMLDOC01-appb-C000047
　Ｂ－１２：下記構造の樹脂（酸基を有するグラフト樹脂、主鎖に付記された数値は質量比であり、側鎖に付記された数値は繰り返し単位の数である。重量平均分子量１３０００、酸価１９ｍｇＫＯＨ／ｇ）の２０質量％ＰＧＭＥＡ溶液
Figure JPOXMLDOC01-appb-C000048
 B-12: Resin having the following structure (graft resin having an acid group, the numerical value added to the main chain is the mass ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 13000, acid 20 mass% PGMEA solution with a value of 19 mgKOH / g)
Figure JPOXMLDOC01-appb-C000048
（溶剤）
　Ｋ－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）
　Ｋ－２：プロピレングリコールモノメチルエーテル（ＰＧＭＥ）
　Ｋ－３：シクロペンタノン
　Ｋ－４：シクロヘキサノン
　Ｋ－５：酢酸シクロヘキシル
　Ｋ－６：１，４－ジアセトキシブタン
　Ｋ－７：ジエチレングリコールモノエチルエーテルアセタート
　Ｋ－８：３－エトキシプロピオン酸エチル
　Ｋ－９：３－ペンタノン
　Ｋ－１０：３－メチルシクロヘキサノン
　Ｋ－１１：４－メチルシクロヘキサノン
　Ｋ－１２：２－ヘプタノン
　Ｋ－１３：ガンマブチロラクトン
　Ｋ－１４：二酢酸ブタン－１，３－ジイル
　Ｋ－１５：ジプロピレングリコールメチルエーテルアセタート
　Ｋ－１６：ジアセトンアルコール (solvent)
K-1: Propylene glycol monomethyl ether acetate (PGMEA)
K-2: Propylene glycol monomethyl ether (PGME)
K-3: Cyclopentanone K-4: Cyclohexanone K-5: Cyclohexanone acetate K-6: 1,4-diacetoxybutane K-7: Diethylene glycol monoethyl ether acetate K-8: 3-Ethyl ethoxypropionate K -9: 3-Pentanone K-10: 3-Methylcyclohexanone K-11: 4-Methylcyclohexanone K-12: 2-Heptanone K-13: Gamma butyrolactone K-14: Butane diacetate-1,3-diyl K- 15: Dipropylene glycol methyl ether acetate K-16: Diacetone alcohol
＜着色組成物の製造＞
　下記の表に記載の原料を混合して、着色組成物を調製した。なお、樹脂の配合量の値は、固形分２０質量％の樹脂溶液での配合量の値である。下記表に、着色組成物の全固形分中における色材の含有量を「色材含有量」の欄に示す。また、着色組成物の全固形分中における特定化合物の含有量を「特定化合物含有量」の欄に示す。
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000054
 <Manufacturing of coloring composition>
The raw materials listed in the table below were mixed to prepare a colored composition. The value of the blending amount of the resin is the value of the blending amount in the resin solution having a solid content of 20% by mass. In the table below, the content of the coloring material in the total solid content of the coloring composition is shown in the column of "coloring material content". In addition, the content of the specific compound in the total solid content of the coloring composition is shown in the column of "Specific compound content".
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000054
　上記表の略語で記載した原料のうち、分散液および樹脂以外の原料は以下の通りである。 Among the raw materials described by the abbreviations in the above table, the raw materials other than the dispersion liquid and the resin are as follows.
（重合性モノマー）
　Ｍ－１～Ｍ－３：下記構造の化合物
Figure JPOXMLDOC01-appb-C000055
 (Polymerizable monomer)
M-1 to M-3: Compounds with the following structure
Figure JPOXMLDOC01-appb-C000055
（光重合開始剤）
　Ｇ－１、Ｇ－２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000056
 　Ｇ－３：Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（ＢＡＳＦ社製、オキシム化合物）
　Ｇ－４：Ｉｒｇａｃｕｒｅ　ＯＸＥ０２（ＢＡＳＦ社製、オキシム化合物）
　Ｇ－５：Ｏｍｎｉｒａｄ　３７９（ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社製、α－アミノケトン化合物） (Photopolymerization initiator)
G-1, G-2: Compounds with the following structure
Figure JPOXMLDOC01-appb-C000056
 G-3: Irgure OXE01 (Oxime compound manufactured by BASF)
G-4: Irgure OXE02 (Oxime compound manufactured by BASF)
G-5: Omnirad 379 (α-aminoketone compound manufactured by IGM Resins B.V.)
（特定化合物）
　化合物１～６：下記構造の化合物（構造式中のｔ－Ｂｕはｔｅｒｔ－ブチル基である。）
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
 (Specific compound)
Compounds 1 to 6: Compounds having the following structure (t-Bu in the structural formula is a tert-butyl group).
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
（界面活性剤）
　Ｉ－１：下記構造の化合物（重量平均分子量１４０００）の１質量％ＰＧＭＥＡ溶液。下記の式中、繰り返し単位の割合を示す％はモル％である。
Figure JPOXMLDOC01-appb-C000059
 (Surfactant)
I-1: A 1% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000). In the following formula,% indicating the ratio of the repeating unit is mol%.
Figure JPOXMLDOC01-appb-C000059
（その他添加剤）
　Ａ－１：ＥＨＰＥ３１５０（（株）ダイセル製、２，２’－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物）
　酸化防止剤１：下記構造の化合物（フェノール系酸化防止剤、構造式中のｔ－Ｂｕはｔｅｒｔ－ブチル基である）
　酸化防止剤２：下記構造の化合物（フェノール系酸化防止剤、構造式中のｔ－Ｂｕはｔｅｒｔ－ブチル基である）
　酸化防止剤３：下記構造の化合物（リン系酸化防止剤）
Figure JPOXMLDOC01-appb-C000060
 (Other additives)
A-1: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol)
Antioxidant 1: Compound with the following structure (phenolic antioxidant, t-Bu in the structural formula is tert-butyl group)
Antioxidant 2: A compound having the following structure (phenolic antioxidant, t-Bu in the structural formula is a tert-butyl group)
Antioxidant 3: Compound with the following structure (phosphorus antioxidant)
Figure JPOXMLDOC01-appb-C000060
（溶剤）
　Ｋ－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）
　Ｋ－２：プロピレングリコールモノメチルエーテル（ＰＧＭＥ） (solvent)
K-1: Propylene glycol monomethyl ether acetate (PGMEA)
K-2: Propylene glycol monomethyl ether (PGME)
＜耐熱性＞
（分光変動）
　ガラスウエハ上に、各着色組成物をスピンコート法で塗布し、次いで、ホットプレートを使用して１００℃で１２０秒加熱処理（プリベーク）し、次いでｉ線で１０００ｍＪ／ｃｍ２の露光量で露光し、次いで、２００℃で５分間加熱を行い、表に記載する膜厚の膜を作製した。膜付きのガラスウエハを１２０℃に設定した高温庫に１０００時間保管し、耐熱性試験を実施した。耐熱性試験前後の膜について、大塚電子（株）製のＭＣＰＤ－３０００を用い波長４００～７００ｎｍの光の透過率を測定し、透過率の変化量の最大値（ΔＴｍａｘ）を求め、以下の基準にて耐熱性試験後の分光変動を評価した。ここで、透過率の変化量とは、耐熱性試験前後の膜の透過率の差分（｜耐熱性試験前の膜の透過率－耐熱性試験後の膜の透過率｜）のことであり、透過率の変化量の最大値（ΔＴｍａｘ）とは、耐熱性試験前後の膜の、透過率の変化量が最も大きい波長における透過率の変化量のことである。
〔評価基準〕
　Ａ：ΔＴｍａｘが１％未満である
　Ｂ：ΔＴｍａｘが１％以上３％未満である
　Ｃ：ΔＴｍａｘが３％以上５％未満である
　Ｄ：ΔＴｍａｘが５％以上である <Heat resistance>
(Spectroscopic fluctuation)
Each coloring composition is applied onto a glass wafer by a spin coating method, then heat-treated (prebaked) at 100 ° C. for 120 seconds using a hot plate, and then exposed to an exposure amount of 1000 mJ / cm 2 by i-ray. Then, heating was performed at 200 ° C. for 5 minutes to prepare a film having the film thickness shown in the table. The glass wafer with a film was stored in a high temperature chamber set at 120 ° C. for 1000 hours, and a heat resistance test was carried out. For the film before and after the heat resistance test, the transmittance of light with a wavelength of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., and the maximum value (ΔTmax) of the amount of change in transmittance was obtained. The spectral variation after the heat resistance test was evaluated in. Here, the amount of change in the transmittance is the difference in the transmittance of the film before and after the heat resistance test (| the transmittance of the film before the heat resistance test-the transmittance of the film after the heat resistance test |). The maximum value (ΔTmax) of the change amount of the transmittance is the change amount of the transmittance at the wavelength where the change amount of the transmittance is the largest before and after the heat resistance test.
〔Evaluation criteria〕
A: ΔTmax is less than 1% B: ΔTmax is 1% or more and less than 3% C: ΔTmax is 3% or more and less than 5% D: ΔTmax is 5% or more
（色ムラ）
　ガラスウエハ上に、下地層形成用組成物（ＣＴ－４０００、富士フイルムエレクトロニクスマテリアルズ（株）製）を膜厚が０．１μｍとなるようにスピンコート法で塗布し、ホットプレートを用いて２２０℃で１時間加熱して下地層を形成した。この下地層付きガラスウエハ上に各着色組成物をポストベーク後の膜厚が表に記載する膜厚になるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱して組成物層を形成した。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＋、キヤノン（株）製）を使用し、３６５ｎｍの波長の光を５００ｍＪ／ｃｍ２の露光量で露光した。
　露光後の組成物層に対し、テトラメチルアンモニウムハイドロオキサイドの０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにて水を用いてリンスを行い、更に純水にて水洗いを行った。その後、水滴を高圧のエアーで飛ばし、ガラスウエハを自然乾燥させたのち、ホットプレートを用いて２２０℃で３００秒間ポストベークを行い、表に記載の膜厚の膜を形成した。
　得られた膜について、１２０℃に設定した高温庫に１０００時間保管し、耐熱性試験を実施した。耐熱性試験前後の膜が形成されたガラスウエハ（評価用基板）を用いて輝度分布を下記方法で解析し、平均からのずれが±１０％以上である画素数をもとに色ムラの評価を行った。
　輝度分布の測定方法について説明する。評価用基板を光学顕微鏡の観測レンズと光源との間に設置して光を観測レンズに向けて照射し、その透過光状態をデジタルカメラが設置された光学顕微鏡ＭＸ－５０（オリンパス社製）を用いて観察した。膜表面の撮影は、任意に選択した５つの領域に対して行った。撮影画像の輝度を０～２５５までの２５６階調の濃度分布として数値化して保存した。この画像から輝度分布を解析し、平均からのズレが±１０％を超える画素数にて色ムラを評価した。評価基準は以下の通りである。Ａ～Ｃの評価であれば実用上問題ないと判断する。
　Ａ：平均からのズレが±１０％を超える画素数が１０００以下である
　Ｂ：平均からのズレが±１０％を超える画素数が１０００を超え３０００以下である
　Ｃ：平均からのズレが±１０％を超える画素数が３０００を超え５０００以下である
　Ｄ：平均からのズレが±１０％を超える画素数が５０００を超える (Color unevenness)
A composition for forming a base layer (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a glass wafer by a spin coating method so that the film thickness is 0.1 μm, and 220 using a hot plate. The underlayer was formed by heating at ° C. for 1 hour. Each coloring composition was applied onto the glass wafer with a base layer by a spin coating method so that the film thickness after post-baking would be the film thickness shown in the table. Then, using a hot plate, the composition layer was formed by heating at 100 ° C. for 2 minutes. Next, the composition layer was exposed to light having a wavelength of 365 nm at an exposure amount of 500 mJ / cm 2 using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.).
The composition layer after exposure was paddle-developed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was rinsed with water in a spin shower and then washed with pure water. Then, the water droplets were blown off with high-pressure air, the glass wafer was naturally dried, and then post-baked at 220 ° C. for 300 seconds using a hot plate to form a film having the film thickness shown in the table.
The obtained film was stored in a high temperature chamber set at 120 ° C. for 1000 hours, and a heat resistance test was carried out. The luminance distribution is analyzed by the following method using a glass wafer (evaluation substrate) on which a film is formed before and after the heat resistance test, and color unevenness is evaluated based on the number of pixels whose deviation from the average is ± 10% or more. Was done.
The method of measuring the luminance distribution will be described. An evaluation substrate is installed between the observation lens of the optical microscope and the light source to irradiate the observation lens with light, and the transmitted light state is measured by the optical microscope MX-50 (manufactured by Olympus) equipped with a digital camera. Observed using. Imaging of the film surface was performed on five arbitrarily selected regions. The brightness of the captured image was quantified and saved as a density distribution of 256 gradations from 0 to 255. The luminance distribution was analyzed from this image, and the color unevenness was evaluated with the number of pixels whose deviation from the average exceeded ± 10%. The evaluation criteria are as follows. If the evaluation is A to C, it is judged that there is no practical problem.
A: The number of pixels whose deviation from the average exceeds ± 10% is 1000 or less. B: The number of pixels whose deviation from the average exceeds ± 10% is more than 1000 and 3000 or less. C: The deviation from the average is ± 10. The number of pixels exceeding% exceeds 3000 and is 5000 or less. D: The deviation from the average exceeds ± 10%. The number of pixels exceeds 5000.
＜密着性＞
　直径８インチ（＝２０３．２ｍｍ）のシリコンウエハ上に下地層形成用組成物（ＣＴ－４０００、富士フイルムエレクトロニクスマテリアルズ（株）製）を膜厚が０．１μｍとなるようにスピンコート法で塗布し、ホットプレートを用いて２２０℃で１時間加熱して下地層を形成した。この下地層付きの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表に記載する膜厚になるようにスピンコート法で塗布した。次いで、ホットプレートを用いて１００℃で２分間加熱して組成物層を形成した。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＋、キヤノン（株）製）を使用し、一辺１．１μｍの正方ピクセルがそれぞれ基板上の４ｍｍ×３ｍｍの領域に配列されたマスクパターンを介して、３６５ｎｍの波長の光を５００ｍＪ／ｃｍ２の露光量で照射して露光した。露光後の組成物層に対し、テトラメチルアンモニウムハイドロオキサイドの０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにて水を用いてリンスを行い、更に純水にて水洗いを行った。その後、水滴を高圧のエアーで飛ばし、シリコンウエハを自然乾燥させたのち、ホットプレートを用いて２２０℃で３００秒間ポストベークを行い、画素を形成した。得られた画素について、光学顕微鏡を用いて観察し、全画素中シリコンウエハに密着している画素の数をカウントして密着性を評価した。Ａ～Ｃが使用に問題ない範囲である。
〔評価基準〕
　Ａ：すべての画素がシリコンウエハに密着している。
　Ｂ：シリコンウエハに密着している画素が全画素の９８％以上１００％未満である。
　Ｃ：シリコンウエハに密着している画素が全画素の９５％以上９８％未満である。
　Ｄ：シリコンウエハに密着している画素が全画素の９５％未満である。 <Adhesion>
A composition for forming a base layer (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is placed on a silicon wafer having a diameter of 8 inches (= 203.2 mm) by a spin coating method so that the film thickness is 0.1 μm. It was applied and heated at 220 ° C. for 1 hour using a hot plate to form an underlayer. On the silicon wafer with the base layer, each coloring composition was applied by a spin coating method so that the film thickness after post-baking became the film thickness shown in the table. Then, the composition layer was formed by heating at 100 ° C. for 2 minutes using a hot plate. Next, using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.) for this composition layer, square pixels having a side of 1.1 μm were arranged in a 4 mm × 3 mm region on the substrate, respectively. Through the mask pattern, light having a wavelength of 365 nm was irradiated with an exposure amount of 500 mJ / cm 2 for exposure. The composition layer after exposure was paddle-developed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was rinsed with water in a spin shower and then washed with pure water. Then, water droplets were blown off with high-pressure air, the silicon wafer was naturally dried, and then post-baked at 220 ° C. for 300 seconds using a hot plate to form pixels. The obtained pixels were observed using an optical microscope, and the number of pixels in close contact with the silicon wafer among all the pixels was counted to evaluate the adhesion. A to C are in the range where there is no problem in use.
〔Evaluation criteria〕
A: All pixels are in close contact with the silicon wafer.
B: The number of pixels in close contact with the silicon wafer is 98% or more and less than 100% of all the pixels.
C: The number of pixels in close contact with the silicon wafer is 95% or more and less than 98% of all the pixels.
D: The number of pixels in close contact with the silicon wafer is less than 95% of all the pixels.
＜混色＞
　カラスウエハ上に下地層形成用組成物（ＣＴ－４０００、富士フイルムエレクトロニクスマテリアルズ（株）製）を膜厚が０．１μｍとなるようにスピンコート法で塗布し、ホットプレートを用いて２２０℃で１時間加熱して下地層を形成した。この下地層付きガラスウエハ上に各着色組成物をポストベーク後の膜厚が表に記載する膜厚になるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱して組成物層を形成した。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＋、キヤノン（株）製）を使用し、３６５ｎｍの波長の光を１０００ｍＪ／ｃｍ２の露光量で露光した。次いで、露光後の組成物層が形成されているガラスウエハをスピン・シャワー現像機（ＤＷ－３０型、（株）ケミトロニクス製）の水平回転テーブル上に載置し、ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ（株）製）の６０％希釈液を用いて２３℃で６０秒間パドル現像を行った。次いで、ガラスウエハを真空チャック方式で水平回転テーブルに固定し、回転装置によってガラスウエハを回転数５０ｒｐｍで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行い、その後スプレー乾燥した。さらに、２００℃のホットプレートを用いて４８０秒間加熱処理（ポストベーク）を行い、１層目の着色膜を得た。得られた１層目の着色膜上に、混色評価用の着色組成物をプリベーク後の膜厚が０．６μｍになるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間加熱処理（プリベーク）を行い、１層目の着色膜上に混色評価用の着色組成物層（２層目）が形成された積層カラーフィルタを得た。次いで、得られた積層カラーフィルタを１層目の着色画素の形成と同様の方法で現像、リンス及びスプレー乾燥を施して、混色評価用の着色組成物層を現像除去した。
　１層目の着色膜の作製直後と、混色評価用の着色組成物層を現像除去後の１層目の着色膜の最大透過率の分光変動（ΔＴ％ｍａｘ）をＭＣＰＤ－３０００（大塚電子（株）製）を使用して測定し、１層目の着色膜上に残る２層目の着色組成物の残渣混色を評価した。最大透過率とは、１層目の着色膜の作製直後と、混色評価用の着色組成物層を現像除去後の１層目の着色膜の透過率の変化量であって、透過率の変化量が最も大きい波長における透過率の変化量のことである。最大透過率の分光変動（ΔＴ％ｍａｘ）が小さいほど残渣混色が発生しにくいとみなされ、より望ましい。Ａ～Ｃが使用に問題ない範囲である。
　なお、実施例Ｂ１～Ｂ９以外については、混色評価用の着色組成物には、分散液Ｂ９の６５質量部と、樹脂Ｂ－９の６質量部と重合性モノマーＭ－２の２．８質量部と、光重合開始剤Ｇ－３の０．８質量部と、界面活性剤Ｉ－１の５質量部と、溶剤Ｋ－１の２０．４質量部とを混合して調製した着色組成物を用いた。また、実施例Ｂ１～Ｂ９については、混色評価用の着色組成物には実施例Ｒ１の着色組成物を用いた。
〔評価基準〕
Ａ：ΔＴ％ｍａｘが１．５％以下である。
Ｂ：ΔＴ％ｍａｘが１．５％より大きく２．０％以下である。
Ｃ：ΔＴ％ｍａｘが２．０％より大きく２．５％以下である。
Ｄ：ΔＴ％ｍａｘが２．５％より大きい。 <Mixing color>
A composition for forming a base layer (CT-4000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a crow wafer by a spin coating method so that the film thickness is 0.1 μm, and the temperature is 220 ° C. using a hot plate. The underlayer was formed by heating for 1 hour. Each coloring composition was applied onto the glass wafer with a base layer by a spin coating method so that the film thickness after post-baking would be the film thickness shown in the table. Then, using a hot plate, the composition layer was formed by heating at 100 ° C. for 2 minutes. Next, the composition layer was exposed to light having a wavelength of 365 nm at an exposure amount of 1000 mJ / cm 2 using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.). Next, the glass wafer on which the composition layer after exposure was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM) was placed. Paddle development was performed at 23 ° C. for 60 seconds using a 60% diluted solution manufactured by Electronics Materials Co., Ltd. Next, the glass wafer is fixed to a horizontal rotary table by a vacuum chuck method, and while the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in a shower shape from a ejection nozzle to perform a rinse treatment. And then spray dried. Further, heat treatment (post-baking) was performed for 480 seconds using a hot plate at 200 ° C. to obtain a first-layer colored film. A coloring composition for color mixing evaluation was applied onto the obtained first colored film using a spin coater so that the film thickness after prebaking was 0.6 μm, and 120 using a hot plate at 100 ° C. Heat treatment (pre-baking) was performed for seconds to obtain a laminated color filter in which a coloring composition layer (second layer) for color mixing evaluation was formed on the first coloring film. Next, the obtained laminated color filter was developed, rinsed and spray-dried in the same manner as in the formation of the first colored pixel, and the colored composition layer for color mixing evaluation was developed and removed.
The spectral variation (ΔT% max) of the maximum transmittance of the first colored film immediately after the preparation of the first colored film and after the development and removal of the colored composition layer for color mixing evaluation was measured by MCPD-3000 (Otsuka Electronics (Otsuka Electronics Co., Ltd.). The color mixture of the residue of the second layer coloring composition remaining on the first layer coloring film was evaluated. The maximum transmittance is the amount of change in the transmittance of the first colored film immediately after the production of the first colored film and after the development and removal of the colored composition layer for color mixing evaluation, and is the change in the transmittance. It is the amount of change in transmittance at the wavelength with the largest amount. The smaller the spectral variation (ΔT% max) of the maximum transmittance, the less likely it is that residual color mixing will occur, which is more desirable. A to C are in the range where there is no problem in use.
Except for Examples B1 to B9, the coloring composition for color mixture evaluation includes 65 parts by mass of the dispersion liquid B9, 6 parts by mass of the resin B-9, and 2.8 parts by mass of the polymerizable monomer M-2. A coloring composition prepared by mixing 0.8 parts by mass of a photopolymerization initiator G-3, 5 parts by mass of a surfactant I-1, and 20.4 parts by mass of a solvent K-1. Was used. Further, for Examples B1 to B9, the coloring composition of Example R1 was used as the coloring composition for color mixing evaluation.
〔Evaluation criteria〕
A: ΔT% max is 1.5% or less.
B: ΔT% max is greater than 1.5% and 2.0% or less.
C: ΔT% max is larger than 2.0% and 2.5% or less.
D: ΔT% max is greater than 2.5%.
　上記結果を下記表に示す。 The above results are shown in the table below.
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　上記表に示すように、実施例は、耐熱性試験後も分光変動が小さく、色ムラの小さい膜を形成することができた。 As shown in the above table, in the examples, it was possible to form a film having a small spectral fluctuation and a small color unevenness even after the heat resistance test.
　密着性の評価において、下地層形成用組成物を、ＣＴ－４０００（富士フイルムエレクトロニクスマテリアルズ（株）製）から以下で調製した下地層形成用組成物１～１１に変更し、これらの下地層形成用組成物を用いて膜厚が３ｎｍとなるようにスピンコート法で塗布し、ホットプレートを用いて２２０℃で５分加熱して下地層を形成し、得られた下地層付きのシリコンウエハ上に各実施例の着色組成物を用いて同様の手順により密着性を評価した場合であっても、各実施例と同様の効果が得られた。 In the evaluation of adhesion, the composition for forming a base layer was changed from CT-4000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) to the compositions for forming a base layer 1 to 11 prepared below, and these base layers were changed. A silicon wafer with a base layer obtained by applying a forming composition to a film thickness of 3 nm by a spin coating method and heating at 220 ° C. for 5 minutes using a hot plate to form a base layer. Even when the adhesion was evaluated by the same procedure using the coloring composition of each example above, the same effect as that of each example was obtained.
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
（樹脂）
　樹脂Ｃ－１：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２００００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－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２５０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－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２００００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－４：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１５０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－５：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２００００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－６：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２２０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－７：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２３０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－８：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２２０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－９：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１３０００）のＰＧＭＥＡ３０質量％溶液
　樹脂Ｃ－１０：下記構造の樹脂（重量平均分子量１５０００）のＰＧＭＥＡ３０質量％溶液
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
 (resin)
Resin C-1: PGMEA 30% by mass solution of resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 20000) Resin C-2: Resin having the following structure (the numerical value added to the main chain is molar) Ratio. PGMEA 30% by mass solution with a weight average molecular weight of 25,000 Resin C-3: PGMEA 30% by mass solution with a resin having the following structure (the numerical value attached to the main chain is a molar ratio. Weight average molecular weight of 20000). : PGMEA 30% by mass solution of resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 15000) Resin C-5: Resin having the following structure (the numerical value added to the main chain is the molar ratio. PGMEA 30% by mass solution having a weight average molecular weight of 20000) Resin C-6: PGMEA 30% by mass solution having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 22000) PGMEA 30% by mass solution Resin C-7: of the following structure PGMEA 30% by mass solution of resin (value added to the main chain is the molar ratio. Weight average molecular weight 23000) Resin C-8: Resin having the following structure (value added to the main chain is the molar ratio. Weight average molecular weight 22000) ) PGMEA 30% by mass solution Resin C-9: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 13000) PGMEA 30% by mass solution Resin C-10: Resin having the following structure (weight average) PGMEA 30% by mass solution having a molecular weight of 15,000)
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
（界面活性剤）
　界面活性剤１：下記構造の化合物（重量平均分子量１４０００、繰り返し単位の割合を示す％はモル％である。）
Figure JPOXMLDOC01-appb-C000067
 　界面活性剤２：ＫＦ６００１（信越化学工業（株）製、シロキサン系界面活性剤） (Surfactant)
Surfactant 1: A compound having the following structure (weight average molecular weight 14000,% indicating the ratio of repeating units is mol%).
Figure JPOXMLDOC01-appb-C000067
 Surfactant 2: KF6001 (manufactured by Shin-Etsu Chemical Co., Ltd., siloxane-based surfactant)
（溶剤）
　溶剤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)
Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)
（実施例１００１）
　シリコンウエハ上に、緑色着色組成物を製膜後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量で２μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、緑色着色組成物をパターニングして緑色画素を形成した。赤色着色組成物、青色着色組成物についても同様のプロセスでパターニングして、赤色画素、青色画素を順次形成して、緑色画素、赤色画素および青色画素を有するカラーフィルタを形成した。このカラーフィルタにおいては、緑色画素がベイヤーパターンで形成されており、その隣接する領域に、赤色画素、青色画素がアイランドパターンで形成されている。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。なお、緑色着色組成物としては、実施例Ｇ１の着色組成物を使用した。赤色着色組成物としては、実施例Ｒ１の着色組成物を使用した。青色着色組成物としては、実施例Ｂ１の着色組成物を使用した。 (Example 1001)
The green coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 μm square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Then, the green coloring composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate. The red coloring composition and the blue coloring composition were also patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having green pixels, red pixels and blue pixels. In this color filter, green pixels are formed by a Bayer pattern, and red pixels and blue pixels are formed by an island pattern in an adjacent region thereof. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability. As the green coloring composition, the coloring composition of Example G1 was used. As the red coloring composition, the coloring composition of Example R1 was used. As the blue coloring composition, the coloring composition of Example B1 was used.
（実施例１００２）
　シリコンウエハ上に、シアン色着色組成物を製膜後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置ＦＰＡ－３０００ｉ５＋（キヤノン（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量で２μｍ四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、シアン色着色組成物をパターニングしてシアン色画素を形成した。黄色着色組成物、マゼンタ色着色組成物についても同様のプロセスでパターニングして、黄色画素、マゼンタ色画素を順次形成して、シアン色画素、黄色画素およびマゼンタ色画素を有するカラーフィルタを形成した。このカラーフィルタにおいては、シアン色画素がベイヤーパターンで形成されており、その隣接する領域に、黄色画素、マゼンタ色画素がアイランドパターンで形成されている。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。なお、シアン色着色組成物としては、実施例Ｃ１の着色組成物を使用した。黄色着色組成物としては、実施例Ｙ１の着色組成物を使用した。マゼンタ色着色組成物としては、実施例Ｍ１の着色組成物を使用した。 (Example 1002)
A cyan-colored composition was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) , exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 μm square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Then, by heating at 200 ° C. for 5 minutes using a hot plate, the cyan-colored composition was patterned to form cyan-colored pixels. The yellow coloring composition and the magenta coloring composition were also patterned by the same process to sequentially form yellow pixels and magenta color pixels to form a color filter having cyan color pixels, yellow pixels and magenta color pixels. In this color filter, cyan pixels are formed by a Bayer pattern, and yellow pixels and magenta pixels are formed by an island pattern in an adjacent region thereof. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability. As the cyan coloring composition, the coloring composition of Example C1 was used. As the yellow coloring composition, the coloring composition of Example Y1 was used. As the magenta coloring composition, the coloring composition of Example M1 was used.

Claims (18)

  1. 　有機顔料を含む色材と、樹脂と、フェノール系酸化防止剤のフェノール性ヒドロキシ基を加熱により脱離可能な保護基で保護した化合物Ａと、を含む着色組成物であり、
    　前記着色組成物の全固形分中に前記色材を４０質量％以上含む、着色組成物。     A coloring composition comprising a coloring material containing an organic pigment, a resin, and a compound A in which a phenolic hydroxy group of a phenolic antioxidant is protected by a protecting group that can be desorbed by heating.
    A coloring composition containing 40% by mass or more of the coloring material in the total solid content of the coloring composition.
  2. 　前記着色組成物の全固形分中に前記化合物Ａを１～１０質量％含む、請求項１に記載の着色組成物。 The coloring composition according to claim 1, wherein the compound A is contained in an amount of 1 to 10% by mass in the total solid content of the coloring composition.
  3. 　前記有機顔料の１００質量部に対して前記化合物Ａを２～２５質量部含む、請求項１または２に記載の着色組成物。 The coloring composition according to claim 1 or 2, which contains 2 to 25 parts by mass of the compound A with respect to 100 parts by mass of the organic pigment.
  4. 　有機顔料を含む色材と、樹脂と、式（ＡＯ－１）で表される化合物と、を含む着色組成物であり、
    　前記着色組成物の全固形分中に前記色材を４０質量％以上含む、着色組成物；
    Figure JPOXMLDOC01-appb-C000001
     　式中、Ｒ１は、置換基を表し、
    　Ｒ２は、－ＣＯＯＲ１１、－ＣＨ２－ＣＨ＝ＣＲ１２Ｒ１３、－ＣＨ２（－Ｏ－ＬＲ１）ｑ－Ｏ－Ｒ１４またはＳｉＲ１５Ｒ１６Ｒ１７を表し、
    　Ｒ１１、Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７はそれぞれ独立してアルキル基を表し、
    　Ｒ１２およびＲ１３はそれぞれ独立して水素原子またはアルキル基を表し、
    　ＬＲ１はアルキレン基を表し、
    　ｑは０または１を表し、
    　ｑが１の場合、ＬＲ１とＲ１４は結合して環を形成していてもよく、
    　ｍは０～４の整数を表し、
    　ｎは１～１０の整数を表し、
    　Ｘ１はｎ価の基を表す。     A coloring composition containing a coloring material containing an organic pigment, a resin, and a compound represented by the formula (AO-1).
    A coloring composition containing 40% by mass or more of the coloring material in the total solid content of the coloring composition;
    Figure JPOXMLDOC01-appb-C000001
     In the formula, R 1 represents a substituent and represents
    R 2 represents -COOR 11 , -CH 2- CH = CR 12 R 13 , -CH 2 (-OL R1 ) q- O-R 14 or SiR 15 R 16 R 17 .
    R 11 , R 14 , R 15 , R 16 and R 17 each independently represent an alkyl group.
    R 12 and R 13 independently represent a hydrogen atom or an alkyl group, respectively.
    LR1 represents an alkylene group
    q represents 0 or 1 and represents
    When q is 1, L R1 and R 14 may be combined to form a ring.
    m represents an integer from 0 to 4 and represents
    n represents an integer from 1 to 10 and represents
    X 1 represents an n-valent group.
  5. 　前記着色組成物の全固形分中に前記式（ＡＯ－１）で表される化合物を１～１０質量％含む、請求項４に記載の着色組成物。 The coloring composition according to claim 4, wherein the total solid content of the coloring composition contains 1 to 10% by mass of the compound represented by the formula (AO-1).
  6. 　前記有機顔料の１００質量部に対して前記式（ＡＯ－１）で表される化合物を２～２５質量部含む、請求項４または５に記載の着色組成物。 The coloring composition according to claim 4 or 5, which contains 2 to 25 parts by mass of the compound represented by the formula (AO-1) with respect to 100 parts by mass of the organic pigment.
  7. 　前記有機顔料は緑色顔料、黄色顔料および赤色顔料から選ばれる少なくとも１種を含む、請求項１～６のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 6, wherein the organic pigment contains at least one selected from a green pigment, a yellow pigment and a red pigment.
  8. 　前記有機顔料は緑色顔料を含み、前記緑色顔料はフタロシアニン化合物を含む、請求項１～６のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 6, wherein the organic pigment contains a green pigment, and the green pigment contains a phthalocyanine compound.
  9. 　前記樹脂は酸基を有するグラフト樹脂を含む、請求項１～８のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 8, wherein the resin contains a graft resin having an acid group.
  10. 　前記グラフト樹脂の酸価が２０～１５０ｍｇＫＯＨ／ｇである、請求項９に記載の着色組成物。 The coloring composition according to claim 9, wherein the acid value of the graft resin is 20 to 150 mgKOH / g.
  11. 　前記グラフト樹脂の重量平均分子量が３０００～３５０００である、請求項９または１０に記載の着色組成物。 The colored composition according to claim 9 or 10, wherein the graft resin has a weight average molecular weight of 3000 to 35000.
  12. 　更に、光重合開始剤と重合性化合物とを含む、請求項１～１１のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 11, further comprising a photopolymerization initiator and a polymerizable compound.
  13. 　前記光重合開始剤は、芳香族環に電子求引性基が導入された芳香族環基を有するオキシム化合物を含む、請求項１２に記載の着色組成物。 The coloring composition according to claim 12, wherein the photopolymerization initiator contains an oxime compound having an aromatic ring group in which an electron-attracting group is introduced into the aromatic ring.
  14. 　更にフェノール系酸化防止剤を含む、請求項１～１３のいずれか１項に記載の着色組成物。 The coloring composition according to any one of claims 1 to 13, further comprising a phenolic antioxidant.
  15. 　請求項１～１４のいずれか１項に記載の着色組成物を用いて得られる膜。 A film obtained by using the coloring composition according to any one of claims 1 to 14.
  16. 　請求項１５に記載の膜を含むカラーフィルタ。 A color filter containing the film according to claim 15.
  17. 　請求項１５に記載の膜を含む固体撮像素子。 A solid-state image sensor including the film according to claim 15.
  18. 　請求項１５に記載の膜を含む画像表示装置。 An image display device including the film according to claim 15.
PCT/JP2021/024431 2020-07-02 2021-06-29 Coloring composition, film, color filter, solid-state imaging element, and image display device WO2022004683A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010211200A (en) * 2009-02-16 2010-09-24 Fujifilm Corp Pigment dispersion composition, colored curable composition, color filter, liquid crystal display device, and solid-state image sensor
JP2016038569A (en) * 2014-08-05 2016-03-22 株式会社Adeka Photosensitive composition
WO2017030005A1 (en) * 2015-08-17 2017-02-23 株式会社Adeka Composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010211200A (en) * 2009-02-16 2010-09-24 Fujifilm Corp Pigment dispersion composition, colored curable composition, color filter, liquid crystal display device, and solid-state image sensor
JP2016038569A (en) * 2014-08-05 2016-03-22 株式会社Adeka Photosensitive composition
WO2017030005A1 (en) * 2015-08-17 2017-02-23 株式会社Adeka Composition

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