WO2024116819A1 - Color filter, and display device - Google Patents

Color filter, and display device Download PDF

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Publication number
WO2024116819A1
WO2024116819A1 PCT/JP2023/040871 JP2023040871W WO2024116819A1 WO 2024116819 A1 WO2024116819 A1 WO 2024116819A1 JP 2023040871 W JP2023040871 W JP 2023040871W WO 2024116819 A1 WO2024116819 A1 WO 2024116819A1
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group
mass
colored layer
substituent
parts
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PCT/JP2023/040871
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French (fr)
Japanese (ja)
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力飛 塚本
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株式会社Ｄｎｐファインケミカル
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Publication of WO2024116819A1 publication Critical patent/WO2024116819A1/en

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    • 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
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to a color filter and a display device.
  • Color filters are used in these liquid crystal display devices and organic light-emitting display devices. For example, when a color image is formed in an LCD display device, the light that passes through the color filter is directly colored with the color of each pixel that makes up the color filter, and these colors of light are combined to form a color image.
  • white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements may be used as light sources in this case.
  • organic light-emitting display devices use color filters for color adjustment, etc.
  • a color filter generally has a substrate, a colored layer formed on the substrate and including colored patterns of the three primary colors, red, green, and blue, and a light-shielding portion formed on the substrate so as to partition each colored pattern.
  • a method for forming such a colored layer a method is known in which a colored resin composition, in which a curable binder component and the like are added to a colorant dispersion liquid in which a colorant is dispersed, is applied to a substrate and cured.
  • a colored resin composition in which a curable binder component and the like are added to a colorant dispersion liquid in which a colorant is dispersed
  • Patent Document 1 discloses a colorant dispersion liquid and a colored resin composition that contain a specific lake colorant, a phthalocyanine pigment, and a specific acidic dispersant, and states that the colored resin composition has excellent dispersibility and storage stability even when the specific lake colorant and the phthalocyanine pigment are mixed in a desired range, and is capable of forming a colored layer that has improved substrate adhesion and coating uniformity.
  • Patent Document 2 discloses a colored resin composition containing a specific phthalocyanine dye, and states that the colored resin composition has sufficient brightness for practical use and is capable of forming a pattern in which the generation of foreign matter is suppressed.
  • a halogenated zinc phthalocyanine coloring material in which a substituent is bonded via an ether bond (-O-) has good solvent solubility and can be dissolved in a solvent as a dye and used in a colored resin composition.
  • the present invention has been made in consideration of the above-mentioned circumstances, and aims to provide a color filter in which the occurrence of development residues on the blue or green colored layer is suppressed when a colored resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent is used as a resin composition for forming a green colored layer, and a display device using the color filter and having excellent display characteristics.
  • a color filter comprising at least a substrate and a colored layer provided on the substrate,
  • the colored layer includes a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded thereto via an ether bond; and a blue colored layer containing at least one lake colorant selected from the group consisting of a colorant represented by the following general formula (1-1) and a colorant represented by the following general formula (1-2):
  • A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a ⁇ bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain.
  • B c- represents a c-valent polyacid anion.
  • R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R ii , and R iv and R v may bond to form a ring structure.
  • R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group.
  • Ar 1 represents a divalent aromatic group which may have a substituent.
  • a plurality of R i to R vii and Ar 1 may be the same or different.
  • a and c represent integers of 2 or more, and b and d represent integers of 1 or more.
  • e is 0 or 1, and when e is 0, no bond exists.
  • f and g represent integers of 0 to 4, and f+e and g+e are 0 to 4. Multiple e, f, and g may be the same or different.
  • R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure.
  • R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group.
  • Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R I to R VIII and Ar 2 may be the same or different.
  • E m- represents an m-valent polyacid anion.
  • m represents an integer of 2 or more; j is 0 or 1, and when j is 0, no bond exists; k and l represent integers of 0 to 4, and k+j and l+j are 0 to 4. Multiple j, k and l may be the same or different.
  • X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -OR D , and R D represents a monovalent organic group. However, at least one of X 1 to X 16 represents a halogen atom, and at least one of X 1 to X 16 represents -OR D. )
  • a colored resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent is used as a resin composition for forming a green colored layer, it is possible to provide a color filter in which the occurrence of development residues on the blue or green colored layer is suppressed, and a display device using the color filter and having excellent display characteristics.
  • FIG. 1 is a schematic diagram showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic diagram showing an example of a display device of the present invention.
  • FIG. 3 is a schematic diagram showing another example of the display device of the present invention.
  • light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation
  • radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 ⁇ m or less and electron beams.
  • the term "(meth)acrylic” refers to both acrylic and methacrylic
  • the term "(meth)acrylate” refers to both acrylate and methacrylate.
  • the use of "to" indicating a range of values is used to mean that the values before and after it are included as the lower limit and upper limit.
  • the color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate,
  • the colored layer includes a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded thereto via an ether bond; and a blue colored layer containing at least one lake colorant selected from the group consisting of a colorant represented by the following general formula (1-1) and a colorant represented by the following general formula (1-2):
  • A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a ⁇ bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain.
  • B c- represents a c-valent polyacid anion.
  • R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R ii , and R iv and R v may bond to form a ring structure.
  • R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group.
  • Ar 1 represents a divalent aromatic group which may have a substituent.
  • a plurality of R i to R vii and Ar 1 may be the same or different.
  • a and c represent integers of 2 or more, and b and d represent integers of 1 or more.
  • e is 0 or 1, and when e is 0, no bond exists.
  • f and g represent integers of 0 to 4, and f+e and g+e are 0 to 4. Multiple e, f, and g may be the same or different.
  • R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure.
  • R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group.
  • Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R I to R VIII and Ar 2 may be the same or different.
  • E m- represents an m-valent polyacid anion.
  • m represents an integer of 2 or more; j is 0 or 1, and when j is 0, no bond exists; k and l represent integers of 0 to 4, and k+j and l+j are 0 to 4. Multiple j, k and l may be the same or different.
  • the color filter according to the present invention has a color layer that includes a green color layer containing a halogenated zinc phthalocyanine color material having a substituent bonded via an ether bond in combination with a blue color layer containing the specific lake color material, and therefore can be a color filter in which the generation of development residues on the blue color layer or the green color layer is suppressed.
  • the halogenated zinc phthalocyanine coloring material to which the substituent is bonded via an ether bond has good solvent solubility.
  • a resin composition for forming a blue colored layer is applied onto a green colored layer in which a halogenated zinc phthalocyanine colorant is present in molecular form
  • the halogenated zinc phthalocyanine colorant is likely to interact with the copper phthalocyanine pigment in the resin composition for forming a blue colored layer, resulting in development residues of the blue resin composition.
  • a green colored layer containing a halogenated zinc phthalocyanine coloring material to which a substituent is bonded via the ether bond is used in combination with a blue colored layer containing the specific lake coloring material.
  • the blue colored layer of the present invention contains at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1-1) and the coloring material represented by the general formula (1-2), and the lake coloring material has a skeleton different from that of the halogenated zinc phthalocyanine coloring material.
  • the green colored layer in which the halogenated zinc phthalocyanine colorant in which blue development residues are suppressed is present in molecular form has improved transmittance
  • the blue colored layer containing the specific lake colorant in which green development residues are suppressed also has improved transmittance, so it is estimated that the brightness of the entire color filter is also improved.
  • FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention.
  • the color filter 10 according to the present invention has a substrate 1, light-shielding portions 2 formed on the substrate 1, and color layers 3 formed between the light-shielding portions 2 and including a red color layer 3R, a green color layer 3G, and a blue color layer 3B.
  • the substrate may be a transparent substrate, a silicon substrate, or a transparent or silicon substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed, as described below.
  • a transparent substrate a silicon substrate, or a transparent or silicon substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed, as described below.
  • other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed.
  • the transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used in general color filters can be used.
  • the transparent substrate include transparent rigid materials with no flexibility, such as quartz glass, non-alkali glass, and synthetic quartz plate, and transparent flexible materials with flexibility, such as transparent resin films, optical resin plates, and flexible glass.
  • the thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 ⁇ m to 1 mm depending on the application of the color filter of the present invention.
  • the light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate, and can be the same as that used as a light-shielding portion in a general color filter.
  • the pattern shape of the light-shielding part is not particularly limited, and examples thereof include stripe-like and matrix-like shapes.
  • the light-shielding part may be a thin metal film such as chromium formed by sputtering, vacuum deposition, or the like.
  • the light-shielding part may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder.
  • a resin layer containing light-shielding particles there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.
  • the film thickness of the light-shielding part is set to approximately 0.2 ⁇ m or more and 0.4 ⁇ m or less in the case of a thin metal film, and is set to approximately 0.5 ⁇ m or more and 2 ⁇ m or less in the case of a black pigment dispersed or dissolved in a binder resin.
  • the colored layer used in the color filter of the present invention comprises a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond; and a blue colored layer containing at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2).
  • the colored layer is usually formed in the opening of the light-shielding part on the substrate, and usually has a colored pattern of three or more colors.
  • the colored layer of the present invention includes at least the green colored layer and the blue colored layer, and may further include a red colored layer.
  • the arrangement of the colored layers is not particularly limited, and may be, for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, a four-pixel arrangement type, etc.
  • the width, area, etc. of the colored layers may be set arbitrarily.
  • the thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but it is usually preferable that the thickness is in the range of 1 ⁇ m to 5 ⁇ m.
  • the colored layer usually contains a binder component in order to impart film-forming properties and adhesion to the coated surface.
  • the colored layer of the present invention may be a cured product of a colored resin composition that contains a colorant, a binder component, and optionally a dispersant, a solvent, and further other components.
  • the colored layers of each color will be described in detail below.
  • the green colored layer used in the present invention contains a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond.
  • the green colored layer may be a cured product of a colored resin composition that contains the specific halogenated zinc phthalocyanine coloring material, a binder component, a solvent, and, if necessary, a dispersant and other components.
  • the coloring material in the green colored layer contains a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond, and may further contain other coloring materials.
  • the halogenated zinc phthalocyanine coloring material may have high solvent solubility in order to easily exert the effects of the present invention.
  • the halogenated zinc phthalocyanine coloring material may have a solubility at 25°C in 100g of at least one solvent selected from the group consisting of glycol alkyl ether acetates, glycol monoalkyl ethers, and glycol alkyl acetates of 0.1g or more, 0.5g or more, 8g or more, 10g or more, or 15g or more.
  • the halogenated zinc phthalocyanine coloring material may have a solubility at 25°C in 100g of at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1-methoxy-2 butanol, propylene glycol monopropyl ether, and diethylene glycol ethyl methyl ether of 0.1g or more, 0.5g or more, 8g or more, 10g or more, or 15g or more.
  • the upper limit of the solubility is not limited, but may be 20 g or less.
  • the phthalocyanine compound represented by the following general formula (2) is preferred in terms of brightness and solubility.
  • X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -OR D , and R D represents a monovalent organic group. However, at least one of X 1 to X 16 represents a halogen atom, and at least one of X 1 to X 16 represents -OR D. )
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the halogen atoms may be the same or different from each other.
  • the halogen atoms in X 1 to X 16 preferably include at least a fluorine atom, and more preferably are all fluorine atoms.
  • the number of halogen atoms in X 1 to X 16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more.
  • the number of halogen atoms in X 1 to X 16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less.
  • the number of halogen atoms in X 1 to X 16 may be 8.
  • 6 to 10, and more preferably 7 to 9 of X 1 to X 16 are fluorine atoms.
  • X 1 to X 16 may be a hydrogen atom.
  • the number of hydrogen atoms among X 1 to X 16 may be appropriately selected depending on the adjustment of the color tone, and may be 0 to 8, 0 to 4, or 0 to 2.
  • R D in -O-R D is a monovalent organic group.
  • the organic group refers to a group containing carbon atoms.
  • R D may be a hydrocarbon group or a heterocyclic group which may have a substituent.
  • Examples of the hydrocarbon group include linear, branched, or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
  • the linear or branched aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • the cyclic aliphatic hydrocarbon group may be an alicyclic hydrocarbon group having 3 to 20 carbon atoms
  • the aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • the heterocyclic group may be a nitrogen-containing heterocycle, a sulfur-containing heterocycle, an oxygen-containing heterocycle, or the like, and may be either an aromatic ring or a non-aromatic ring.
  • Examples of the linear or branched aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group.
  • heterocyclic group examples include groups having one free valence, such as a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring.
  • groups having one free valence such as a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazo
  • examples of the substituent include a halogen atom, -OR d1 , -COR d1 , -COOR d1 (wherein R d1 is a hydrocarbon group or a heterocyclic group), and specific examples thereof include an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like.
  • R D in -O-R D is preferably an aromatic hydrocarbon group which may have a substituent, from the viewpoints of controlling crystallinity (suppressing deposition of foreign matter) during coating film curing (baking) and imparting solubility, and is preferably a monovalent group represented by the following formula (3):
  • R d1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent
  • R d2 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms
  • p is an integer of 1 to 3
  • q is an integer of 0 to 2.
  • examples of the substituents of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include an alkoxy group having 1 to 5 carbon atoms and a hydroxyl group.
  • R d1 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and particularly preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent.
  • the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms.
  • R d1 is a substituted alkyl group, it is preferably a group having an alkoxy group having 1 to 5 carbon atoms as a substituent.
  • p is preferably 1 or 2, and more preferably 1.
  • -CO-W-R d1 is preferably bonded to the 3- or 4-position relative to -O- in the above formula (3), and more preferably bonded to the 4-position.
  • the two -CO-W-R d1 are preferably bonded to the 3- and 5-positions or the 2- and 4-positions relative to -O-, and more preferably bonded to the 3- and 5-positions.
  • q is preferably 0 or 1, and more preferably 0.
  • Preferred specific examples of the group represented by the above formula (3) include groups represented by each of the following formulas (3-1) to (3-10), but are not limited thereto.
  • the number of -O-R D in X 1 to X 16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more, from the viewpoint of obtaining a desired transmission spectrum (high brightness) and controlling the crystallinity specific to the phthalocyanine compound during coating film curing (baking) (suppressing precipitation of foreign matter).
  • the number of -O-R D in X 1 to X 16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less.
  • the number of -O-R D in X 1 to X 16 may be 8.
  • X 1 to X 16 , X 2 , X 3 , X 6 , X 7 , X 10 , X 11 , X 14 and X 15 are -O-R D , and it is particularly preferable that all of X 2 , X 3 , X 6 , X 7 , X 10 , X 11 , X 14 and X 15 are groups -O-R D and the remaining (X 1 , X 4 , X 5 , X 8 , X 9 , X 12 , X 13 and X 16 ) are halogen atoms.
  • Preferred specific examples of the phthalocyanine compound represented by general formula (2) include, but are not limited to, the compounds represented by the following formulas (2-1) to (2-5).
  • a conventionally known manufacturing method can be appropriately selected and used as a manufacturing method for the halogenated phthalocyanine colorant.
  • a manufacturing method in which a phthalonitrile compound and a metal salt are subjected to a cyclization reaction in a molten state or in an organic solvent can be preferably used, and manufacturing can be performed by referring to, for example, JP-A-2014-43556 and JP-A-2020-42263.
  • the phthalonitrile compound used as the starting material can also be synthesized by appropriately selecting a conventionally known manufacturing method, or a commercially available product can be used.
  • the coloring material may further contain other coloring materials in addition to the specific halogenated zinc phthalocyanine coloring material.
  • the other coloring materials are not particularly limited as long as they can produce the desired color, and various organic pigments, inorganic pigments, dyes, dye salt compounds, etc. can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically, those assigned the following Color Index (C.I.) numbers.
  • the other coloring material may be one or more selected from the group consisting of a yellow coloring material and other green coloring materials. From the viewpoint of color adjustment of the green colored layer, a yellow coloring material is preferable, but other green coloring materials or other coloring materials may be included within a range that does not impair the effects of the present invention.
  • Yellow colorants include, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129 , 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and derivative pigments thereof, and yellow dyes such as coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, and quinophthalone dyes.
  • yellow dyes such as coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, and
  • quinophthalone-based coloring materials are preferable because they have good heat resistance and light resistance and high transmittance. Quinophthalone-based coloring materials are also preferable because they have a hue suitable for use in color filters.
  • the quinophthalone coloring material refers to a coloring material synthesized by condensation of a quinoline derivative such as quinaldine with a phthalic anhydride derivative or a naphthalic anhydride derivative, and may be any of a pigment, a dye, and a dye salt-forming compound.
  • examples of quinophthalone pigments include C.I. Pigment Yellow 138 and the like.
  • examples of quinophthalone dyes include C.I. Disperse Yellow 54, 64, 67, 134, 149, and 160, and C.I. Solvent Yellow 114 and 157.
  • green colorants include green pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63, and green dyes such as squarylium, triarylmethane, anthraquinone, coumarin, cyanine, or azo dyes.
  • green pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63
  • green dyes such as squarylium, triarylmethane, anthraquinone, coumarin, cyanine, or azo dyes.
  • the content ratio of the specific halogenated zinc phthalocyanine coloring material to the entire coloring material may be appropriately adjusted according to the desired chromaticity, is not particularly limited, and may be 100% by mass based on the entire coloring material including the specific halogenated zinc phthalocyanine coloring material.
  • the specific halogenated zinc phthalocyanine coloring material may be contained in an amount of 30% to 95% by mass based on the entire coloring material including the specific halogenated zinc phthalocyanine coloring material from the viewpoint of desired chromaticity adjustment, and the lower limit may be 40 parts by mass or more, or 50 parts by mass or more, and the upper limit may be 85 parts by mass or less, or 80 parts by mass or less.
  • the yellow coloring material when a yellow coloring material is contained, the yellow coloring material is appropriately selected and used alone or in combination of two or more kinds.
  • the content ratio of the yellow coloring material relative to the specific halogenated zinc phthalocyanine coloring material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited.
  • the content ratio of the yellow coloring material may be 0 parts by mass to 233 parts by mass relative to 100 parts by mass of the specific halogenated zinc phthalocyanine coloring material
  • the lower limit may be 5 parts by mass or more, 18 parts by mass or more, or 25 parts by mass or more
  • the upper limit may be 150 parts by mass or less, or 100 parts by mass or less.
  • the green colorant other than the specific halogenated zinc phthalocyanine colorant when a green colorant other than the specific halogenated zinc phthalocyanine colorant is contained, the green colorant other than the specific halogenated zinc phthalocyanine colorant is appropriately selected and used alone or in combination of two or more.
  • the content ratio of the green coloring material different from the specific halogenated zinc phthalocyanine coloring material to the specific halogenated zinc phthalocyanine coloring material may be appropriately adjusted to a desired chromaticity within a range in which the effects of the present invention are not impaired.
  • the content ratio of the green coloring material different from the specific halogenated zinc phthalocyanine coloring material may be, for example, 0 parts by mass to 50 parts by mass relative to 100 parts by mass of the specific halogenated zinc phthalocyanine coloring material, the lower limit may be 5 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, and the upper limit may be 30 parts by mass or less, or 20 parts by mass or less.
  • the content ratio of the green coloring material including the specific halogenated zinc phthalocyanine coloring material to the entire coloring material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity.
  • the content ratio of the yellow coloring material relative to the green coloring material containing the specific halogenated zinc phthalocyanine coloring material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity.
  • it is preferable to contain 5 parts by mass to 233 parts by mass of the yellow coloring material relative to 100 parts by mass of the green coloring material containing the specific halogenated zinc phthalocyanine coloring material or it may contain 18 parts by mass to 150 parts by mass, or it may contain 25 parts by mass to 100 parts by mass.
  • the coloring material may further contain other coloring materials in addition to the green coloring material and the yellow coloring material, as long as the effects of the present invention are not impaired.
  • the total content of the specific zinc halide phthalocyanine coloring material and the yellow coloring material may be 70% by mass to 100% by mass, particularly 80% by mass to 100% by mass, 90% by mass to 100% by mass, or even 100% by mass.
  • the content of the coloring material is not particularly limited.
  • the total content of the coloring material is, for example, preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, based on the total solid content of the green colored layer and the colored resin composition for forming the green colored layer, from the viewpoint of dispersibility and dispersion stability. If it is equal to or greater than the above lower limit, the green colored layer when the colored resin composition for forming the green colored layer is applied to a predetermined film thickness (usually 1.0 ⁇ m to 5.0 ⁇ m) has a sufficient color density.
  • the total content of the coloring material is preferably 35% by mass to 50% by mass, more preferably 40% by mass to 45% by mass, based on the total solid content of the green colored layer and the colored resin composition for forming the green colored layer.
  • the solid content refers to everything other than the solvent described below, including monomers dissolved in the solvent.
  • the colored resin composition used in the present invention contains a binder component to impart film-forming properties and adhesion to the coated surface. It is preferable to contain a curable binder component to impart sufficient hardness to the coating film.
  • the curable binder component is not particularly limited, and a curable binder component used to form a colored layer of a conventionally known color filter can be appropriately used.
  • the colored layer may contain a cured product of the binder component.
  • the curable binder component for example, a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder component containing a thermosetting resin that can be polymerized and cured by heating can be used.
  • a photosensitive binder component having alkali developability is preferably used.
  • the photosensitive binder component may further contain a thermosetting binder component.
  • the photosensitive binder component include a positive-type photosensitive binder component and a negative-type photosensitive binder component.
  • the positive-type photosensitive binder component include a composition containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitivity-imparting component.
  • the negative photosensitive binder component a composition containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
  • a negative photosensitive binder component is preferred from the viewpoint of easily forming a pattern by a photolithography method using an existing process.
  • the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator that constitute the negative photosensitive binder component will be described below.
  • the alkali-soluble resin used in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those that are soluble in an alkaline developer used in forming a pattern.
  • an alkali-soluble resin can be defined as one having an acid value of 40 mgKOH/g or more.
  • the preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group.
  • alkali-soluble resins include (meth)acrylic resins such as (meth)acrylic copolymers having a carboxy group and styrene-(meth)acrylic copolymers having a carboxy group, and epoxy (meth)acrylate resins having a carboxy group.
  • alkali-soluble resins can be appropriately selected from conventionally known alkali-soluble resins.
  • the photopolymerizable compound used in the present invention is not particularly limited as long as it is polymerizable by a photoinitiator.
  • a compound having two or more ethylenically unsaturated bonds is preferably used, and in particular, a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
  • Such a polyfunctional (meth)acrylate can be appropriately selected from conventionally known photopolymerizable compounds. Specific examples include those described in JP-A-2013-029832.
  • paragraphs 0177 to 0179 of WO 2020/071041 can be referred to as a photopolymerizable compound.
  • the photoinitiator used in the colored resin composition of the present invention is not particularly limited, and one or more types may be appropriately selected from various conventionally known initiators and used in combination.
  • the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and oxime ester compounds.
  • the photoinitiator reference can be made to, for example, paragraphs 0180 to 0184 of WO 2020/071041.
  • the total content of the binder components is preferably 5% to 90% by mass, preferably 10% to 80% by mass, more preferably 20% to 70% by mass, and even more preferably 30% to 60% by mass, based on the total solid content of the colored resin composition, in terms of film-forming properties and adhesion of the colored layer to the substrate surface to be coated.
  • a dispersant in the green colored layer and the colored resin composition for forming the green colored layer of the present invention, when a colorant is dispersed, a dispersant may be further contained from the viewpoints of colorant dispersibility and colorant dispersion stability.
  • the dispersant can be appropriately selected from conventionally known dispersants.
  • cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used as the dispersant.
  • the surfactants polymer dispersants are preferred because they can be uniformly and finely dispersed.
  • polymeric dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides and their bases obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the following three compounds: polyesters having free carboxyl groups, polyamides, or co-condensates of esters and amides (polyester
  • a polymer dispersant that contains nitrogen atoms in the main chain or side chain and has an amine value a polymer having a structural unit represented by the following general formula (I) as described in JP 2016-224447 A, or a dispersant that is at least one of a block copolymer and a salt-type block copolymer having a structural unit represented by the following general formula (I) as described in WO 2016/104493 A, may be used, because the main chain skeleton is not easily thermally decomposed and has high heat resistance.
  • R1 represents a hydrogen atom or a methyl group
  • A represents a divalent linking group
  • R2 and R3 each independently represent a hydrogen atom or a hydrocarbon group which may contain a heteroatom, and R2 and R3 may be bonded to each other to form a ring structure.
  • the colored resin composition for forming the colored layer used to form the colored layer of the present invention may contain a solvent.
  • the solvent to be used is not particularly limited as long as it is an organic solvent that does not react with each component in the colored resin composition and can dissolve or disperse them.
  • the solvent can be used alone or in combination of two or more kinds.
  • WO 2016/104493 may be referred to as appropriate.
  • the specific zinc halide phthalocyanine coloring material diffused in the system absorbs exposure light and is prone to lose radical generation from the photoinitiator, so in order to compensate for this, it is preferable to include a sensitizer in combination with the photoinitiator.
  • a sensitizer in combination with the photoinitiator.
  • Examples of the thiol-based sensitizer include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups.
  • Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate.
  • polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).
  • the content of a sensitizer when included, can be, for example, 0.5% by mass to 10% by mass based on the total solid content of the colored resin composition from the viewpoint of coating film curability.
  • the content is more preferably within the range of 1% by mass to 6% by mass, and even more preferably 2% by mass to 5% by mass based on the total solid content of the colored resin composition.
  • antioxidants In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, other components can be appropriately selected and used from components used in conventionally known colored layers.
  • other components include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, cissing inhibitors, aggregation inhibitors, ultraviolet absorbers, and adhesion promoters.
  • antioxidant include those described in WO 2016/104493.
  • surfactant and plasticizer include those described in JP-A-2013-029832.
  • the blue colored layer used in the present invention contains at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2).
  • the blue colored layer may be a cured product of a colored resin composition that contains a color material including the specific lake color material, a binder component, and optionally a dispersant, a solvent, and further other components.
  • a color material including the specific lake color material, a binder component, and optionally a dispersant, a solvent, and further other components.
  • the coloring material in the blue colored layer includes at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1-1) and the coloring material represented by the general formula (1-2), and may further include other coloring materials.
  • the colorant represented by the general formula (1-1) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the colorant, the anion and the cation are not simply ionic bonded one molecule to one molecule, but a molecular association in which a plurality of molecules associate via ionic bonds can be formed, so that the apparent molecular weight is significantly increased compared to the molecular weight of conventional lake pigments.
  • a in the general formula (1-1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a ⁇ bond, and the organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain.
  • the organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, and N in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, and N in the carbon chain. Since the carbon atom directly bonded to N does not have a ⁇ bond, the color properties such as color tone and transmittance of the cationic color-developing moiety are not affected by the linking group A or other color-developing moieties, and can maintain the same color as the monomer.
  • the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be linear, branched or cyclic, as long as the terminal carbon atom directly bonded to N does not have a ⁇ bond, and a carbon atom other than the terminal may have an unsaturated bond or may have a substituent, and the carbon chain may contain O, S or N.
  • a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
  • the aromatic group having an aliphatic hydrocarbon group for A includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, which may have a substituent and may be a heterocycle containing O, S or N.
  • A contains a cyclic aliphatic hydrocarbon group or an aromatic group.
  • Examples of the cyclic aliphatic hydrocarbon group include groups containing cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2,6 ]decane, and adamantane.
  • Examples of the aromatic group include groups containing a benzene ring and a naphthalene ring.
  • examples of the aromatic group include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, and aromatic groups substituted with two alkylene groups having 1 to 20 carbon atoms, such as xylylene groups.
  • A is an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at an end directly bonded to N, and the carbon chain may contain O, S, or N.
  • A is an aliphatic hydrocarbon group having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at an end directly bonded to N, and the carbon chain may contain O, S, or N, and among these, it is even more preferable that A has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.
  • the two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include the same cyclic aliphatic hydrocarbon groups as those mentioned above, with cyclohexane and cyclopentane being preferred.
  • A is a substituent represented by the following general formula (1a).
  • R xi represents an alkylene group having 1 to 3 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent; R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; p represents an integer of 1 to 3; and q and r each independently represent an integer of 0 to 4.
  • the plurality of R xi , R xii , R xiii , and r may be the same or different from each other.
  • R xi is preferably an alkylene group having 1 to 3 carbon atoms.
  • Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group. Among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and the alkyl group may be linear or branched.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and the alkoxy group may be linear or branched.
  • Examples of the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms in R xii and R xiii are the same as the substituents that may be possessed by R xi .
  • the number of cyclohexane (cyclohexylene group) is 2 or more and 4 or less, that is, p is 1 or more and 3 or less, from the viewpoint of heat resistance, and it is more preferable that p is 1 or more and 2 or less.
  • the number of substituents R xii and R xiii in the cyclohexylene group is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 to 3, more preferably 1 to 2. That is, q and r are preferably integers of 1 to 3, more preferably q and r are integers of 1 to 2.
  • linking groups A include, but are not limited to, the following:
  • the alkyl group in R i to R v is not particularly limited.
  • it may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, among which a linear or branched alkyl group having 1 to 8 carbon atoms may be used. From the viewpoint of brightness and heat resistance, a linear or branched alkyl group having 1 to 5 carbon atoms may be used.
  • the alkyl group in R i to R v may be an ethyl group or a methyl group.
  • the substituent that the alkyl group may have is not particularly limited, but may be, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, or the like.
  • an aralkyl group such as a benzyl group may be used.
  • the aryl group in R i to R v is not particularly limited. Examples thereof include a phenyl group and a naphthyl group. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group.
  • R i to R v each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or that R ii and R iii , and R iv and R v are bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.
  • At least one of R ii to R v is a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R ii to R v be a cycloalkyl group or an aryl group, intermolecular interactions due to steric hindrance are reduced, and the effect of heat on the color-developing site can be suppressed, which is considered to result in excellent heat resistance.
  • R ii to R v is a substituent represented by the following general formula (1b) or (1c).
  • R xiv , R xv , and R xvi each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
  • R xvii , R xviii , and R xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
  • the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched.
  • the alkoxy group having 1 to 4 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched. Examples of the substituent that the alkyl group and alkoxy group may have include a halogen atom and a hydroxyl group.
  • R xiv , R xv , and R xvi is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent
  • at least one of R xiv and R xv is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
  • R xvii , R xviii , and R xix is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent
  • at least one of R xvii and R xviii is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
  • R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group.
  • the alkyl group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched.
  • the substituent that the alkyl group may have is not particularly limited, but examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • the alkoxy group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
  • Examples of the substituent that the alkoxy group may have include, but are not particularly limited to, an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • Examples of the halogen atom in R vi and R vii include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the number of substitutions of R vi and R vii that is, f and g each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 to 1.
  • a plurality of f and g may be the same or different.
  • R vi and R vii may be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, and in particular, they are preferably substituted at the meta position based on the substitution position of the amino group represented by -NR ii R iii or -NR iv R v .
  • the divalent aromatic group in Ar 1 is not particularly limited.
  • the aromatic group in Ar 1 may be a heterocyclic group in addition to an aromatic hydrocarbon group consisting of a carbon ring.
  • Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring, as well as benzene ring; and chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene.
  • the chain polycyclic hydrocarbon may have O, S, or N in the chain skeleton, such as diphenyl ether.
  • examples of the heterocycle in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, etc., 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, etc., and condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline, etc.
  • These aromatic groups may further have, as a substituent, an alkyl group, an alkoxy group, a hydroxyl group, a
  • a plurality of R i to R vii and Ar 1 present in one molecule may be the same or different. Depending on the combination of R i to R vii and Ar 1 , a desired color can be adjusted.
  • the valence a in A is the number of color-developing cationic moieties that make up the cation, and a is an integer of 2 or more.
  • the cation valence a is 2 or more, so it has excellent heat resistance, and it is preferable that the cation valence a is 3 or more.
  • There is no particular upper limit for a but from the viewpoint of ease of production, it is preferable that a is 4 or less, and more preferably 3 or less.
  • the cation represented by general formula (A) has excellent heat resistance and is easily prevented from changing in color when heated, so it is preferable that the molecular weight is 1200 or more, and preferably 1300 or more.
  • the anion moiety (B c- ) is a c-valent polyacid anion, and is a divalent or higher anion, from the viewpoints of high luminance and excellent heat resistance.
  • the upper limit of c is not limited, but may be an integer of 6 or less from the viewpoint of ease of production.
  • the polyacid anion formed by condensing a plurality of oxoacids may be an isopolyacid anion ( MmOn ) c- or a heteropolyacid anion ( XlMmOn ) c- .
  • M represents a polyatom
  • X represents a heteroatom
  • m represents the composition ratio of the polyatoms
  • n represents the composition ratio of the oxygen atoms.
  • the polyatom M include Mo, W, V, Ti, and Nb.
  • the heteroatom X include Si, P, As, S, Fe, and Co.
  • a counter cation such as Na + or H + may be partially contained.
  • polyacids having one or more elements selected from tungsten (W) and molybdenum (Mo) are preferred because of their excellent heat resistance.
  • examples of such polyacids include isopolyacids such as tungstate ion [W 10 O 32 ] 4 ⁇ and molybdate ion [Mo 6 O 19 ] 2 ⁇ , and heteropolyacids such as phosphotungstate ion [PW 12 O 40 ] 3 ⁇ , [P 2 W 18 O 62 ] 6 ⁇ , silicotungstate ion [SiW 12 O 40 ] 4 ⁇ , phosphomolybdate ion [PMo 12 O 40 ] 3 ⁇ , silicomolybdate ion [SiMo 12 O 40 ] 4 ⁇ , and phosphotungstomolybdate ion [PW 12 -s Mo s O 40 ] 3 ⁇ (s is an integer of 1 to 11), [P 2 W 18-t Mo t O 62 ] 6 ⁇
  • tungsten (W) and molybdenum (Mo) from the viewpoints of heat resistance and ease of availability of raw materials, heteropolyacids are preferable among the above, and heteropolyacids containing phosphorus (P) are more preferable.
  • any one of phosphotungstomolybdate ion [PW 10 Mo 2 O 40 ] 3 ⁇ , [PW 11 Mo 1 O 40 ] 3 ⁇ , and phosphotungstate ion [PW 12 O 40 ] 3 ⁇ is more preferable from the viewpoint of heat resistance.
  • b represents the number of cations
  • d represents the number of anions in the molecular association
  • b and d represent integers of 1 or more.
  • the multiple cations in the molecular association may be of one type alone or a combination of two or more types.
  • d is 2 or more
  • the multiple anions in the molecular association may be of one type alone or a combination of two or more types.
  • the upper limit of b is not limited, but may be an integer of 6 or less from the viewpoint of ease of production.
  • the upper limit of d is not limited, but may be an integer of 4 or less from the viewpoint of ease of production.
  • the lake colorant represented by the general formula (1-1) used in the present invention one containing at least a triarylmethane skeleton is preferably used.
  • the lake colorant represented by the general formula (1-1) can be prepared by referring to, for example, International Publication No. 2012/144520 and International Publication No. 2018/003706.
  • R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure.
  • R I to R VI may each be the same as R i to R v in the general formula (1-1) described above.
  • R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group, and these may be the same as R vi and R vii in the general formula (1-1) described above.
  • Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and Ar 2 may be the same as the aromatic heterocyclic group of Ar 1 in the above-mentioned general formula (1-1).
  • E m- represents an m-valent polyacid anion
  • the m-valent polyacid anion may be the same as the c-valent polyacid anion in the above-mentioned general formula (1-1).
  • m represents the number of cations and the number of anions, and is an integer of 2 or more.
  • the multiple cations in the general formula (1-2) may be one type alone or two or more types in combination.
  • the anions may be one type alone or two or more types in combination.
  • j is 0 or 1, and when j is 0, no bond exists.
  • j in the general formula (1-2) may be the same as e in the general formula (1-1) described above.
  • k and l in the general formula (1-2) may be the same as f and g in the general formula (1-1) described above.
  • the lake colorant represented by the general formula (1-2) can be prepared, for example, by referring to JP-A-2017-16099.
  • the coloring material may contain, in addition to the specific lake coloring material, other coloring materials in order to adjust the color tone within a range that does not impair the effects of the present invention.
  • the other coloring materials known pigments, dyes, lake coloring materials, etc. can be used alone or in combination of two or more kinds.
  • blue coloring materials include known organic blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and triarylmethane lake colorants different from the colorants represented by the general formula (1-1) and the colorants represented by the general formula (1-2).
  • purple colorants known organic purple pigments such as C.I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.
  • red to reddish purple colorants include xanthene dyes and xanthene-based dye lake colorants described in, for example, WO 2020/071041, JP 2018-100323, WO 2014/123125, and the like.
  • the basic-treated blue phthalocyanine pigment refers to a blue phthalocyanine pigment having a structure derived from a basic compound.
  • a blue phthalocyanine pigment having a structure derived from a basic compound for example, a blue phthalocyanine pigment containing a basic compound such as a colorant derivative having a basic site can be mentioned as a suitable example.
  • the phthalocyanine pigment used in the basic treatment is preferably a copper phthalocyanine pigment, because it has relatively excellent brightness.
  • the copper phthalocyanine pigment used in the basic treatment may be a crude copper phthalocyanine pigment, or may be a copper phthalocyanine pigment having an ⁇ -type, ⁇ -type, ⁇ -type, ⁇ -type, or other crystal structure.
  • the copper phthalocyanine pigment used in the basic treatment is preferably at least one selected from the group consisting of a copper phthalocyanine pigment having an ⁇ -type crystal structure and a copper phthalocyanine pigment having a ⁇ -type crystal structure, because it has excellent dispersion stability.
  • a colorant derivative having a basic site or a derivative of a colorless compound having a basic site is preferably used.
  • the term "having a basic site” refers to an embodiment in which a basic group is present as a substituent, or an embodiment in which an acidic group in the substituent forms a salt with a basic compound, etc.
  • examples of the basic site possessed by the colorant derivative or the derivative of the colorless compound include an amino group, an ammonium sulfonate, a sulfonamide group having an amino group, an amide group having an amino group, a basic heterocyclic group, and the like.
  • the basic treatment can be carried out with reference to paragraphs 0064 to 0077 of WO 2020/071041.
  • the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant may be appropriately adjusted according to the desired chromaticity, and is not particularly limited, and may be 100% by mass relative to the entire colorant including the rake colorant.
  • the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant including the rake colorant may be 15% by mass or more from the viewpoint of desired chromaticity adjustment.
  • the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant may be 19% by mass or more, 28% by mass or more, 40% by mass or more, or 50% by mass or more.
  • the upper limit of the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant including the rake colorant is not particularly limited, but from the viewpoint of adjusting to the desired chromaticity, it may be 95% by mass or less, 85% by mass or less, or 80% by mass or less.
  • the other coloring material may be 0% by mass relative to the total coloring material including the lake coloring material.
  • the other coloring material when the other coloring material is contained, from the viewpoint of desired chromaticity adjustment, the other coloring material may be 5% by mass or more, 15% by mass or more, or 20% by mass or more relative to the total coloring material including the lake coloring material. From the viewpoint of suppressing the generation of residues and improving brightness while adjusting to the desired chromaticity, the other coloring material may be 85% by mass or less, 81% by mass or less, 72% by mass or less, 60% by mass or less, or 50% by mass or less relative to the total coloring material including the lake coloring material.
  • the dispersant used as necessary may be the same as that used in the green colored layer.
  • the acidic dispersant preferably contains a polymer having at least one selected from the structural units represented by the following general formula (II), since this improves the dispersibility and heat resistance of the lake colorant and can suppress the chromaticity change of the lake colorant after heating.
  • L 1 is a direct bond or a divalent linking group
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a hydroxyl group, a hydrocarbon group, -[CH(R 3 )-CH(R 4 )-O] x1 -R 5 , -[(CH 2 ) y1 -O] z1 -R 5 , or a monovalent group represented by -O-R 6
  • R 6 is a hydrocarbon group, -[CH(R 3 )-CH(R 4 )-O] x1 -R 5 , -[(CH 2 ) y1 -O] z1 -R 5 , -C(R 7 )(R 8 )-C(R 9 )(R 10 )-OH, or a monovalent group represented by -CH 2 -C(R 11 )(R 12 )-CH 2 -OH.
  • R 3 and R 4 are each independently a hydrogen atom or a methyl group
  • R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond, and R 7 and R 9 may be bonded to each other to form a ring structure.
  • the ring structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon group having one or more selected from an ether bond and an ester bond.
  • the hydrocarbon group may have a substituent.
  • X represents a hydrogen atom or an organic cation.
  • x1 represents an integer of 1 or more and 18 or less
  • y1 represents an integer of 1 or more and 5 or less
  • z1 represents an integer of 1 or more and 18 or less.
  • acidic dispersants include dispersants having an acidic group.
  • the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group.
  • the acidic group contained in the dispersant of the other acidic dispersant is preferably a carboxy group in terms of excellent dispersibility.
  • the acid value of the other acidic dispersant is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more, from the viewpoint of excellent dispersibility.
  • the acid value of the other acidic dispersant is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and even more preferably 180 mgKOH/g or less.
  • polymeric dispersants having a carboxy group are preferred, since their use in combination with a polymer having at least one type of structural unit selected from those represented by the general formula (II) improves the suppression of development residues.
  • the red colored layer used in the present invention may be a cured product of a colored resin composition that contains a colorant including a red colorant, a binder component, and optionally a dispersant, a solvent, and may further contain other components.
  • a colorant including a red colorant, a binder component, and optionally a dispersant, a solvent
  • the red colored layer and each component contained in the resin composition for forming the red colored layer will be described, but since the binder component, dispersant, solvent, and other components may be the same as those of the green colored layer, their description will be omitted here.
  • organic pigments are preferably used because they have high color development and high heat resistance.
  • examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically, compounds having the following Color Index (C.I.) numbers:
  • Red colorants include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 24
  • R 61 and R 62 each independently represent a 4-chlorophenyl group or a 4-bromophenyl group.
  • the red colorant in terms of expanding the color gamut, it is preferable to use a diketopyrrolopyrrole pigment, and the diketopyrrolopyrrole content is preferably 30% by mass or more, and more preferably 40% by mass or more, of the total amount of the colorant.
  • the diketopyrrolopyrrole pigment include C.I. Pigment Red 254, 255, 264, 272, and 291, and the diketopyrrolopyrrole pigment represented by the general formula (i), and among these, at least one selected from C.I. Pigment Red 254, 272, and 291, and the diketopyrrolopyrrole pigment represented by the general formula (i) in which R 61 and R 62 are each a 4-bromophenyl group, is preferred.
  • the red colorant preferably contains a diketopyrrolopyrrole pigment and C.I. Pigment Red 177 or C.I. Pigment Red 202 in terms of chromaticity adjustment.
  • the red colorant contains at least C.I. Pigment Red 202 from the viewpoint of brightness.
  • coloring materials may be used as the coloring material from the viewpoints of color adjustment, brightness improvement, and resolubility improvement.
  • examples of other coloring materials include yellow coloring materials and orange coloring materials.
  • yellow colorants include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and derivative pigments of C.I. Pigment Yellow 150.
  • examples of orange colorants include C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73.
  • the total content of the red coloring material may be 100% by mass relative to the total amount of the coloring material, but is usually 50% by mass or more, and preferably 70% by mass or more, while it may be 99% by mass or less, or 90% by mass or less.
  • the total content of the other coloring materials other than the red coloring material may be 0 mass % relative to the total amount of the coloring materials, but may be 1 mass % or more, or may be 10 mass % or more, and on the other hand, it is usually 50 mass % or less, and preferably 30 mass % or less.
  • the method for producing the colored resin composition can be the same as the method for producing a resin composition for a colored layer of a general color filter, and for example, the colored resin composition can be produced by mixing the above-mentioned components in a solvent.
  • the colored resin composition can be produced by mixing and stirring a dispersant in advance in a solvent to prepare a dispersant solution, and mixing a color material, a binder component, and other components in the dispersant solution.
  • the manufacturing method of the colored layer is not particularly limited, and a manufacturing method of the colored layer in the conventionally known manufacturing method of color filters can be appropriately selected and used. For example, it can be manufactured by appropriately selecting according to the curing property of the binder component.
  • the binder component is a photosensitive resin composition containing a photosensitive binder
  • a so-called photolithography method can be mentioned.
  • a coating film of the colored resin composition can be patterned and applied as necessary, and the coating film can be dried and then heated to obtain the colored resin composition.
  • an inkjet method can be mentioned.
  • the colored layer can be formed by the following method.
  • a colored resin composition of any one color for example, red
  • a coating means such as spray coating, dip coating, bar coating, roll coating, or spin coating to form a wet coating film.
  • the wet coating film is dried using a hot plate or oven, and then exposed to light through a mask having a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer, etc., to form a photosensitive coating film.
  • light sources used for exposure include ultraviolet light from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc., and electron beams.
  • the amount of exposure is appropriately adjusted depending on the light source used and the thickness of the coating film.
  • a heat treatment may be carried out.
  • the heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition used, the thickness of the coating film, and the like.
  • the coating is developed using a developer to dissolve and remove the unexposed areas, forming a coating film in the desired pattern.
  • the developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent.
  • This alkaline solution may contain an appropriate amount of a surfactant.
  • Conventional development methods can be used.
  • the developer is usually washed away and the cured coating film of the colored resin composition is dried to form a colored layer of one color (e.g., red).
  • a heat treatment may be performed to sufficiently cure the coating film.
  • the heating conditions may be, for example, 200 to 250°C.
  • a colored layer is formed in the same manner as above using a colored resin composition of another color (e.g., green), and then a colored layer is formed in the same manner as above using a colored resin composition of yet another color (e.g., blue), thereby producing a color filter having three colored layers, for example, a green colored layer, a blue colored layer, and a red colored layer.
  • a colored resin composition of another color e.g., green
  • a colored resin composition of yet another color e.g., blue
  • the color filter of the present invention may be formed with, in addition to the above-mentioned substrate, light-shielding portion, and colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning the liquid crystal material, columnar spacers, etc.
  • the color filter of the present invention is not limited to the configurations exemplified above, and any known configuration generally used in color filters can be appropriately selected and used.
  • the display device according to the present invention is characterized by having the color filter according to the present invention.
  • the configuration of the display device according to the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
  • a liquid crystal display device of the present invention comprises the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. Such a liquid crystal display device of the present invention will be described with reference to the drawings.
  • FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 15 located between the color filter 10 and the counter substrate 20.
  • FIG. 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention.
  • a liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 15 located between the color filter 10 and the counter substrate 20.
  • FIG. 2 shows an example in which an alignment film 13a is located on the colored layer 3 side of the color filter 10 and an alignment film 13b is located on the counter substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Furthermore, FIG. 2 shows an example in which the liquid crystal display device 40 has a polarizing plate 25a located on the outside of the color filter 10, a polarizing plate 25b located on the outside of the counter substrate 20, and a backlight 30 located outside the polarizing plate 25b located on the counter substrate 20 side of the liquid crystal display device 40.
  • the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may have any known configuration as a liquid crystal display device generally using color filters.
  • the driving method of the liquid crystal display device of the present invention is not particularly limited, and any driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention.
  • the counter substrate can be appropriately selected depending on the driving method of the liquid crystal display device of the present invention.
  • various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.
  • the liquid crystal layer can be formed by any method generally used for producing liquid crystal cells, such as a vacuum injection method or a liquid crystal dropping method.
  • a vacuum injection method for example, a liquid crystal cell is prepared in advance using a color filter and an opposing substrate, the liquid crystal is heated to make it an isotropic liquid, the liquid crystal is injected into the liquid crystal cell in the isotropic liquid state using the capillary effect, and the liquid crystal layer is formed by sealing with an adhesive. The liquid crystal cell is then gradually cooled to room temperature to align the enclosed liquid crystal.
  • liquid crystal dropping method for example, a sealant is applied to the periphery of a color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like, the color filter and the opposing substrate are superimposed under reduced pressure, and bonded together via the sealant, thereby forming a liquid crystal layer.
  • the liquid crystal cell is then gradually cooled to room temperature, whereby the enclosed liquid crystal can be aligned.
  • the backlight used in the liquid crystal display device of the present invention can be appropriately selected depending on the application of the liquid crystal display device.
  • the backlight can include a cold cathode fluorescent lamp (CCFL), a white LED, or a backlight unit using a white organic EL as a light source.
  • CCFL cold cathode fluorescent lamp
  • white LED white LED
  • white organic EL white organic EL
  • Examples of white LEDs include a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED, and a green phosphor, a white LED that obtains white light by mixing a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG phosphor, and a white LED that obtains white light by mixing an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor, etc.
  • Quantum dots may be used as the phosphor.
  • the light-emitting display device according to the present invention is characterized by having the color filter according to the present invention described above and a light-emitting body. Such a light-emitting display device of the present invention will be described with reference to the drawings. As shown in Fig. 3, the light-emitting display device 100 of the present invention has a color filter 10 and a light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the light-emitting body 80.
  • Examples of the lamination method of the light-emitting body 80 include a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter, and a method of bonding the light-emitting body 80 formed on a separate substrate onto the inorganic oxide film 60.
  • the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components of the light-emitting body 80 may be appropriately selected from known components.
  • the light-emitting display device 100 thus produced can be applied to, for example, both passively driven organic EL displays and actively driven organic EL displays.
  • the light-emitting display device of the present invention is not limited to the light-emitting display device having the configuration shown in FIG. 3, but may have any known configuration as a light-emitting display device that generally uses color filters.
  • the present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
  • the intermediate of the halogenated zinc phthalocyanine coloring material was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity).
  • the zinc phthalocyanine halide colorant and the lake colorant were analyzed by MALDI-TOF-MS (Shimadzu Corporation, MALDI-8020).
  • the acid value was determined by a method according to the method described in JIS K 0070:1992.
  • the weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The following synthesis examples and examples were carried out at 25° C. unless otherwise specified.
  • Intermediate 1 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 1 is shown below.
  • Intermediate 2 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 2 is shown below.
  • Intermediate 3 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 3 is shown below.
  • the obtained press cake was made into a slurry with 300 parts by mass of water, and 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, stirred at 65°C for 4 hours, filtered, washed with water and dried to obtain blue colorant derivative 1 having a basic site to be used for surface treatment. It was confirmed that the obtained blue colorant derivative 1 having a basic site has a structure represented by the following chemical formula. (TOF-MS: 768.35)
  • C.I. Pigment Blue 15:6 ⁇ -type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC
  • 5 parts by mass of the blue colorant derivative 1 having a basic site were dry-ground in an attritor at 60°C for 1.5 hours.
  • the ground product was further mixed with 5 parts by mass of the blue colorant derivative 1 having a basic site to obtain the desired basic-treated phthalocyanine pigment, basic-treated phthalocyanine pigment 1.
  • AIBN ⁇ , ⁇ '-azobisisobutyronitrile
  • the reaction solution was cooled to 80° C., 8.74 parts by mass of Karenz MOI (Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by mass solution of macromonomer MM-1.
  • the obtained macromonomer MM-1 had a mass average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw/Mn) of 2.10.
  • a mixed solution of 67.34 parts by mass of the macromonomer MM-1 solution (solid content 33.33 parts by mass), 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to obtain a 25.0% by mass solution of graft copolymer A1.
  • the obtained graft copolymer A1 was measured by GPC to find that it had a mass average molecular weight (Mw) of 10,570, a number average molecular weight (Mn) of 4,370 and a molecular weight distribution (Mw/Mn) of 2.42.
  • glycidyl methacrylate 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the solution was heated at 110° C. for 10 hours to react the carboxylic acid group of the main chain methacrylic acid with the epoxy group of the glycidyl methacrylate. During the reaction, air was bubbled into the reaction solution to prevent polymerization of the glycidyl methacrylate. The reaction was followed by measuring the acid value of the solution.
  • GMA glycidyl methacrylate
  • triethylamine 0.2 parts by mass of triethylamine
  • p-methoxyphenol 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution,
  • the obtained alkali-soluble resin A was a resin in which a side chain having an ethylenically unsaturated bond was introduced using GMA to a main chain formed by copolymerization of BzMA, MMA, and MAA, and had an acid value of 74 mg KOH/g and a mass average molecular weight of 12000.
  • the alkali-soluble resin A solution had a solid content of 40 mass%.
  • Pigment Green 58 (FASTOGEN GREEN A350, manufactured by DIC Corporation) as a coloring material
  • 16.25 parts by mass of the alkali-soluble resin A solution, 61.00 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle, and the mixture was shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary disintegration, and then the zirconia beads with a particle size of 2.0 mm were taken out, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and the mixture was dispersed for 3 hours with a paint shaker as a main disintegration in the same manner to obtain a G58 dispersion.
  • a paint shaker manufactured by Asada Iron Works Co., Ltd.
  • Green Composition CG1 32.63 parts by mass of the G58 dispersion, 11.66 parts by mass of the Y138 dispersion, 21.48 parts by mass of the above-mentioned photosensitive binder component CR-1, 0.13 parts by mass of a sensitizer (pentaerythritol tetrakis(3-mercaptobutyrate), Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 33.73 parts by mass of PGMEA were added to obtain a green composition CG1.
  • a sensitizer penentaerythritol tetrakis(3-mercaptobutyrate)
  • Karenz MT-PE1 manufactured by Showa Denko
  • a fluorine-based surfactant Mega
  • a colorant dispersion liquid R177 was obtained in the same manner as in the preparation of colorant dispersion liquid R254, except that C.I. Pigment Red 177 was used instead of C.I. Pigment Red 254 as a colorant in the preparation of colorant dispersion liquid R254.
  • Red Composition R1 2.77 parts by mass of colorant dispersion R254, 19.89 parts by mass of colorant dispersion R177, 31.69 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 45.27 parts by mass of PGMEA were added to obtain a red composition R1.
  • a fluorine-based surfactant Megafac F559, manufactured by DIC Corporation
  • KBM503 silane coupling agent
  • PGMEA 45.27 parts by mass of PGMEA
  • Colorant dispersion liquid R254 was obtained in the same manner as in the preparation of colorant dispersion liquid R254 of Production Example R1.
  • (2) Preparation of Colorant Dispersion Liquid R202 A colorant dispersion liquid R202 was obtained in the same manner as in the preparation of colorant dispersion liquid R254, except that C.I. Pigment Red 202 was used instead of C.I. Pigment Red 254 as a colorant in the preparation of colorant dispersion liquid R254.
  • Red Composition R2 3.86 parts by mass of colorant dispersion liquid R254, 9.55 parts by mass of colorant dispersion liquid R202, 36.14 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 50.08 parts by mass of PGMEA were added to obtain a red composition R2.
  • a fluorine-based surfactant Megafac F559, manufactured by DIC Corporation
  • KBM503 silane coupling agent
  • PGMEA 50.08 parts by mass of PGMEA
  • Red Composition R3 3.82 parts by mass of colorant dispersion liquid R291, 9.28 parts by mass of colorant dispersion liquid R202, 36.48 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 50.04 parts by mass of PGMEA were added to obtain a red composition R3.
  • a fluorine-based surfactant Megafac F559, manufactured by DIC Corporation
  • KBM503 silane coupling agent
  • PGMEA 50.04 parts by mass of PGMEA
  • Example 1 Formation of color filter substrate in the order of red ⁇ green ⁇ blue
  • a curable resin composition for a black matrix was prepared in the same manner as in Example 1 of Japanese Patent No. 4833777, and a black matrix (10 ⁇ m wide) was formed on a glass substrate ("NA35" manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm in the same manner as in paragraph 0085 of Japanese Patent No. 4833777.
  • Red composition R1 was applied using a spin coater so that the film thickness after post-baking would be 2.3 ⁇ m. Then, the coating was dried by heating on a hot plate at 80°C for 3 minutes.
  • a chrome mask with an opening size of 80 ⁇ m ⁇ 250 ⁇ m was placed on the pattern photomask (chrome mask) and exposed to ultraviolet light of 40 mJ/ cm2 using an ultra-high pressure mercury lamp to form a post-exposure coating film on the glass substrate.
  • the coating was spin-developed using a 0.05 wt% potassium hydroxide aqueous solution as a developer, and developed by incubating in the developer for 60 seconds and then washing with pure water to obtain a red coating film in an independent fine line pattern. This was post-baked in a clean oven at 230°C for 25 minutes to form a red colored layer in an independent fine line pattern.
  • the green colored layer G1 was used instead of the red colored layer R1, and was applied by a spin coater so that the film thickness after post-baking was 2.3 ⁇ m.
  • a pattern photomask chrome mask
  • the blue composition B1 was used instead of the red composition R1, and the blue composition B1 was applied by a spin coater so that the film thickness after post-baking would be 2.3 ⁇ m.
  • a pattern photomask (chrome mask) was used to obtain an independent thin line patterned blue colored layer at a specified position different from the portion on which the red and green colored layers were formed.
  • a color filter substrate having colored layers of three colors, RGB, was manufactured.
  • Example 1-2 Formation of color filter substrate in the order of red ⁇ blue ⁇ green
  • a color filter substrate was produced in the same manner as in Example 1-1, except that the order of forming the colored layers was changed to red, blue, and green.
  • Example 2 (Examples 2 to 8, Comparative Examples 1 to 3)
  • Example 1 at least one of the red composition, the green composition, and the blue composition was changed as shown in Tables 1 and 2.
  • Example 2-1 to 8-1 and Comparative Examples 1-1 to 3-1 color filter substrates were produced in the order of red ⁇ green ⁇ blue
  • Examples 2-2 to 8-2 and Comparative Examples 1-2 to 3-2 color filter substrates were produced in the order of red ⁇ blue ⁇ green in the same manner as in Example 1.
  • Example 9-1 and Comparative Examples 4-1 to 5-1 color filter substrates were produced in the order of red ⁇ green ⁇ blue, and in Example 9-2 and Comparative Examples 4-2 to 5-2, color filter substrates were produced in the order of red ⁇ blue ⁇ green, in the same manner as in Example 1, except that at least one of the red composition, green composition, and blue composition in Example 1 was changed as shown in Tables 3 and 4.
  • the optical performance was evaluated using the obtained color filter substrate.
  • the central positions of the red colored layer, the green colored layer, and the blue colored layer in the width direction (80 ⁇ m) were subjected to spectroscopic measurement using a spectroscopic characteristic measuring device LCF (manufactured by Otsuka Electronics Co., Ltd.), and the chromaticity (x, y) and luminance (Y) of each color were calculated.
  • the measured values of each color were used to calculate the white chromaticity and luminance.
  • the increase rate of white luminance (Y-up rate) was calculated by taking the white luminance of the color filter substrate of Comparative Example 2, which corresponds to the conventional color filter, as the standard (100%).
  • the Y-up rate of white luminance was judged as follows: ⁇ when it was 103% or more, ⁇ when it was 102.0% or more and less than 103%, and ⁇ when it was less than 102.0%.
  • the glass plate on which the coating layer was formed was exposed to light at a specified position with an opening of 90 mm ⁇ 30 mm using a dedicated mask, and then shower-developed for 60 seconds using a 0.05 mass % potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water.
  • the substrate on which the red colored layer was formed was then baked at 230 ° C. for 30 minutes.
  • a green composition was applied onto the substrate on which the red colored layer was formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red colored layer was formed, and then the composition was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. At this stage, the residue on the red colored layer was evaluated. Then, the substrate on which the red and green colored layers were formed was baked at 230°C for 30 minutes.
  • a blue composition was applied onto the substrate on which the red and green colored layers were formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red and green colored layers were formed, and then the composition was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. At this stage, the residue on the red and green colored layers was evaluated. Then, the substrate on which the red, green, and blue colored layers were formed was baked at 230°C for 30 minutes.
  • the residue on each colored layer was evaluated by visually observing the monochrome exposed area (90 mm ⁇ 30 mm) of the glass substrate after the formation of the above colored layer, and then wiping it thoroughly with a lens cleaner soaked in ethanol (manufactured by Toray Industries, Inc., product name: Toraysee MK Clean Cloth), and visually observing the degree of coloration of the lens cleaner.
  • B No development residue was observed by visual inspection, and slight discoloration of the lens cleaner was observed.
  • C A slight development residue was observed by visual inspection, and discoloration of the lens cleaner was observed.
  • Comparative Examples 1 and 4 are color filter substrates including a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond in combination with a blue colored layer containing a blue phthalocyanine pigment and a purple pigment, and therefore were prone to development residues on the blue or green colored layer.
  • Comparative Examples 2 and 5 are color filter substrates including a green colored layer containing a conventionally known green pigment in combination with a blue colored layer containing a blue phthalocyanine pigment and a purple pigment. Although development residues were unlikely to occur, the brightness was poor.
  • Comparative Example 3 is a color filter substrate including a green coloring layer containing a conventionally known green pigment in combination with a blue coloring layer containing the specific lake color material. Therefore, although development residues were less likely to occur, the brightness was inferior.
  • the color filter substrate includes a green color layer containing a halogenated zinc phthalocyanine color material having a substituent bonded via an ether bond in combination with a blue color layer containing the specific lake color material, and therefore it was revealed that the occurrence of development residues on the blue color layer or the green color layer was suppressed.
  • the green colored layer in which the halogenated zinc phthalocyanine coloring material in which blue development residue is suppressed exists in molecular form has an improved transmittance
  • the blue colored layer containing the specific lake coloring material in which green development residue is suppressed also has an improved transmittance, and therefore the white luminance of the entire color filter was also improved.

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Abstract

This color filter comprises at least a substrate and a colored layer provided on the substrate, wherein the colored layer includes: a green colored layer containing a halogenated zinc phthalocyanine coloring material in which a substituent is bound via an ether bond; and a blue colored layer containing a lake coloring material having a specific structure.

Description

カラーフィルタ、及び表示装置Color filter and display device
　本発明は、カラーフィルタ、及び表示装置に関する。 The present invention relates to a color filter and a display device.
　近年、パーソナルコンピューターの発達、特に携帯用パーソナルコンピューターの発達に伴って、液晶ディスプレイの需要が増加している。モバイルディスプレイ（携帯電話、スマートフォン、タブレットＰＣ）の普及率も高まっており、益々液晶ディスプレイの市場は拡大する状況にある。また、最近においては、自発光により視認性が高い有機ＥＬディスプレイのような有機発光表示装置も、次世代画像表示装置として注目されている。これらの画像表示装置の性能においては、コントラストや色再現性の向上といったさらなる高画質化が望まれている。 In recent years, the demand for LCD displays has increased with the development of personal computers, especially portable personal computers. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for LCD displays is expanding further. In addition, organic light-emitting display devices such as organic EL displays, which have high visibility due to their self-luminous nature, have recently been attracting attention as next-generation image display devices. There is a demand for even higher image quality in the performance of these image display devices, such as improved contrast and color reproducibility.
　これらの液晶表示装置や有機発光表示装置には、カラーフィルタが用いられる。例えば液晶表示装置のカラー画像の形成は、カラーフィルタを通過した光がそのままカラーフィルタを構成する各画素の色に着色されて、それらの色の光が合成されてカラー画像を形成する。その際の光源としては、従来の冷陰極管のほか、白色発光の有機発光素子や白色発光の無機発光素子が利用される場合がある。また、有機発光表示装置では、色調整などのためにカラーフィルタを用いる。 Color filters are used in these liquid crystal display devices and organic light-emitting display devices. For example, when a color image is formed in an LCD display device, the light that passes through the color filter is directly colored with the color of each pixel that makes up the color filter, and these colors of light are combined to form a color image. In addition to conventional cold cathode fluorescent lamps, white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements may be used as light sources in this case. Also, organic light-emitting display devices use color filters for color adjustment, etc.
　近年の傾向として、画像表示装置の省電力化が求められており、バックライトの利用効率を向上させるためにカラーフィルタの高輝度化が特に求められている。特にモバイルディスプレイ（携帯電話、スマートフォン、タブレットＰＣ）では大きな課題である。 In recent years, there has been a trend toward power saving in image display devices, and there is a particular demand for color filters with higher brightness to improve the efficiency of backlight usage. This is a major issue, especially for mobile displays (cell phones, smartphones, tablet PCs).
　ここで、カラーフィルタは、一般的に、基板と、基板上に形成され、赤、緑、青の三原色の着色パターンを含む着色層と、各着色パターンを区画するように基板上に形成された遮光部とを有している。
　このような着色層の形成方法として、色材を分散させた色材分散液に硬化性バインダー成分等を添加した着色樹脂組成物を基材に塗布し硬化する方法などが知られている。
　カラーフィルタの高輝度化の要求に伴って、色材として、微細化した顔料を使用したり、より高透過率な染料やレーキ色材を使用する検討が行われている。 Here, a color filter generally has a substrate, a colored layer formed on the substrate and including colored patterns of the three primary colors, red, green, and blue, and a light-shielding portion formed on the substrate so as to partition each colored pattern.
As a method for forming such a colored layer, a method is known in which a colored resin composition, in which a curable binder component and the like are added to a colorant dispersion liquid in which a colorant is dispersed, is applied to a substrate and cured.
In response to the demand for higher brightness of color filters, the use of finely divided pigments as coloring materials, and the use of dyes and lake coloring materials with higher transmittance are being investigated.
　特許文献１には、特定のレーキ色材とフタロシアニン顔料と特定の酸性分散剤を含む色材分散液及び着色樹脂組成物等が開示され、当該着色樹脂組成物は特定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能であると記載されている。 Patent Document 1 discloses a colorant dispersion liquid and a colored resin composition that contain a specific lake colorant, a phthalocyanine pigment, and a specific acidic dispersant, and states that the colored resin composition has excellent dispersibility and storage stability even when the specific lake colorant and the phthalocyanine pigment are mixed in a desired range, and is capable of forming a colored layer that has improved substrate adhesion and coating uniformity.
　一方で、特許文献２には、特定のフタロシアニン系染料を含有する着色樹脂組成物が開示され、当該着色樹脂組成物は輝度が実用上十分であり、異物の発生が抑制されたパターンを形成可能であると記載されている。 On the other hand, Patent Document 2 discloses a colored resin composition containing a specific phthalocyanine dye, and states that the colored resin composition has sufficient brightness for practical use and is capable of forming a pattern in which the generation of foreign matter is suppressed.
国際公開第２０２０／０７１０４１号International Publication No. 2020/071041 特開２０２０－０４２２６３号JP 2020-042263 A
　例えば特許文献２に記載されているような、エーテル結合（－Ｏ－）を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材は、溶剤溶解性が良好なため、染料として溶剤に溶解して着色樹脂組成物に用いられ得る。しかしながら、このように溶剤に溶解されたハロゲン化亜鉛フタロシアニン色材を含む着色樹脂組成物を緑色着色層形成用樹脂組成物として用いると、基板上に、赤、緑、青の三原色の着色パターンをこの順で製造する際に、緑色着色層上に青色の現像残渣が発生し、赤、青、緑の順で製造する際には青色着色層上に緑色の現像残渣が発生しやすいという問題があった。緑色着色層上に青色の現像残渣が発生したり、青色着色層上に緑色の現像残渣が発生すると、輝度低下、色度ズレが発生して製品規格を外れるという問題が生じる。 For example, as described in Patent Document 2, a halogenated zinc phthalocyanine coloring material in which a substituent is bonded via an ether bond (-O-) has good solvent solubility and can be dissolved in a solvent as a dye and used in a colored resin composition. However, when a colored resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent in this way is used as a resin composition for forming a green colored layer, there is a problem that when a colored pattern of the three primary colors of red, green, and blue is produced in this order on a substrate, blue development residues tend to occur on the green colored layer, and when the patterns are produced in the order of red, blue, and green, green development residues tend to occur on the blue colored layer. When blue development residues occur on the green colored layer or green development residues occur on the blue colored layer, problems arise in that brightness decreases and chromaticity shifts occur, resulting in deviations from product specifications.
　本発明は、上記実情に鑑みてなされたものであり、溶剤に溶解されたハロゲン化亜鉛フタロシアニン色材を含む着色樹脂組成物を緑色着色層形成用樹脂組成物として用いた場合に、青色着色層又は緑色着色層上の現像残渣発生が抑制されたカラーフィルタ、及び、当該カラーフィルタを用いた表示特性に優れた表示装置を提供することを目的とする。 The present invention has been made in consideration of the above-mentioned circumstances, and aims to provide a color filter in which the occurrence of development residues on the blue or green colored layer is suppressed when a colored resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent is used as a resin composition for forming a green colored layer, and a display device using the color filter and having excellent display characteristics.
　すなわち、本発明は以下の［１］～［４］に関する。
［１］基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、
　前記着色層は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む、緑色着色層と、
　下記一般式（１－１）で表される色材及び下記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含む、青色着色層と、を含む、カラーフィルタ。 That is, the present invention relates to the following [1] to [4].
[1] A color filter comprising at least a substrate and a colored layer provided on the substrate,
The colored layer includes a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded thereto via an ether bond;
and a blue colored layer containing at least one lake colorant selected from the group consisting of a colorant represented by the following general formula (1-1) and a colorant represented by the following general formula (1-2):
Figure JPOXMLDOC01-appb-C000004
 （一般式（１－１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000004
 (In general formula (1-1), A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain. B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , and R iv and R v may bond to form a ring structure. R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 1 represents a divalent aromatic group which may have a substituent. A plurality of R i to R vii and Ar 1 may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent integers of 0 to 4, and f+e and g+e are 0 to 4. Multiple e, f, and g may be the same or different.
Figure JPOXMLDOC01-appb-C000005
 （一般式（１－２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000005
 (In general formula (1-2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure. R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R I to R VIII and Ar 2 may be the same or different. E m- represents an m-valent polyacid anion.
m represents an integer of 2 or more; j is 0 or 1, and when j is 0, no bond exists; k and l represent integers of 0 to 4, and k+j and l+j are 0 to 4. Multiple j, k and l may be the same or different.
［２］前記ハロゲン化亜鉛フタロシアニン色材が、下記一般式（２）で表されるフタロシアニン化合物である、前記［１］に記載のカラーフィルタ。 [2] The color filter according to [1], wherein the halogenated zinc phthalocyanine colorant is a phthalocyanine compound represented by the following general formula (2):
Figure JPOXMLDOC01-appb-C000006
 （一般式（２）中、Ｘ１～Ｘ１６はそれぞれ独立に、水素原子、ハロゲン原子、又は－Ｏ－ＲＤを表し、ＲＤは１価の有機基を表す。ただし、Ｘ１～Ｘ１６のうち１つ以上はハロゲン原子を表し、Ｘ１～Ｘ１６のうち１つ以上は－Ｏ－ＲＤを表す。）
Figure JPOXMLDOC01-appb-C000006
 (In the general formula (2), X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -OR D , and R D represents a monovalent organic group. However, at least one of X 1 to X 16 represents a halogen atom, and at least one of X 1 to X 16 represents -OR D. )
［３］前記着色層が、少なくともＣ．Ｉ．ピグメントレッド２０２を含む赤色着色層を、更に含む、前記［１］又は［２］に記載のカラーフィルタ。
［４］前記［１］～［３］のいずれか１項に記載のカラーフィルタを有することを特徴とする表示装置。 [3] The color filter according to [1] or [2], wherein the colored layer further includes a red colored layer containing at least C.I. Pigment Red 202.
[4] A display device comprising the color filter according to any one of [1] to [3] above.
　本発明によれば、溶剤に溶解されたハロゲン化亜鉛フタロシアニン色材を含む着色樹脂組成物を緑色着色層形成用樹脂組成物として用いた場合に、青色着色層又は緑色着色層上の現像残渣発生が抑制されたカラーフィルタ、及び、当該カラーフィルタを用いた表示特性に優れた表示装置を提供することができる。 According to the present invention, when a colored resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent is used as a resin composition for forming a green colored layer, it is possible to provide a color filter in which the occurrence of development residues on the blue or green colored layer is suppressed, and a display device using the color filter and having excellent display characteristics.
図１は、本発明のカラーフィルタの一例を示す概略図である。FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. 図２は、本発明の表示装置の一例を示す概略図である。FIG. 2 is a schematic diagram showing an example of a display device of the present invention. 図３は、本発明の表示装置の他の一例を示す概略図である。FIG. 3 is a schematic diagram showing another example of the display device of the present invention.
　以下、本発明に係るカラーフィルタ、表示装置について、順に詳細に説明する。
　なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長５μｍ以下の電磁波、及び電子線のことをいう。
　本発明において（メタ）アクリルとは、アクリル及びメタクリルの各々を表し、（メタ）アクリレートとは、アクリレート及びメタクリレートの各々を表す。
　また、本明細書において数値範囲を示す「～」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。 The color filter and the display device according to the present invention will be described in detail below.
In the present invention, light includes electromagnetic waves with wavelengths in the visible and invisible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less and electron beams.
In the present invention, the term "(meth)acrylic" refers to both acrylic and methacrylic, and the term "(meth)acrylate" refers to both acrylate and methacrylate.
In addition, in this specification, the use of "to" indicating a range of values is used to mean that the values before and after it are included as the lower limit and upper limit.
Ｉ．カラーフィルタ
　本発明に係るカラーフィルタは、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、
　前記着色層は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む、緑色着色層と、
　下記一般式（１－１）で表される色材及び下記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含む、青色着色層と、を含む。 I. Color Filter The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate,
The colored layer includes a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded thereto via an ether bond;
and a blue colored layer containing at least one lake colorant selected from the group consisting of a colorant represented by the following general formula (1-1) and a colorant represented by the following general formula (1-2):
Figure JPOXMLDOC01-appb-C000007
 （一般式（１－１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000007
 (In general formula (1-1), A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain. B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , and R iv and R v may bond to form a ring structure. R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 1 represents a divalent aromatic group which may have a substituent. A plurality of R i to R vii and Ar 1 may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent integers of 0 to 4, and f+e and g+e are 0 to 4. Multiple e, f, and g may be the same or different.
Figure JPOXMLDOC01-appb-C000008
 （一般式（１－２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000008
 (In general formula (1-2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure. R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R I to R VIII and Ar 2 may be the same or different. E m- represents an m-valent polyacid anion.
m represents an integer of 2 or more; j is 0 or 1, and when j is 0, no bond exists; k and l represent integers of 0 to 4, and k+j and l+j are 0 to 4. Multiple j, k and l may be the same or different.
　本発明に係るカラーフィルタは、着色層が、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む緑色着色層に、前記特定のレーキ色材を含む青色着色層を組み合わせて含むことから、青色着色層又は緑色着色層上の現像残渣発生が抑制されたカラーフィルタとすることができる。
　前述のように、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材は、溶剤溶解性が良好である。そのため、溶剤に溶解されたハロゲン化亜鉛フタロシアニン色材を含む着色樹脂組成物を緑色着色層形成用樹脂組成物として用いると、基板上に、緑、青の順で着色パターンを製造する際に、緑色着色層上に青色の現像残渣が発生し、青、緑の順で着色パターンを製造する際には青色着色層上に緑色の現像残渣が発生しやすいという問題があった。この問題は、前記ハロゲン化亜鉛フタロシアニン色材が緑色着色層形成用樹脂組成物または緑色着色層中に分子状で存在することに起因すると考えられる。先に形成された青色着色層上に、ハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層形成用樹脂組成物が塗布されると、ハロゲン化亜鉛フタロシアニン色材が青色着色層中の銅フタロシアニン顔料と相互作用しやすく、緑色樹脂組成物の現像残渣が発生すると考えられる。また、ハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層上に、青色着色層形成用樹脂組成物が塗布されても同様に、ハロゲン化亜鉛フタロシアニン色材が青色着色層形成用樹脂組成物中の銅フタロシアニン顔料と相互作用しやすく、青色樹脂組成物の現像残渣が発生すると考えられる。
　それに対して本発明では、前記エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む緑色着色層に、前記特定のレーキ色材を含む青色着色層を組み合わせて用いる。本発明の青色着色層には、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材が含まれ、当該レーキ色材はハロゲン化亜鉛フタロシアニン色材と骨格が異なる。そのため、製造時に青色着色層上に、ハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層形成用樹脂組成物が塗布されても、また、ハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層上に、青色着色層形成用樹脂組成物が塗布されても、相互作用し難くなって、現像残渣が抑制されると考えられる。
　また、青色現像残渣が抑制されたハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層は透過率が向上したものであり、緑色現像残渣が抑制された前記特定のレーキ色材を含む青色着色層も透過率が向上したものであることから、カラーフィルタ全体の輝度も向上すると推定される。 The color filter according to the present invention has a color layer that includes a green color layer containing a halogenated zinc phthalocyanine color material having a substituent bonded via an ether bond in combination with a blue color layer containing the specific lake color material, and therefore can be a color filter in which the generation of development residues on the blue color layer or the green color layer is suppressed.
As described above, the halogenated zinc phthalocyanine coloring material to which the substituent is bonded via an ether bond has good solvent solubility. Therefore, when a coloring resin composition containing a halogenated zinc phthalocyanine coloring material dissolved in a solvent is used as a resin composition for forming a green coloring layer, there is a problem that when a coloring pattern is produced on a substrate in the order of green and blue, blue development residues are generated on the green coloring layer, and when a coloring pattern is produced in the order of blue and green, green development residues are easily generated on the blue coloring layer. This problem is considered to be caused by the halogenated zinc phthalocyanine coloring material being present in a molecular form in the resin composition for forming a green coloring layer or in the green coloring layer. When a resin composition for forming a green coloring layer in which a halogenated zinc phthalocyanine coloring material is present in a molecular form is applied onto a previously formed blue coloring layer, it is considered that the halogenated zinc phthalocyanine coloring material is likely to interact with the copper phthalocyanine pigment in the blue coloring layer, and development residues of the green resin composition are generated. Similarly, when a resin composition for forming a blue colored layer is applied onto a green colored layer in which a halogenated zinc phthalocyanine colorant is present in molecular form, it is believed that the halogenated zinc phthalocyanine colorant is likely to interact with the copper phthalocyanine pigment in the resin composition for forming a blue colored layer, resulting in development residues of the blue resin composition.
In contrast, in the present invention, a green colored layer containing a halogenated zinc phthalocyanine coloring material to which a substituent is bonded via the ether bond is used in combination with a blue colored layer containing the specific lake coloring material. The blue colored layer of the present invention contains at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1-1) and the coloring material represented by the general formula (1-2), and the lake coloring material has a skeleton different from that of the halogenated zinc phthalocyanine coloring material. Therefore, even if a resin composition for forming a green colored layer in which a halogenated zinc phthalocyanine coloring material exists in a molecular form is applied onto a blue colored layer during production, or even if a resin composition for forming a blue colored layer is applied onto a green colored layer in which a halogenated zinc phthalocyanine coloring material exists in a molecular form, it is considered that interaction is unlikely to occur, and development residues are suppressed.
In addition, the green colored layer in which the halogenated zinc phthalocyanine colorant in which blue development residues are suppressed is present in molecular form has improved transmittance, and the blue colored layer containing the specific lake colorant in which green development residues are suppressed also has improved transmittance, so it is estimated that the brightness of the entire color filter is also improved.
　このような本発明に係るカラーフィルタについて、図を参照しながら説明する。図１は、本発明のカラーフィルタの一例を示す概略断面図である。図１によれば、本発明のカラーフィルタ１０は、基板１と、基板１上に形成された遮光部２と、遮光部２間に形成された赤色着色層３Ｒ、緑色着色層３Ｇおよび青色着色層３Ｂを含む着色層３を有している。 The color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. According to FIG. 1, the color filter 10 according to the present invention has a substrate 1, light-shielding portions 2 formed on the substrate 1, and color layers 3 formed between the light-shielding portions 2 and including a red color layer 3R, a green color layer 3G, and a blue color layer 3B.
［基板］
　基板としては、後述する透明基板、シリコン基板、及び、透明基板又はシリコン基板上にアルミニウム、銀、銀／銅／パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、ＴＦＴ等のトランジスタ、回路等が形成されていてもよい。 [substrate]
The substrate may be a transparent substrate, a silicon substrate, or a transparent or silicon substrate on which an aluminum, silver, or silver/copper/palladium alloy thin film is formed, as described below. On these substrates, other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed.
　本発明のカラーフィルタにおける透明基板としては、可視光に対して透明な基材であればよく、特に限定されず、一般的なカラーフィルタに用いられる透明基板を使用することができる。具体的には、石英ガラス、無アルカリガラス、合成石英板等の可撓性のない透明なリジッド材、あるいは、透明樹脂フィルム、光学用樹脂板、フレキシブルガラス等の可撓性を有する透明なフレキシブル材が挙げられる。
　当該透明基板の厚みは、特に限定されるものではないが、本発明のカラーフィルタの用途に応じて、例えば１００μｍ～１ｍｍ程度のものを使用することができる。 The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used in general color filters can be used. Specifically, examples of the transparent substrate include transparent rigid materials with no flexibility, such as quartz glass, non-alkali glass, and synthetic quartz plate, and transparent flexible materials with flexibility, such as transparent resin films, optical resin plates, and flexible glass.
The thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 μm to 1 mm depending on the application of the color filter of the present invention.
［遮光部］
　本発明のカラーフィルタにおける遮光部は、前記基板上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
　当該遮光部のパターン形状としては、特に限定されず、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。 [Light-shielding part]
The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding part is not particularly limited, and examples thereof include stripe-like and matrix-like shapes. The light-shielding part may be a thin metal film such as chromium formed by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding part may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.
　遮光部の膜厚としては、金属薄膜の場合は０．２μｍ以上０．４μｍ以下程度で設定され、黒色顔料をバインダー樹脂中に分散又は溶解させたものである場合は０．５μｍ以上２μｍ以下程度で設定される。 The film thickness of the light-shielding part is set to approximately 0.2 μm or more and 0.4 μm or less in the case of a thin metal film, and is set to approximately 0.5 μm or more and 2 μm or less in the case of a black pigment dispersed or dissolved in a binder resin.
［着色層］
　本発明のカラーフィルタに用いられる着色層は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む、緑色着色層と、
　前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含む、青色着色層と、を含むことを特徴とする。 [Colored layer]
The colored layer used in the color filter of the present invention comprises a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond;
and a blue colored layer containing at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2).
　着色層は、通常、前記基板上の前記遮光部の開口部に形成され、通常３色以上の着色パターンから構成される。本発明の着色層は少なくとも前記緑色着色層と、前記青色着色層を含み、更に赤色着色層を含むものであってよい。
　また、当該着色層の配列としては、特に限定されず、例えば、ストライプ型、モザイク型、トライアングル型、４画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は任意に設定することができる。
　当該着色層の厚みは、塗布方法、着色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、１μｍ～５μｍの範囲であることが好ましい。 The colored layer is usually formed in the opening of the light-shielding part on the substrate, and usually has a colored pattern of three or more colors. The colored layer of the present invention includes at least the green colored layer and the blue colored layer, and may further include a red colored layer.
The arrangement of the colored layers is not particularly limited, and may be, for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, a four-pixel arrangement type, etc. The width, area, etc. of the colored layers may be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but it is usually preferable that the thickness is in the range of 1 μm to 5 μm.
　着色層は、成膜性や被塗工面に対する密着性を付与するために、通常バインダー成分を含有する。本発明の着色層は、色材と、バインダー成分と、必要に応じて分散剤と、溶剤と、更に他の成分を含んでよい着色樹脂組成物の硬化物であってよい。
　以下、各色の着色層について詳細に説明する。 The colored layer usually contains a binder component in order to impart film-forming properties and adhesion to the coated surface. The colored layer of the present invention may be a cured product of a colored resin composition that contains a colorant, a binder component, and optionally a dispersant, a solvent, and further other components.
The colored layers of each color will be described in detail below.
＜緑色着色層＞
　本発明に用いられる緑色着色層は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む。
　緑色着色層は、前記特定のハロゲン化亜鉛フタロシアニン色材と、バインダー成分と、溶剤と、更に必要に応じて分散剤や他の成分を含んでよい着色樹脂組成物の硬化物であってよい。
　以下、緑色着色層及び緑色着色層形成用樹脂組成物に含まれる各成分について、説明する。 <Green colored layer>
The green colored layer used in the present invention contains a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond.
The green colored layer may be a cured product of a colored resin composition that contains the specific halogenated zinc phthalocyanine coloring material, a binder component, a solvent, and, if necessary, a dispersant and other components.
Hereinafter, the green colored layer and each component contained in the resin composition for forming the green colored layer will be described.
（色材）
　緑色着色層における色材は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含み、さらに他の色材を含んでもよい。 (Coloring material)
The coloring material in the green colored layer contains a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond, and may further contain other coloring materials.
（(エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材)）
　前記ハロゲン化亜鉛フタロシアニン色材は、本発明の効果を発揮しやすい点から、溶剤溶解性が高いものであってよい。前記ハロゲン化亜鉛フタロシアニン色材は、グリコールアルキルエーテルアセテート類、グリコールモノアルキルエーテル類、及びグリコールアルキルアセテート類からなる群から選択される少なくとも１種の溶剤１００ｇに対する２５℃の溶解度が０．１ｇ以上であってよく、０．５ｇ以上であってよく、８ｇ以上であってよく、１０ｇ以上であってよく、１５ｇ以上であってよい。前記ハロゲン化亜鉛フタロシアニン色材は、プロピレングリコールモノメチルエーテルアセテート、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エチルエーテル、１－メトキシ－２ブタノール、プロピレングリコールモノプロピルエーテル、及びジエチレングリコールエチルメチルエーテルからなる群から選択される少なくとも１種の溶剤１００ｇに対する２５℃の溶解度が０．１ｇ以上であってよく、０．５ｇ以上であってよく、８ｇ以上であってよく、１０ｇ以上であってよく、１５ｇ以上であってよい。当該溶解度の上限値は限定されるものではないが、２０ｇ以下であってよい。 ((Halogenated zinc phthalocyanine coloring material with a substituent bonded via an ether bond))
The halogenated zinc phthalocyanine coloring material may have high solvent solubility in order to easily exert the effects of the present invention. The halogenated zinc phthalocyanine coloring material may have a solubility at 25°C in 100g of at least one solvent selected from the group consisting of glycol alkyl ether acetates, glycol monoalkyl ethers, and glycol alkyl acetates of 0.1g or more, 0.5g or more, 8g or more, 10g or more, or 15g or more. The halogenated zinc phthalocyanine coloring material may have a solubility at 25°C in 100g of at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1-methoxy-2 butanol, propylene glycol monopropyl ether, and diethylene glycol ethyl methyl ether of 0.1g or more, 0.5g or more, 8g or more, 10g or more, or 15g or more. The upper limit of the solubility is not limited, but may be 20 g or less.
　エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材としては、中でも、下記一般式（２）で表されるフタロシアニン化合物であることが、輝度と溶解性の点から、好ましい。 Among halogenated zinc phthalocyanine colorants in which a substituent is bonded via an ether bond, the phthalocyanine compound represented by the following general formula (2) is preferred in terms of brightness and solubility.
Figure JPOXMLDOC01-appb-C000009
 （一般式（２）中、Ｘ１～Ｘ１６はそれぞれ独立に、水素原子、ハロゲン原子、又は－Ｏ－ＲＤを表し、ＲＤは１価の有機基を表す。ただし、Ｘ１～Ｘ１６のうち１つ以上はハロゲン原子を表し、Ｘ１～Ｘ１６のうち１つ以上は－Ｏ－ＲＤを表す。）
Figure JPOXMLDOC01-appb-C000009
 (In the general formula (2), X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -OR D , and R D represents a monovalent organic group. However, at least one of X 1 to X 16 represents a halogen atom, and at least one of X 1 to X 16 represents -OR D. )
　Ｘ１～Ｘ１６において、ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。なお、上記式（２）中にハロゲン原子を２個以上有する場合、それら複数個のハロゲン原子は各々同一でも互いに異なっていてもよい。Ｘ１～Ｘ１６におけるハロゲン原子は、色味の点から、少なくともフッ素原子を含むことが好ましく、全てフッ素原子であることがより好ましい。 In X 1 to X 16 , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the above formula (2) has two or more halogen atoms, the halogen atoms may be the same or different from each other. In terms of color, the halogen atoms in X 1 to X 16 preferably include at least a fluorine atom, and more preferably are all fluorine atoms.
　Ｘ１～Ｘ１６におけるハロゲン原子の数は、高輝度化の点から、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、７個以上であることが更に好ましい。また、Ｘ１～Ｘ１６におけるハロゲン原子の数は、１２個以下であることが好ましく、１０個以下であることがより好ましく、９個以下であることが更に好ましい。Ｘ１～Ｘ１６におけるハロゲン原子の数は８個であってよい。
　中でも色味、極大吸収波長域の点から、Ｘ１～Ｘ１６のうち６～１０個、中でも７～９個は、フッ素原子であることが好ましい。 From the viewpoint of increasing brightness, the number of halogen atoms in X 1 to X 16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more. The number of halogen atoms in X 1 to X 16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less. The number of halogen atoms in X 1 to X 16 may be 8.
In particular, from the standpoint of color and maximum absorption wavelength region, it is preferred that 6 to 10, and more preferably 7 to 9 of X 1 to X 16 are fluorine atoms.
　Ｘ１～Ｘ１６は、水素原子であっても良い。Ｘ１～Ｘ１６のうちの水素原子の個数は、色味の調整により適宜選択されれば良いが、０～８個であってよく、０～４個であってよく、０～２個であって良い。 X 1 to X 16 may be a hydrogen atom. The number of hydrogen atoms among X 1 to X 16 may be appropriately selected depending on the adjustment of the color tone, and may be 0 to 8, 0 to 4, or 0 to 2.
　－Ｏ－ＲＤにおけるＲＤは、１価の有機基である。ここで有機基とは炭素原子を含む基をいう。ＲＤは、置換基を有していてもよい炭化水素基又は複素環基が挙げられる。炭化水素基としては、直鎖、分岐、又は環状の脂肪族炭化水素基、芳香族炭化水素基及びこれらの組み合わせが挙げられる。直鎖若しくは分岐の脂肪族炭化水素基としては炭素数１～１０の直鎖若しくは分岐の脂肪族炭化水素基であってよく、環状の脂肪族炭化水素基としては、炭素数３～２０の脂環式炭化水素基であってよく、芳香族炭化水素基としては、炭素数６～２０の芳香族炭化水素基であってよく、複素環基としては窒素含有複素環、硫黄含有複素環、酸素含有複素環等が挙げられ、芳香環及び非芳香環のいずれであってもよい。 R D in -O-R D is a monovalent organic group. Here, the organic group refers to a group containing carbon atoms. R D may be a hydrocarbon group or a heterocyclic group which may have a substituent. Examples of the hydrocarbon group include linear, branched, or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. The linear or branched aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, the cyclic aliphatic hydrocarbon group may be an alicyclic hydrocarbon group having 3 to 20 carbon atoms, the aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the heterocyclic group may be a nitrogen-containing heterocycle, a sulfur-containing heterocycle, an oxygen-containing heterocycle, or the like, and may be either an aromatic ring or a non-aromatic ring.
　直鎖若しくは分岐の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられ、脂環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基等が挙げられる。
　また、芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ビフェニル基等が挙げられる。
　また、複素環基としては、例えば、１個の遊離原子価を有する、フラン環、チオフェン環、ピロール環、２Ｈ－ピラン環、４Ｈ－チオピラン環、ピリジン環、１，３－オキサゾール環、イソオキサゾール環、１，３－チアゾール環、イソチアゾール環、イミダ ゾール環、ピラゾール環、フラザン環、ピラジン環、ピリミジン環、ピリダジン環等の基等が挙げられる。 Examples of the linear or branched aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group.
Examples of the heterocyclic group include groups having one free valence, such as a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring.
　ＲＤの炭化水素基又は複素環基が置換基を有する場合、当該置換基としては、ハロゲン原子、－ＯＲｄ１、－ＣＯＲｄ１、－ＣＯＯＲｄ１（ここで、Ｒｄ１は炭化水素基又は複素環基）等が挙げられ、具体的にはアルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基等が挙げられる。 When the hydrocarbon group or heterocyclic group of R D has a substituent, examples of the substituent include a halogen atom, -OR d1 , -COR d1 , -COOR d1 (wherein R d1 is a hydrocarbon group or a heterocyclic group), and specific examples thereof include an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and the like.
　－Ｏ－ＲＤにおけるＲＤは、塗膜硬化（ベーク）時の結晶性制御（異物の析出抑制）、溶解性の付与の点から、中でも置換基を有してもよい芳香族炭化水素基であることが好ましく、下記式（３）で表される１価の基であることが好ましい。 R D in -O-R D is preferably an aromatic hydrocarbon group which may have a substituent, from the viewpoints of controlling crystallinity (suppressing deposition of foreign matter) during coating film curing (baking) and imparting solubility, and is preferably a monovalent group represented by the following formula (3):
Figure JPOXMLDOC01-appb-C000010
 （式（３）中、－Ｗ－は単結合又は－Ｏ－であり、Ｒｄ１は、置換基を有していてもよい炭素数１～１０の脂肪族炭化水素基、置換基を有していてもよい炭素数３～１２の脂環式炭化水素基、又は置換基を有していてもよい炭素数６～２０の芳香族炭化水素基である。Ｒｄ２は、ハロゲン原子、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基である。ｐは１～３の整数であり、ｑは０～２の整数である。但し、ｐが２又は３の場合、複数のＷ、Ｒｄ１はそれぞれ同一でも異なっていてもよく、ｑが２の場合、複数のＲｄ２はそれぞれ同一でも異なっていてもよい。＊は、式（２）中のフタロシアニン骨格との結合位置を示す。）
Figure JPOXMLDOC01-appb-C000010
 (In formula (3), -W- is a single bond or -O-; R d1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; R d2 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; p is an integer of 1 to 3, and q is an integer of 0 to 2. However, when p is 2 or 3, multiple Ws and R d1s may be the same or different, and when q is 2, multiple R d2s may be the same or different. * indicates a bonding position with the phthalocyanine skeleton in formula (2).)
　上記式（３）において、上記脂肪族炭化水素基、脂環式炭化水素基、及び芳香族炭化水素基の置換基としては、炭素数１～５のアルコキシ基、水酸基を挙げることができる。Ｒｄ１は、置換基を有していてもよい炭素数１～１０の脂肪族炭化水素基であることが好ましく、置換基を有していてもよい炭素数１～１０のアルキル基であることが特に好ましい。当該アルキル基は、好ましくは炭素数１～５のアルキル基であり、より好ましくは炭素数１～５の直鎖状アルキル基である。Ｒｄ１が置換アルキル基である場合、置換基として炭素数１～５のアルコキシ基を有する基であることが好ましい。
　ｐは１又は２が好ましく、１がより好ましい。ｐ＝１の場合、－ＣＯ－Ｗ－Ｒｄ１は、上記式（３）の－Ｏ－に対して３位又は４位に結合していることが好ましく、４位に結合していることがより好ましい。ｐ＝２の場合、２個の－ＣＯ－Ｗ－Ｒｄ１は、－Ｏ－に対して３，５位又は２，４位に結合していることが好ましく、３，５位に結合していることがより好ましい。
　ｑは０又は１が好ましく、０がより好ましい。
　上記式（３）で表される基の好ましい具体例としては、下記式（３－１）～式（３－１０）のそれぞれで表される基が挙げられるが、これらに限定されるものではない。 In the above formula (3), examples of the substituents of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include an alkoxy group having 1 to 5 carbon atoms and a hydroxyl group. R d1 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and particularly preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms. When R d1 is a substituted alkyl group, it is preferably a group having an alkoxy group having 1 to 5 carbon atoms as a substituent.
p is preferably 1 or 2, and more preferably 1. When p=1, -CO-W-R d1 is preferably bonded to the 3- or 4-position relative to -O- in the above formula (3), and more preferably bonded to the 4-position. When p=2, the two -CO-W-R d1 are preferably bonded to the 3- and 5-positions or the 2- and 4-positions relative to -O-, and more preferably bonded to the 3- and 5-positions.
q is preferably 0 or 1, and more preferably 0.
Preferred specific examples of the group represented by the above formula (3) include groups represented by each of the following formulas (3-1) to (3-10), but are not limited thereto.
Figure JPOXMLDOC01-appb-C000011
 （式（３－１）～式（３－１０）において、＊は、式（２）中のフタロシアニン骨格との結合位置を示す。）
Figure JPOXMLDOC01-appb-C000011
 (In formulas (3-1) to (3-10), * indicates the bonding position with the phthalocyanine skeleton in formula (2).)
　Ｘ１～Ｘ１６における－Ｏ－ＲＤの数は、所望の透過スペクトル（高輝度）を得る点、及び塗膜硬化（ベーク）時のフタロシアニン化合物特有の結晶性制御（異物の析出抑制）の点から、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、７個以上であることが更に好ましい。また、Ｘ１～Ｘ１６における－Ｏ－ＲＤの数は、１２個以下であることが好ましく、１０個以下であることがより好ましく、９個以下であることが更に好ましい。Ｘ１～Ｘ１６における－Ｏ－ＲＤの数は８個であってよい。
　所望の透過スペクトル（高輝度）を得る点から、Ｘ１～Ｘ１６は、Ｘ２、Ｘ３、Ｘ６、Ｘ７、Ｘ１０、Ｘ１１、Ｘ１４及びＸ１５のうち、少なくとも４個以上が－Ｏ－ＲＤであることが好ましく、Ｘ２、Ｘ３、Ｘ６、Ｘ７、Ｘ１０、Ｘ１１、Ｘ１４及びＸ１５の全てが基－Ｏ－ＲＤであって、残り（Ｘ１、Ｘ４、Ｘ５、Ｘ８、Ｘ９、Ｘ１２、Ｘ１３及びＸ１６）がハロゲン原子であることが特に好ましい。 The number of -O-R D in X 1 to X 16 is preferably 4 or more, more preferably 6 or more, and even more preferably 7 or more, from the viewpoint of obtaining a desired transmission spectrum (high brightness) and controlling the crystallinity specific to the phthalocyanine compound during coating film curing (baking) (suppressing precipitation of foreign matter). The number of -O-R D in X 1 to X 16 is preferably 12 or less, more preferably 10 or less, and even more preferably 9 or less. The number of -O-R D in X 1 to X 16 may be 8.
From the viewpoint of obtaining a desired transmission spectrum (high brightness), it is preferable that at least four of X 1 to X 16 , X 2 , X 3 , X 6 , X 7 , X 10 , X 11 , X 14 and X 15 , are -O-R D , and it is particularly preferable that all of X 2 , X 3 , X 6 , X 7 , X 10 , X 11 , X 14 and X 15 are groups -O-R D and the remaining (X 1 , X 4 , X 5 , X 8 , X 9 , X 12 , X 13 and X 16 ) are halogen atoms.
　一般式（２）で表されるフタロシアニン化合物の好ましい具体例としては、下記式（２－１）～（２－５）のそれぞれで表される化合物が挙げられるがこれらに限定されるものではない。 Preferred specific examples of the phthalocyanine compound represented by general formula (2) include, but are not limited to, the compounds represented by the following formulas (2-1) to (2-5).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　ハロゲン化フタロシアニン色材の製造方法としては、従来公知の製法を適宜選択して用いることができる。例えば、溶融状態または有機溶剤中で、フタロニトリル化合物と金属塩とを環化反応する製法が好ましく使用でき、例えば、特開２０１４－４３５５６号公報や、特開２０２０－４２２６３号公報を参照して製造することができる。出発原料に用いられるフタロニトリル化合物についても、従来公知の製造方法を適宜選択して合成することができ、市販品を用いても良い。 A conventionally known manufacturing method can be appropriately selected and used as a manufacturing method for the halogenated phthalocyanine colorant. For example, a manufacturing method in which a phthalonitrile compound and a metal salt are subjected to a cyclization reaction in a molten state or in an organic solvent can be preferably used, and manufacturing can be performed by referring to, for example, JP-A-2014-43556 and JP-A-2020-42263. The phthalonitrile compound used as the starting material can also be synthesized by appropriately selecting a conventionally known manufacturing method, or a commercially available product can be used.
（（他の色材））
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、色材は、前記特定のハロゲン化亜鉛フタロシアニン色材の他に、更に他の色材を含んでもよい。
　他の色材は、所望の発色が可能なものであればよく、特に限定されず、種々の有機顔料、無機顔料、染料、染料の造塩化合物等を、単独で又は２種以上混合して用いることができる。中でも有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス（Ｃ．Ｉ．；Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ　社発行）においてピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物、具体的には、下記のようなカラーインデックス（Ｃ．Ｉ．）番号が付されているものを挙げることができる。
　他の色材としては、黄色色材、及び他の緑色色材からなる群から選択される１種以上であってよい。緑色着色層の色調整の点から、黄色色材であることが好ましいが、本発明の効果を損なわない範囲で他の緑色色材や、その他の色材を含んでもよい。 ((Other colorants))
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the coloring material may further contain other coloring materials in addition to the specific halogenated zinc phthalocyanine coloring material.
The other coloring materials are not particularly limited as long as they can produce the desired color, and various organic pigments, inorganic pigments, dyes, dye salt compounds, etc. can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically, those assigned the following Color Index (C.I.) numbers.
The other coloring material may be one or more selected from the group consisting of a yellow coloring material and other green coloring materials. From the viewpoint of color adjustment of the green colored layer, a yellow coloring material is preferable, but other green coloring materials or other coloring materials may be included within a range that does not impair the effects of the present invention.
　黄色色材としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５５、６０、６１、６５、７１、７３、７４、８１、８３、９３、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１６、１１７、１１９、１２０、１２６、１２７、１２８、１２９、１３８、１３９、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６６、１６８、１７５、１８５、２３１、及びこれらの誘導体顔料等の黄色顔料、クマリン系染料、シアニン系染料、メロシアニン系染料、アゾ系染料、メチン系染料、アゾメチン系染料、キノフタロン系染料等の黄色染料等が挙げられる。 Yellow colorants include, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129 , 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 231, and derivative pigments thereof, and yellow dyes such as coumarin dyes, cyanine dyes, merocyanine dyes, azo dyes, methine dyes, azomethine dyes, and quinophthalone dyes.
　黄色色材としては、中でも耐熱性及び耐光性が良好で、透過率が高い点から、キノフタロン系色材であることが好ましい。また、キノフタロン系色材は、カラーフィルタ用途に適した色相を有する点でも好ましい。
　キノフタロン系色材とは、キナルジン等のキノリン誘導体と、無水フタル酸誘導体又は無水ナフタル酸誘導体との縮合により合成される色材をいい、顔料、染料、染料の造塩化合物のいずれであってもよい。
　キノフタロン系色材のうち、キノフタロン顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１３８等が挙げられる。
　キノフタロン染料としては、例えば、Ｃ．Ｉ．ディスパースイエロー５４、６４、６７、１３４、１４９、１６０、Ｃ．Ｉ．ソルベントイエロー１１４、１５７等が挙げられる。 As the yellow coloring material, quinophthalone-based coloring materials are preferable because they have good heat resistance and light resistance and high transmittance. Quinophthalone-based coloring materials are also preferable because they have a hue suitable for use in color filters.
The quinophthalone coloring material refers to a coloring material synthesized by condensation of a quinoline derivative such as quinaldine with a phthalic anhydride derivative or a naphthalic anhydride derivative, and may be any of a pigment, a dye, and a dye salt-forming compound.
Among the quinophthalone colorants, examples of quinophthalone pigments include C.I. Pigment Yellow 138 and the like.
Examples of quinophthalone dyes include C.I. Disperse Yellow 54, 64, 67, 134, 149, and 160, and C.I. Solvent Yellow 114 and 157.
　他の緑色色材としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５、５８、５９、６２、６３等の緑色顔料、スクアリリウム、トリアリールメタン、アントラキノン、クマリン、シアニン、またはアゾ染料等の緑色染料等が挙げられる。 Other green colorants include green pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63, and green dyes such as squarylium, triarylmethane, anthraquinone, coumarin, cyanine, or azo dyes.
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、色材全体に対する前記特定のハロゲン化亜鉛フタロシアニン色材の含有割合は、所望の色度に合わせて適宜調整されればよく、特に限定されず、前記特定のハロゲン化亜鉛フタロシアニン色材を含む色材全体に対して、１００質量％であってもよい。本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、他の色材を含有する場合には、所望の色度調整の点から、前記特定のハロゲン化亜鉛フタロシアニン色材を含む色材全体に対して、前記特定のハロゲン化亜鉛フタロシアニン色材を３０質量％～９５質量％含有してもよく、当該下限値は４０質量部以上であってよく、５０質量部以上であってよく、当該上限値は８５質量部以下であってよく、８０質量部以下であってもよい。 In the green colored layer of the present invention and the colored resin composition for forming the green colored layer, the content ratio of the specific halogenated zinc phthalocyanine coloring material to the entire coloring material may be appropriately adjusted according to the desired chromaticity, is not particularly limited, and may be 100% by mass based on the entire coloring material including the specific halogenated zinc phthalocyanine coloring material. In the green colored layer of the present invention and the colored resin composition for forming the green colored layer, when other coloring materials are contained, the specific halogenated zinc phthalocyanine coloring material may be contained in an amount of 30% to 95% by mass based on the entire coloring material including the specific halogenated zinc phthalocyanine coloring material from the viewpoint of desired chromaticity adjustment, and the lower limit may be 40 parts by mass or more, or 50 parts by mass or more, and the upper limit may be 85 parts by mass or less, or 80 parts by mass or less.
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、黄色色材を含有する場合、黄色色材は、適宜選択され、１種単独又は２種以上混合して用いられる。
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、前記特定のハロゲン化亜鉛フタロシアニン色材に対する黄色色材の含有割合は、所望の色度に合わせて適宜調整されればよく、特に限定されない。中でも、所望の色度調整の点から、黄色色材の含有割合は、前記特定のハロゲン化亜鉛フタロシアニン色材を１００質量部に対して、０質量部～２３３質量部であってよく、当該下限値は５質量部以上であってよく、１８質量部以上であってよく、２５質量部以上であってもよく、当該上限値は１５０質量部以下であってよく、１００質量部以下であってもよい。 In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, when a yellow coloring material is contained, the yellow coloring material is appropriately selected and used alone or in combination of two or more kinds.
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the content ratio of the yellow coloring material relative to the specific halogenated zinc phthalocyanine coloring material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. In particular, from the viewpoint of desired chromaticity adjustment, the content ratio of the yellow coloring material may be 0 parts by mass to 233 parts by mass relative to 100 parts by mass of the specific halogenated zinc phthalocyanine coloring material, the lower limit may be 5 parts by mass or more, 18 parts by mass or more, or 25 parts by mass or more, and the upper limit may be 150 parts by mass or less, or 100 parts by mass or less.
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、前記特定のハロゲン化亜鉛フタロシアニン色材とは異なる緑色色材を含有する場合、前記特定のハロゲン化亜鉛フタロシアニン色材とは異なる緑色色材は、適宜選択され、１種単独又は２種以上混合して用いられる。
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、前記特定のハロゲン化亜鉛フタロシアニン色材に対する、前記特定のハロゲン化亜鉛フタロシアニン色材とは異なる緑色色材の含有割合は、本発明の効果が損なわれない範囲内で所望の色度に適宜調整されればよい。所望の色度調整、輝度調整の点から、前記特定のハロゲン化亜鉛フタロシアニン色材とは異なる緑色色材の含有割合は、前記特定のハロゲン化亜鉛フタロシアニン色材を１００質量部に対して、例えば、０質量部～５０質量部であってよく、当該下限値は５質量部以上であってよく、１０質量部以上であってよく、１５質量部以上であってよく、当該上限値は３０質量部以下であってよく、２０質量部以下であってもよい。 In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, when a green colorant other than the specific halogenated zinc phthalocyanine colorant is contained, the green colorant other than the specific halogenated zinc phthalocyanine colorant is appropriately selected and used alone or in combination of two or more.
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the content ratio of the green coloring material different from the specific halogenated zinc phthalocyanine coloring material to the specific halogenated zinc phthalocyanine coloring material may be appropriately adjusted to a desired chromaticity within a range in which the effects of the present invention are not impaired. In terms of desired chromaticity adjustment and brightness adjustment, the content ratio of the green coloring material different from the specific halogenated zinc phthalocyanine coloring material may be, for example, 0 parts by mass to 50 parts by mass relative to 100 parts by mass of the specific halogenated zinc phthalocyanine coloring material, the lower limit may be 5 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, and the upper limit may be 30 parts by mass or less, or 20 parts by mass or less.
　また、本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、前記特定のハロゲン化亜鉛フタロシアニン色材以外の緑色色材を更に含有する場合、色材全体に対する前記特定のハロゲン化亜鉛フタロシアニン色材を含む緑色色材の含有割合は、所望の色度に合わせて適宜調整されればよく、特に限定されない。中でも、所望の色度調整、輝度調整の点から、色材全体に対して、前記特定のハロゲン化亜鉛フタロシアニン色材を含む緑色色材を３０質量％～９５質量％含有することが好ましく、５０質量％～８０質量％含有することがより好ましい。
　また、前記特定のハロゲン化亜鉛フタロシアニン色材を含む緑色色材に対する黄色色材の含有割合は、所望の色度に合わせて適宜調整されればよく、特に限定されない。中でも、所望の色度調整、輝度調整の点から、前記特定のハロゲン化亜鉛フタロシアニン色材を含む緑色色材を１００質量部に対して、黄色色材を５質量部～２３３質量部含有することが好ましく、１８質量部～１５０質量部含有してもよく、２５質量部～１００質量部含有してもよい。 In addition, in the green colored layer and the colored resin composition for forming the green colored layer of the present invention, when a green coloring material other than the specific halogenated zinc phthalocyanine coloring material is further contained, the content ratio of the green coloring material including the specific halogenated zinc phthalocyanine coloring material to the entire coloring material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. Among them, from the viewpoint of the desired chromaticity adjustment and brightness adjustment, it is preferable to contain 30 mass% to 95 mass% of the green coloring material including the specific halogenated zinc phthalocyanine coloring material, and more preferably 50 mass% to 80 mass%.
The content ratio of the yellow coloring material relative to the green coloring material containing the specific halogenated zinc phthalocyanine coloring material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. In particular, from the viewpoint of desired chromaticity adjustment and brightness adjustment, it is preferable to contain 5 parts by mass to 233 parts by mass of the yellow coloring material relative to 100 parts by mass of the green coloring material containing the specific halogenated zinc phthalocyanine coloring material, or it may contain 18 parts by mass to 150 parts by mass, or it may contain 25 parts by mass to 100 parts by mass.
　また、本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物においては、本発明の効果が損なわれない範囲で、色材中に、緑色色材及び黄色色材以外の他の色材を更に含んでいても良いが、前記特定のハロゲン化亜鉛フタロシアニン色材と、黄色色材との合計含有量は、色材全体に対して、７０質量％～１００質量％であってよく、中でも８０質量％～１００質量％であってよく、９０質量％～１００質量％であってよく、１００質量％であってもよい。 In addition, in the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the coloring material may further contain other coloring materials in addition to the green coloring material and the yellow coloring material, as long as the effects of the present invention are not impaired. The total content of the specific zinc halide phthalocyanine coloring material and the yellow coloring material may be 70% by mass to 100% by mass, particularly 80% by mass to 100% by mass, 90% by mass to 100% by mass, or even 100% by mass.
　本発明に係る緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、色材の含有量は、特に限定されない。色材の合計含有量は、分散性及び分散安定性の点から、緑色着色層及び当該緑色着色層形成用着色樹脂組成物の固形分全量に対して、例えば好ましくは２０質量％～５０質量％、より好ましくは２５質量％～４５質量％の範囲内である。上記下限値以上であれば、緑色着色層形成用着色樹脂組成物を所定の膜厚（通常は１．０μｍ～５．０μｍ）に塗布した際の緑色着色層が充分な色濃度を有する。また、上記上限値以下であれば、保存安定性に優れると共に、充分な硬度や、基板との密着性を有する着色層を得ることができる。特に色材濃度が高い緑色着色層を形成する場合には、色材の合計含有量は、緑色着色層及び当該緑色着色層形成用着色樹脂組成物の固形分全量に対して、好ましくは３５質量％～５０質量％、より好ましくは４０質量％～４５質量％の範囲内である。
　尚、本発明において固形分は、後述する溶剤以外のもの全てであり、溶剤中に溶解しているモノマー等も含まれる。 In the green colored layer and the colored resin composition for forming the green colored layer according to the present invention, the content of the coloring material is not particularly limited. The total content of the coloring material is, for example, preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, based on the total solid content of the green colored layer and the colored resin composition for forming the green colored layer, from the viewpoint of dispersibility and dispersion stability. If it is equal to or greater than the above lower limit, the green colored layer when the colored resin composition for forming the green colored layer is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) has a sufficient color density. Also, if it is equal to or less than the above upper limit, a colored layer having excellent storage stability, sufficient hardness, and adhesion to the substrate can be obtained. In particular, when forming a green colored layer having a high coloring material concentration, the total content of the coloring material is preferably 35% by mass to 50% by mass, more preferably 40% by mass to 45% by mass, based on the total solid content of the green colored layer and the colored resin composition for forming the green colored layer.
In the present invention, the solid content refers to everything other than the solvent described below, including monomers dissolved in the solvent.
（バインダー成分）
　本発明に用いられる着色樹脂組成物は、成膜性や被塗工面に対する密着性を付与するためにバインダー成分を含有する。塗膜に充分な硬度を付与するために、硬化性バインダー成分を含有することが好ましい。硬化性バインダー成分としては、特に限定されず、従来公知のカラーフィルタの着色層を形成するのに用いられる硬化性バインダー成分を適宜用いることができる。着色層は、バインダー成分の硬化物を含むものであって良い。
　硬化性バインダー成分としては、例えば、可視光線、紫外線、電子線等により重合硬化させることができる光硬化性樹脂を含む光硬化性バインダー成分や、加熱により重合硬化させることができる熱硬化性樹脂を含む熱硬化性バインダー成分を含むものを用いることができる。 (Binder component)
The colored resin composition used in the present invention contains a binder component to impart film-forming properties and adhesion to the coated surface. It is preferable to contain a curable binder component to impart sufficient hardness to the coating film. The curable binder component is not particularly limited, and a curable binder component used to form a colored layer of a conventionally known color filter can be appropriately used. The colored layer may contain a cured product of the binder component.
As the curable binder component, for example, a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder component containing a thermosetting resin that can be polymerized and cured by heating can be used.
　着色層を形成する際にフォトリソグラフィー工程を用いる場合には、アルカリ現像性を有する感光性バインダー成分が好適に用いられる。なお、感光性バインダー成分に、熱硬化性バインダー成分を更に用いてもよい。
　感光性バインダー成分としては、ポジ型感光性バインダー成分とネガ型感光性バインダー成分が挙げられる。ポジ型感光性バインダー成分としては、例えば、アルカリ可溶性樹脂と、感光性付与成分としてｏ－キノンジアジド基含有化合物とを含んだ組成物等が挙げられる。 When a photolithography process is used to form the colored layer, a photosensitive binder component having alkali developability is preferably used. The photosensitive binder component may further contain a thermosetting binder component.
Examples of the photosensitive binder component include a positive-type photosensitive binder component and a negative-type photosensitive binder component. Examples of the positive-type photosensitive binder component include a composition containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitivity-imparting component.
　一方、ネガ型感光性バインダー成分としては、アルカリ可溶性樹脂と、多官能モノマーと、光開始剤を少なくとも含有する組成物が好適に用いられる。
　本発明に係る着色樹脂組成物においては、ネガ型感光性バインダー成分であることが、フォトリソグラフィー法によって既存のプロセスを用いて簡便にパターンを形成できる点から好ましい。
　以下、ネガ型感光性バインダー成分を構成する、アルカリ可溶性樹脂と、多官能モノマーと、光開始剤について説明する。 On the other hand, as the negative photosensitive binder component, a composition containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
In the colored resin composition according to the present invention, a negative photosensitive binder component is preferred from the viewpoint of easily forming a pattern by a photolithography method using an existing process.
The alkali-soluble resin, the polyfunctional monomer, and the photoinitiator that constitute the negative photosensitive binder component will be described below.
（（アルカリ可溶性樹脂））
　本発明に用いられるアルカリ可溶性樹脂は酸性基を有するものであり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
　本発明において、アルカリ可溶性樹脂とは、酸価が４０ｍｇＫＯＨ／ｇ以上であることを目安にすることができる。
　本発明における好ましいアルカリ可溶性樹脂は、酸性基、通常カルボキシ基を有する樹脂であり、具体的には、例えば、カルボキシ基を有する（メタ）アクリル系共重合体及びカルボキシ基を有するスチレン－（メタ）アクリル系共重合体等の（メタ）アクリル系樹脂、カルボキシ基を有するエポキシ（メタ）アクリレート樹脂等が挙げられる。
　これらのアルカリ可溶性樹脂は、従来公知のアルカリ可溶性樹脂の中から適宜選択して用いることができる。アルカリ可溶性樹脂としては、例えば、国際公開第２０２０／０７１０４１号の段落０１５９～０１７６を参照することができる。 ((Alkali-soluble resin))
The alkali-soluble resin used in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those that are soluble in an alkaline developer used in forming a pattern.
In the present invention, an alkali-soluble resin can be defined as one having an acid value of 40 mgKOH/g or more.
The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specific examples of the alkali-soluble resin include (meth)acrylic resins such as (meth)acrylic copolymers having a carboxy group and styrene-(meth)acrylic copolymers having a carboxy group, and epoxy (meth)acrylate resins having a carboxy group.
These alkali-soluble resins can be appropriately selected from conventionally known alkali-soluble resins. For the alkali-soluble resins, for example, reference can be made to paragraphs 0159 to 0176 of WO 2020/071041.
（（光重合性化合物））
　本発明に用いられる光重合性化合物は、光開始剤によって重合可能なものであればよく、特に限定されず、通常、エチレン性不飽和結合を２つ以上有する化合物が好適に用いられ、特にアクリロイル基又はメタクリロイル基を２つ以上有する、多官能（メタ）アクリレートであることが好ましい。
　このような多官能（メタ）アクリレートとしては、従来公知の光重合性化合物の中から適宜選択して用いることができる。具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のもの等が挙げられる。また、光重合性化合物としては、例えば、国際公開第２０２０／０７１０４１号の段落０１７７～０１７９を参照することができる。 (Photopolymerizable Compound)
The photopolymerizable compound used in the present invention is not particularly limited as long as it is polymerizable by a photoinitiator. In general, a compound having two or more ethylenically unsaturated bonds is preferably used, and in particular, a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such a polyfunctional (meth)acrylate can be appropriately selected from conventionally known photopolymerizable compounds. Specific examples include those described in JP-A-2013-029832. In addition, for example, paragraphs 0177 to 0179 of WO 2020/071041 can be referred to as a photopolymerizable compound.
（（光開始剤））
　本発明の着色樹脂組成物において用いられる光開始剤としては、特に制限はなく、従来公知の各種開始剤の中から、１種又は２種以上を適宜選択して組み合わせて用いることができる。
　光開始剤としては、例えば、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α－アミノケトン、ビイミダゾール類、Ｎ，Ｎ－ジメチルアミノベンゾフェノン、ハロメチル－Ｓ－トリアジン系化合物、チオキサントン、オキシムエステル化合物等を挙げることができる。
　光開始剤としては、例えば、国際公開第２０２０／０７１０４１号の段落０１８０～０１８４を参照することができる。 (Photoinitiator)
The photoinitiator used in the colored resin composition of the present invention is not particularly limited, and one or more types may be appropriately selected from various conventionally known initiators and used in combination.
Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and oxime ester compounds.
For the photoinitiator, reference can be made to, for example, paragraphs 0180 to 0184 of WO 2020/071041.
　バインダー成分の合計含有量は、成膜性、被塗工面である基板表面への着色層の密着性の点から、着色樹脂組成物の固形分全量に対して５質量％～９０質量％、好ましくは１０質量％～８０質量％、より好ましくは２０質量％～７０質量％、更に好ましくは３０質量％～６０質量％の割合で配合するのが好ましい。 The total content of the binder components is preferably 5% to 90% by mass, preferably 10% to 80% by mass, more preferably 20% to 70% by mass, and even more preferably 30% to 60% by mass, based on the total solid content of the colored resin composition, in terms of film-forming properties and adhesion of the colored layer to the substrate surface to be coated.
（分散剤）
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物においては、色材を分散させる場合には、色材分散性と色材分散安定性の点から、分散剤を更に含んでいても良い。
　本発明において分散剤は、従来公知の分散剤の中から適宜選択して用いることができる。分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子分散剤が好ましい。 (Dispersant)
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, when a colorant is dispersed, a dispersant may be further contained from the viewpoints of colorant dispersibility and colorant dispersion stability.
In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. For example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactants can be used as the dispersant. Among the surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.
　高分子分散剤としては、例えば、ポリアクリル酸エステル等の不飽和カルボン酸エステルの（共）重合体類；ポリアクリル酸等の不飽和カルボン酸の（共）重合体の（部分）アミン塩、（部分）アンモニウム塩や（部分）アルキルアミン塩類；ヒドロキシ基含有ポリアクリル酸エステル等のヒドロキシ基含有不飽和カルボン酸エステルの（共）重合体やそれらの変性物；ポリウレタン類；不飽和ポリアミド類；ポリシロキサン類；長鎖ポリアミノアミドリン酸塩類；ポリエチレンイミン誘導体（ポリ（低級アルキレンイミン）と遊離カルボキシ基含有ポリエステルとの反応により得られるアミドやそれらの塩基）；ポリアリルアミン誘導体（ポリアリルアミンと、遊離のカルボキシ基を有するポリエステル、ポリアミド又はエステルとアミドの共縮合物（ポリエステルアミド）の３種の化合物の中から選ばれる１種以上の化合物とを反応させて得られる反応生成物）等が挙げられる。 Examples of polymeric dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides and their bases obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the following three compounds: polyesters having free carboxyl groups, polyamides, or co-condensates of esters and amides (polyesteramides)).
　中でも分散性の点から、主鎖又は側鎖に窒素原子を含み、アミン価を有する高分子分散剤としては、中でも、主鎖骨格が熱分解し難く、耐熱性が高い点から、例えば特開２０１６－２２４４４７号に記載されているような下記一般式（Ｉ）で表される構成単位を有する重合体や、国際公開２０１６／１０４４９３号に記載されているような下記一般式（Ｉ）で表される構成単位を有するブロック共重合体及び塩型ブロック共重合体の少なくとも１種である分散剤を用いてもよい。 In particular, from the viewpoint of dispersibility, as a polymer dispersant that contains nitrogen atoms in the main chain or side chain and has an amine value, a polymer having a structural unit represented by the following general formula (I) as described in JP 2016-224447 A, or a dispersant that is at least one of a block copolymer and a salt-type block copolymer having a structural unit represented by the following general formula (I) as described in WO 2016/104493 A, may be used, because the main chain skeleton is not easily thermally decomposed and has high heat resistance.
Figure JPOXMLDOC01-appb-C000015
 （一般式（Ｉ）中、Ｒ１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ２及びＲ３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ２及びＲ３が互いに結合して環構造を形成してもよい。）
Figure JPOXMLDOC01-appb-C000015
 (In general formula (I), R1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R2 and R3 each independently represent a hydrogen atom or a hydrocarbon group which may contain a heteroatom, and R2 and R3 may be bonded to each other to form a ring structure.)
　前記一般式（Ｉ）の各符号の説明や、前記一般式（Ｉ）で表される構成単位を有する共重合体や塩型共重合体については、特開２０１６－２２４４４７号や、国際公開２０１６／１０４４９３号を適宜参照することができる。
　また、分散剤の含有量についても、特開２０１６－２２４４４７号や、国際公開２０１６／１０４４９３号を適宜参照することができる。 For the explanation of each symbol in the general formula (I) and the copolymer or salt-type copolymer having a constitutional unit represented by the general formula (I), refer to JP-A-2016-224447 and WO 2016/104493 as appropriate.
In addition, the content of the dispersant can be appropriately referred to JP 2016-224447 A and WO 2016/104493 A.
（溶剤）
　本発明の着色層を形成するために用いられる着色層形成用着色樹脂組成物には、溶剤が含まれていてもよい。用いられる溶剤としては、着色樹脂組成物中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは２種以上組み合わせて使用することができる。
　溶剤の具体例や含有量としては、国際公開２０１６／１０４４９３号を適宜参照することができる。 (solvent)
The colored resin composition for forming the colored layer used to form the colored layer of the present invention may contain a solvent. The solvent to be used is not particularly limited as long as it is an organic solvent that does not react with each component in the colored resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more kinds.
For specific examples of the solvent and its content, WO 2016/104493 may be referred to as appropriate.
（増感剤）
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物においては、系内に拡散した前記特定のハロゲン化亜鉛フタロシアニン色材が、露光光を吸収し、光開始剤からのラジカル発生を損失しやすいため、それを補う点から、前記光開始剤と組み合わせて増感剤を含むことが好ましい。中でも、（メタ）アクリル重合系の反応性が良好な点から、チオール系増感剤を含むことが好ましく、前記オキシムエステル化合物の光開始剤にチオール系増感剤を組み合わせて含むことがより好ましい。 (Sensitizer)
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the specific zinc halide phthalocyanine coloring material diffused in the system absorbs exposure light and is prone to lose radical generation from the photoinitiator, so in order to compensate for this, it is preferable to include a sensitizer in combination with the photoinitiator. Among them, it is preferable to include a thiol-based sensitizer in terms of good reactivity of the (meth)acrylic polymerization system, and it is more preferable to include a thiol-based sensitizer in combination with the photoinitiator of the oxime ester compound.
　チオール系増感剤としては、チオール基が１つの単官能チオール化合物、チオール基が２つ以上の多官能チオール化合物が挙げられる。
　単官能チオール化合物としては、例えば、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、２－メルカプト－５－メトキシベンゾチアゾール、２－メルカプト－５－メトキシベンゾイミダゾール、３－メルカプトプロピオン酸、３－メルカプトプロピオン酸メチル、３－メルカプトプロピオン酸エチル、３－メルカプトプロピオン酸オクチル等が挙げられる。
　多官能チオール化合物としては、例えば、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、およびテトラエチレングリコールビス（３－メルカプトプロピオネート）等が挙げられる。 Examples of the thiol-based sensitizer include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups.
Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate.
Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、増感剤が含まれる場合の含有量としては、塗膜硬化性の点から、着色樹脂組成物の固形分全量に対して例えば、０．５質量％～１０質量％用いることができる。増感剤が含まれる場合の含有量は、着色樹脂組成物の固形分全量に対して、より好ましくは１質量％～６質量％、さらに好ましくは２質量％～５質量％の範囲内である。 In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, the content of a sensitizer, when included, can be, for example, 0.5% by mass to 10% by mass based on the total solid content of the colored resin composition from the viewpoint of coating film curability. In the case where a sensitizer is included, the content is more preferably within the range of 1% by mass to 6% by mass, and even more preferably 2% by mass to 5% by mass based on the total solid content of the colored resin composition.
（その他の成分）
　本発明の緑色着色層及び当該緑色着色層形成用着色樹脂組成物において、その他の成分としては、従来公知の着色層に用いられる成分を適宜選択して用いることができる。
　その他の成分としては、例えば、酸化防止剤、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、ハジキ防止剤、凝集防止剤、紫外線吸収剤、密着促進剤等などが挙げられる。
　酸化防止剤の具体例としては、例えば、国際公開２０１６／１０４４９３号に記載のものが挙げられる。
　また、界面活性剤及び可塑剤の具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のものが挙げられる。 (Other ingredients)
In the green colored layer and the colored resin composition for forming the green colored layer of the present invention, other components can be appropriately selected and used from components used in conventionally known colored layers.
Examples of other components include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, cissing inhibitors, aggregation inhibitors, ultraviolet absorbers, and adhesion promoters.
Specific examples of the antioxidant include those described in WO 2016/104493.
Specific examples of the surfactant and plasticizer include those described in JP-A-2013-029832.
＜青色着色層＞
　本発明に用いられる青色着色層は、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含む。
　青色着色層は、前記特定のレーキ色材を含む色材と、バインダー成分と、必要に応じて分散剤と、溶剤と、更に他の成分を含んでよい着色樹脂組成物の硬化物であってよい。
　以下、青色着色層及び青色着色層形成用樹脂組成物に含まれる各成分について、説明するが、バインダー成分、溶剤、及びその他の成分については、前記緑色着色層と同様であってよいので、ここでの説明を省略する。 <Blue colored layer>
The blue colored layer used in the present invention contains at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2).
The blue colored layer may be a cured product of a colored resin composition that contains a color material including the specific lake color material, a binder component, and optionally a dispersant, a solvent, and further other components.
Below, the blue colored layer and each component contained in the resin composition for forming the blue colored layer will be described, but since the binder component, solvent, and other components may be the same as those of the green colored layer, their description will be omitted here.
（色材）
　青色着色層における色材は、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含み、さらに他の色材を含んでもよい。 (Coloring material)
The coloring material in the blue colored layer includes at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1-1) and the coloring material represented by the general formula (1-2), and may further include other coloring materials.
（（前記レーキ色材））
　前記一般式（１－１）で表される色材は、２価以上のアニオンと、２価以上のカチオンとを含むため、当該色材の凝集体においては、アニオンとカチオンが単に１分子対１分子でイオン結合しているのではなく、イオン結合を介して複数の分子が会合する分子会合体を形成し得ることから、見かけの分子量が、従来のレーキ顔料の分子量に比べて格段に増大する。このような分子会合体の形成により固体状態での凝集力がより高まり、熱運動を低下させ、イオン対の解離やカチオン部の分解を抑制でき、従来のレーキ顔料に比べて退色し難いと推定される。 ((The above-mentioned lake color material))
Since the colorant represented by the general formula (1-1) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the colorant, the anion and the cation are not simply ionic bonded one molecule to one molecule, but a molecular association in which a plurality of molecules associate via ionic bonds can be formed, so that the apparent molecular weight is significantly increased compared to the molecular weight of conventional lake pigments. The formation of such a molecular association increases the cohesive force in the solid state, reduces thermal motion, and suppresses dissociation of ion pairs and decomposition of the cation moiety, and it is presumed that the colorant is less prone to fading than conventional lake pigments.
　前記一般式（１－１）におけるＡは、Ｎ（窒素原子）と直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ（酸素原子）、Ｓ（硫黄原子）、Ｎ（窒素原子）等のヘテロ原子が含まれていてもよいものである。すなわち、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎ等のヘテロ原子が含まれてもよい脂肪族炭化水素基、又は、Ｎと直接結合する末端に脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎ等のヘテロ原子が含まれてもよい芳香族基を表す。Ｎと直接結合する炭素原子がπ結合を有しないため、カチオン性の発色部位が有する色調や透過率等の色特性は、連結基Ａや他の発色部位の影響を受けず、単量体と同様の色を保持することができる。 　A in the general formula (1-1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. That is, the organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, and N in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, and N in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color properties such as color tone and transmittance of the cationic color-developing moiety are not affected by the linking group A or other color-developing moieties, and can maintain the same color as the monomer.
　Ａにおいて、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基は、Ｎと直接結合する末端の炭素原子がπ結合を有しなければ、直鎖、分岐又は環状のいずれであってもよく、末端以外の炭素原子が不飽和結合を有していてもよく、置換基を有していてもよく、炭素鎖中に、Ｏ、Ｓ、Ｎが含まれていてもよい。例えば、カルボニル基、カルボキシ基、オキシカルボニル基、アミド基等が含まれていてもよく、水素原子が更にハロゲン原子等に置換されていてもよい。
　また、Ａにおいて上記脂肪族炭化水素基を有する芳香族基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基を有する、単環又は多環芳香族基が挙げられ、置換基を有していてもよく、Ｏ、Ｓ、Ｎが含まれる複素環であってもよい。
　中でも、骨格の堅牢性の点から、Ａは、環状の脂肪族炭化水素基又は芳香族基を含むことが好ましい。
　環状の脂肪族炭化水素基としては、シクロヘキサン、シクロペンタン、ノルボルナン、ビシクロ［２．２．２］オクタン、トリシクロ［５．２．１．０２，６］デカン、アダマンタンを含む基等が挙げられる。また、芳香族基としては、例えば、ベンゼン環、ナフタレン環を含む基等が挙げられる。例えば、Ａが２価の有機基の場合、炭素数１～２０の直鎖、分岐、又は環状のアルキレン基や、キシリレン基等の炭素数１～２０のアルキレン基を２個置換した芳香族基等が挙げられる。 In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be linear, branched or cyclic, as long as the terminal carbon atom directly bonded to N does not have a π bond, and a carbon atom other than the terminal may have an unsaturated bond or may have a substituent, and the carbon chain may contain O, S or N. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
In addition, the aromatic group having an aliphatic hydrocarbon group for A includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, which may have a substituent and may be a heterocycle containing O, S or N.
Among these, from the viewpoint of the robustness of the skeleton, it is preferable that A contains a cyclic aliphatic hydrocarbon group or an aromatic group.
Examples of the cyclic aliphatic hydrocarbon group include groups containing cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2,6 ]decane, and adamantane. Examples of the aromatic group include groups containing a benzene ring and a naphthalene ring. For example, when A is a divalent organic group, examples of the aromatic group include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, and aromatic groups substituted with two alkylene groups having 1 to 20 carbon atoms, such as xylylene groups.
　本発明においては、堅牢性と、分子運動の自由度を両立して、耐熱性を向上する点から、Ａが、２個以上の環状脂肪族炭化水素基を有し、Ｎと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基であることが好ましい。Ａは、２個以上のシクロアルキレン基を有し、Ｎと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基であることがより好ましく、中でも、２個以上の環状脂肪族炭化水素基が直鎖又は分岐の脂肪族炭化水素基で連結した構造を有することが更に好ましい。
　２個以上ある環状脂肪族炭化水素基は、それぞれ同一であっても異なっていてもよく、例えば、前記環状の脂肪族炭化水素基と同様のものが挙げられ、中でもシクロヘキサン、シクロペンタンが好ましい。 In the present invention, from the viewpoint of improving heat resistance by achieving both robustness and freedom of molecular motion, it is preferable that A is an aliphatic hydrocarbon group having two or more cyclic aliphatic hydrocarbon groups, having a saturated aliphatic hydrocarbon group at an end directly bonded to N, and the carbon chain may contain O, S, or N. It is more preferable that A is an aliphatic hydrocarbon group having two or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at an end directly bonded to N, and the carbon chain may contain O, S, or N, and among these, it is even more preferable that A has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.
The two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include the same cyclic aliphatic hydrocarbon groups as those mentioned above, with cyclohexane and cyclopentane being preferred.
　本発明においては、耐熱性の点から、中でも、前記Ａが、下記一般式（１ａ）で表される置換基であることが好ましい。 In the present invention, from the viewpoint of heat resistance, it is particularly preferable that A is a substituent represented by the following general formula (1a).
Figure JPOXMLDOC01-appb-C000016
 （一般式（１ａ）中、Ｒｘｉは置換基として炭素数１以上４以下のアルキル基、又は炭素数１以上４以下のアルコキシ基を有してもよい炭素数１以上３以下のアルキレン基を表し、Ｒｘｉｉ及びＲｘｉｉｉは各々独立に炭素数１以上４以下のアルキル基、又は炭素数１以上４以下のアルコキシ基を表し、ｐは１以上３以下の整数を、ｑ及びｒは各々独立に０以上４以下の整数を表す。Ｒｘｉ、Ｒｘｉｉ、Ｒｘｉｉｉ及びｒが複数ある場合、当該複数あるＲｘｉ、Ｒｘｉｉ、Ｒｘｉｉｉ及びｒは互いに同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000016
 (In general formula (1a), R xi represents an alkylene group having 1 to 3 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent; R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; p represents an integer of 1 to 3; and q and r each independently represent an integer of 0 to 4. When there are a plurality of R xi , R xii , R xiii , and r, the plurality of R xi , R xii , R xiii , and r may be the same or different from each other.)
　堅牢性と、発色部位の熱運動との両立に優れ、耐熱性が向上する点から、Ｒｘｉにおける炭素数１以上３以下のアルキレン基であることが好ましい。このようなアルキレン基としては、メチレン基、エチレン基、プロピレン基等が挙げられ、中でもメチレン基又はエチレン基が好ましく、メチレン基がより好ましい。
　炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。
　また、炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。 From the viewpoint of achieving excellent compatibility between fastness and thermal motion of the color-forming site and improving heat resistance, R xi is preferably an alkylene group having 1 to 3 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group. Among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and the alkyl group may be linear or branched.
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and the alkoxy group may be linear or branched.
　Ｒｘｉｉ及びＲｘｉｉｉにおける、炭素数１以上４以下のアルキル基、及び、炭素数１以上４以下のアルコキシ基は、前記Ｒｘｉが有してもよい置換基と同様のものが挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms in R xii and R xiii are the same as the substituents that may be possessed by R xi .
　一般式（１ａ）において、シクロヘキサン（シクロヘキシレン基）は２個以上４個以下、即ち、ｐが１以上３以下であることが、耐熱性の点から好ましく、中でもｐが１以上２以下であることがより好ましい。
　またシクロヘキシレン基が有する置換基Ｒｘｉｉ及びＲｘｉｉｉの置換数は、特に限定されないが、耐熱性の点から、１個以上３個以下であることが好ましく、１個以上２個以下であることがより好ましい。即ちｑ及びｒが１以上３以下の整数であることが好ましく、ｑ及びｒが１以上２以下の整数であることが好ましい。 In the general formula (1a), it is preferable that the number of cyclohexane (cyclohexylene group) is 2 or more and 4 or less, that is, p is 1 or more and 3 or less, from the viewpoint of heat resistance, and it is more preferable that p is 1 or more and 2 or less.
The number of substituents R xii and R xiii in the cyclohexylene group is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 to 3, more preferably 1 to 2. That is, q and r are preferably integers of 1 to 3, more preferably q and r are integers of 1 to 2.
　このような連結基Ａの好適な具体例としては、以下のものが挙げられるが、これらに限定されるものではない。 Specific examples of suitable linking groups A include, but are not limited to, the following:
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　Ｒｉ～Ｒｖにおけるアルキル基は、特に限定されない。例えば、炭素数１～２０の直鎖、分岐状又は環状のアルキル基等が挙げられ、中でも、炭素数が１～８の直鎖又は分岐のアルキル基であることが挙げられ、炭素数が１～５の直鎖又は分岐のアルキル基であることが、輝度及び耐熱性の点から挙げられ、Ｒｉ～Ｒｖにおけるアルキル基がエチル基又はメチル基であることが挙げられる。アルキル基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられ、置換されたアルキル基としては、ベンジル基のようなアラルキル基等が挙げられる。
　Ｒｉ～Ｒｖにおけるアリール基は、特に限定されない。例えば、フェニル基、ナフチル基等が挙げられる。アリール基が有してもよい置換基としては、例えばアルキル基、ハロゲン原子、アルコキシ基、水酸基等が挙げられる。
　中でも化学的安定性の点からＲｉ～Ｒｖとしては、各々独立に、水素原子、炭素数１～５のアルキル基、フェニル基、又は、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合してピロリジン環、ピペリジン環、モルホリン環を形成していることが好ましい。 The alkyl group in R i to R v is not particularly limited. For example, it may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, among which a linear or branched alkyl group having 1 to 8 carbon atoms may be used. From the viewpoint of brightness and heat resistance, a linear or branched alkyl group having 1 to 5 carbon atoms may be used. The alkyl group in R i to R v may be an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, but may be, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, or the like. As the substituted alkyl group, an aralkyl group such as a benzyl group may be used.
The aryl group in R i to R v is not particularly limited. Examples thereof include a phenyl group and a naphthyl group. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group.
Among these, from the viewpoint of chemical stability, it is preferable that R i to R v each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or that R ii and R iii , and R iv and R v are bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.
　耐熱性の点からは、Ｒｉｉ～Ｒｖのうち少なくとも一つが、置換基を有してもよいシクロアルキル基、又は、置換基を有していてもよいアリール基であることが好ましい。Ｒｉｉ～Ｒｖのうち少なくとも一つが、シクロアルキル基、又は、アリール基を有することにより、立体障害による分子間相互作用が低減するため、発色部位の熱に対する影響を抑制できるため、耐熱性に優れていると考えられる。 From the viewpoint of heat resistance, it is preferable that at least one of R ii to R v is a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. By having at least one of R ii to R v be a cycloalkyl group or an aryl group, intermolecular interactions due to steric hindrance are reduced, and the effect of heat on the color-developing site can be suppressed, which is considered to result in excellent heat resistance.
　耐熱性の点からは、Ｒｉｉ～Ｒｖのうち少なくとも一つが、下記一般式（１ｂ）又は、下記一般式（１ｃ）で表される置換基であることが好ましい。 From the viewpoint of heat resistance, it is preferable that at least one of R ii to R v is a substituent represented by the following general formula (1b) or (1c).
Figure JPOXMLDOC01-appb-C000018
 （一般式（１ｂ）中、Ｒｘｉｖ、Ｒｘｖ、及びＲｘｖｉは各々独立に水素原子、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基を表す。）
Figure JPOXMLDOC01-appb-C000018
 (In general formula (1b), R xiv , R xv , and R xvi each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.)
Figure JPOXMLDOC01-appb-C000019
 （一般式（１ｃ）中、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘは各々独立に水素原子、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基を表す。）
Figure JPOXMLDOC01-appb-C000019
 (In general formula (1c), R xvii , R xviii , and R xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.)
　Ｒｘｉｖ、Ｒｘｖ、Ｒｘｖｉ、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘにおける炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。また、炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。
　前記アルキル基及びアルコキシ基が有してもよい置換基としては、ハロゲン原子、水酸基等が挙げられる。 In R xiv , R xv , R xvi , R xvii , R xviii , and R xix , the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. In addition, the alkoxy group having 1 to 4 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched.
Examples of the substituent that the alkyl group and alkoxy group may have include a halogen atom and a hydroxyl group.
　前記一般式（１ｂ）で表される置換基を有する場合、耐熱性の点から、Ｒｘｉｖ、Ｒｘｖ、及びＲｘｖｉの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることが好ましく、Ｒｘｉｖ及びＲｘｖの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることがより好ましい。 When the substituent represented by the general formula (1b) is present, from the viewpoint of heat resistance, it is preferable that at least one of R xiv , R xv , and R xvi is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and it is more preferable that at least one of R xiv and R xv is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
　また前記一般式（１ｃ）で表される置換基を有する場合、耐熱性の点から、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることが好ましく、Ｒｘｖｉｉ及びＲｘｖｉｉｉの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることがより好ましい。 In addition, when the substituent represented by the general formula (1c) is present, from the viewpoint of heat resistance, it is preferable that at least one of R xvii , R xviii , and R xix is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and it is more preferable that at least one of R xvii and R xviii is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
　一般式（１ｂ）で表される置換基、及び、一般式（１ｃ）で表される置換基の好適な具体例としては、以下のものが挙げられるが、これらに限定されるものではない。 Specific examples of suitable substituents represented by general formula (1b) and general formula (1c) include, but are not limited to, the following:
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　Ｒｖｉ及びＲｖｉｉは各々独立に置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ｒｖｉ及びＲｖｉｉにおけるアルキル基としては、特に限定されないが、炭素数が１以上８以下の直鎖、又は分岐を有するアルキル基であることが好ましく、炭素数が１以上４以下のアルキル基であることがより好ましい。炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。アルキル基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。
　また、Ｒｖｉ及びＲｖｉｉにおけるアルコキシ基としては、特に限定されないが、炭素数が１以上８以下の直鎖、又は分岐を有するアルコキシ基であることが好ましく、炭素数が１以上４以下のアルコキシ基であることがより好ましい。炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。アルコキシ基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。
　Ｒｖｉ及びＲｖｉｉにおけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　Ｒｖｉ及びＲｖｉｉの置換数、即ち、ｆ及びｇはそれぞれ独立に０以上４以下の整数を表し、中でも０以上２以下であることが好ましく、０以上１以下であることがより好ましい。複数あるｆ及びｇはそれぞれ同一であっても異なっていてもよい。
　また、Ｒｖｉ及びＲｖｉｉは、トリアリールメタン骨格、又は、キサンテン骨格内の共鳴構造を有する芳香環のいずれの部位に置換されていてもよいが、中でも、－ＮＲｉｉＲｉｉｉ又は－ＮＲｉｖＲｖで表されるアミノ基の置換位置を基準にメタ位に置換されていることが好ましい。 R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched. The substituent that the alkyl group may have is not particularly limited, but examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
The alkoxy group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched. Examples of the substituent that the alkoxy group may have include, but are not particularly limited to, an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
Examples of the halogen atom in R vi and R vii include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of substitutions of R vi and R vii , that is, f and g each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 to 1. A plurality of f and g may be the same or different.
Furthermore, R vi and R vii may be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, and in particular, they are preferably substituted at the meta position based on the substitution position of the amino group represented by -NR ii R iii or -NR iv R v .
　Ａｒ１における２価の芳香族基は特に限定されない。Ａｒ１における芳香族基は、炭素環からなる芳香族炭化水素基の他、複素環基であってもよい。芳香族炭化水素基における芳香族炭化水素としては、ベンゼン環の他、ナフタレン環、テトラリン環、インデン環、フルオレン環、アントラセン環、フェナントレン環等の縮合多環芳香族炭化水素；ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環式炭化水素が挙げられる。当該鎖状多環式炭化水素においては、ジフェニルエーテル等のように鎖状骨格中にＯ、Ｓ、Ｎを有していてもよい。一方、複素環基における複素環としては、フラン、チオフェン、ピロール、オキサゾール、チアゾール、イミダゾール、ピラゾール等の５員複素環；ピラン、ピロン、ピリジン、ピロン、ピリダジン、ピリミジン、ピラジン等の６員複素環；ベンゾフラン、チオナフテン、インドール、カルバゾール、クマリン、ベンゾ－ピロン、キノリン、イソキノリン、アクリジン、フタラジン、キナゾリン、キノキサリン等の縮合多環式複素環が挙げられる。これらの芳香族基は更に置換基として、アルキル基、アルコキシ基、水酸基、ハロゲン原子、及び、これらで置換されていても良いフェニル基等を有していてもよい。 The divalent aromatic group in Ar 1 is not particularly limited. The aromatic group in Ar 1 may be a heterocyclic group in addition to an aromatic hydrocarbon group consisting of a carbon ring. Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring, as well as benzene ring; and chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, or N in the chain skeleton, such as diphenyl ether. On the other hand, examples of the heterocycle in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, etc., 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, etc., and condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline, etc. These aromatic groups may further have, as a substituent, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a phenyl group which may be substituted therewith, etc.
　１分子内に複数あるＲｉ～Ｒｖｉｉ及びＡｒ１は、同一であっても異なっていてもよい。Ｒｉ～Ｒｖｉｉ及びＡｒ１の組み合わせにより、所望の色に調整することができる。 A plurality of R i to R vii and Ar 1 present in one molecule may be the same or different. Depending on the combination of R i to R vii and Ar 1 , a desired color can be adjusted.
　Ａにおける価数ａは、カチオンを構成する発色性カチオン部位の数であり、ａは２以上の整数である。このレーキ色材においては、カチオンの価数ａが２以上であるため、耐熱性に優れており、中でも、カチオンの価数ａが３以上であることが好ましい。ａの上限は特に限定されないが、製造の容易性の点から、ａが４以下であることが好ましく、３以下であることがより好ましい。 The valence a in A is the number of color-developing cationic moieties that make up the cation, and a is an integer of 2 or more. In this lake colorant, the cation valence a is 2 or more, so it has excellent heat resistance, and it is preferable that the cation valence a is 3 or more. There is no particular upper limit for a, but from the viewpoint of ease of production, it is preferable that a is 4 or less, and more preferably 3 or less.
　一般式（Ａ）で表されるカチオンは、耐熱性に優れ、加熱時の色変化が抑制され易い点から、分子量が１２００以上であることが好ましく、１３００以上であることが好ましい。 The cation represented by general formula (A) has excellent heat resistance and is easily prevented from changing in color when heated, so it is preferable that the molecular weight is 1200 or more, and preferably 1300 or more.
　一般式（１－１）で表される色材において、アニオン部（Ｂｃ－）は、高輝度で耐熱性に優れる点から、ｃ価のポリ酸アニオンであって、２価以上のアニオンである。ｃの上限値は限定されないが、製造の容易性の点から、６以下の整数であってよい。 In the color material represented by the general formula (1-1), the anion moiety (B c- ) is a c-valent polyacid anion, and is a divalent or higher anion, from the viewpoints of high luminance and excellent heat resistance. The upper limit of c is not limited, but may be an integer of 6 or less from the viewpoint of ease of production.
　複数のオキソ酸が縮合したポリ酸アニオンとしては、イソポリ酸アニオン（ＭｍＯｎ）ｃ－であってもヘテロポリ酸アニオン（ＸｌＭｍＯｎ）ｃ－であってもよい。上記イオン式中、Ｍはポリ原子、Ｘはヘテロ原子、ｍはポリ原子の組成比、ｎは酸素原子の組成比を表す。ポリ原子Ｍとしては、例えば、Ｍｏ、Ｗ、Ｖ、Ｔｉ、Ｎｂ等が挙げられる。またヘテロ原子Ｘとしては、例えば、Ｓｉ、Ｐ、Ａｓ、Ｓ、Ｆｅ、Ｃｏ等が挙げられる。また、一部にＮａ＋やＨ＋等の対カチオンが含まれていてもよい。
　中でも、耐熱性に優れる点から、タングステン（Ｗ）及びモリブデン（Ｍｏ）より選択される１種以上の元素を有するポリ酸であることが好ましい。
　このようなポリ酸としては、例えば、イソポリ酸である、タングステン酸イオン［Ｗ１０Ｏ３２］４－、モリブデン酸イオン［Ｍｏ６Ｏ１９］２－や、ヘテロポリ酸である、リンタングステン酸イオン［ＰＷ１２Ｏ４０］３－、［Ｐ２Ｗ１８Ｏ６２］６－、ケイタングステン酸イオン［ＳｉＷ１２Ｏ４０］４－、リンモリブデン酸イオン［ＰＭｏ１２Ｏ４０］３－、ケイモリブデン酸イオン［ＳｉＭｏ１２Ｏ４０］４－、リンタングストモリブデン酸イオン［ＰＷ１２－ｓＭｏｓＯ４０］３－（ｓは１以上１１以下の整数）、［Ｐ２Ｗ１８－ｔＭｏｔＯ６２］６－（ｔは１以上１７以下の整数）、ケイタングストモリブデン酸イオン［ＳｉＷ１２－ｕＭｏｕＯ４０］４－（ｕは１以上１１以下の整数）等が挙げられる。タングステン（Ｗ）及びモリブデン（Ｍｏ）の少なくとも１種を含むポリ酸としては、耐熱性の点、及び原料入手の容易さの点から、上記の中でもヘテロポリ酸であることが好ましく、更にリン（Ｐ）を含むヘテロポリ酸であることがより好ましい。
　さらに、リンタングストモリブデン酸イオン［ＰＷ１０Ｍｏ２Ｏ４０］３－、［ＰＷ１１Ｍｏ１Ｏ４０］３－、リンタングステン酸イオン［ＰＷ１２Ｏ４０］３－、のいずれかであることが耐熱性の点からさらに好ましい。 The polyacid anion formed by condensing a plurality of oxoacids may be an isopolyacid anion ( MmOn ) c- or a heteropolyacid anion ( XlMmOn ) c- . In the above ionic formula, M represents a polyatom, X represents a heteroatom , m represents the composition ratio of the polyatoms, and n represents the composition ratio of the oxygen atoms. Examples of the polyatom M include Mo, W, V, Ti, and Nb. Examples of the heteroatom X include Si, P, As, S, Fe, and Co. In addition, a counter cation such as Na + or H + may be partially contained.
Among these, polyacids having one or more elements selected from tungsten (W) and molybdenum (Mo) are preferred because of their excellent heat resistance.
Examples of such polyacids include isopolyacids such as tungstate ion [W 10 O 32 ] 4− and molybdate ion [Mo 6 O 19 ] 2− , and heteropolyacids such as phosphotungstate ion [PW 12 O 40 ] 3− , [P 2 W 18 O 62 ] 6− , silicotungstate ion [SiW 12 O 40 ] 4− , phosphomolybdate ion [PMo 12 O 40 ] 3− , silicomolybdate ion [SiMo 12 O 40 ] 4− , and phosphotungstomolybdate ion [PW 12 -s Mo s O 40 ] 3− (s is an integer of 1 to 11), [P 2 W 18-t Mo t O 62 ] 6− . (t is an integer of 1 or more and 17 or less), and silicotungstomolybdate ion [SiW 12-u Mo u O 40 ] 4- (u is an integer of 1 or more and 11 or less). As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), from the viewpoints of heat resistance and ease of availability of raw materials, heteropolyacids are preferable among the above, and heteropolyacids containing phosphorus (P) are more preferable.
Furthermore, any one of phosphotungstomolybdate ion [PW 10 Mo 2 O 40 ] 3− , [PW 11 Mo 1 O 40 ] 3− , and phosphotungstate ion [PW 12 O 40 ] 3− is more preferable from the viewpoint of heat resistance.
　一般式（１－１）におけるｂはカチオンの数を、ｄは分子会合体中のアニオンの数を示し、ｂ及びｄは１以上の整数を表す。ｂが２以上の場合、分子会合体中に複数あるカチオンは、１種単独であっても、２種以上が組み合わされていてもよい。また、ｄが２以上の場合、分子会合体中に複数あるアニオンは、１種単独であっても、２種以上が組み合わされていてもよい。ｂの上限値は限定されないが、製造の容易性の点から、６以下の整数であってよい。また、ｄの上限値は限定されないが、製造の容易性の点から、４以下の整数であってよい。 In general formula (1-1), b represents the number of cations, d represents the number of anions in the molecular association, and b and d represent integers of 1 or more. When b is 2 or more, the multiple cations in the molecular association may be of one type alone or a combination of two or more types. When d is 2 or more, the multiple anions in the molecular association may be of one type alone or a combination of two or more types. The upper limit of b is not limited, but may be an integer of 6 or less from the viewpoint of ease of production. The upper limit of d is not limited, but may be an integer of 4 or less from the viewpoint of ease of production.
　一般式（１－１）におけるｅは、０又は１の整数であり、ｅが０のとき結合は存在しない。ｅ＝０はトリアリールメタン骨格を表し、ｅ＝１はキサンテン骨格を表す。複数あるｅは同一であっても異なっていてもよい。本発明に用いられる一般式（１－１）で表されるレーキ色材においては、少なくともトリアリールメタン骨格を含むものが好適に用いられる。
　なお、一般式（１－１）で表されるレーキ色材としては、例えば、国際公開第２０１２／１４４５２０号パンフレット、国際公開第２０１８／００３７０６号パンフレットを参考にして調製することができる。 In the general formula (1-1), e is an integer of 0 or 1, and when e is 0, there is no bond. e=0 represents a triarylmethane skeleton, and e=1 represents a xanthene skeleton. Multiple e's may be the same or different. In the lake colorant represented by the general formula (1-1) used in the present invention, one containing at least a triarylmethane skeleton is preferably used.
The lake colorant represented by the general formula (1-1) can be prepared by referring to, for example, International Publication No. 2012/144520 and International Publication No. 2018/003706.
　一方、一般式（１－２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよいものである。ＲＩ～ＲＶＩは各々、前述の一般式（１－１）のＲｉ～Ｒｖと同様であって良い。
　一般式（１－２）中、ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表すが、これらも前述の一般式（１－１）のＲｖｉ及びＲｖｉｉと同様であって良い。
　一般式（１－２）中、Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表すが、当該Ａｒ２は、前述の一般式（１－１）のＡｒ１のうち、芳香族複素環基と同様であって良い。
　また、一般式（１－２）中、Ｅｍ－はｍ価のポリ酸アニオンを表すが、当該ｍ価のポリ酸アニオンは、前述の一般式（１－１）のｃ価のポリ酸アニオンと同様であって良い。 On the other hand, in the general formula (1-2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure. R I to R VI may each be the same as R i to R v in the general formula (1-1) described above.
In the general formula (1-2), R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group, and these may be the same as R vi and R vii in the general formula (1-1) described above.
In the general formula (1-2), Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and Ar 2 may be the same as the aromatic heterocyclic group of Ar 1 in the above-mentioned general formula (1-1).
In addition, in the general formula (1-2), E m- represents an m-valent polyacid anion, and the m-valent polyacid anion may be the same as the c-valent polyacid anion in the above-mentioned general formula (1-1).
　一般式（１－２）中、ｍは、カチオンの数及びアニオンの数を示し、２以上の整数を表す。一般式（１－２）中に複数あるカチオンは、１種単独であっても、２種以上が組み合わされていてもよい。また、アニオンについても、１種単独であっても、２種以上が組み合わされていてもよい。
　一般式（１－２）中、ｊは０又は１であり、ｊが０のとき結合は存在しない。一般式（１－２）中のｊは、前述の一般式（１－１）のｅと同様であって良い。また、一般式（１－２）中のｋ及びｌは、前述の一般式（１－１）のｆ及びｇと同様であって良い。
　なお、一般式（１－２）で表されるレーキ色材としては、例えば、特開２０１７－１６０９９号公報を参考にして調製することができる。 In the general formula (1-2), m represents the number of cations and the number of anions, and is an integer of 2 or more. The multiple cations in the general formula (1-2) may be one type alone or two or more types in combination. Similarly, the anions may be one type alone or two or more types in combination.
In the general formula (1-2), j is 0 or 1, and when j is 0, no bond exists. j in the general formula (1-2) may be the same as e in the general formula (1-1) described above. Furthermore, k and l in the general formula (1-2) may be the same as f and g in the general formula (1-1) described above.
The lake colorant represented by the general formula (1-2) can be prepared, for example, by referring to JP-A-2017-16099.
（（他の色材））
　本発明の青色着色層及び青色着色層形成用着色樹脂組成物において、色材は、本発明の効果を損なわない範囲で、色調を調整するために、前記特定のレーキ色材の他に、更に他の色材を含んでもよい。
　他の色材としては公知の顔料、染料、レーキ色材等を、単独で又は２種以上混合して用いることができる。 ((Other colorants))
In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, the coloring material may contain, in addition to the specific lake coloring material, other coloring materials in order to adjust the color tone within a range that does not impair the effects of the present invention.
As the other coloring materials, known pigments, dyes, lake coloring materials, etc. can be used alone or in combination of two or more kinds.
　他の色材としては、中でも他の青色色材、紫色色材、赤色色材が好ましく用いられるがこれらに限定されるものではない。
　他の青色色材として、Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６等公知の有機青色顔料、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材とは異なるトリアリールメタン系レーキ色材等。
　紫色色材として、Ｃ．Ｉ．ピグメントバイオレット１、１４、１５、１９、２３、２９、３２、３３、３６、３７、３８等の公知の有機紫色顔料。
　赤色乃至赤紫色色材として、例えば、国際公開第２０２０／０７１０４１号公報、特開２０１８－１００３２３号公報、国際公開第２０１４／１２３１２５号公報等に記載等のキサンテン染料及びキサンテン系染料のレーキ色材等。 As the other coloring materials, among others, other blue coloring materials, purple coloring materials, and red coloring materials are preferably used, but are not limited thereto.
Other blue colorants include known organic blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and triarylmethane lake colorants different from the colorants represented by the general formula (1-1) and the colorants represented by the general formula (1-2).
As purple colorants, known organic purple pigments such as C.I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.
Examples of red to reddish purple colorants include xanthene dyes and xanthene-based dye lake colorants described in, for example, WO 2020/071041, JP 2018-100323, WO 2014/123125, and the like.
　他の色材としては、中でも、混合安定性の点から、塩基性処理された青色フタロシアニン顔料であることが好ましい。塩基性処理された青色フタロシアニン顔料とは、塩基性化合物に由来する構造を有する青色フタロシアニン顔料をいう。
　塩基性化合物に由来する構造を有する青色フタロシアニン顔料としては、例えば、塩基性部位を有する色材誘導体等の塩基性化合物を含む青色フタロシアニン顔料が好適なものとして挙げられる。
　塩基性処理に用いられるフタロシアニン顔料としては、比較的輝度に優れる点から、銅フタロシアニン顔料が好ましい。塩基性処理に用いられる銅フタロシアニン顔料としては、粗製銅フタロシアニン顔料であっても良いし、α型、β型、γ型、ε型などの結晶構造を有する銅フタロシアニン顔料であっても良い。塩基性処理に用いられる銅フタロシアニン顔料としては、中でも、分散安定性に優れる点から、ε型の結晶構造を有する銅フタロシアニン顔料、及びβ型の結晶構造を有する銅フタロシアニン顔料よりなる群から選択される１種以上であることが好ましい。 Among the other coloring materials, a basic-treated blue phthalocyanine pigment is preferable from the viewpoint of mixing stability. The basic-treated blue phthalocyanine pigment refers to a blue phthalocyanine pigment having a structure derived from a basic compound.
As a blue phthalocyanine pigment having a structure derived from a basic compound, for example, a blue phthalocyanine pigment containing a basic compound such as a colorant derivative having a basic site can be mentioned as a suitable example.
The phthalocyanine pigment used in the basic treatment is preferably a copper phthalocyanine pigment, because it has relatively excellent brightness. The copper phthalocyanine pigment used in the basic treatment may be a crude copper phthalocyanine pigment, or may be a copper phthalocyanine pigment having an α-type, β-type, γ-type, ε-type, or other crystal structure. The copper phthalocyanine pigment used in the basic treatment is preferably at least one selected from the group consisting of a copper phthalocyanine pigment having an ε-type crystal structure and a copper phthalocyanine pigment having a β-type crystal structure, because it has excellent dispersion stability.
　前記塩基性処理には、塩基性部位を有する色材誘導体や、塩基性部位を有する無色化合物の誘導体が好適に用いられる。
　本発明において、塩基性部位を有するとは、置換基として塩基性基を有する態様、置換基において酸性基と塩基性化合物とが塩形成している態様等が挙げられる。
　本発明で色材誘導体又は無色化合物の誘導体が有する塩基性部位としては、例えば、アミノ基、スルホン酸アンモニウム塩、又は、アミノ基を有するスルホンアミド基、アミノ基を有するアミド基、塩基性複素環基等が挙げられる。
　前記塩基性処理としては、国際公開第２０２０／０７１０４１号の段落００６４～００７７を参照して行うことができる。 In the basic treatment, a colorant derivative having a basic site or a derivative of a colorless compound having a basic site is preferably used.
In the present invention, the term "having a basic site" refers to an embodiment in which a basic group is present as a substituent, or an embodiment in which an acidic group in the substituent forms a salt with a basic compound, etc.
In the present invention, examples of the basic site possessed by the colorant derivative or the derivative of the colorless compound include an amino group, an ammonium sulfonate, a sulfonamide group having an amino group, an amide group having an amino group, a basic heterocyclic group, and the like.
The basic treatment can be carried out with reference to paragraphs 0064 to 0077 of WO 2020/071041.
　本発明の青色着色層及び当該青色着色層形成用着色樹脂組成物において、色材全体に対する前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有割合は、所望の色度に合わせて適宜調整されればよく、特に限定されず、前記レーキ色材を含む色材全体に対して、１００質量％であってもよい。本発明の青色着色層及び当該青色着色層形成用着色樹脂組成物において、他の色材を含有する場合には、所望の色度調整の点から、前記レーキ色材を含む色材全体に対して、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有割合は１５質量％以上であってよい。所望の色度に合わせながら、残渣発生を抑制し、輝度も向上する点から、色材全体に対して、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有割合は、１９質量％以上であってよく、２８質量％以上であってよく、４０質量％以上であってよく、５０質量％以上であってよい。他の色材を含有する場合に、前記レーキ色材を含む色材全体に対して、前記一般式（１－１）で表される色材及び前記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有割合の上限値は、特に限定されるものではないが、所望の色度に調整する点から、９５質量％以下であってよく、８５質量％以下であってよく、８０質量％以下であってよい。
　本発明の青色着色層及び当該青色着色層形成用着色樹脂組成物において、前記レーキ色材を含む色材全体に対して、他の色材は０質量％であってもよい。本発明の青色着色層及び当該青色着色層形成用着色樹脂組成物において、他の色材を含有する場合には、所望の色度調整の点から、前記レーキ色材を含む色材全体に対して、他の色材は、５質量％以上であってよく、１５質量％以上であってよく、２０質量％以上であってよい。所望の色度に合わせながら、残渣発生を抑制し、輝度も向上する点から、前記レーキ色材を含む色材全体に対して、他の色材は、８５質量％以下であってよく、８１質量％以下であってよく、７２質量％以下であってよく、６０質量％以下であってよく、５０質量％以下であってよい。 In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant may be appropriately adjusted according to the desired chromaticity, and is not particularly limited, and may be 100% by mass relative to the entire colorant including the rake colorant. In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, when other colorants are contained, the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant including the rake colorant may be 15% by mass or more from the viewpoint of desired chromaticity adjustment. From the viewpoint of suppressing the generation of residues and improving brightness while adjusting to the desired chromaticity, the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant may be 19% by mass or more, 28% by mass or more, 40% by mass or more, or 50% by mass or more. When other colorants are contained, the upper limit of the content ratio of at least one rake colorant selected from the group consisting of the colorant represented by the general formula (1-1) and the colorant represented by the general formula (1-2) relative to the entire colorant including the rake colorant is not particularly limited, but from the viewpoint of adjusting to the desired chromaticity, it may be 95% by mass or less, 85% by mass or less, or 80% by mass or less.
In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, the other coloring material may be 0% by mass relative to the total coloring material including the lake coloring material. In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, when the other coloring material is contained, from the viewpoint of desired chromaticity adjustment, the other coloring material may be 5% by mass or more, 15% by mass or more, or 20% by mass or more relative to the total coloring material including the lake coloring material. From the viewpoint of suppressing the generation of residues and improving brightness while adjusting to the desired chromaticity, the other coloring material may be 85% by mass or less, 81% by mass or less, 72% by mass or less, 60% by mass or less, or 50% by mass or less relative to the total coloring material including the lake coloring material.
（分散剤）
　本発明の青色着色層及び当該青色着色層形成用着色樹脂組成物において、必要に応じて用いられる分散剤は、前記緑色着色層と同様であってもよいが、中でも、酸性分散剤を用いることが、前記レーキ色材の分散性の点から好ましい。
　中でも酸性分散剤は、前記レーキ色材の分散性と耐熱性を向上し、加熱後のレーキ色材の色度変化を抑制可能な点から、下記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体を含むことが好ましい。 (Dispersant)
In the blue colored layer and the colored resin composition for forming the blue colored layer of the present invention, the dispersant used as necessary may be the same as that used in the green colored layer. Among them, it is preferable to use an acidic dispersant from the viewpoint of dispersibility of the lake color material.
Among them, the acidic dispersant preferably contains a polymer having at least one selected from the structural units represented by the following general formula (II), since this improves the dispersibility and heat resistance of the lake colorant and can suppress the chromaticity change of the lake colorant after heating.
Figure JPOXMLDOC01-appb-C000021
 （一般式（ＩＩ）中、Ｌ１は、直接結合又は２価の連結基、Ｒ１は、水素原子又はメチル基、Ｒ２は、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であり、Ｒ６は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、－Ｃ（Ｒ７）（Ｒ８）－Ｃ（Ｒ９）（Ｒ１０）－ＯＨ、又は、－ＣＨ２－Ｃ（Ｒ１１）（Ｒ１２）－ＣＨ２－ＯＨで示される１価の基である。
　Ｒ３及びＲ４は、それぞれ独立に水素原子又はメチル基であり、Ｒ５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ、－ＣＯ－ＣＨ＝ＣＨ２、－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２又は－ＣＨ２ＣＯＯＲ１３で示される１価の基であり、Ｒ１３は水素原子又は炭素数が１個以上５個以下のアルキル基である。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２は、それぞれ独立に、水素原子、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基であり、Ｒ７及びＲ９は、互いに結合して環構造を形成してもよい。上記環状構造を形成した場合、当該環状構造が更に置換基Ｒ１４を有していてもよく、Ｒ１４は、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基である。前記炭化水素基は、置換基を有していてもよい。Ｘは、水素原子又は有機カチオンを表す。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。）
Figure JPOXMLDOC01-appb-C000021
 (In general formula (II), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydroxyl group, a hydrocarbon group, -[CH(R 3 )-CH(R 4 )-O] x1 -R 5 , -[(CH 2 ) y1 -O] z1 -R 5 , or a monovalent group represented by -O-R 6 , and R 6 is a hydrocarbon group, -[CH(R 3 )-CH(R 4 )-O] x1 -R 5 , -[(CH 2 ) y1 -O] z1 -R 5 , -C(R 7 )(R 8 )-C(R 9 )(R 10 )-OH, or a monovalent group represented by -CH 2 -C(R 11 )(R 12 )-CH 2 -OH.
R 3 and R 4 are each independently a hydrogen atom or a methyl group, R 5 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO, -CO-CH=CH 2 , -CO-C(CH 3 )=CH 2 or a monovalent group represented by -CH 2 COOR 13 , R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond, and R 7 and R 9 may be bonded to each other to form a ring structure. When the ring structure is formed, the ring structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon group having one or more selected from an ether bond and an ester bond. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 or more and 18 or less, y1 represents an integer of 1 or more and 5 or less, and z1 represents an integer of 1 or more and 18 or less.
　前記一般式（ＩＩ）で表される構成単位の各符号、及び、前記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体は、国際公開第２０２０／０７１０４１号の段落００８８～０１２８を参照することができる。 For the symbols of the structural units represented by the general formula (II) and for the polymer having at least one selected from the structural units represented by the general formula (II), see paragraphs 0088 to 0128 of WO 2020/071041.
　また、その他の酸性分散剤としては、酸性基を有する分散剤が挙げられる。ここで酸性基としては、例えば、カルボキシ基、スルホン酸基、若しくはリン酸基等が挙げられるが、その他の酸性分散剤の分散剤に含まれる酸性基としては、中でもカルボキシ基であることが、分散性に優れる点から好ましい。 Other acidic dispersants include dispersants having an acidic group. Examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. However, the acidic group contained in the dispersant of the other acidic dispersant is preferably a carboxy group in terms of excellent dispersibility.
　その他の酸性分散剤の酸価は、分散性に優れる点から、４０ｍｇＫＯＨ／ｇ以上であることが好ましく、５０ｍｇＫＯＨ／ｇ以上であることがより好ましく、７０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。一方で、現像残渣抑制の点から、その他の酸性分散剤の酸価は２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１９０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１８０ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。 The acid value of the other acidic dispersant is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more, from the viewpoint of excellent dispersibility. On the other hand, from the viewpoint of suppressing development residues, the acid value of the other acidic dispersant is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and even more preferably 180 mgKOH/g or less.
　その他の酸性分散剤としては、前記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体と組み合わせて用いることにより、現像残渣の抑制性が向上する点から、カルボキシ基を有する高分子分散剤であることが好ましい。中でも、前記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体に組み合わせて、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含むことが、現像残渣の抑制性が向上し、且つ、塗膜の均一性がより良好になる点から好ましい。 As other acidic dispersants, polymeric dispersants having a carboxy group are preferred, since their use in combination with a polymer having at least one type of structural unit selected from those represented by the general formula (II) improves the suppression of development residues. In particular, it is preferred to further include a block copolymer including an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth)acrylate ester in combination with a polymer having at least one type of structural unit selected from those represented by the general formula (II), since this improves the suppression of development residues and improves the uniformity of the coating film.
　このようなその他の酸性分散剤、及び酸性分散剤の含有割合としては、国際公開第２０２０／０７１０４１号の段落０１３２～０１４５を参照することができる。 For such other acidic dispersants and the content ratio of the acidic dispersants, please refer to paragraphs 0132 to 0145 of WO 2020/071041.
＜赤色着色層＞
　本発明に用いられる赤色着色層は、赤色色材を含む色材と、バインダー成分と、必要に応じて分散剤と、溶剤と、更に他の成分を含んでよい着色樹脂組成物の硬化物であってよい。
　以下、赤色着色層及び赤色着色層形成用樹脂組成物に含まれる各成分について、説明するが、バインダー成分、分散剤、溶剤、及びその他の成分については、前記緑色着色層と同様であってよいので、ここでの説明を省略する。 <Red colored layer>
The red colored layer used in the present invention may be a cured product of a colored resin composition that contains a colorant including a red colorant, a binder component, and optionally a dispersant, a solvent, and may further contain other components.
Below, the red colored layer and each component contained in the resin composition for forming the red colored layer will be described, but since the binder component, dispersant, solvent, and other components may be the same as those of the green colored layer, their description will be omitted here.
（色材）
　赤色色材としては、中でも有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス（Ｃ．Ｉ．；Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ　社発行）においてピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物、具体的には、下記のようなカラーインデックス（Ｃ．Ｉ．）番号が付されているものを挙げることができる。 (Coloring material)
Among the red coloring materials, organic pigments are preferably used because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically, compounds having the following Color Index (C.I.) numbers:
　赤色色材としては、例えば、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１０、１１、１２、１４、１５、１６、１７、１８、１９、２１、２２、２３、３０、３１、３２、３７、３８、４０、４１、４２、４８：１、４８：２、４８：３、４８：４、４９：１、４９：２、５０：１、５２：１、５３：１、５７、５７：１、５７：２、５８：２、５８：４、６０：１、６３：１、６３：２、６４：１、８１：１、８３、８８、９０：１、９７、１０１、１０２、１０４、１０５、１０６、１０８、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４９、１５０、１５１、１６６、１６８、１７０、１７１、１７２、１７４、１７５、１７６、１７７、１７８、１７９、１８０、１８５、１８７、１８８、１９０、１９３、１９４、２０２、２０６、２０７、２０８、２０９、２１５、２１６、２２０、２２４、２２６、２４２、２４３、２４５、２５４、２５５、２６４、２６５、２６９、２７２、２９１等、及び下記一般式（ｉ）で表されるジケトピロロピロール顔料等から選ばれる少なくとも１種であってよい。 Red colorants include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291, etc., and at least one selected from diketopyrrolopyrrole pigments represented by the following general formula (i).
Figure JPOXMLDOC01-appb-C000022
 （一般式（ｉ）中、Ｒ６１及びＲ６２は、それぞれ独立に、４－クロロフェニル基、又は４－ブロモフェニル基である。）
Figure JPOXMLDOC01-appb-C000022
 (In general formula (i), R 61 and R 62 each independently represent a 4-chlorophenyl group or a 4-bromophenyl group.)
　赤色色材としては、色域を拡大する点からは、ジケトピロロピロール顔料を用いることが好ましく、ジケトピロロピロール含量を色材全量中に３０質量％以上含有することが好ましく、４０質量％以上含有することがより好ましい。
　ジケトピロロピロール顔料としては、例えば、Ｃ．Ｉ．ピグメントレッド２５４、２５５、２６４、２７２、２９１、及び前記一般式（ｉ）で表されるジケトピロロピロール顔料が挙げられ、中でもＣ．Ｉ．ピグメントレッド２５４、２７２、２９１、及び前記一般式（ｉ）においてＲ６１及びＲ６２がそれぞれ４－ブロモフェニル基であるジケトピロロピロール顔料から選ばれる少なくとも１種が好ましい。 As the red colorant, in terms of expanding the color gamut, it is preferable to use a diketopyrrolopyrrole pigment, and the diketopyrrolopyrrole content is preferably 30% by mass or more, and more preferably 40% by mass or more, of the total amount of the colorant.
Examples of the diketopyrrolopyrrole pigment include C.I. Pigment Red 254, 255, 264, 272, and 291, and the diketopyrrolopyrrole pigment represented by the general formula (i), and among these, at least one selected from C.I. Pigment Red 254, 272, and 291, and the diketopyrrolopyrrole pigment represented by the general formula (i) in which R 61 and R 62 are each a 4-bromophenyl group, is preferred.
　赤色色材としては、ジケトピロロピロール系顔料と、Ｃ．Ｉ．ピグメントレッド１７７又はＣ．Ｉ．ピグメントレッド２０２とを含むことが、色度調整の点から好ましい。 The red colorant preferably contains a diketopyrrolopyrrole pigment and C.I. Pigment Red 177 or C.I. Pigment Red 202 in terms of chromaticity adjustment.
　また、赤色色材としては、少なくともＣ．Ｉ．ピグメントレッド２０２を含むことが、輝度の点から好ましい。 In addition, it is preferable that the red colorant contains at least C.I. Pigment Red 202 from the viewpoint of brightness.
　色材には、色調整の点、輝度向上、再溶解性向上の点から、更にその他の色材を用いてもよい。その他の色材としては、例えば、黄色色材、オレンジ色色材等が挙げられる。
　黄色色材としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５５、６０、６１、６５、７１、７３、７４、８１、８３、９３、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１６、１１７、１１９、１２０、１２６、１２７、１２８、１２９、１３８、１３９、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６６、１６８、１７５、１８５、及びＣ．Ｉ．ピグメントイエロー１５０の誘導体顔料等が挙げられる。
　オレンジ色色材としては、例えば、Ｃ．Ｉ．ピグメントオレンジ１、５、１３、１４、１６、１７、２４、３４、３６、３８、４０、４３、４６、４９、５１、６１、６３、６４、７１、７３等が挙げられる。 Other coloring materials may be used as the coloring material from the viewpoints of color adjustment, brightness improvement, and resolubility improvement. Examples of other coloring materials include yellow coloring materials and orange coloring materials.
Examples of yellow colorants include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and derivative pigments of C.I. Pigment Yellow 150.
Examples of orange colorants include C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73.
　本発明の赤色着色層及び当該赤色着色層形成用着色樹脂組成物に用いられる色材において、赤色色材の合計含有量は、色材全量に対して、１００質量％であってよいが、通常、５０質量％以上であり、好ましくは７０質量％以上であってよく、一方で、９９質量％以下であってよく、９０質量％以下であってよい。
　本発明の赤色着色層及び当該赤色着色層形成用着色樹脂組成物に用いられる色材において、赤色色材以外のその他の色材の合計含有量は、色材全量に対して、０質量％であってよいが、１質量％以上であってよく、１０質量％以上であってよく、一方で、通常、５０質量％以下であり、好ましくは３０質量％以下であってよい。 In the coloring material used in the red colored layer of the present invention and the colored resin composition for forming the red colored layer, the total content of the red coloring material may be 100% by mass relative to the total amount of the coloring material, but is usually 50% by mass or more, and preferably 70% by mass or more, while it may be 99% by mass or less, or 90% by mass or less.
In the coloring material used in the red colored layer of the present invention and the colored resin composition for forming the red colored layer, the total content of the other coloring materials other than the red coloring material may be 0 mass % relative to the total amount of the coloring materials, but may be 1 mass % or more, or may be 10 mass % or more, and on the other hand, it is usually 50 mass % or less, and preferably 30 mass % or less.
＜着色樹脂組成物の製造方法＞
　着色樹脂組成物の製造方法としては、一般的なカラーフィルタの着色層用樹脂組成物の製造方法と同様とすることができ、例えば、溶剤中に上記した各成分を混合して調製することにより製造することができる。また、例えば、溶剤中に予め分散剤を混合、攪拌して分散剤溶液を調製し、上記分散剤溶液中に色材、バインダー成分、その他の成分を混合させて調製することにより製造することもできる。 <Method of producing colored resin composition>
The method for producing the colored resin composition can be the same as the method for producing a resin composition for a colored layer of a general color filter, and for example, the colored resin composition can be produced by mixing the above-mentioned components in a solvent. In addition, for example, the colored resin composition can be produced by mixing and stirring a dispersant in advance in a solvent to prepare a dispersant solution, and mixing a color material, a binder component, and other components in the dispersant solution.
＜着色層の製造方法＞
　着色層の製造方法としては、特に限定されず、従来公知のカラーフィルタの製造方法における着色層の製造方法を適宜選択して用いることができる。例えばバインダー成分の硬化性に合わせて、適宜選択して製造することができる。例えば、バインダー成分が感光性バインダーを含む感光性樹脂組成物の場合には所謂フォトリソグラフィー法が挙げられる。また、バインダー成分が熱硬化性バインダーを含む樹脂組成物の場合には、着色樹脂組成物の塗膜を必要に応じてパターニングして塗布し、該塗膜を乾燥させたのち、加熱することにより得ることができる。パターニングして塗布する方法としては、例えばインクジェット法などを挙げることができる。 <Method of manufacturing colored layer>
The manufacturing method of the colored layer is not particularly limited, and a manufacturing method of the colored layer in the conventionally known manufacturing method of color filters can be appropriately selected and used. For example, it can be manufactured by appropriately selecting according to the curing property of the binder component. For example, in the case where the binder component is a photosensitive resin composition containing a photosensitive binder, a so-called photolithography method can be mentioned. In addition, in the case where the binder component is a resin composition containing a thermosetting binder, a coating film of the colored resin composition can be patterned and applied as necessary, and the coating film can be dried and then heated to obtain the colored resin composition. As a method of patterning and applying, for example, an inkjet method can be mentioned.
　当該着色層は、例えば、前記着色樹脂組成物が感光性樹脂組成物の場合、下記の方法により形成することができる。
　まず、いずれか１色（例えば赤色）の着色樹脂組成物を、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法などの塗布手段を用いて前記基板上に塗布して、ウェット塗膜を形成させる。
　次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させたのち、これに、所定のパターンのマスクを介して露光し、アルカリ可溶性樹脂及び多官能モノマー等を光重合反応させて、感光性の塗膜とする。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。
　また、露光後に重合反応を促進させるために、加熱処理を行ってもよい。加熱条件は、使用する着色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択される。 When the colored resin composition is a photosensitive resin composition, for example, the colored layer can be formed by the following method.
First, a colored resin composition of any one color (for example, red) is applied onto the substrate by a coating means such as spray coating, dip coating, bar coating, roll coating, or spin coating to form a wet coating film.
Next, the wet coating film is dried using a hot plate or oven, and then exposed to light through a mask having a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer, etc., to form a photosensitive coating film. Examples of light sources used for exposure include ultraviolet light from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc., and electron beams. The amount of exposure is appropriately adjusted depending on the light source used and the thickness of the coating film.
In order to promote the polymerization reaction after the exposure, a heat treatment may be carried out. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition used, the thickness of the coating film, and the like.
　次に、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。 Then, the coating is developed using a developer to dissolve and remove the unexposed areas, forming a coating film in the desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. This alkaline solution may contain an appropriate amount of a surfactant. Conventional development methods can be used.
　現像処理後は、通常、現像液の洗浄、着色樹脂組成物の硬化塗膜の乾燥が行われ、いずれか１色（例えば赤色）の着色層が形成される。なお、現像処理後に、塗膜を十分に硬化させるために加熱処理を行ってもよい。加熱条件としては特に限定はないが、例えば、２００～２５０℃であってよい。 After the development process, the developer is usually washed away and the cured coating film of the colored resin composition is dried to form a colored layer of one color (e.g., red). After the development process, a heat treatment may be performed to sufficiently cure the coating film. There are no particular limitations on the heating conditions, but the heating conditions may be, for example, 200 to 250°C.
　次いで別の１色（例えば緑色）の着色樹脂組成物を用いて、前記と同様に着色層を形成し、更に別の１色（例えば青色）の着色樹脂組成物を用いて、前記と同様に着色層を形成することにより、例えば緑色着色層、青色着色層、及び赤色着色層の３色の着色層を有するカラーフィルタを製造することができる。 　Then, a colored layer is formed in the same manner as above using a colored resin composition of another color (e.g., green), and then a colored layer is formed in the same manner as above using a colored resin composition of yet another color (e.g., blue), thereby producing a color filter having three colored layers, for example, a green colored layer, a blue colored layer, and a red colored layer.
　なお、本発明のカラーフィルタは、上記基板、遮光部及び着色層以外にも、例えば、オーバーコート層や透明電極層、さらには液晶材料を配向させるための配向膜や、柱状スペーサ等が形成されたものであってもよい。本発明のカラーフィルタは、前記例示された構成に限定されるものではなく、一般的にカラーフィルタに用いられている公知の構成を適宜選択して用いることができる。 In addition, the color filter of the present invention may be formed with, in addition to the above-mentioned substrate, light-shielding portion, and colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning the liquid crystal material, columnar spacers, etc. The color filter of the present invention is not limited to the configurations exemplified above, and any known configuration generally used in color filters can be appropriately selected and used.
ＩＩ．表示装置
　本発明に係る表示装置は、前記本発明に係るカラーフィルタを有することを特徴とする。本発明において表示装置の構成は特に限定されず、従来公知の表示装置の中から適宜選択することができ、例えば、液晶表示装置や、有機発光表示装置などが挙げられる。 The display device according to the present invention is characterized by having the color filter according to the present invention. The configuration of the display device according to the present invention is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
　［液晶表示装置］
　本発明の液晶表示装置は、前述した本発明に係るカラーフィルタと、対向基板と、前記カラーフィルタと前記対向基板との間に形成された液晶層とを有することを特徴とする。
　このような本発明の液晶表示装置について、図を参照しながら説明する。図２は、本発明の液晶表示装置の一例を示す概略図である。図２に例示するように本発明の液晶表示装置４０は、カラーフィルタ１０と、ＴＦＴアレイ基板等を有する対向基板２０と、上記カラーフィルタ１０と上記対向基板２０との間に位置する液晶層１５とを有している。図２においては、カラーフィルタ１０の着色層３側に配向膜１３ａと対向基板２０側に配向膜１３ｂが位置し、当該２つの配向膜１３ａ及び１３ｂの間に液晶層１５が位置している例について示している。さらに、図２においては、液晶表示装置４０が、カラーフィルタ１０の外側に位置する偏光板２５ａ、及び、対向基板２０の外側に位置する偏光板２５ｂと、液晶表示装置４０の対向基板２０側に位置する偏光板２５ｂよりも外側に位置するバックライト３０とを有する例を示している。
　なお、本発明の液晶表示装置は、この図２に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた液晶表示装置として公知の構成とすることができる。 [Liquid crystal display device]
A liquid crystal display device of the present invention comprises the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 15 located between the color filter 10 and the counter substrate 20. FIG. 2 shows an example in which an alignment film 13a is located on the colored layer 3 side of the color filter 10 and an alignment film 13b is located on the counter substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Furthermore, FIG. 2 shows an example in which the liquid crystal display device 40 has a polarizing plate 25a located on the outside of the color filter 10, a polarizing plate 25b located on the outside of the counter substrate 20, and a backlight 30 located outside the polarizing plate 25b located on the counter substrate 20 side of the liquid crystal display device 40.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may have any known configuration as a liquid crystal display device generally using color filters.
　本発明の液晶表示装置の駆動方式としては、特に限定はなく一般的に液晶表示装置に用いられている駆動方式を採用することができる。このような駆動方式としては、例えば、ＴＮ方式、ＩＰＳ方式、ＯＣＢ方式、及びＭＶＡ方式等を挙げることができる。本発明においてはこれらのいずれの方式であっても好適に用いることができる。
　また、対向基板としては、本発明の液晶表示装置の駆動方式等に応じて適宜選択して用いることができる。
　さらに、液晶層を構成する液晶としては、本発明の液晶表示装置の駆動方式等に応じて、誘電異方性の異なる各種液晶、及びこれらの混合物を用いることができる。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and any driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention.
The counter substrate can be appropriately selected depending on the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.
　液晶層の形成方法としては、一般に液晶セルの作製方法として用いられる方法を使用することができ、例えば、真空注入方式や液晶滴下方式等が挙げられる。
　真空注入方式では、例えば、あらかじめカラーフィルタ及び対向基板を用いて液晶セルを作製し、液晶を加温することにより等方性液体とし、キャピラリー効果を利用して液晶セルに液晶を等方性液体の状態で注入し、接着剤で封止することにより液晶層を形成することができる。その後、液晶セルを常温まで徐冷することにより、封入された液晶を配向させることができる。
　また液晶滴下方式では、例えば、カラーフィルタの周縁にシール剤を塗布し、このカラーフィルタを液晶が等方相になる温度まで加熱し、ディスペンサー等を用いて液晶を等方性液体の状態で滴下し、カラーフィルタ及び対向基板を減圧下で重ね合わせ、シール剤を介して接着させることにより、液晶層を形成することができる。その後、液晶セルを常温まで徐冷することにより、封入された液晶を配向させることができる。 The liquid crystal layer can be formed by any method generally used for producing liquid crystal cells, such as a vacuum injection method or a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and an opposing substrate, the liquid crystal is heated to make it an isotropic liquid, the liquid crystal is injected into the liquid crystal cell in the isotropic liquid state using the capillary effect, and the liquid crystal layer is formed by sealing with an adhesive. The liquid crystal cell is then gradually cooled to room temperature to align the enclosed liquid crystal.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of a color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like, the color filter and the opposing substrate are superimposed under reduced pressure, and bonded together via the sealant, thereby forming a liquid crystal layer. The liquid crystal cell is then gradually cooled to room temperature, whereby the enclosed liquid crystal can be aligned.
　また、本発明の液晶表示装置に用いられるバックライトとしては、液晶表示装置の用途に応じて適宜選択して用いることができる。バックライトとしては、例えば、冷陰極蛍光管（ＣＣＦＬ：Ｃｏｌｄ　Ｃａｔｈｏｄｅ　Ｆｌｕｏｒｅｓｃｅｎｔ　Ｌａｍｐ）の他、白色ＬＥＤ、白色有機ＥＬを光源とするバックライトユニットを具備することができる。
　白色ＬＥＤとしては、例えば、赤色ＬＥＤと緑色ＬＥＤと青色ＬＥＤを組み合わせて混色により白色光を得る白色ＬＥＤ、青色ＬＥＤと赤色ＬＥＤと緑色蛍光体を組み合わせて混色により白色光を得る白色ＬＥＤ、青色ＬＥＤと赤色発光蛍光体と緑色発光蛍光体を組み合わせて混色により白色光を得る白色ＬＥＤ、青色ＬＥＤとＹＡＧ系蛍光体の混色により白色光を得る白色ＬＥＤ、紫外線ＬＥＤと赤色発光蛍光体と緑色発光蛍光体と青色発光蛍光体を組み合わせて混色により白色光を得る白色ＬＥＤ等を挙げることができる。前記蛍光体としては、量子ドットを用いても良い。 The backlight used in the liquid crystal display device of the present invention can be appropriately selected depending on the application of the liquid crystal display device. For example, the backlight can include a cold cathode fluorescent lamp (CCFL), a white LED, or a backlight unit using a white organic EL as a light source.
Examples of white LEDs include a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, a white LED that obtains white light by mixing a blue LED, a red LED, and a green phosphor, a white LED that obtains white light by mixing a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG phosphor, and a white LED that obtains white light by mixing an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor, etc. Quantum dots may be used as the phosphor.
　［発光表示装置］
　本発明に係る発光表示装置は、前述した本発明に係るカラーフィルタと、発光体とを有することを特徴とする。
　このような本発明の発光表示装置について、図を参照しながら説明する。図３に例示するように本発明の発光表示装置１００は、カラーフィルタ１０と、発光体８０とを有している。カラーフィルタ１０と、発光体８０との間に、有機保護層５０や無機酸化膜６０を有していても良い。 [Light-emitting display device]
The light-emitting display device according to the present invention is characterized by having the color filter according to the present invention described above and a light-emitting body.
Such a light-emitting display device of the present invention will be described with reference to the drawings. As shown in Fig. 3, the light-emitting display device 100 of the present invention has a color filter 10 and a light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the light-emitting body 80.
　発光体８０の積層方法としては、例えば、カラーフィルタ上面へ透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６を逐次形成していく方法や、別基板上へ形成した発光体８０を無機酸化膜６０上に貼り合わせる方法などが挙げられる。発光体８０における、透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６、その他の構成は、公知のものを適宜用いることができる。このようにして作製された発光表示装置１００は、例えば、パッシブ駆動方式の有機ＥＬディスプレイにもアクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。
　なお、本発明の発光表示装置は、この図３に示される構成の発光表示装置に限定されるものではなく、一般的にカラーフィルタが用いられた発光表示装置として公知の構成とすることができる。 Examples of the lamination method of the light-emitting body 80 include a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter, and a method of bonding the light-emitting body 80 formed on a separate substrate onto the inorganic oxide film 60. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components of the light-emitting body 80 may be appropriately selected from known components. The light-emitting display device 100 thus produced can be applied to, for example, both passively driven organic EL displays and actively driven organic EL displays.
The light-emitting display device of the present invention is not limited to the light-emitting display device having the configuration shown in FIG. 3, but may have any known configuration as a light-emitting display device that generally uses color filters.
　以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。
　ハロゲン化亜鉛フタロシアニン色材の中間体は、ＬＣ－ＭＳ（アジレントテクノロジー製、四重極ＬＣ／ＭＳ、Ａｇｉｌｅｎｔ１２６０　Ｉｎｆｉｎｉｔｙ）で分析した。
　ハロゲン化亜鉛フタロシアニン色材及びレーキ色材は、ＭＡＬＤＩ－ＴＯＦ－ＭＳ（島津製作所製、ＭＡＬＤＩ－８０２０）で分析した。
　酸価は、ＪＩＳ　Ｋ　００７０：１９９２に記載の方法に準ずる方法により求めた。
　質量平均分子量（Ｍｗ）は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により標準ポリスチレン換算値として求めた。
　以下の合成例や実施例は、特に記載のない限り、２５℃で行った。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The intermediate of the halogenated zinc phthalocyanine coloring material was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity).
The zinc phthalocyanine halide colorant and the lake colorant were analyzed by MALDI-TOF-MS (Shimadzu Corporation, MALDI-8020).
The acid value was determined by a method according to the method described in JIS K 0070:1992.
The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
The following synthesis examples and examples were carried out at 25° C. unless otherwise specified.
（合成例１：染料１（ハロゲン化亜鉛フタロシアニン色材）の合成）
　５００ｍｌナスフラスコに、テトラフルオロフタロニトリル５．０ｇ（２５．０ｍｍｏｌ）と、炭酸カリウム６．９１ｇ（５０ｍｍｏｌ）とアセトン２５ｍｌを投入し、溶解するまで室温で攪拌した。
　次に、２５ｍｌのアセトンで溶解した４－ヒドロキシ安息香酸エチル８．３１ｇ（５０．０ｍｍｏｌ）を先のナスフラスコに、氷浴中で攪拌しながら、１時間かけて滴下ロートで投入し、投入後１時間攪拌した。
　反応終了後、炭酸カリウムをろ過で取り除き、得られた反応溶液について、エバポレーターで溶媒を溜去し、得られたオイル状の生成物をジクロロメタンに溶解させて、純水で分液処理を行った。
　分液後の有機層について、イソプロピルアルコール中で再結晶処理を行い、中間体１を得た。
　中間体１は、ＬＣ－ＭＳ（アジレントテクノロジー製、四重極ＬＣ／ＭＳ、Ａｇｉｌｅｎｔ１２６０　Ｉｎｆｉｎｉｔｙ）で分析したところ、下記構造を有していた。更に中間体１の代表的な化学構造式を下記に示す。 (Synthesis Example 1: Synthesis of Dye 1 (Halide Zinc Phthalocyanine Colorant))
In a 500 ml recovery flask, 5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone were placed and stirred at room temperature until dissolved.
Next, 8.31 g (50.0 mmol) of ethyl 4-hydroxybenzoate dissolved in 25 ml of acetone was added to the above-mentioned recovery flask using a dropping funnel over a period of 1 hour while stirring in an ice bath, and the mixture was stirred for 1 hour after the addition.
After the reaction was completed, potassium carbonate was removed by filtration, the solvent was removed from the resulting reaction solution using an evaporator, and the resulting oily product was dissolved in dichloromethane and separated with pure water.
After separation, the organic layer was recrystallized in isopropyl alcohol to obtain intermediate 1.
Intermediate 1 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 1 is shown below.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　５０ｍｌフラスコに中間体１を５．００ｇ（１０．１５ｍｍｏｌ）とベンゾニトリル１５．０ｍｌを投入し、１００℃程度で溶解し、次いで、ヨウ化亜鉛０．９７ｇ（３．０５ｍｍｏｌ）を投入し、１４０℃で１５時間攪拌しながら反応させた。
　反応液を室温まで冷ました後にメタノール１５０ｍｌ中に反応液を滴下し、発生した析出物を３０分攪拌した後に、ろ紙で回収し、メタノールにて数回、ビーカー中での攪拌と、ろ過を繰り返して洗浄した。
　得られた生成物を乾燥し、染料１を得た。代表的な化学構造式を下記に示す。
　得られた染料１は、プロピレングリコールモノメチルエーテルアセテート１００ｇに対して２５℃で少なくとも０．５ｇ溶解した。 In a 50 ml flask, 5.00 g (10.15 mmol) of intermediate 1 and 15.0 ml of benzonitrile were added and dissolved at about 100° C., and then 0.97 g (3.05 mmol) of zinc iodide was added and reacted with stirring at 140° C. for 15 hours.
After the reaction solution was cooled to room temperature, it was dropped into 150 ml of methanol. The resulting precipitate was stirred for 30 minutes and then collected on filter paper. It was washed by repeatedly stirring in a beaker and filtering with methanol several times.
The resulting product was dried to obtain Dye 1. A representative chemical structural formula is shown below.
At least 0.5 g of the obtained dye 1 was dissolved in 100 g of propylene glycol monomethyl ether acetate at 25°C.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（合成例２：染料２（ハロゲン化亜鉛フタロシアニン色材）の合成）
　５００ｍｌナスフラスコに、テトラフルオロフタロニトリル５．０ｇ（２５．０ｍｍｏｌ）と、炭酸カリウム６．９１ｇ（５０ｍｍｏｌ）とアセトン２５ｍｌを投入し、溶解するまで室温で攪拌した。
　次に、２５ｍｌのアセトンで溶解した４－ヒドロキシ安息香酸メチル７．６１ｇ（５０．０ｍｍｏｌ）を先のナスフラスコに、氷浴中で攪拌しながら、１時間かけて滴下ロートで投入し、投入後１時間攪拌した。
　反応終了後、炭酸カリウムをろ過で取り除き、得られた反応溶液について、エバポレーターで溶媒を溜去し、得られたオイル状の生成物をジクロロメタンに溶解させて、純水で分液処理を行った。
　分液後の有機層について、イソプロピルアルコール中で再結晶処理を行い、中間体２を得た。
　中間体２は、ＬＣ－ＭＳ（アジレントテクノロジー製、四重極ＬＣ／ＭＳ、Ａｇｉｌｅｎｔ１２６０　Ｉｎｆｉｎｉｔｙ）で分析したところ、下記構造を有していた。更に中間体２の代表的な化学構造式を下記に示す。 (Synthesis Example 2: Synthesis of Dye 2 (Halide Zinc Phthalocyanine Colorant))
In a 500 ml recovery flask, 5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone were placed and stirred at room temperature until dissolved.
Next, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate dissolved in 25 ml of acetone was added to the above-mentioned recovery flask using a dropping funnel over a period of 1 hour while stirring in an ice bath, and the mixture was stirred for 1 hour after the addition.
After the reaction was completed, potassium carbonate was removed by filtration, the solvent was removed from the resulting reaction solution using an evaporator, and the resulting oily product was dissolved in dichloromethane and separated with pure water.
After separation, the organic layer was recrystallized in isopropyl alcohol to obtain intermediate 2.
Intermediate 2 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 2 is shown below.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　５０ｍｌフラスコに中間体２を４．７１ｇ（１０．１５ｍｍｏｌ）とベンゾニトリル１５．０ｍｌを投入し、１００℃程度で溶解し、次いで、ヨウ化亜鉛０．９７ｇ（３．０５ｍｍｏｌ）を投入し、１４０℃で１５時間攪拌しながら反応させた。
　反応液を室温まで冷ました後にメタノール１５０ｍｌ中に反応液を滴下し、発生した析出物を３０分攪拌した後に、ろ紙で回収し、メタノールにて数回、ビーカー中での攪拌と、ろ過を繰り返して洗浄した。
　得られた生成物を乾燥し、染料２を得た。代表的な化学構造式を下記に示す。
　得られた染料２は、プロピレングリコールモノメチルエーテルアセテート１００ｇに対して２５℃で少なくとも０．５ｇ溶解した。 4.71 g (10.15 mmol) of intermediate 2 and 15.0 ml of benzonitrile were placed in a 50 ml flask and dissolved at about 100° C., and then 0.97 g (3.05 mmol) of zinc iodide was added and reacted with stirring at 140° C. for 15 hours.
After the reaction solution was cooled to room temperature, it was dropped into 150 ml of methanol. The resulting precipitate was stirred for 30 minutes and then collected on filter paper. It was washed by repeatedly stirring in a beaker and filtering with methanol several times.
The resulting product was dried to obtain Dye 2. A representative chemical structural formula is shown below.
At least 0.5 g of the resulting dye 2 was dissolved in 100 g of propylene glycol monomethyl ether acetate at 25°C.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（合成例３：染料３（ハロゲン化亜鉛フタロシアニン色材）の合成）
　５００ｍｌナスフラスコに、テトラフルオロフタロニトリル５．０ｇ（２５．０ｍｍｏｌ）と、炭酸カリウム６．９１ｇ（５０ｍｍｏｌ）とアセトン２５ｍｌを投入し、溶解するまで室温で攪拌した。
　次に、２５ｍｌのアセトンで溶解した４－ヒドロキシ安息香酸ｎ－プロピル９．０１ｇ（５０．０ｍｍｏｌ）を先のナスフラスコに、氷浴中で攪拌しながら、１時間かけて滴下ロートで投入し、投入後１時間攪拌した。
　反応終了後、炭酸カリウムをろ過で取り除き、得られた反応溶液について、エバポレーターで溶媒を溜去し、得られたオイル状の生成物をジクロロメタンに溶解させて、純水で分液処理を行った。
　分液後の有機層について、イソプロピルアルコール中で再結晶処理を行い、中間体３を得た。
　中間体３は、ＬＣ－ＭＳ（アジレントテクノロジー製、四重極ＬＣ／ＭＳ、Ａｇｉｌｅｎｔ１２６０　Ｉｎｆｉｎｉｔｙ）で分析したところ、下記構造を有していた。更に中間体３の代表的な化学構造式を下記に示す。 (Synthesis Example 3: Synthesis of Dye 3 (Halide Zinc Phthalocyanine Colorant))
In a 500 ml recovery flask, 5.0 g (25.0 mmol) of tetrafluorophthalonitrile, 6.91 g (50 mmol) of potassium carbonate, and 25 ml of acetone were placed and stirred at room temperature until dissolved.
Next, 9.01 g (50.0 mmol) of n-propyl 4-hydroxybenzoate dissolved in 25 ml of acetone was added to the above-mentioned recovery flask using a dropping funnel over a period of 1 hour while stirring in an ice bath, and the mixture was stirred for 1 hour after the addition.
After the reaction was completed, potassium carbonate was removed by filtration, the solvent was removed from the resulting reaction solution using an evaporator, and the resulting oily product was dissolved in dichloromethane and separated with pure water.
After separation, the organic layer was recrystallized in isopropyl alcohol to obtain intermediate 3.
Intermediate 3 was analyzed by LC-MS (Agilent Technologies, quadrupole LC/MS, Agilent 1260 Infinity) and found to have the following structure: A representative chemical structural formula of Intermediate 3 is shown below.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　５０ｍｌフラスコに中間体３を５．２８ｇ（１０．１５ｍｍｏｌ）とベンゾニトリル１５．０ｍｌを投入し、１００℃程度で溶解し、次いで、ヨウ化亜鉛０．９７ｇ（３．０５ｍｍｏｌ）を投入し、１４０℃で１５時間攪拌しながら反応させた。
　反応液を室温まで冷ました後にメタノール１５０ｍｌ中に反応液を滴下し、発生した析出物を３０分攪拌した後に、ろ紙で回収し、メタノールにて数回、ビーカー中での攪拌と、ろ過を繰り返して洗浄した。
　得られた生成物を乾燥し、染料３を得た。代表的な化学構造式を下記に示す。
　得られた染料３は、プロピレングリコールモノメチルエーテルアセテート１００ｇに対して２５℃で少なくとも０．５ｇ溶解した。 5.28 g (10.15 mmol) of intermediate 3 and 15.0 ml of benzonitrile were placed in a 50 ml flask and dissolved at about 100° C., and then 0.97 g (3.05 mmol) of zinc iodide was added and reacted with stirring at 140° C. for 15 hours.
After the reaction solution was cooled to room temperature, it was dropped into 150 ml of methanol. The resulting precipitate was stirred for 30 minutes and then collected on filter paper. It was washed by repeatedly stirring in a beaker and filtering with methanol several times.
The resulting product was dried to obtain Dye 3. A representative chemical structural formula is shown below.
At least 0.5 g of the obtained dye 3 was dissolved in 100 g of propylene glycol monomethyl ether acetate at 25°C.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（合成例４：レーキ色材１の合成）
（１）中間体１の合成
　特開２０１８－３０１３号に記載の中間体Ａ－２、中間体Ｂ－１、及び化合物１－３の製造方法を参照して、下記化学式（ａ）で示される中間体１を得た（収率８７％）。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）　（ｍ／ｚ）：６７７（＋）、２価
・元素分析値：ＣＨＮ実測値　（８１．８１％、７．３１％、５．８５％）；理論値（８１．７７％、７．３６％、５．９０％） (Synthesis Example 4: Synthesis of Lake Colorant 1)
(1) Synthesis of Intermediate 1 By referring to the production methods of Intermediate A-2, Intermediate B-1, and Compound 1-3 described in JP-A-2018-3013, Intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%).
The resulting compound was confirmed to be the desired compound based on the following analytical results.
MS (ESI) (m / z): 677 (+), divalent elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（２）レーキ色材１の合成
　関東化学製１２タングストリン酸・ｎ水和物２．５９ｇ（０．７６ｍｍｏｌ）をメタノール４０ｍＬ、水４０ｍＬの混合液に加熱溶解させ、前記化学式（ａ）で示される中間体１　１．６ｇ（１．１９ｍｍｏｌ）を加え、１時間攪拌した。沈殿物を濾取し、水で洗浄した。得られた沈殿物を減圧乾燥して下記化学式（ｂ）で示されるレーキ色材１を（収率９５％）得た。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・３１Ｐ　ＮＭＲ（ｄ－ｄｍｓｏ、ｐｐｍ）δ－１５．１５
・ＭＳ（ＭＡＬＤＩ）　（ｍ／ｚ）：１３５５（Ｍ＋）、２８７９（ＭＨ２ －）
・元素分析値：ＣＨＮ実測値　（３５．５５％、３．２４％、２．６１％）；理論値（３５．６１％、３．２０％、２．５７％）
・蛍光Ｘ線分析：ＭｏＷ実測比　（０％、１００％）；理論値（０％、１００％） (2) Synthesis of Lake Colorant 1 2.59 g (0.76 mmol) of 12-tungstophosphoric acid n-hydrate manufactured by Kanto Chemical was dissolved in a mixture of 40 mL of methanol and 40 mL of water by heating, and 1.6 g (1.19 mmol) of intermediate 1 represented by the above chemical formula (a) was added and stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain Lake Colorant 1 represented by the following chemical formula (b) (yield 95%).
The resulting compound was confirmed to be the desired compound based on the following analytical results.
31P NMR (d-dmso, ppm) δ-15.15
MS (MALDI) (m/z): 1355 (M + ), 2879 (MH 2 − )
Elemental analysis: CHN measured (35.55%, 3.24%, 2.61%); theoretical (35.61%, 3.20%, 2.57%)
Fluorescent X-ray analysis: MoW actual ratio (0%, 100%); theoretical value (0%, 100%)
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（合成例５：塩基性処理フタロシアニン顔料１の合成）
　反応容器中、クロロスルホン酸３００質量部および銅フタロシアニン３０質量部を加え、完全に溶解した後、塩化チオニル２４質量部を加え、徐々に昇温して１０１℃で３時間反応させた。その反応液を氷水９０００質量部中に注入し、撹拌後、濾過、水洗した。得られたプレスケーキを水３００質量部でスラリーとした後、１，１－ジエチル－１，５－ジアザペンタン１３質量部を加え、６５℃で４時間撹拌した後、濾過、水洗、乾燥し、表面処理に用いられる塩基性部位を有する青色色材誘導体１を得た。得られた塩基性部位を有する青色色材誘導体１について、下記化学式の構造であることを確認した。（ＴＯＦ－ＭＳ：７６８．３５） (Synthesis Example 5: Synthesis of Basic-treated Phthalocyanine Pigment 1)
In a reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added and completely dissolved, and then 24 parts by mass of thionyl chloride was added and the temperature was gradually raised to 101°C for 3 hours to react. The reaction liquid was poured into 9000 parts by mass of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts by mass of water, and 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, stirred at 65°C for 4 hours, filtered, washed with water and dried to obtain blue colorant derivative 1 having a basic site to be used for surface treatment. It was confirmed that the obtained blue colorant derivative 1 having a basic site has a structure represented by the following chemical formula. (TOF-MS: 768.35)
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　市販のＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６（ε型銅フタロシアニン顔料、ＤＩＣ製　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　Ａ５１０）１００質量部と、前記塩基性部位を有する青色色材誘導体１の５質量部とをアトライターで６０℃にて１．５時間乾式粉砕した。この粉砕生成物に、更に前記塩基性部位を有する青色色材誘導体１の５質量部を混合することにより、目的とする塩基性処理されたフタロシアニン顔料である、塩基性処理フタロシアニン顔料１を得た。 100 parts by mass of commercially available C.I. Pigment Blue 15:6 (ε-type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC) and 5 parts by mass of the blue colorant derivative 1 having a basic site were dry-ground in an attritor at 60°C for 1.5 hours. The ground product was further mixed with 5 parts by mass of the blue colorant derivative 1 having a basic site to obtain the desired basic-treated phthalocyanine pigment, basic-treated phthalocyanine pigment 1.
（合成例６：酸性分散剤Ａ１の合成）
　（１）マクロモノマーＭＭ－１の合成
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、プロピレングリコールモノメチルエーテルアセテート（略称ＰＧＭＥＡ）８０．０質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。メタクリル酸メチル５０．０質量部、メタクリル酸－ｎ－ブチル３０．０質量部、メタクリル酸ベンジル２０．０質量部、２－メルカプトエタノール４．０質量部、ＰＧＭＥＡ３０質量部、α，α’－アゾビスイソブチロニトリル（略称ＡＩＢＮ）１．０質量部の混合溶液を１．５時間かけて滴下し、さらに３時間反応した。次に、窒素気流を止めて、この反応溶液を８０℃に冷却し、カレンズＭＯＩ（昭和電工製）８．７４質量部、ジラウリン酸ジブチルすず０．１２５質量部、ｐ－メトキシフェノール０．１２５質量部、及びＰＧＭＥＡ１０質量部、を加えて３時間攪拌することで、マクロモノマーＭＭ－１の４９．５質量％溶液を得た。得られたマクロモノマーＭＭ－１は、ＧＰＣ測定の結果、質量平均分子量（Ｍｗ）４０１０、数平均分子量（Ｍｎ）１９１０、分子量分布（Ｍｗ／Ｍｎ）２．１０であった。 (Synthesis Example 6: Synthesis of Acidic Dispersant A1)
(1) Synthesis of Macromonomer MM-1 A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA), and heated to a temperature of 90° C. while stirring under a nitrogen stream. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (abbreviated as AIBN) was added dropwise over 1.5 hours, and the reaction was continued for another 3 hours. Next, the nitrogen gas flow was stopped, the reaction solution was cooled to 80° C., 8.74 parts by mass of Karenz MOI (Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added, and the mixture was stirred for 3 hours to obtain a 49.5% by mass solution of macromonomer MM-1. As a result of GPC measurement, the obtained macromonomer MM-1 had a mass average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw/Mn) of 2.10.
（２）グラフト共重合体Ａ１の合成
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、ＰＧＭＥＡ８５．０質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。前記マクロモノマーＭＭ－１溶液６７．３４質量部（固形分３３．３３質量部）、メタクリル酸グリシジル（略称ＧＭＡ）１６．６７質量部、ｎ－ドデシルメルカプタン１．２４質量部、ＰＧＭＥＡ２５．０質量部、ＡＩＢＮ０．５質量部の混合溶液を１．５時間かけて滴下し、３時間加熱攪拌したのち、ＡＩＢＮ０．１０質量部、ＰＧＭＥＡ１０．０質量部の混合液を１０分かけて滴下し、さらに同温で１時間熟成することで、グラフト共重合体Ａ１の２５．０質量％溶液を得た。得られたグラフト共重合体Ａ１は、ＧＰＣ測定の結果、質量平均分子量（Ｍｗ）１０５７０、数平均分子量（Ｍｎ）４３７０、分子量分布（Ｍｗ／Ｍｎ）２．４２であった。 (2) Synthesis of Graft Copolymer A1 A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA, and heated to a temperature of 90° C. while stirring under a nitrogen stream. A mixed solution of 67.34 parts by mass of the macromonomer MM-1 solution (solid content 33.33 parts by mass), 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to obtain a 25.0% by mass solution of graft copolymer A1. The obtained graft copolymer A1 was measured by GPC to find that it had a mass average molecular weight (Mw) of 10,570, a number average molecular weight (Mn) of 4,370 and a molecular weight distribution (Mw/Mn) of 2.42.
（３）前記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ１）の製造
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、ＰＧＭＥＡ２７．８０質量部、フェニルホスホン酸（製品名「ＰＰＡ」日産化学製）９．２７質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。前記グラフト共重合体Ａ１の１００．０質量部を３０分かけて滴下し、２時間加熱攪拌することで、前記一般式（ＩＩ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ１）溶液（固形分２５．０質量％）を得た。得られた酸性分散剤Ａ１のＧＭＡとＰＰＡのエステル化反応の進行は、酸価測定と１Ｈ－ＮＭＲ測定によって確認した（エポキシ由来のピークが消失していることを確認）。得られた酸性分散剤Ａ１の酸価は９８ｍｇＫＯＨ／ｇであった。 (3) Production of a polymer (acidic dispersant A1) having at least one selected from the structural units represented by the general formula (II) A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA" manufactured by Nissan Chemical Co., Ltd.), and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. 100.0 parts by mass of the graft copolymer A1 was dropped over 30 minutes, and the mixture was heated and stirred for 2 hours to obtain a polymer (acidic dispersant A1) solution (solid content 25.0% by mass) having at least one selected from the structural units represented by the general formula (II). The progress of the esterification reaction of GMA and PPA in the obtained acidic dispersant A1 was confirmed by acid value measurement and 1 H-NMR measurement (confirmation that the peak derived from epoxy had disappeared). The acid value of the obtained acidic dispersant A1 was 98 mg KOH / g.
（合成例７：酸性分散剤Ａ２（カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体）の合成）
　国際公開２０１６／１３２８６３号に記載の実施例１を参照し、ＭＭＡ２０質量部、ＢＭＡ４０質量部のブロックと、アクリル酸（ＭＡＡ）２０質量部、ＢＭＡ２０質量部のブロックと、ＭＭＡ２０質量部、ＢＭＡ４０質量部のブロックとを有する、トリブロック共重合体を合成した。得られたブロック共重合体は、質量平均分子量（Ｍｗ）１１０００、分子量分布（Ｍｗ／Ｍｎ）１．５０、酸価１３０ｍｇＫＯＨ／ｇだった。 (Synthesis Example 7: Synthesis of Acidic Dispersant A2 (Block Copolymer Including A Block Including Structural Units Derived from Carboxy Group-Containing Ethylenically Unsaturated Monomer and B Block Including Structural Units Derived from (Meth)acrylic Acid Alkyl Ester)
With reference to Example 1 described in International Publication WO 2016/132863, a triblock copolymer having a block of 20 parts by mass of MMA and 40 parts by mass of BMA, a block of 20 parts by mass of acrylic acid (MAA) and 20 parts by mass of BMA, and a block of 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized. The obtained block copolymer had a mass average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw/Mn) of 1.50, and an acid value of 130 mgKOH/g.
（合成例８：塩基性分散剤１の合成）
　分散剤として、国際公開２０１６／１０４４９３号の段落０３０２に記載の合成例ＩＩ－２の分散剤ｂの製造と同様にして、塩基性分散剤１（塩型ブロック共重合体）溶液を調製した（固形分４０質量％）。 (Synthesis Example 8: Synthesis of Basic Dispersant 1)
As a dispersant, a basic dispersant 1 (salt-type block copolymer) solution was prepared in the same manner as in the production of dispersant b in Synthesis Example II-2 described in paragraph 0302 of WO 2016/104493 (solid content 40% by mass).
（合成例９：アルカリ可溶性樹脂Ａの合成）
　ベンジルメタクリレート（ＢｚＭＡ）４０質量部、メチルメタクリレート（ＭＭＡ）１５質量部、メタクリル酸（ＭＡＡ）２５質量部、及びアゾビスイソブチロニトリル（ＡＩＢＮ）３質量部の混合液を、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１５０質量部を入れた重合槽中に、窒素気流下、１００℃で、３時間かけて滴下した。滴下終了後、更に１００℃で、３時間加熱し、重合体溶液を得た。この重合体溶液の質量平均分子量は、７０００であった。
　次に、得られた重合体溶液に、グリシジルメタクリレート（ＧＭＡ）２０質量部、トリエチルアミン０．２質量部、及びｐ－メトキシフェノール０．０５質量部を添加し、１１０℃で１０時間加熱することにより、主鎖メタクリル酸のカルボン酸基と、グリシジルメタクリレートのエポキシ基との反応を行った。反応中は、グリシジルメタクリレートの重合を防ぐために、反応溶液中に、空気をバブリングさせた。
　尚、反応は溶液の酸価を測定することで追跡した。得られたアルカリ可溶性樹脂Ａは、ＢｚＭＡとＭＭＡ、ＭＡＡの共重合により形成された主鎖にＧＭＡを用いてエチレン性不飽和結合を有する側鎖を導入した樹脂であり、酸価７４ｍｇＫＯＨ／ｇ、質量平均分子量１２０００であった。アルカリ可溶性樹脂Ａ溶液は、固形分４０質量％であった。 (Synthesis Example 9: Synthesis of alkali-soluble resin A)
A mixture of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azobisisobutyronitrile (AIBN) was dropped into a polymerization tank containing 150 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) at 100° C. under a nitrogen gas flow over 3 hours. After the dropwise addition, the mixture was further heated at 100° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the solution was heated at 110° C. for 10 hours to react the carboxylic acid group of the main chain methacrylic acid with the epoxy group of the glycidyl methacrylate. During the reaction, air was bubbled into the reaction solution to prevent polymerization of the glycidyl methacrylate.
The reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin A was a resin in which a side chain having an ethylenically unsaturated bond was introduced using GMA to a main chain formed by copolymerization of BzMA, MMA, and MAA, and had an acid value of 74 mg KOH/g and a mass average molecular weight of 12000. The alkali-soluble resin A solution had a solid content of 40 mass%.
（合成例１０：アルカリ可溶性樹脂Ｂの合成）
　重合槽に、ＰＧＭＥＡを１５０質量部仕込み、窒素雰囲気下で１００℃に昇温した後、メタクリル酸（ＭＡＡ）２２質量部、シクロヘキシルメタクリレート（ＣＨＭＡ）６４質量部及びパーブチルＯ（日油株式会社製）６質量部、連鎖移動剤（ｎ－ドデシルメルカプタン）２質量部を１．５時間かけて連続的に滴下した。その後、１００℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から２時間後に重合禁止剤として、ｐ－メトキシフェノール０．１質量部を添加して重合を停止した。
　次に、空気を吹き込みながら、エポキシ基含有化合物としてグリシジルメタクリレート（ＧＭＡ）１４質量部を添加して、１１０℃に昇温した後、トリエチルアミン０．８質量部を添加して１１０℃で１５時間付加反応させ、アルカリ可溶性樹脂Ｂ溶液（質量平均分子量（Ｍｗ）９，０００、酸価９０ｍｇＫＯＨ／ｇ、固形分４０質量％）を得た。 (Synthesis Example 10: Synthesis of alkali-soluble resin B)
A polymerization tank was charged with 150 parts by mass of PGMEA and heated to 100° C. under a nitrogen atmosphere, and then 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100° C., and 2 hours after completion of the dropwise addition of the main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing in air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the temperature was raised to 110° C., after which 0.8 parts by mass of triethylamine was added and an addition reaction was carried out at 110° C. for 15 hours to obtain an alkali-soluble resin B solution (mass average molecular weight (Mw) 9,000, acid value 90 mgKOH/g, solid content 40% by mass).
（合成例１１：Ｙ１３８スルホン酸誘導体の合成）
　国際公開第２０１４／０６９４１６号公報の合成例２のＣ．Ｉ．ピグメントイエロー１３８のモノスルホン酸誘導体の合成と同様にして、Ｃ．Ｉ．ピグメントイエロー１３８のモノスルホン酸誘導体を合成した。 (Synthesis Example 11: Synthesis of Y138 sulfonic acid derivative)
A monosulfonic acid derivative of C.I. Pigment Yellow 138 was synthesized in the same manner as in the synthesis of a monosulfonic acid derivative of C.I. Pigment Yellow 138 in Synthesis Example 2 of WO 2014/069416.
　（調製例１：感光性バインダー成分ＣＲ－１の調製）
　合成例９で得られたアルカリ可溶性樹脂Ａ溶液（固形分４０質量％）１９．１３質量部に対して、光重合性化合物としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）（アロニックスＭ４０３、東亜合成製）１７．８５質量部、光開始剤としてオキシムエステル系光開始剤（ＰＢＧ－３０５７、常州強力電子新材料社製）２．２５質量部、オキシムエステル系光開始剤（ＮＣＩ－８３１Ｅ、ＡＤＥＫＡ製）２．２５質量部、ＰＧＭＥＡ５８．５３質量部を加えて、感光性バインダー成分ＣＲ－１を得た。 (Preparation Example 1: Preparation of Photosensitive Binder Component CR-1)
To 19.13 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Synthesis Example 9, 17.85 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toa Gosei) as a photopolymerizable compound, 2.25 parts by mass of an oxime ester photoinitiator (PBG-3057, manufactured by Changzhou New Strong Electronic Materials Co., Ltd.) as a photoinitiator, 2.25 parts by mass of an oxime ester photoinitiator (NCI-831E, manufactured by ADEKA), and 58.53 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-1.
　（調製例２：感光性バインダー成分ＣＲ－２の調製）
　合成例１０で得られたアルカリ可溶性樹脂Ｂ溶液（固形分４０質量％）３６．５質量部に対して、光重合性化合物としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）（アロニックスＭ４０２、東亜合成製）２１．９質量部、光開始剤としてα－アミノアセトフェノン系光開始剤（イルガキュア９０７、ＢＡＳＦ製）１．１質量部、フルオレン骨格を有するオキシムエステル系光開始剤（ＳＰＩ－０４、三養製）１．３質量部、チオキサントン系光開始剤（カヤキュアーＤＥＴＸ－Ｓ、日本化薬製）０．３質量部、酸化防止剤（ＩＲＧＡＮＯＸ１０１０、ＢＡＳＦ製）０．８質量部、ＰＧＭＥＡ３８．１質量部を加えて、感光性バインダー成分ＣＲ－２を得た。 (Preparation Example 2: Preparation of Photosensitive Binder Component CR-2)
To 36.5 parts by mass of the alkali-soluble resin B solution (solid content 40% by mass) obtained in Synthesis Example 10, 21.9 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M402, manufactured by Toa Gosei) as a photopolymerizable compound, 1.1 parts by mass of an α-aminoacetophenone-based photoinitiator (Irgacure 907, manufactured by BASF) as a photoinitiator, 1.3 parts by mass of an oxime ester-based photoinitiator having a fluorene skeleton (SPI-04, manufactured by Sanyo), 0.3 parts by mass of a thioxanthone-based photoinitiator (Kayacure DETX-S, manufactured by Nippon Kayaku), 0.8 parts by mass of an antioxidant (IRGANOX1010, manufactured by BASF), and 38.1 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-2.
　（調製例３：感光性バインダー成分ＣＲ－３の調製）
　合成例９で得られたアルカリ可溶性樹脂Ａ溶液（固形分４０質量％）１３．８０質量部に対して、光重合性化合物としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）（アロニックスＭ４０３、東亜合成製）２２．０８質量部、光開始剤としてオキシムエステル系光開始剤（ＰＢＧ－３０５７、常州強力電子新材料社製）２．４０質量部、ＰＧＭＥＡ６１．７２質量部を加えて、感光性バインダー成分ＣＲ－３を得た。 (Preparation Example 3: Preparation of Photosensitive Binder Component CR-3)
To 13.80 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Synthesis Example 9, 22.08 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toa Gosei Co., Ltd.) as a photopolymerizable compound, 2.40 parts by mass of an oxime ester-based photoinitiator (PBG-3057, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) as a photoinitiator, and 61.72 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-3.
（製造例Ｇ１）
（１）Ｙ１３８分散液の調製
　分散剤として前記塩基性分散剤１溶液を１３．００質量部、色材としてＣ．Ｉ．ピグメントイエロー１３８（クロモファインイエロー６２０６ＥＣ、大日精化工業（株）製）を１３．００質量部と、前記アルカリ可溶性樹脂Ａ溶液を１３．００質量部、ＰＧＭＥＡを６１．００質量部、粒径２．０ｍｍジルコニアビーズ１００質量部をマヨネーズビンに入れ、予備解砕としてペイントシェーカー（浅田鉄工（株）製）にて１時間振とうし、次いで粒径２．０ｍｍジルコニアビーズを取り出し、粒径０．１ｍｍのジルコニアビーズ２００質量部を加えて、同様に本解砕としてペイントシェーカーにて４時間分散を行い、Ｙ１３８分散液を得た。
（２）緑色組成物Ｇ１の製造
　合成例１の染料１を２．９０質量部、Ｙ１３８分散液を１７．６０質量部、上記感光性バインダー成分ＣＲ－１を３２．４０質量部、増感剤（ペンタエリスリトールテトラキス（３－メルカプトブチレート）、カレンズＭＴ－ＰＥ１、昭和電工製）を０．１９質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、シランカップリング剤（ＫＢＭ５０３、信越シリコーン製）を０．３４質量部、ＰＧＭＥＡを３４．０８質量部、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）を１２．４５質量部加え、緑色組成物Ｇ１を得た。 (Production Example G1)
(1) Preparation of Y138 Dispersion 13.00 parts by mass of the basic dispersant 1 solution as a dispersant, 13.00 parts by mass of C.I. Pigment Yellow 138 (Chromofine Yellow 6206EC, manufactured by Dainichi Seika Chemicals Co., Ltd.) as a coloring material, 13.00 parts by mass of the alkali-soluble resin A solution, 61.00 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle, and the mixture was shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary crushing, and then the zirconia beads with a particle size of 2.0 mm were taken out, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and similarly dispersed for 4 hours with a paint shaker as a main crushing to obtain a Y138 dispersion.
(2) Production of Green Composition G1 2.90 parts by mass of Dye 1 of Synthesis Example 1, 17.60 parts by mass of Y138 dispersion, 32.40 parts by mass of the above-mentioned photosensitive binder component CR-1, 0.19 parts by mass of a sensitizer (pentaerythritol tetrakis(3-mercaptobutyrate), Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), 34.08 parts by mass of PGMEA, and 12.45 parts by mass of propylene glycol monomethyl ether (PGME) were added to obtain a green composition G1.
（製造例Ｇ２～Ｇ３）
　製造例Ｇ１において、合成例１の染料１の代わりに、合成例２の染料２、または合成例３の染料３を用いた以外は、製造例Ｇ１と同様にして、緑色組成物Ｇ２及びＧ３を製造した。 (Production Examples G2 to G3)
Green compositions G2 and G3 were produced in the same manner as in Production Example G1, except that dye 2 in Synthesis Example 2 or dye 3 in Synthesis Example 3 was used instead of dye 1 in Synthesis Example 1 in Production Example G1.
（製造例ＣＧ１）
（１）Ｙ１３８分散液の調製
　製造例Ｇ１と同様にして、Ｙ１３８分散液を得た。
（２）Ｇ５８分散液の調製
　前記塩基性分散剤１溶液を９．７５質量部、色材としてＣ．Ｉ．ピグメントグリーン５８（ＦＡＳＴＯＧＥＮ　ＧＲＥＥＮ　Ａ３５０、ＤＩＣ株式会社製）を１３．００質量部と、前記アルカリ可溶性樹脂Ａ溶液を１６．２５質量部、ＰＧＭＥＡを６１．００質量部、粒径２．０ｍｍジルコニアビーズ１００質量部をマヨネーズビンに入れ、予備解砕としてペイントシェーカー（浅田鉄工（株）製）にて１時間振とうし、次いで粒径２．０ｍｍジルコニアビーズを取り出し、粒径０．１ｍｍのジルコニアビーズ２００質量部を加えて、同様に本解砕としてペイントシェーカーにて３時間分散を行い、Ｇ５８分散液を得た。
（３）緑色組成物ＣＧ１の製造
　Ｇ５８分散液を３２．６３質量部、Ｙ１３８分散液を１１．６６質量部、上記感光性バインダー成分ＣＲ－１を２１．４８質量部、増感剤（ペンタエリスリトールテトラキス（３－メルカプトブチレート）、カレンズＭＴ－ＰＥ１、昭和電工製）を０．１３質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、シランカップリング剤（ＫＢＭ５０３、信越シリコーン製）を０．３４質量部、ＰＧＭＥＡを３３．７３質量部加え、緑色組成物ＣＧ１を得た。 (Production Example CG1)
(1) Preparation of Y138 Dispersion A Y138 dispersion was obtained in the same manner as in Production Example G1.
(2) Preparation of G58 Dispersion 9.75 parts by mass of the basic dispersant 1 solution, 13.00 parts by mass of C.I. Pigment Green 58 (FASTOGEN GREEN A350, manufactured by DIC Corporation) as a coloring material, 16.25 parts by mass of the alkali-soluble resin A solution, 61.00 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle, and the mixture was shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a preliminary disintegration, and then the zirconia beads with a particle size of 2.0 mm were taken out, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and the mixture was dispersed for 3 hours with a paint shaker as a main disintegration in the same manner to obtain a G58 dispersion.
(3) Production of Green Composition CG1 32.63 parts by mass of the G58 dispersion, 11.66 parts by mass of the Y138 dispersion, 21.48 parts by mass of the above-mentioned photosensitive binder component CR-1, 0.13 parts by mass of a sensitizer (pentaerythritol tetrakis(3-mercaptobutyrate), Karenz MT-PE1, manufactured by Showa Denko), 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 33.73 parts by mass of PGMEA were added to obtain a green composition CG1.
（製造例Ｂ１）
（１）レーキ色材１の色材分散液の調製
　合成例４のレーキ色材１を１０質量部と、合成例６の酸性分散剤Ａ１溶液を２０質量部（有効固形分　５．０質量部）と、合成例１０のアルカリ可溶性樹脂Ｂ溶液を７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡを６２．５質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで４時間分散し、レーキ色材１の色材分散液を得た。
（２）塩基性処理フタロシアニン顔料１の色材分散液の調製
　合成例５の塩基性処理フタロシアニン顔料１を１０質量部と、合成例７の酸性分散剤Ａ２溶液を１６．７質量部（有効固形分　５．０質量部）と、合成例１０のアルカリ可溶性樹脂Ｂ溶液を７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡを６５．８質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで６時間分散し、塩基性処理フタロシアニン顔料１の色材分散液を得た。
（３）青色組成物Ｂ１の製造
　レーキ色材１の色材分散液を１２．８３質量部、塩基性処理フタロシアニン顔料１の色材分散液を１７．１３質量部、調製例２の感光性バインダー成分ＣＲ－２を３８．６７質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、ＰＧＭＥＡを３１．３４質量部とを混合し、青色組成物Ｂ１を得た。 (Production Example B1)
(1) Preparation of colorant dispersion of lake colorant 1 10 parts by weight of lake colorant 1 of Synthesis Example 4, 20 parts by weight (effective solid content 5.0 parts by weight) of the acidic dispersant A1 solution of Synthesis Example 6, 7.5 parts by weight (effective solid content 3.0 parts by weight) of the alkali-soluble resin B solution of Synthesis Example 10, and 62.5 parts by weight of PGMEA were mixed, and the mixture was dispersed in a paint shaker (manufactured by Asada Iron Works) with 2 mm zirconia beads for 1 hour as pre-dispersion and further with 0.1 mm zirconia beads for 4 hours as main dispersion to obtain a colorant dispersion of lake colorant 1.
(2) Preparation of Colorant Dispersion of Basic Treated Phthalocyanine Pigment 1 10 parts by mass of the basic treated phthalocyanine pigment 1 of Synthesis Example 5, 16.7 parts by mass of the acidic dispersant A2 solution of Synthesis Example 7 (effective solid content 5.0 parts by mass), 7.5 parts by mass of the alkali-soluble resin B solution of Synthesis Example 10 (effective solid content 3.0 parts by mass), and 65.8 parts by mass of PGMEA were mixed, and the mixture was pre-dispersed with 2 mm zirconia beads for 1 hour in a paint shaker (manufactured by Asada Iron Works), and further dispersed with 0.1 mm zirconia beads for 6 hours as a main dispersion, to obtain a colorant dispersion of basic treated phthalocyanine pigment 1.
(3) Production of Blue Composition B1 12.83 parts by mass of the colorant dispersion of Lake Colorant 1, 17.13 parts by mass of the colorant dispersion of Basic-Treated Phthalocyanine Pigment 1, 38.67 parts by mass of the photosensitive binder component CR-2 of Preparation Example 2, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), and 31.34 parts by mass of PGMEA were mixed to obtain a blue composition B1.
（製造例ＣＢ１）
（１）塩基性処理フタロシアニン顔料１の色材分散液の調製
　製造例Ｂ１と同様にして、塩基性処理フタロシアニン顔料１の色材分散液を得た。
（２）塩基性処理フタロシアニン顔料１とｐｉｇｍｅｎｔ ｖｉｏｌｅｔ２３の共分散色材分散液１の調製
　合成例５の塩基性処理フタロシアニン顔料１を９質量部と、ｐｉｇｍｅｎｔ　ｖｉｏｌｅｔ２３（シグマアルドリッチジャパン製）を１質量部と、合成例７の酸性分散剤Ａ２溶液を１６．７質量部（有効固形分　５．０質量部）と、合成例１０のアルカリ可溶性樹脂Ｂ溶液を７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡを６５．８質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで６時間分散し、共分散色材分散液１を得た。
（３）青色組成物ＣＢ１の製造
　前記塩基性処理フタロシアニン顔料１の色材分散液を１８．９５質量部、前記共分散色材分散液１を１７．４９質量部、調製例２の感光性バインダー成分ＣＲ－２を３４．７８質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、ＰＧＭＥＡを２８．７５質量部とを混合し、青色組成物ＣＢ１を得た。 (Production Example CB1)
(1) Preparation of Colorant Dispersion of Basic Treated Phthalocyanine Pigment 1 A colorant dispersion of basic treated phthalocyanine pigment 1 was obtained in the same manner as in Production Example B1.
(2) Preparation of Co-Dispersion Colorant Dispersion Liquid 1 of Basic Treated Phthalocyanine Pigment 1 and Pigment Violet 23 9 parts by mass of the basic treated phthalocyanine pigment 1 of Synthesis Example 5, 1 part by mass of Pigment Violet 23 (Sigma-Aldrich Japan), 16.7 parts by mass of the acidic dispersant A2 solution of Synthesis Example 7 (effective solid content 5.0 parts by mass), 7.5 parts by mass of the alkali-soluble resin B solution of Synthesis Example 10 (effective solid content 3.0 parts by mass), and 65.8 parts by mass of PGMEA were mixed, and the mixture was pre-dispersed with 2 mm zirconia beads for 1 hour in a paint shaker (Asada Iron Works), and further dispersed with 0.1 mm zirconia beads for 6 hours as a main dispersion, to obtain a co-dispersion colorant dispersion liquid 1.
(3) Production of Blue Composition CB1 18.95 parts by mass of the colorant dispersion of the basic-treated phthalocyanine pigment 1, 17.49 parts by mass of the co-dispersed colorant dispersion 1, 34.78 parts by mass of the photosensitive binder component CR-2 of Preparation Example 2, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), and 28.75 parts by mass of PGMEA were mixed to obtain a blue composition CB1.
（製造例Ｂ２）
　製造例Ｂ１で得られた青色組成物Ｂ１と、比較製造例１で得られた青色組成物ＣＢ１とを５０：５０（質量比）で混合することにより、青色組成物Ｂ２を得た。 (Production Example B2)
The blue composition B1 obtained in Production Example B1 and the blue composition CB1 obtained in Comparative Production Example 1 were mixed in a mass ratio of 50:50 to obtain a blue composition B2.
（製造例Ｂ３）
　製造例Ｂ１で得られた青色組成物Ｂ１と、比較製造例１で得られた青色組成物ＣＢ１とを３５：６５（質量比）で混合することにより、青色組成物Ｂ３を得た。 (Production Example B3)
The blue composition B1 obtained in Production Example B1 and the blue composition CB1 obtained in Comparative Production Example 1 were mixed in a mass ratio of 35:65 to obtain a blue composition B3.
（製造例Ｂ４）
　製造例Ｂ１で得られた青色組成物Ｂ１と、比較製造例１で得られた青色組成物ＣＢ１とを３０：７０（質量比）で混合することにより、青色組成物Ｂ４を得た。 (Manufacture example B4)
The blue composition B1 obtained in Production Example B1 and the blue composition CB1 obtained in Comparative Production Example 1 were mixed in a mass ratio of 30:70 to obtain a blue composition B4.
（製造例Ｂ５）
　製造例Ｂ１と同様に調製したレーキ色材１の色材分散液を２３．０６質量部、調製例２の感光性バインダー成分ＣＲ－２を４２．８１質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、ＰＧＭＥＡを３４．１０質量部とを混合し、青色組成物Ｂ５を得た。 (Manufacture example B5)
23.06 parts by mass of the colorant dispersion of Lake Colorant 1 prepared in the same manner as in Preparation Example B1, 42.81 parts by mass of the photosensitive binder component CR-2 of Preparation Example 2, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), and 34.10 parts by mass of PGMEA were mixed together to obtain a blue composition B5.
（製造例ＣＢ２）
（１）塩基性処理フタロシアニン顔料１の色材分散液の調製
　製造例Ｂ１と同様にして、塩基性処理フタロシアニン顔料１の色材分散液を得た。
（２）塩基性処理フタロシアニン顔料１とｐｉｇｍｅｎｔ ｖｉｏｌｅｔ２３の共分散色材分散液２の調製
　製造例ＣＢ１の共分散色材分散液１の調製において、合成例５の塩基性処理フタロシアニン顔料１を８質量部、ｐｉｇｍｅｎｔ　ｖｉｏｌｅｔ２３（シグマアルドリッチジャパン製）を２質量部に変更した以外は、共分散色材分散液１と同様にして、共分散色材分散液２を得た。
（３）青色組成物ＣＢ２の製造
　前記塩基性処理フタロシアニン顔料１の色材分散液を７．６４質量部、前記共分散色材分散液２を１７．４２質量部、調製例２の感光性バインダー成分ＣＲ－２を４１．６１質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、ＰＧＭＥＡを３３．３０質量部とを混合し、青色組成物ＣＢ２を得た。 (Production Example CB2)
(1) Preparation of Colorant Dispersion of Basic Treated Phthalocyanine Pigment 1 A colorant dispersion of basic treated phthalocyanine pigment 1 was obtained in the same manner as in Production Example B1.
(2) Preparation of Co-Dispersion Colorant Dispersion Liquid 2 of Basic Treated Phthalocyanine Pigment 1 and Pigment Violet 23 In the preparation of the co-dispersion colorant dispersion liquid 1 of Production Example CB1, the basic treated phthalocyanine pigment 1 of Synthesis Example 5 was changed to 8 parts by mass, and Pigment Violet 23 (manufactured by Sigma-Aldrich Japan) was changed to 2 parts by mass, and the same procedure as for the preparation of the co-dispersion colorant dispersion liquid 1 was carried out to obtain a co-dispersion colorant dispersion liquid 2.
(3) Production of Blue Composition CB2 7.64 parts by mass of the colorant dispersion liquid of the basic-treated phthalocyanine pigment 1, 17.42 parts by mass of the co-dispersed colorant dispersion liquid 2, 41.61 parts by mass of the photosensitive binder component CR-2 of Preparation Example 2, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), and 33.30 parts by mass of PGMEA were mixed to obtain a blue composition CB2.
（製造例Ｒ１）
（１）色材分散液Ｒ２５４の調製
　色材（Ｃ．Ｉ．ピグメントレッド２５４）を１２．４質量部、分散剤として調製例４で得られた塩基性ブロック共重合体１のＰＧＭＥＡ溶液（固形分４０質量％）を１６．２質量部、Ｙ１３８スルホン酸誘導体を０．７質量部、調製例１で得られたアルカリ可溶性樹脂Ａ溶液を９．８質量部と、ＰＧＭＥＡ６１．０質量部と、粒径２．０ｍｍジルコニアビーズ１００質量部をマヨネーズビンに入れ、予備解砕としてペイントシェーカー（浅田鉄工（株）製）にて１時間振とうし、次いで粒径２．０ｍｍジルコニアビーズを取り出し、粒径０．１ｍｍのジルコニアビーズ２００質量部を加えて、同様に本解砕としてペイントシェーカーにて８時間分散を行い、色材分散液Ｒ２５４を得た。
（２）色材分散液Ｒ１７７の調製
　色材分散液Ｒ２５４の調製において、色材としてＣ．Ｉ．ピグメントレッド２５４の代わりに、Ｃ．Ｉ．ピグメントレッド１７７を用いた以外は色材分散液Ｒ２５４の調製と同様にして、色材分散液Ｒ１７７を得た。
（３）赤色組成物Ｒ１の製造
　色材分散液Ｒ２５４を２．７７質量部、色材分散液Ｒ１７７を１９．８９質量部、上記感光性バインダー成分ＣＲ－３を３１．６９質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、シランカップリング剤（ＫＢＭ５０３、信越シリコーン製）を０．３４質量部、ＰＧＭＥＡを４５．２７質量部加え、赤色組成物Ｒ１を得た。 (Production Example R1)
(1) Preparation of Colorant Dispersion Liquid R254 12.4 parts by mass of a colorant (C.I. Pigment Red 254), 16.2 parts by mass of a PGMEA solution (solid content 40% by mass) of the basic block copolymer 1 obtained in Preparation Example 4 as a dispersant, 0.7 parts by mass of a Y138 sulfonic acid derivative, 9.8 parts by mass of the alkali-soluble resin A solution obtained in Preparation Example 1, 61.0 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing, then the zirconia beads with a particle size of 2.0 mm were removed, 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and similarly, dispersion was performed for 8 hours with a paint shaker as main crushing to obtain colorant dispersion liquid R254.
(2) Preparation of Colorant Dispersion Liquid R177 A colorant dispersion liquid R177 was obtained in the same manner as in the preparation of colorant dispersion liquid R254, except that C.I. Pigment Red 177 was used instead of C.I. Pigment Red 254 as a colorant in the preparation of colorant dispersion liquid R254.
(3) Production of Red Composition R1 2.77 parts by mass of colorant dispersion R254, 19.89 parts by mass of colorant dispersion R177, 31.69 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 45.27 parts by mass of PGMEA were added to obtain a red composition R1.
（製造例Ｒ２）
（１）色材分散液Ｒ２５４の調製
　製造例Ｒ１の色材分散液Ｒ２５４の調製と同様にして色材分散液Ｒ２５４を得た。
（２）色材分散液Ｒ２０２の調製
　色材分散液Ｒ２５４の調製において、色材としてＣ．Ｉ．ピグメントレッド２５４の代わりに、Ｃ．Ｉ．ピグメントレッド２０２を用いた以外は色材分散液Ｒ２５４の調製と同様にして、色材分散液Ｒ２０２を得た。
（３）赤色組成物Ｒ２の製造
　色材分散液Ｒ２５４を３．８６質量部、色材分散液Ｒ２０２を９．５５質量部、上記感光性バインダー成分ＣＲ－３を３６．１４質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、シランカップリング剤（ＫＢＭ５０３、信越シリコーン製）を０．３４質量部、ＰＧＭＥＡを５０．０８質量部加え、赤色組成物Ｒ２を得た。 (Production example R2)
(1) Preparation of Colorant Dispersion Liquid R254 Colorant dispersion liquid R254 was obtained in the same manner as in the preparation of colorant dispersion liquid R254 of Production Example R1.
(2) Preparation of Colorant Dispersion Liquid R202 A colorant dispersion liquid R202 was obtained in the same manner as in the preparation of colorant dispersion liquid R254, except that C.I. Pigment Red 202 was used instead of C.I. Pigment Red 254 as a colorant in the preparation of colorant dispersion liquid R254.
(3) Production of Red Composition R2 3.86 parts by mass of colorant dispersion liquid R254, 9.55 parts by mass of colorant dispersion liquid R202, 36.14 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 50.08 parts by mass of PGMEA were added to obtain a red composition R2.
（製造例Ｒ３）
（１）色材分散液Ｒ２９１の調製
　前記色材分散液Ｒ２５４の調製において、色材としてＣ．Ｉ．ピグメントレッド２５４の代わりに、Ｃ．Ｉ．ピグメントレッド２９１を用いた以外は色材分散液Ｒ２５４の調製と同様にして、色材分散液Ｒ２９１を得た。
（２）色材分散液Ｒ２０２の調製
　製造例Ｒ２の色材分散液Ｒ２０２の調製と同様にして色材分散液Ｒ２０２を得た。
（３）赤色組成物Ｒ３の製造
　色材分散液Ｒ２９１を３．８２質量部、色材分散液Ｒ２０２を９．２８質量部、上記感光性バインダー成分ＣＲ－３を３６．４８質量部、フッ素系界面活性剤（メガファックＦ５５９、ＤＩＣ（株）製）を０．０３質量部、シランカップリング剤（ＫＢＭ５０３、信越シリコーン製）を０．３４質量部、ＰＧＭＥＡを５０．０４質量部加え、赤色組成物Ｒ３を得た。 (Manufacturing example R3)
(1) Preparation of Colorant Dispersion Liquid R291 A colorant dispersion liquid R291 was obtained in the same manner as in the preparation of the colorant dispersion liquid R254, except that C.I. Pigment Red 291 was used instead of C.I. Pigment Red 254 as a colorant in the preparation of the colorant dispersion liquid R254.
(2) Preparation of Colorant Dispersion Liquid R202 Colorant dispersion liquid R202 was obtained in the same manner as in the preparation of colorant dispersion liquid R202 of Production Example R2.
(3) Production of Red Composition R3 3.82 parts by mass of colorant dispersion liquid R291, 9.28 parts by mass of colorant dispersion liquid R202, 36.48 parts by mass of the above-mentioned photosensitive binder component CR-3, 0.03 parts by mass of a fluorine-based surfactant (Megafac F559, manufactured by DIC Corporation), 0.34 parts by mass of a silane coupling agent (KBM503, manufactured by Shin-Etsu Silicones), and 50.04 parts by mass of PGMEA were added to obtain a red composition R3.
（実施例１）
（実施例１－１：赤→緑→青の順でカラーフィルタ基板の形成）
　特許第４８３３７７７号の実施例１のブラックマトリクス用硬化性樹脂組成物と同様にブラックマトリクス用硬化性樹脂組成物を調製し、特許第４８３３７７７号の段落００８５と同様にして、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製「ＮＡ３５」）上に、ブラックマトリクス（１０μｍ幅）を形成した。赤色組成物Ｒ１を、ポストベーク後の膜厚が２．３μｍになるようにスピンコーターを用いて塗布した。
　その後、８０℃のホットプレート上で３分間加熱乾燥を行った。開口寸法８０μｍ×２５０μｍのクロムマスクを配置したパターンフォトマスク（クロムマスク）を介して、超高圧水銀灯を用いて４０ｍＪ／ｃｍ２の紫外線で露光することにより、ガラス基板上に露光後塗膜を形成した。次いで、０．０５ｗｔ％水酸化カリウム水溶液を現像液としてスピン現像し、現像液に６０秒間接液させた後に純水で洗浄することで現像処理し、独立細線パターン状の赤色塗膜を得た。これを２３０℃のクリーンオーブンで２５分間ポストベークすることにより、独立細線パターン状の赤色着色層を形成した。
　前記赤色着色層が形成されているガラス基板上に、赤色組成物Ｒ１の代わりに緑色組成物Ｇ１を用い、ポストベーク後の膜厚が２．３μｍになるようにスピンコーターを用いて塗布した。前記と同様にして、パターンフォトマスク（クロムマスク）を用いて赤色着色層が形成されている部分とは異なる規定位置に、独立細線パターン状の緑色着色層を得た。
　前記赤色及び緑色着色層が形成されているガラス基板上に、赤色組成物Ｒ１の代わりに青色組成物Ｂ１を用い、ポストベーク後の膜厚が２．３μｍになるようにスピンコーターを用いて塗布した。前記と同様にして、パターンフォトマスク（クロムマスク）を用いて、赤色及び緑色着色層が形成されている部分とは異なる規定位置に、独立細線パターン状の青色着色層を得た。
　このようにしてＲＧＢ３色の着色層が形成されたカラーフィルタ基板を製造した。 Example 1
(Example 1-1: Formation of color filter substrate in the order of red → green → blue)
A curable resin composition for a black matrix was prepared in the same manner as in Example 1 of Japanese Patent No. 4833777, and a black matrix (10 μm wide) was formed on a glass substrate ("NA35" manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm in the same manner as in paragraph 0085 of Japanese Patent No. 4833777. Red composition R1 was applied using a spin coater so that the film thickness after post-baking would be 2.3 μm.
Then, the coating was dried by heating on a hot plate at 80°C for 3 minutes. A chrome mask with an opening size of 80 μm×250 μm was placed on the pattern photomask (chrome mask) and exposed to ultraviolet light of 40 mJ/ cm2 using an ultra-high pressure mercury lamp to form a post-exposure coating film on the glass substrate. Next, the coating was spin-developed using a 0.05 wt% potassium hydroxide aqueous solution as a developer, and developed by incubating in the developer for 60 seconds and then washing with pure water to obtain a red coating film in an independent fine line pattern. This was post-baked in a clean oven at 230°C for 25 minutes to form a red colored layer in an independent fine line pattern.
On the glass substrate on which the red colored layer was formed, the green colored layer G1 was used instead of the red colored layer R1, and was applied by a spin coater so that the film thickness after post-baking was 2.3 μm. In the same manner as above, a pattern photomask (chrome mask) was used to obtain an independent thin line patterned green colored layer at a specified position different from the part on which the red colored layer was formed.
On the glass substrate on which the red and green colored layers were formed, the blue composition B1 was used instead of the red composition R1, and the blue composition B1 was applied by a spin coater so that the film thickness after post-baking would be 2.3 μm. In the same manner as above, a pattern photomask (chrome mask) was used to obtain an independent thin line patterned blue colored layer at a specified position different from the portion on which the red and green colored layers were formed.
In this manner, a color filter substrate having colored layers of three colors, RGB, was manufactured.
（実施例１－２：赤→青→緑の順でカラーフィルタ基板の形成）
　着色層の形成順序を、赤→青→緑に変更した以外は、実施例１－１と同様にして、カラーフィルタ基板を製造した。 (Example 1-2: Formation of color filter substrate in the order of red → blue → green)
A color filter substrate was produced in the same manner as in Example 1-1, except that the order of forming the colored layers was changed to red, blue, and green.
（実施例２～８、比較例１～３）
　実施例１において、赤色組成物、緑色組成物、及び青色組成物の少なくとも１つを、表１及び表２に示すように変更した以外は、実施例１と同様にして、実施例２－１～８－１、比較例１－１～３－１において赤→緑→青の順でカラーフィルタ基板を製造し、実施例２－２～８－２、比較例１－２～３－２において赤→青→緑の順でカラーフィルタ基板を製造した。 (Examples 2 to 8, Comparative Examples 1 to 3)
In Example 1, at least one of the red composition, the green composition, and the blue composition was changed as shown in Tables 1 and 2. In Examples 2-1 to 8-1 and Comparative Examples 1-1 to 3-1, color filter substrates were produced in the order of red → green → blue, and in Examples 2-2 to 8-2 and Comparative Examples 1-2 to 3-2, color filter substrates were produced in the order of red → blue → green in the same manner as in Example 1.
（実施例９、比較例４～５）
　実施例１において、赤色組成物、緑色組成物、及び青色組成物の少なくとも１つを、表３及び表４に示すように変更した以外は、実施例１と同様にして、実施例９－１、比較例４－１～５－１において赤→緑→青の順でカラーフィルタ基板を製造し、実施例９－２、比較例４－２～５－２において赤→青→緑の順でカラーフィルタ基板を製造した。 (Example 9, Comparative Examples 4 to 5)
In Example 9-1 and Comparative Examples 4-1 to 5-1, color filter substrates were produced in the order of red → green → blue, and in Example 9-2 and Comparative Examples 4-2 to 5-2, color filter substrates were produced in the order of red → blue → green, in the same manner as in Example 1, except that at least one of the red composition, green composition, and blue composition in Example 1 was changed as shown in Tables 3 and 4.
＜光学性能＞
　実施例及び比較例のそれぞれにおいて、得られたカラーフィルタ基板を用いて光学性能評価を行った。
　赤色着色層、緑色着色層、青色着色層の幅方向（８０μｍ）の各中央位置を、分光特性測定装置　ＬＣＦ（大塚電子製）を用いて分光測定し、各色の色度（ｘ、ｙ）および輝度（Ｙ）を算出し、各色の測定値を用いてホワイト色度および輝度を算出した。
　ホワイト輝度の上昇率（Ｙアップ率）は、従来カラーフィルタに相当する比較例２のカラーフィルタ基板のホワイト輝度を基準（１００％）として、算出した。
　ホワイト輝度のＹアップ率が、１０３％以上を〇、１０２．０％以上１０３％未満を△、１０２．０％未満を×として、判定した。 <Optical performance>
In each of the examples and comparative examples, the optical performance was evaluated using the obtained color filter substrate.
The central positions of the red colored layer, the green colored layer, and the blue colored layer in the width direction (80 μm) were subjected to spectroscopic measurement using a spectroscopic characteristic measuring device LCF (manufactured by Otsuka Electronics Co., Ltd.), and the chromaticity (x, y) and luminance (Y) of each color were calculated. The measured values of each color were used to calculate the white chromaticity and luminance.
The increase rate of white luminance (Y-up rate) was calculated by taking the white luminance of the color filter substrate of Comparative Example 2, which corresponds to the conventional color filter, as the standard (100%).
The Y-up rate of white luminance was judged as follows: ◯ when it was 103% or more, Δ when it was 102.0% or more and less than 103%, and × when it was less than 102.0%.
＜現像残渣評価＞
（１）赤→緑→青の順で塗布した場合の赤色及び緑色着色層上の現像残渣評価
　赤色組成物を、厚み０．７ｍｍで１００ｍｍ×１００ｍｍのガラス基板（ＮＨテクノグラス（株）社製、「ＮＡ３５」）上に、スピンコーターを用いて塗布した後、ホットプレートを用いて６０℃で３分間乾燥することにより、厚さ２．５μｍの塗布層を形成した。次に、上記塗布層が形成されたガラス板を、専用マスクを用いて規定位置で開口部９０ｍｍ×３０ｍｍを露光後、アルカリ現像液として０．０５質量％水酸化カリウム水溶液を用いて６０秒間シャワー現像し、イオン交換水で洗浄した。その後上記赤色着色層が形成された基板について、２３０℃３０分のベイクを行った。
　赤色着色層が形成された基板の上に、緑色組成物をスピンコーターを用いて塗布し、赤色着色層が形成されている部分とは異なる規定位置で専用マスクを用いて開口部９０ｍｍ×３０ｍｍを露光後、アルカリ現像液として０．０５質量％水酸化カリウム水溶液を用いて６０秒間シャワー現像し、イオン交換水で洗浄した。この段階で、赤色着色層上の残渣評価を行った。その後上記赤色及び緑色着色層が形成された基板について、２３０℃３０分のベイクを行った。
　赤色及び緑色着色層が形成された基板の上に、青色組成物をスピンコーターを用いて塗布し、赤色及び緑色着色層が形成されている部分とは異なる規定位置で専用マスクを用いて開口部９０ｍｍ×３０ｍｍを露光後、アルカリ現像液として０．０５質量％水酸化カリウム水溶液を用いて６０秒間シャワー現像し、イオン交換水で洗浄した。この段階で、赤色及び緑色着色層上の残渣評価を行った。その後赤色、緑色、及び青色着色層が形成された基板について、２３０℃３０分のベイクを行った。
　各着色層上の残渣の評価は、上記着色層の形成後のガラス基板の単色露光部（９０ｍｍ×３０ｍｍ）を、目視により観察した後、エタノールを含ませたレンズクリーナー（東レ社製、商品名トレシーＭＫクリーンクロス）で十分に拭き取り、そのレンズクリーナーの着色度合いを目視で観察した。
（現像残渣評価基準）
Ａ：目視により現像残渣が確認されず、レンズクリーナーが全く着色しなかった
Ｂ：目視により現像残渣が確認されず、レンズクリーナーの着色がわずかに確認された
Ｃ：目視により現像残渣がわずかに確認され、レンズクリーナーの着色が確認された <Evaluation of development residue>
(1) Evaluation of development residues on red and green colored layers when coated in the order of red → green → blue The red composition was applied to a 100 mm × 100 mm glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater, and then dried at 60 ° C. for 3 minutes using a hot plate to form a coating layer with a thickness of 2.5 μm. Next, the glass plate on which the coating layer was formed was exposed to light at a specified position with an opening of 90 mm × 30 mm using a dedicated mask, and then shower-developed for 60 seconds using a 0.05 mass % potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. The substrate on which the red colored layer was formed was then baked at 230 ° C. for 30 minutes.
A green composition was applied onto the substrate on which the red colored layer was formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red colored layer was formed, and then the composition was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. At this stage, the residue on the red colored layer was evaluated. Then, the substrate on which the red and green colored layers were formed was baked at 230°C for 30 minutes.
A blue composition was applied onto the substrate on which the red and green colored layers were formed using a spin coater, and an opening of 90 mm x 30 mm was exposed using a dedicated mask at a specified position different from the part on which the red and green colored layers were formed, and then the composition was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and washed with ion-exchanged water. At this stage, the residue on the red and green colored layers was evaluated. Then, the substrate on which the red, green, and blue colored layers were formed was baked at 230°C for 30 minutes.
The residue on each colored layer was evaluated by visually observing the monochrome exposed area (90 mm × 30 mm) of the glass substrate after the formation of the above colored layer, and then wiping it thoroughly with a lens cleaner soaked in ethanol (manufactured by Toray Industries, Inc., product name: Toraysee MK Clean Cloth), and visually observing the degree of coloration of the lens cleaner.
(Development Residue Evaluation Criteria)
A: No development residue was observed by visual inspection, and the lens cleaner was not discolored at all. B: No development residue was observed by visual inspection, and slight discoloration of the lens cleaner was observed. C: A slight development residue was observed by visual inspection, and discoloration of the lens cleaner was observed.
（２）赤→青→緑の順で塗布した場合の赤色及び青色着色層上の現像残渣評価
　着色層の形成順を赤→青→緑に変更した以外は、前記（１）赤→緑→青の順で塗布した場合の赤色及び緑色着色層上の現像残渣評価と同様にして、赤色及び青色着色層上の現像残渣評価を行った。 (2) Evaluation of development residues on red and blue colored layers when coated in the order of red → blue → green Except for changing the order of forming the colored layers to red → blue → green, the evaluation of development residues on the red and blue colored layers was performed in the same manner as in (1) Evaluation of development residues on red and green colored layers when coated in the order of red → green → blue.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
［結果のまとめ］
　比較例１及び４は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む緑色着色層に、青色フタロシアニン顔料と紫色顔料を含む青色着色層とを組み合わせて含むカラーフィルタ基板であるため、青色着色層又は緑色着色層上の現像残渣発生しやすいものであった。
　比較例２及び５は、従来公知の緑色顔料を含む緑色着色層に、青色フタロシアニン顔料と紫色顔料を含む青色着色層とを組み合わせて含むカラーフィルタ基板であるため、現像残渣発生し難いものの、輝度が劣るものであった。
　比較例３は、従来公知の緑色顔料を含む緑色着色層に、前記特定のレーキ色材を含む青色着色層とを組み合わせて含むカラーフィルタ基板であるため、現像残渣発生し難いものの、輝度が劣るものであった。
　実施例１～９は、着色層が、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む緑色着色層に、前記特定のレーキ色材を含む青色着色層を組み合わせて含むカラーフィルタ基板であるため、青色着色層又は緑色着色層上の現像残渣発生が抑制されることが明らかにされた。
　また、青色現像残渣が抑制されたハロゲン化亜鉛フタロシアニン色材が分子状で存在する緑色着色層は、中でも透過率が向上したものであり、緑色現像残渣が抑制された前記特定のレーキ色材を含む青色着色層も、中でも透過率が向上したものであることから、カラーフィルタ全体のホワイト輝度も向上したものであった。 [Summary of results]
Comparative Examples 1 and 4 are color filter substrates including a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded via an ether bond in combination with a blue colored layer containing a blue phthalocyanine pigment and a purple pigment, and therefore were prone to development residues on the blue or green colored layer.
Comparative Examples 2 and 5 are color filter substrates including a green colored layer containing a conventionally known green pigment in combination with a blue colored layer containing a blue phthalocyanine pigment and a purple pigment. Although development residues were unlikely to occur, the brightness was poor.
Comparative Example 3 is a color filter substrate including a green coloring layer containing a conventionally known green pigment in combination with a blue coloring layer containing the specific lake color material. Therefore, although development residues were less likely to occur, the brightness was inferior.
In Examples 1 to 9, the color filter substrate includes a green color layer containing a halogenated zinc phthalocyanine color material having a substituent bonded via an ether bond in combination with a blue color layer containing the specific lake color material, and therefore it was revealed that the occurrence of development residues on the blue color layer or the green color layer was suppressed.
In addition, the green colored layer in which the halogenated zinc phthalocyanine coloring material in which blue development residue is suppressed exists in molecular form has an improved transmittance, and the blue colored layer containing the specific lake coloring material in which green development residue is suppressed also has an improved transmittance, and therefore the white luminance of the entire color filter was also improved.
　１　基板
　２　遮光部
　３　着色層
　１０　カラーフィルタ
　１３ａ、１３ｂ　配向膜
　１５　液晶層
　２０　対向基板
　２５ａ、２５ｂ　偏光板
　３０　バックライト
　４０　液晶表示装置
　５０　有機保護層
　６０　無機酸化膜
　７１　透明陽極
　７２　正孔注入層
　７３　正孔輸送層
　７４　発光層
　７５　電子注入層
　７６　陰極
　８０　発光体
　１００発光表示装置 REFERENCE SIGNS LIST 1 Substrate 2 Light shielding portion 3 Colored layer 10 Color filter 13a, 13b Alignment film 15 Liquid crystal layer 20 Counter substrate 25a, 25b Polarizing plate 30 Backlight 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Emitter 100 Light emitting display device

Claims (4)

  1. 　基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、
    　前記着色層は、エーテル結合を介して置換基が結合したハロゲン化亜鉛フタロシアニン色材を含む、緑色着色層と、
    　下記一般式（１－１）で表される色材及び下記一般式（１－２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を含む、青色着色層と、を含む、カラーフィルタ。
    Figure JPOXMLDOC01-appb-C000001
     （一般式（１－１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
    　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000002
     （一般式（１－２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
    　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）     A color filter including at least a substrate and a colored layer provided on the substrate,
    The colored layer includes a green colored layer containing a halogenated zinc phthalocyanine coloring material having a substituent bonded thereto via an ether bond;
    and a blue colored layer containing at least one lake colorant selected from the group consisting of a colorant represented by the following general formula (1-1) and a colorant represented by the following general formula (1-2):
    Figure JPOXMLDOC01-appb-C000001
     (In general formula (1-1), A represents an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at an end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain. B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , and R iv and R v may bond to form a ring structure. R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 1 represents a divalent aromatic group which may have a substituent. A plurality of R i to R vii and Ar 1 may be the same or different.
    a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent integers of 0 to 4, and f+e and g+e are 0 to 4. Multiple e, f, and g may be the same or different.
    Figure JPOXMLDOC01-appb-C000002
     (In general formula (1-2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V and R VI may be bonded to form a ring structure. R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom, or a cyano group. Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R I to R VIII and Ar 2 may be the same or different. E m- represents an m-valent polyacid anion.
    m represents an integer of 2 or more; j is 0 or 1, and when j is 0, no bond exists; k and l represent integers of 0 to 4, and k+j and l+j are 0 to 4. Multiple j, k and l may be the same or different.
  2. 　前記ハロゲン化亜鉛フタロシアニン色材が、下記一般式（２）で表されるフタロシアニン化合物である、請求項１に記載のカラーフィルタ。
    Figure JPOXMLDOC01-appb-C000003
     （一般式（２）中、Ｘ１～Ｘ１６はそれぞれ独立に、水素原子、ハロゲン原子、又は－Ｏ－ＲＤを表し、ＲＤは１価の有機基を表す。ただし、Ｘ１～Ｘ１６のうち１つ以上はハロゲン原子を表し、Ｘ１～Ｘ１６のうち１つ以上は－Ｏ－ＲＤを表す。）     2. The color filter according to claim 1, wherein the halogenated zinc phthalocyanine coloring material is a phthalocyanine compound represented by the following general formula (2):
    Figure JPOXMLDOC01-appb-C000003
     (In the general formula (2), X 1 to X 16 each independently represent a hydrogen atom, a halogen atom, or -OR D , and R D represents a monovalent organic group. However, at least one of X 1 to X 16 represents a halogen atom, and at least one of X 1 to X 16 represents -OR D. )
  3. 　前記着色層が、少なくともＣ．Ｉ．ピグメントレッド２０２を含む赤色着色層を、更に含む、請求項１又は２に記載のカラーフィルタ。 The color filter according to claim 1 or 2, wherein the colored layer further includes a red colored layer containing at least C.I. Pigment Red 202.
  4. 　請求項１又は２に記載のカラーフィルタを有することを特徴とする表示装置。 A display device comprising the color filter according to claim 1 or 2.
PCT/JP2023/040871 2022-12-01 2023-11-14 Color filter, and display device WO2024116819A1 (en)

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US20170107224A1 (en) * 2015-10-16 2017-04-20 Samsung Sdi Co., Ltd. Novel Compound, Photosensitive Resin Composition Comprising the Same, and Color Filter
KR20170048931A (en) * 2015-10-27 2017-05-10 삼성에스디아이 주식회사 Novel compound,photosensitive resin composition comprising the same and color filter
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JP2012181512A (en) * 2011-02-10 2012-09-20 Fujifilm Corp Colored curable composition and color filter
US20170107224A1 (en) * 2015-10-16 2017-04-20 Samsung Sdi Co., Ltd. Novel Compound, Photosensitive Resin Composition Comprising the Same, and Color Filter
KR20170048931A (en) * 2015-10-27 2017-05-10 삼성에스디아이 주식회사 Novel compound,photosensitive resin composition comprising the same and color filter
US20170253741A1 (en) * 2016-03-02 2017-09-07 Samsung Display Co., Ltd. Dye and dye composition
CN108017650A (en) * 2017-03-08 2018-05-11 先尼科化工（上海）有限公司 A kind of phthalocyanine compound for optical filter and its preparation method and application method
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