WO2015115413A1 - 着色組成物、パターン形成方法、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子、画像表示装置および着色組成物の製造方法 - Google Patents

着色組成物、パターン形成方法、カラーフィルタの製造方法、カラーフィルタ、固体撮像素子、画像表示装置および着色組成物の製造方法 Download PDF

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Publication number
WO2015115413A1
WO2015115413A1 PCT/JP2015/052166 JP2015052166W WO2015115413A1 WO 2015115413 A1 WO2015115413 A1 WO 2015115413A1 JP 2015052166 W JP2015052166 W JP 2015052166W WO 2015115413 A1 WO2015115413 A1 WO 2015115413A1
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Prior art keywords
group
general formula
carbon atoms
dye
ring
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PCT/JP2015/052166
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English (en)
French (fr)
Japanese (ja)
Inventor
金子　祐士
賢 鮫島
宏明 出井
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020167020085A priority Critical patent/KR101892551B1/ko
Priority to CN201580004351.2A priority patent/CN105899549B/zh
Publication of WO2015115413A1 publication Critical patent/WO2015115413A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/16—Monoazo compounds containing chromium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/20—Monoazo compounds containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Definitions

  • the present invention relates to a coloring composition.
  • the present invention also relates to a pattern forming method, a color filter manufacturing method, a color filter, a solid-state imaging device, and an image display device. Moreover, it is related with the manufacturing method of a coloring composition.
  • One of the methods for producing a color filter used for an image display device such as a liquid crystal display device or a solid-state imaging device is a pigment dispersion method.
  • This is a method for producing a color filter by a photolithography method using a dispersed colored photosensitive resin composition. That is, a photosensitive resin composition is applied onto a substrate using a spin coater, a roll coater, or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development to obtain a colored pixel. . By repeating this operation for a desired hue, a color filter is produced.
  • the method described above is stable against light and heat because it uses a pigment, and the positional accuracy is sufficiently secured because patterning is performed by a photolithographic method, and it is suitable as a method for manufacturing a color filter for a color display. It has been widely used.
  • Patent Document 1 and Patent Document 2 are known as photosensitive resin compositions for color filters.
  • Patent Document 1 reports an alkali-soluble resin produced with a specific chain transfer agent in order to improve color resist characteristics.
  • Patent Document 2 discloses that light resistance is improved by a block copolymer of a dye and a light stabilizer.
  • the present inventors have found that the above problem can be solved by using a dye multimer having a specific substituent at the end of the main chain. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 19>.
  • a dye multimer having a dye structure and having a group represented by the general formula (I) or a group represented by the general formula (II) at the end of the main chain, and a color containing a polymerizable compound Composition;
  • ⁇ 3> The colored composition according to ⁇ 1> or ⁇ 2>, further including a pigment.
  • ⁇ 4> The colored composition according to any one of ⁇ 1> to ⁇ 3>, wherein Mw / Mn, which is the degree of dispersion of the dye multimer, is 1.0 to 1.8.
  • ⁇ 5> The colored composition according to any one of ⁇ 1> to ⁇ 4>, further comprising an alkali-soluble resin.
  • ⁇ 6> The colored composition according to any one of ⁇ 1> to ⁇ 5>, wherein the dye multimer is a random polymer of a polymerizable compound containing a dye and another polymerizable compound.
  • ⁇ 7> The colored composition according to any one of ⁇ 1> to ⁇ 6>, wherein the dye multimer contains at least one of dipyrromethene dye, triarylmethane dye, xanthene dye, azo dye, cyanine dye, and squarylium dye .
  • the dye multimer contains at least one of dipyrromethene dye, triarylmethane dye, xanthene dye, azo dye, cyanine dye, and squarylium dye .
  • ⁇ 8> The colored composition according to any one of ⁇ 1> to ⁇ 7>, wherein at least one of the dye multimers is a styrene resin or a (meth) acrylic resin.
  • a and B in the general formula (II) are each independently an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms A composition; provided that R 1 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a carbon atom and a hetero atom; It represents a monovalent heterocyclic group having 3 to 30 atoms in total, and A and B may be connected to each other to form a ring.
  • Z in the general formula (I) is —SR 1 or an aryl group, or A and B in the general formula (II) are each independently a secondary or tertiary alkyl group having 1 to 30 carbon atoms. ⁇ 9>, wherein A and B may be bonded to each other to form a ring.
  • ⁇ 13> A method for producing a color filter, comprising the pattern forming method according to ⁇ 12>.
  • ⁇ 14> A color filter produced using the colored composition according to any one of ⁇ 1> to ⁇ 11> or a color filter produced by the method for producing a color filter according to ⁇ 13>.
  • ⁇ 15> A solid-state imaging device having the color filter according to ⁇ 14>.
  • ⁇ 16> An image display device having the color filter according to ⁇ 14>.
  • ⁇ 17> A method for producing a colored composition, which comprises blending a polymerizable compound after living radical polymerization of a polymerizable compound having a dye structure.
  • ⁇ 18> having a dye structure in the presence of at least one of a compound represented by general formula (Ia), a compound represented by general formula (IIa), and a radical represented by general formula (IIb)
  • the method for producing a colored composition according to ⁇ 17> comprising radical polymerization of a polymerizable compound and another polymerizable compound;
  • Formula (Ia) In general formula (Ia) Z has the same meaning as in general formula (I).
  • C represents a monovalent organic group;
  • D represents a monovalent organic group;
  • Formula (IIb) In general formula (IIb), A and B are synonymous with general formula (II).
  • ⁇ 19> The method for producing a colored composition according to ⁇ 17> or ⁇ 18>, wherein the colored composition is the colored composition according to any one of ⁇ 1> to ⁇ 11>.
  • the present invention it is possible to provide a colored composition having excellent solvent resistance and light resistance. Furthermore, it has become possible to provide a pattern forming method, a color filter manufacturing method, a color filter, a solid-state imaging device, and an image display device using the colored composition. In addition, a method for producing a colored composition can be provided.
  • the coloring composition the pattern forming method, the color filter manufacturing method, the color filter, the solid-state imaging device, and the image display device of the present invention will be described in detail. Moreover, the manufacturing method of a coloring composition is demonstrated.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
  • exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
  • the solid content concentration in this specification refers to the solid content concentration at 25 ° C.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and “(meth) acrylic”
  • "Acryloyl” represents both and / or acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • the monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • process is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • present invention has been made in view of the above situation, and an object thereof is to provide a coloring composition having excellent color characteristics.
  • the weight average molecular weight and the number average molecular weight are defined as polystyrene converted values by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgelgSuper AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
  • the methyl group may be indicated as Me, the ethyl group as Et, the propyl group as Pr, and the phenyl group as PH or Ph.
  • the coloring composition of the present invention has a dye structure and is represented by the group represented by the general formula (I) or the general formula (II). It includes a dye multimer having a group represented by a main chain terminal and a polymerizable compound.
  • the dye multimer used in the present invention is synthesized by living polymerization, for example, the dispersity (Mw / Mn) of the dye multimer can be reduced. That is, it is a dye multimer, and the light resistance can be further improved by reducing the proportion of the high molecular weight component, and the solvent resistance can be improved by reducing the proportion of the low molecular weight component. Can do. Furthermore, heat resistance, applicability, and developability can be further improved.
  • dyes may be applied in place of pigments for the purpose of spectral improvement of color filters. However, since dyes have poor light resistance and heat resistance compared to pigments, color filters to which dyes are applied may have low durability. In the present invention, even when a dye is used as the pigment, these effects can be effectively improved.
  • the colored composition of the present invention preferably further contains a photopolymerization initiator and / or a pigment, and may contain other components such as a crosslinking agent as necessary.
  • the coloring composition of the present invention has a dye structure and has a dye multimer (hereinafter simply referred to as “dye”) having a group represented by the general formula (I) or a group represented by the general formula (II) at the end of the main chain. At least one kind of “multimer”). Two or more dye multimers may be included.
  • a dye multimer is usually a multimer having a partial structure derived from a dye having a maximum absorption wavelength in the range of 400 nm to 780 nm in its molecular structure.
  • the dye multimer of the present invention preferably contains a repeating unit containing a dye monomer, more preferably contains a repeating unit containing a dye monomer and a repeating unit having a polymerizable group. More preferably, it contains a repeating unit containing a repeating unit having a polymerizable group and a repeating unit having an acid group.
  • the dye structure preferably has a cation moiety.
  • the dye multimer functions as, for example, a colorant in the coloring composition of the present invention.
  • the dye multimer of the present invention preferably has a maximum absorption wavelength of 420 to 700 nm, and more preferably 450 to 650 nm.
  • the repeating unit containing a structure derived from a dye is preferably 10 to 100 mol%, preferably 50 to 100 mol% in the dye multimer of the present invention when the total repeating unit is 100 mol%. More preferably, it is 60 to 100 mol%.
  • Z represents a monovalent substituent.
  • Z is a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or the total number of atoms of carbon atoms and hetero atoms 3 to 30 monovalent heterocyclic groups, —OR 1 , —SR 1 , —OC ( ⁇ O) R 1 , —N (R 1 ) (R 2 ), —C ( ⁇ O) OR 1 , —C ( ⁇ O) N (R 1 ) (R 2 ), —P ( ⁇ O) (OR 1 ) 2 , —P ( ⁇ O) (R 1 ) 2 or a monovalent group having a polymer chain is preferred, It is preferably selected from —SR 1 , an aryl group, a heteroaryl group, an amino group substituted with an alkyl group and / or an ary
  • an aryl group is particularly preferably an alkylthio group.
  • the aryl group as Z is preferably a phenyl group or a naphthyl group.
  • the heteroaryl group as Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring compound.
  • the amino group substituted with an alkyl group and / or aryl group as Z is preferably an alkyl group having 1 to 5 carbon atoms or an amino group substituted with a phenyl group.
  • the alkoxy group as Z is preferably an alkoxy group having 2 to 5 carbon atoms.
  • the aryloxy group as Z is preferably a phenoxy group.
  • R 1 and R 2 are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a carbon atom and a hetero atom. And a monovalent heterocyclic group having 3 to 30 atoms in total, the above alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a carbon atom and a hetero atom. These monovalent heterocyclic groups having a total of 3 to 30 atoms, R 1 and R 2 , may be either substituted or unsubstituted. Examples of the substituent when substituted include an alkyl group and an aryl group.
  • R 1 and R 2 are each independently preferably an alkyl group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms or a phenyl group. preferable.
  • a and B each independently represent a monovalent substituent.
  • a and B may be connected to each other to form a ring. * Indicates the binding position to the end of the main chain.
  • the monovalent substituents represented by A and B are each independently preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. More preferably, the alkyl group having 1 to 30 carbon atoms has 3 to 10 carbon atoms.
  • one of A and B is a secondary or tertiary alkyl group having 1 to 30 carbon atoms, and the other is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • one of A and B is tertiary alkyl having 1 to 30 carbon atoms
  • the other of A and B is more preferably an alkyl group having 1 to 30 carbon atoms
  • one of A and B is Particularly preferably, it is a tertiary alkyl group having 1 to 30 carbon atoms
  • the other is a secondary or tertiary alkyl group having 1 to 30 carbon atoms (more preferably a secondary alkyl group having 1 to 30 carbon atoms).
  • the alkyl group having 1 to 30 carbon atoms may have, an aryl group is preferable, and a phenyl group is more preferable.
  • the substituent that the aryl group may have, an aryl group is preferable.
  • these groups may be substituted with other substituents.
  • a and B may be bonded to each other to form a ring.
  • Z in the general formula (I) is —SR 1 or an aryl group
  • a and B in the general formula (II) are each a secondary or tertiary alkyl group having 1 to 30 carbon atoms. (However, A and B may be bonded to each other to form a ring).
  • terminal groups are shown, but the present invention is not limited thereto.
  • Formula (IIb) in general formula (IIb), A and B are synonymous with general formula (II).
  • the terminal inactivation at the time of radical polymerization is in an equilibrium state, and the radical is not apparently deactivated.
  • the dye multimer is preferably a (meth) acrylic resin and / or a styrene resin.
  • the (meth) acrylic resin refers to a resin in which 50 mol% or more of the raw material polymerizable compound is (meth) acrylate
  • the styrene resin refers to 50 mol% or more of the raw material polymerizable compound.
  • a resin in which is styrene Refers to a resin in which is styrene.
  • a (meth) acrylic resin and / or a styrene resin is preferable, and is represented by the general formula (IIa) or the general formula (IIb).
  • a (meth) acrylic resin is preferable.
  • Repeating unit having a dye structure is not particularly defined, but is represented by general formula (A) shown in paragraphs 0276 to 0304 of JP-A-2013-28764, It is preferable that at least one of the structural units represented by the general formula (B) and the general formula (C) is a skeleton. The description of paragraph numbers 0276 to 0304 in JP 2013-28764 is incorporated in the present specification. In this invention, it is preferable that the repeating unit represented by the following general formula (A) is included.
  • the ratio of the repeating unit having a dye structure is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, based on all repeating units constituting the dye multimer.
  • X 1 represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units.
  • X 1 is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but in particular, linking groups represented by the following (XX-1) to (X-24) are preferred, and (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, (XX-18) and (XX- 19), and more preferably selected from vinyl-based linking chains represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), More preferably, it is selected from styrenic linking chains represented by (XX-10) to (XX-17) and vinyl linking chains represented by (XX-24), and (XX-1) and (XX -1) and (
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene).
  • L 1 is preferably also configured to include an anion.
  • L 1 is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH 2 ) n— (n is an integer of 1 to 5).
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently. An example of the case where L 1 contains an anion will be described later.
  • DyeI represents a dye structure derived from a dye compound described later.
  • the dye multimer having the structural unit represented by the general formula (A) includes (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group. It can be synthesized by a method in which a polymer having a highly reactive functional group is reacted with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the highly reactive group.
  • the dye multimer used in the present invention is preferably an addition polymer.
  • the dye multimer having the structural unit represented by the general formula (A) in the present invention was obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. A radical polymer is preferred.
  • the dye structure used in the present invention is not particularly defined, and a known dye structure can be adopted.
  • the dye structure used in the present invention is usually preferably a dye structure containing a cation moiety in the molecule. Specifically, dipyrromethene dye, carbonium dye (diphenylmethane dye, triarylmethane dye, xanthene dye, acridine dye, etc.), azo dye, polymethine dye (oxonol dye, merocyanine dye, arylidene dye, styryl dye, cyanine dye, squarylium dye And a dye structure derived from a dye selected from a subphthalocyanine dye and a metal complex dye thereof.
  • a dye structure derived from a dye selected from dipyrromethene dyes, carbonium dyes, and polymethine dyes is preferable from the viewpoint of color characteristics, and dipyrromethene dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, squarylium dyes. More preferred is a dye structure derived from a dye selected from dipyrromethene dyes, triarylmethane dyes, azo dyes, xanthene dyes, and more preferred is a dye structure derived from dipyrromethene dyes, azo dyes, and xanthene dyes.
  • the dye structure derived from the dye is more preferable, the dye structure derived from the azo dye and the xanthene dye is particularly preferable, and the xanthene dye is most preferable.
  • a cation having such a dye structure is used, heat resistance and light resistance tend to be further improved.
  • the dye structure preferably has a cation.
  • the dye structure preferably used in the present invention will be described in detail.
  • the dipyrromethene dye in the present invention is preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. At one point in these dipyrromethene dye structures, it is attached to the polymer.
  • a compound having a dipyrromethene structure is referred to as a dipyrromethene compound, and a metal or a complex coordinated to a metal compound is referred to as a dipyrromethene metal complex compound.
  • the dipyrromethene metal complex compound is preferably a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, and a tautomer thereof.
  • M dipyrromethene metal complex compound represented by the following general formula (M)
  • a metal or a metal compound a metal compound represented by the following general formula (M)
  • a tautomer thereof a dipyrromethene metal complex compound represented by (7) or the dipyrromethene metal complex compound represented by the following general formula (8) may be mentioned, and the dipyrromethene metal complex compound represented by the general formula (8) is more preferable.
  • One preferred embodiment of the dye structure is represented by the following general formula (M).
  • the compound (dipyrromethene compound) or a tautomer thereof has a dye structure including a metal or a complex coordinated to a metal compound (hereinafter referred to as “specific complex” as appropriate).
  • specific complex a metal compound
  • the following compound forms a cation structure.
  • a metal such as zinc bonded to the nitrogen atom of the general formula (M) can form a cation structure.
  • R 4 to R 10 each independently represents a hydrogen atom or a monovalent substituent, provided that R 4 and R 9 are not bonded to each other to form a ring. .
  • the introduction site in the case of introducing the compound represented by the general formula (M) into the structural units represented by the general formulas (A) to (D) is not particularly limited, but in terms of synthesis compatibility, it is preferable that introduced at any one site R 4 ⁇ R 9, R 4, R 6, it is more preferable that introduced at any one of R 7 and R 9, R 4 and R 9 More preferably, it is introduced in any one of them.
  • Examples of the monovalent substituent in the case where R 4 to R 9 in the general formula (M) represent a monovalent substituent include the substituents mentioned in the section of the substituent group A described later.
  • R 4 to R 9 in the general formula (M) When the monovalent substituents represented by R 4 to R 9 in the general formula (M) are further substitutable groups, they may further have the substituents described for R 4 to R 9. In the case of having two or more substituents, these substituents may be the same or different.
  • R 4 and R 5 , R 5 and R 6 , R 7 and R 8 , and R 8 and R 9 in the general formula (M) are each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered compound.
  • a membered saturated ring or an unsaturated ring may be formed.
  • R 4 and R 9 are not bonded to each other to form a ring.
  • the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they may be substituted with the substituents described for R 4 to R 9 above, and two or more When substituted with a substituent, these substituents may be the same or different.
  • R 4 and R 5 , R 5 and R 6 , R 7 and R 8 , and R 8 and R 9 in general formula (M) are each independently bonded to each other and have no substituent.
  • 6-membered, or 7-membered saturated ring, or unsaturated ring a 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring having no substituent includes, for example, a pyrrole ring, Furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, and pyridazine ring are preferable. Includes a benzene ring or a pyridine ring.
  • R 10 in formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • the halogen atom, alkyl group, aryl group, and heterocyclic group have the same definitions as the halogen atom, alkyl group, aryl group, and heterocyclic group of Substituent Group A described later, and the preferred ranges thereof are also the same. .
  • R 10 represents an alkyl group, an aryl group, or a heterocyclic group
  • the alkyl group, aryl group, and heterocyclic group are groups that can be further substituted, In the case of being substituted with two or more substituents, those substituents may be the same or different.
  • the specific complex in the present invention is a complex in which a dipyrromethene compound represented by the general formula (M) or a tautomer thereof is coordinated to a metal or a metal compound.
  • the metal or metal compound may be any metal or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, Or a bivalent metal chloride is contained.
  • the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and other metals, as well as AlCl, InCl, FeCl, and TiCl.
  • metal chlorides such as SnCl 2 , SiCl 2 and GeCl 2
  • metal oxides such as TiO and VO
  • metal hydroxides such as Si (OH) 2
  • Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex VO is preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn is particularly preferable.
  • R 4 and R 9 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, or an acyl group.
  • R 5 and R 8 are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxy group, or a phosphinoylamino group Carbonyl group, carbamoyl group, imide group, alkylsulfonyl group, ant Rusuruhoniru group or be a sulfamoyl group,; R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, an alkyl group, an alkyl group
  • dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) described in detail below is also a particularly preferable embodiment of the dipyrromethene dye.
  • the dipyrromethene metal complex compound represented by the general formula (7) is a dye structure derived from the dipyrromethene metal complex compound represented by the following general formula (7). is there.
  • the following compound preferably forms a cation structure.
  • Ma in the general formula (7) can form a metal cation structure such as zinc.
  • R 4 to R 9 each independently represents a hydrogen atom or a monovalent substituent
  • R 10 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic ring.
  • Ma represents a metal atom or a metal compound
  • X 1 represents a group capable of binding to Ma
  • X 2 represents a group that neutralizes the charge of Ma
  • X 1 and X 2 represent And may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring together with Ma, provided that R 4 and R 9 are not bonded to each other to form a ring.
  • the dipyrromethene metal complex compound represented by General formula (7) contains a tautomer.
  • the dipyrromethene metal complex compound represented by the general formula (7) is introduced into the structural units represented by the general formulas (A) to (D), but the synthesis compatibility is not limited. In this respect, it is preferably introduced at any one of R 4 to R 9 , more preferably introduced at any one of R 4 , R 6 , R 7 and R 9 , and R 4 and More preferably, it is introduced at any one of R 9 .
  • a method for introducing the alkali-soluble group is any one or two or more of R 4 to R 10 , X 1 and X 2 in the general formula (7).
  • a method in which an alkali-soluble group is added to the substituents of can be used.
  • any of R 4 to R 9 and X 1 is preferable, any of R 4 , R 6 , R 7 and R 9 is more preferable, and any of R 4 and R 9 is more preferable.
  • the dipyrromethene metal complex compound represented by the general formula (7) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.
  • R 4 ⁇ R 9 medium in the general formula (7) has the same meaning as R 4 ⁇ R 9 in the general formula (M), preferable embodiments thereof are also the same.
  • Ma represents a metal atom or a metal compound.
  • the metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included.
  • Metal chlorides, TiO, metal oxides such as V O, and metal hydroxides such as Si (OH) 2 .
  • R 10 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom.
  • X 1 may be any group as long as it is a group capable of binding to Ma.
  • water, alcohols eg, methanol, ethanol, propanol
  • the chelate ” ([1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanoedo), [2] (1996), [3] (1997), etc.) can be mentioned.
  • water, carboxylic acid compounds and alcohols are preferable, and water and carboxylic acid compounds are more preferable.
  • examples of the “group that neutralizes the charge of Ma” represented by X 2 include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. From the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.
  • X 1 and X 2 may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma.
  • the 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated.
  • the 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom. You may do it.
  • R 4 ⁇ R 9 the preferred embodiments described in the general formula (M) in the description of R 4 ⁇ R 9, R 10 is It is a preferred embodiment described in the description of R 10 in the general formula (M), Ma is Zn, Cu, Co, or V ⁇ O, X 1 is water or a carboxylic acid compound, X 2 is a hydroxyl group, Alternatively, it is a carboxylic acid group, and X 1 and X 2 may be bonded to each other to form a 5-membered or 6-membered ring.
  • the dipyrromethene metal complex compound represented by the general formula (8) One preferred embodiment of the dye structure in the cation having the dye structure is a dye structure derived from the dipyrromethene metal complex compound represented by the following general formula (8) It is.
  • the following compound forms a cation structure.
  • Ma in the general formula (8) can form a metal cation structure such as zinc.
  • R 11 and R 16 are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic ring.
  • R 12 to R 15 each independently represents a hydrogen atom or a substituent
  • R 17 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group
  • Ma represents
  • X 2 and X 3 each independently represents NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an aryl group) a sulfonyl group.), a nitrogen atom
  • .Y 1 and Y 2 represents an oxygen atom or a sulfur atom
  • R c is a hydrogen atom, an alkyl group, an alkenyl group, an Lumpur group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group,.
  • .R 11 and Y 1 representing
  • the site for introducing the dipyrromethene metal complex compound represented by the general formula (8) into the structural unit represented by the general formulas (A) to (D) is not particularly limited as long as the effects of the present invention are not impaired.
  • Any one of 11 to R 17 , X 1 , and Y 1 to Y 2 is preferable. Among these, it is preferably introduced at any one of R 11 to R 16 and X 1 in terms of synthesis compatibility, and more preferably any one of R 11 , R 13 , R 14 and R 16 . It is an embodiment inserted in one, and more preferably an embodiment inserted in any one of R 11 and R 16 .
  • the cation having a dye structure When the cation having a dye structure has an alkali-soluble group, it is alkali-soluble in any one or two or more substituents of R 11 to R 17 , X 1 and Y 1 to Y 2 in the general formula (8).
  • a method of providing a group can be used.
  • substituents any of R 11 to R 16 and X 1 is preferred, any of R 11 , R 13 , R 14 and R 16 is more preferred, and any of R 11 and R 16 is more preferred.
  • the dipyrromethene metal complex compound represented by the general formula (8) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.
  • R 12 to R 15 have the same meanings as R 5 to R 8 in the general formula (M), and preferred embodiments are also the same.
  • R 17 has the same meaning as R 10 in the general formula (M), and the preferred embodiment is also the same.
  • Ma is synonymous with Ma in the said General formula (7), and its preferable range is also the same.
  • R 12 and R 15 are each an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile Group, imide group, or carbamoylsulfonyl group is preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group , A carbamoyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are
  • R 13 and R 14 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted.
  • a substituted aryl group preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted.
  • specific examples of more preferable alkyl groups, aryl groups, and heterocyclic groups can be the same as the specific examples listed in the above R 6 and R 7 of the general formula (M).
  • R 11 and R 16 are alkyl groups (preferably linear, branched or cyclic alkyl groups having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl A group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably having a carbon number of 6 to 36, more preferably an aryl group having 6 to 18 carbon atoms, such as a phen
  • R 11 and R 16 are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and an alkyl group, an alkenyl group, an aryl group, a hetero group
  • a cyclic group is more preferable, an alkyl group, an alkenyl group, and an aryl group are more preferable, and an alkyl group is particularly preferable.
  • the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R 11 and R 16 is Further, in the case of a group that can be further substituted, it may be substituted with the substituent described in the section of the substituent group A to be described later, and when it is substituted with two or more substituents, The substituents may be the same or different.
  • X 2 and X 3 each independently represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom.
  • R is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably carbon An alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as a vinyl group, allyl group, 3-buten-1-yl group), aryl group
  • Y 1 and Y 2 each independently represent NR C , a nitrogen atom, or a carbon atom, and R C has the same meaning as R in X 2 and X 3 above, and preferred embodiments are also included. It is the same.
  • R 11 and Y 1 are bonded to each other together with a carbon atom to form a 5-membered ring (eg, cyclopentane ring, pyrrolidine ring, tetrahydrofuran ring, dioxolane ring, tetrahydrothiophene ring, pyrrole ring, furan ring, Thiophene ring, indole ring, benzofuran ring, benzothiophene ring), 6-membered ring (for example, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, dioxane ring, pentamethylene sulfide ring, dithiane ring, benzene ring, A piperidine ring, a piperazine ring, a pyridazine ring, a quinoline ring, a quinazoline
  • R 16 and Y 2 are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane ring, pyrrolidine ring, tetrahydrofuran ring, dioxolane ring, tetrahydrothiophene ring, pyrrole ring, furan ring) , Thiophene ring, indole ring, benzofuran ring, benzothiophene ring), 6-membered ring (for example, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, dioxane ring, pentamethylene sulfide ring, dithiane ring, benzene ring , A piperidine ring, a piperazine ring, a pyridazine ring, a quinoline ring, a quin
  • R 11 and R 16 are each independently preferably a monovalent substituent having a steric parameter —Es ′ value of 1.5 or more, and 2.0 or more. Is more preferably 3.5 or more, and particularly preferably 5.0 or more.
  • the steric parameter-Es' value is a parameter that represents the steric bulk of the substituent, and the literature (JAMacphee, et al, Tetrahedron, Vol.34, pp3553-3562, edited by Ikuo Fujita, Chemical Extension 107, Structure Activity Relationship) And the Drag Design, published on February 20, 1986 (Chemical Doujin)) -Es' value is used.
  • X 1 represents a group capable of binding to Ma, specifically, the same groups as X 1 in General Formula (7) can be mentioned, and preferred embodiments are also the same.
  • a represents 0, 1, or 2.
  • R 12 to R 15 are each independently a preferred embodiment described in the explanation of R 5 to R 8 in the general formula (M).
  • R 17 is a preferred embodiment described in the description of R 10 in the general formula (M)
  • Ma is Zn, Cu, Co, or V ⁇ O
  • X 2 is NR (R is a hydrogen atom, an alkyl group) ), A nitrogen atom, or an oxygen atom
  • X 3 is NR (R is a hydrogen atom, an alkyl group), or an oxygen atom
  • Y 1 is NR C (R C is a hydrogen atom, an alkyl group), a nitrogen atom, Or a carbon atom
  • Y 2 is a nitrogen atom or a carbon atom
  • R 11 and R 16 are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group
  • X 1 Is a group bonded through an oxygen atom, and a
  • R 12 to R 15 are each independently a preferred embodiment described in the description of R 5 to R 8 in the compound represented by the general formula (M).
  • R 17 is a preferred embodiment described in the description of R 10 in the general formula (M)
  • Ma is Zn
  • X 2 and X 3 are oxygen atoms
  • Y 1 is NH.
  • Y 2 is a nitrogen atom
  • R 11 and R 16 are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group
  • X 1 is a group bonded through an oxygen atom.
  • a is 0 or 1.
  • R 11 and Y 1 may be bonded to each other to form a 5- or 6-membered ring, or R 16 and Y 2 may be bonded to each other to form a 5- or 6-membered ring.
  • the molar extinction coefficient of the dipyrromethene metal complex compound represented by the general formulas (7) and (8) is preferably as high as possible from the viewpoint of coloring power.
  • the maximum absorption wavelength ⁇ max is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. By being in this region, a color filter with good color reproducibility can be produced using the colored composition of the present invention.
  • the dye having a dye structure derived from the dipyrromethene dye preferably has an absorbance at the maximum absorption wavelength ( ⁇ max) of 1,000 times or more, more preferably 10,000 times or more with respect to the absorbance at 450 nm. Preferably, it is 100,000 times or more.
  • ⁇ max the maximum absorption wavelength
  • a color filter with higher transmittance can be formed using the colored composition of the present invention, particularly when producing a blue color filter.
  • the maximum absorption wavelength and the molar extinction coefficient are measured with a spectrophotometer carry5 (manufactured by Varian).
  • the melting point of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) should not be too high from the viewpoint of solubility.
  • the dipyrromethene metal complex compounds represented by the above general formula (7) and general formula (8) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, and JP-A-2001-240761. Gazette, 2002-155052 gazette, Japanese Patent No. 3614586 gazette, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.
  • dipyrromethene dye examples include a dipyrromethene dye, but the present invention is not limited thereto.
  • X represents an anion.
  • any hydrogen atom of the following dye structure is bonded to the polymer backbone.
  • (PM-8) and (PM-10) are particularly preferable from the viewpoint of color characteristics and heat resistance.
  • Carbonium Dye ⁇ Carbonium Dye >>> Of the carbonium dyes, triarylmethane dyes and xanthene dyes are preferable.
  • Triarylmethane Dye One of the embodiments of the dye structure according to the present invention has a partial structure derived from a triarylmethane dye (triarylmethane compound).
  • dye it has the partial structure derived from the compound (triarylmethane compound) represented by the following general formula (TP) as a pigment
  • Rtp 1 to Rtp 4 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9
  • Rtp 10 Rtp 10 9 and Rtp 10 represent a hydrogen atom, an alkyl group or an aryl group
  • Rtp 6 , Rtp 7 and Rtp 8 represent a substituent
  • a, b and c represent an integer of 0 to 4.
  • a , B and c are 2 or more
  • Rtp 6 , Rtp 7 and Rtp 8 may be linked to form a ring
  • X ⁇ represents an anion structure.
  • the introduction site in the case of introducing the compound represented by the general formula (TP) into the structural unit represented by the general formula (A) is not particularly limited, but at any one site of Rtp 1 to Rtp 10 It is preferably introduced.
  • a preferred embodiment of the dye structure in the present invention has a partial structure derived from a xanthene dye (xanthene compound).
  • xanthene compound As said pigment
  • R 81 , R 82 , R 83 and R 84 each independently represents a hydrogen atom or a monovalent substituent, and R 85 each independently represents a monovalent substituent.
  • M represents an integer of 0 to 5.
  • X ⁇ represents an anion, or X ⁇ does not exist, and at least one of R 81 , R 82 , R 83 , R 84 and R 85 contains an anion.
  • R 81 and R 82 , R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other to form a 5-, 6-, or 7-membered saturation.
  • a ring or a 5-membered, 6-membered or 7-membered unsaturated ring may be formed.
  • the 5-membered, 6-membered or 7-membered ring formed is a further substitutable group, it may be substituted with the substituents described for R 81 to R 85 above, and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.
  • R 81 and R 82 in the above general formula (J), R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other, and have no substituent.
  • the unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine A ring, a pyrazine ring, and a pyridazine ring are mentioned, Pre
  • R 82 and R 83 are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R 81 and R 84 are preferably a substituted or unsubstituted alkyl group or a phenyl group.
  • R 85 is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. The sulfo group, the sulfonamide group, the carboxyl group, More preferred is an amide group.
  • R 85 is preferably bonded to the adjacent part of carbon linked to the xanthene ring.
  • the substituent that the phenyl group of R 81 and R 84 has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.
  • the compound having a xanthene skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specifically, the methods described in Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.
  • X ⁇ represents an anion
  • the description in the case where the counter anion described later is a different molecule can be referred to, X ⁇ does not exist, and at least one of R 81 , R 82 , R 83 , R 84 , and R 85 is
  • an anion is included, the description in the case where the counter anion is in the same repeating unit can be referred to.
  • R 81 and R 83 are a group represented by the following general formula (2), the other of R 81 and R 83 is a hydrogen atom, and the following general formula (2) ) Or an aryl group or an alkyl group other than the group represented by the general formula (2).
  • R 82 and R 84 may each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • R 1 and R 2 each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group
  • X 1 to X 3 each independently represent a hydrogen atom Alternatively, it represents a monovalent substituent.
  • the dye compound represented by the general formula (1) has a counter anion inside and / or outside the molecule. By setting it as such a structure, the solvent solubility of a coloring composition improves more, As a result, it becomes possible to form the colored layer in which planar unevenness was suppressed more.
  • R 81 and R 83 are a group represented by general formula (2), and the other of R 81 and R 83 is a hydrogen atom, represented by the following general formula (2).
  • both of R 81 and R 83 may be a group represented by the general formula (2).
  • the groups represented by the two general formulas (2) may be the same or different.
  • R 1 and R 2 each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group, and a secondary or tertiary alkyl group having 3 to 12 carbon atoms. Or an isopropyl group.
  • the alkyl group having 3 or more carbon atoms may be linear, branched or cyclic, may have 3 to 24 carbon atoms, may have 3 to 18 carbon atoms, The number may be 3 to 12.
  • propyl group isopropyl group, butyl group (for example, t-butyl group), pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, And cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, It may be a dodecyl group, a cyclopropyl group, a cyclopentyl group or a cyclohexyl group, and may be a propyl group, an isopropyl group, an isoprop
  • the aryl group includes a substituted or unsubstituted aryl group.
  • the substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
  • the heterocycle of the heterocycle group may be a 5-membered or 6-membered ring, and they may be further condensed or not condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle.
  • it may be an aromatic heterocyclic group, such as a pyridine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, Examples thereof include a benzisothiazole ring and a thiadiazole ring, and may be a pyrazole ring, an imidazole ring, a benzoxazole ring, a thiadiazole ring, a pyrazole ring, a thiadiazole ring (1,3,4-thiadiazole ring, 1,2,4- A thiadiazole ring).
  • aromatic heterocyclic group such as a pyridine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring
  • R 1 and R 2 may be an alkyl group having 3 or more carbon atoms, or an alkyl group having 3 to 12 carbon atoms.
  • X 1 to X 3 each independently represents a hydrogen atom or a monovalent substituent.
  • substituent include the substituent group A described later.
  • X 1 to X 3 may be a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkylthio group, a sulfonamide group, or a sulfamoyl group.
  • Examples of the aryl group other than the group represented by the general formula (2) include a phenyl group.
  • the phenyl group may or may not have a substituent.
  • Examples of the substituent include substituent group A described later, and may be an alkyl group or an aryl group.
  • R 82 and R 84 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and the alkyl group and the aryl group may or may not have a substituent.
  • the substituted or unsubstituted alkyl group may be an alkyl group having 1 to 30 carbon atoms.
  • a substituent the same thing as the substituent group A mentioned later is mentioned.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), an n-octyl group, and a 2-ethylhexyl group.
  • the substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
  • R 82 and R 84 may be a hydrogen atom or an alkyl group, and may be a hydrogen atom.
  • R 81 and R 83 may each independently be an aliphatic hydrocarbon group
  • R 82 and R 84 may each independently be an aromatic hydrocarbon group.
  • R 81 and R 83 each independently represents an aliphatic hydrocarbon group, which may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a methyl group, It may be an ethyl group, a propyl group or a butyl group, and may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or an n-butyl group.
  • R 81 and R 83 may be different, but may be the same.
  • the alkyl group as R 81 and R 83 may have a substituent, but may have a substituent.
  • R 82 and R 84 are each independently an aromatic hydrocarbon group, and may be a phenyl group.
  • the aromatic hydrocarbon group as R 82 and R 84 may have a substituent, may be selected from the substituent group A described later, and may be an alkyl group having 1 to 5 carbon atoms. , An ethyl group, a propyl group or a butyl group, or a methyl group, an ethyl group, an n-propyl group or an n-butyl group.
  • At least one of R 81 and R 83 and R 82 and R 84 may be represented by the following general formula (A1-1-2).
  • R 23 to R 25 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, a sulfonyl group.
  • R 22 and R 26 each independently represents an alkyl group having 1 to 5 carbon atoms.
  • R 23 to R 25 may be a hydrogen atom or a halogen atom.
  • R 22 and R 26 may each independently be an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, or a butyl group, and is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. Also good.
  • Each R 85 may independently be a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and may be a fluorine atom or a chlorine atom.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkenyl group, and may be an alkyl group.
  • the aromatic hydrocarbon group may be an aryl group or a phenyl group.
  • any hydrogen atom of the following dye structure is bonded to the polymer backbone.
  • azo dye a known azo dye (for example, substituted azobenzene (specifically described later (AZ-4) to (AZ-6) and the like)) can be appropriately selected and applied.
  • azo dyes known as magenta dyes and yellow dyes can be used, and among them, the following general formula (d), general formula (e), general formula (g), general formula (I-1) ), Azo dyes represented by general formula (I-2) and general formula (V) are preferred.
  • azo dyes represented by the following general formula (d) that are magenta dyes.
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl A represents a sulfonyl group or an arylsulfonyl group, A represents an aryl group or an aromatic heterocyclic group, and Z 1 to Z 3 each independently represents —C (R 5 ) ⁇ , or —N ⁇ .
  • R 5 represents a hydrogen atom or a substituent.
  • R 1 to R 4 each independently represent a hydrogen atom or an alkyl group (preferably a straight chain, branched chain, or cyclic group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms).
  • Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl groups (preferably having a carbon number)
  • a bicyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group ( Preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, such as acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 1 to 10 carbon atoms, More preferably, it is an alkoxycarbonyl group having 1 to 6 carbon atoms, such as methoxycarbonyl or ethoxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 15 carbon atoms, more preferably an aryloxycarbonyl group having 6 to 10 carbon atoms).
  • phenoxycarbonyl a carbamoyl group (preferably A carbamoyl group having 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, such as dimethylcarbamoyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms).
  • An arylsulfonyl group preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthylsulfonyl).
  • R 1 and R 3 are preferably each independently an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
  • R 2 and R 4 are preferably each independently a hydrogen atom or an alkyl group.
  • R 1 to R 4 are substitutable groups, for example, they may be substituted with the substituents described in the above-mentioned Substituent group A section, and in the case of having two or more substituents These substituents may be the same or different.
  • Z 1 to Z 3 each independently represents —C (R 5 ) ⁇ or —N ⁇ , and R 5 represents a hydrogen atom or a substituent.
  • R 5 represents a hydrogen atom or a substituent.
  • the substituent for R 5 include the substituents described in the above-mentioned substituent section.
  • R 5 When the substituent of R 5 is a further substitutable group, for example, it may be substituted with the substituent described in the above-mentioned Substituent group A, and may be substituted with two or more substituents. In some cases, the substituents may be the same or different.
  • Z 1 is preferably —N ⁇
  • Z 3 is —C (R 5 ) ⁇ . is there. More preferably, Z 1 is —N ⁇ and Z 2 and Z 3 are —C (R 5 ) ⁇ .
  • A represents an aryl group or an aromatic heterocyclic group.
  • the aryl group of A and the aromatic heterocyclic group may further have, for example, the substituent described in the above-mentioned substituent section, and when it is substituted with two or more substituents These substituents may be the same or different.
  • A is preferably an aromatic heterocyclic group. More preferably, an imidazole ring, pyrazole ring, triazole ring, thiazole ring, oxazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyrimidine ring, pyrazine ring, benzopyrazole ring, Examples include a benzothiazole ring.
  • sites polymerizable group participate in multimerization is introduced is not particularly limited, in view of synthesis suitability, R 1, R It is preferably introduced into any one or more of 2 and A, more preferably R 1 and / or A.
  • the azo dye represented by the general formula (d) is more preferably an azo dye represented by the following general formula (d ′).
  • R 1 ⁇ R 4 has the same meaning as R 1 ⁇ R 4 in the general formula (d), and preferred ranges are also the same.
  • Ra represents an electron-withdrawing group having a Hammett's substituent constant ⁇ p value of 0.2 or more
  • Rb represents a hydrogen atom or a monovalent substituent.
  • Rc represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group.
  • Examples of the substituent represented by Rb include the substituents described in the section of the substituent group A.
  • an azo dye represented by the following general formula (e) which is a magenta dye is also preferably exemplified.
  • R 11 to R 16 each independently represents a hydrogen atom or a monovalent substituent.
  • R 11 and R 12 , and R 15 and R 16 may be independently bonded to each other to form a ring.
  • R 11 to R 16 each independently represents a hydrogen atom or a monovalent substituent.
  • the monovalent substituent include a halogen atom, an alkyl group having 1 to 30 carbon atoms (here, a saturated aliphatic group including a cycloalkyl group and a bicycloalkyl group), and an alkenyl group having 2 to 30 carbon atoms.
  • a group (which means a cycloalkenyl group or an unsaturated aliphatic group having a double bond including a bicycloalkenyl group), an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a carbon number A heterocyclic group having 3 to 30 carbon atoms, a cyano group, an aliphatic oxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an acyloxy group having 2 to 30 carbon atoms, and a carbamoyloxy group having 1 to 30 carbon atoms
  • An aliphatic oxycarbonyl group having 2 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, and 3 to 3 carbon atoms 0 aryl or heterocyclic azo group, and imide group, each group may further have a substituent.
  • R 11 and R 12 are preferably each independently a hydrogen atom, a heterocyclic group or a cyano group, more preferably a cyano group.
  • R 13 and R 14 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.
  • R 15 and R 16 are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.
  • R 13 R in terms of synthesis compatibility. It is preferably introduced into any one or more of 15 and R 16 , more preferably R 13 and / or R 15 , and still more preferably R 13 .
  • the azo dye represented by the general formula (e) is more preferable.
  • azo dye examples include yellow dyes represented by the following general formula (g), general formula (I-1), general formula (I-2), and general formula (V) (their tautomers). (Including the body).
  • R 34 represents a hydrogen atom or a substituent
  • R 35 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.
  • Z 30 and Z 31 each independently represent —C (R 36 ) ⁇ or —N ⁇
  • R 36 represents a hydrogen atom or a substituent.
  • a 31 represents an aryl group or an aromatic heterocyclic group.
  • R 34 represents a hydrogen atom or a monovalent substituent, and examples thereof include the substituents described in the above-mentioned Substituent Group A section, preferably an aryl group and a heterocyclic group, and more preferably a phenyl group.
  • R 35 represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably alkenyl having 2 to 12 carbon atoms) Groups such as vinyl, allyl, 3-buten-1-yl), aryl groups (preferably aryl groups having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms such as phenyl, naphthyl), hetero A cyclic group (preferably a heterocyclic group having 1 to 24 carbon
  • a methoxycarbonyl group for example, a methoxycarbonyl group, an ethoxycarbonyl group), or a carbamoyl group (preferably a carbamoyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, for example, N, N-dimethylcarbamoyl).
  • a carbamoyl group preferably a carbamoyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, for example, N, N-dimethylcarbamoyl.
  • Z 30 and Z 31 each independently represent —C (R 36 ) ⁇ or —N ⁇ , and R 36 represents a hydrogen atom or a substituent.
  • R 36 represents a hydrogen atom or a substituent.
  • the substituent for R 36 include the substituents described in the above-mentioned Substituent group A section.
  • R 36 is a further substitutable group, for example, it may be substituted with the substituent described in the above-mentioned Substituent group A, and may be substituted with two or more substituents. In some cases, the substituents may be the same or different.
  • Z 30 and Z 31 Z 30 is preferably —N ⁇ and Z 31 is —C (R 36 ) ⁇ .
  • a 31 has the same meaning as A in the general formula (d), and the preferred embodiment is also the same.
  • Ri 1 , Ri 2 and Ri 3 each independently represent a monovalent substituent.
  • a represents an integer of 0 to 5. When a is 2 or more, they may be connected by two adjacent Ri 1 to form a condensed ring.
  • b and c each independently represents an integer of 0 to 4. When b and c are 1 or more, they may be connected by two adjacent Ri 1 to form a condensed ring.
  • a 32 represents the following general formula (IA), general formula (IB), or general formula (IC).
  • R42 represents a hydrogen atom, an alkyl group, or an aryl group.
  • R 43 represents a monovalent substituent.
  • R 44 represents a hydrogen atom, an alkyl group, or an aryl group.
  • R 44 and R 45 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • T represents an oxygen atom or a sulfur atom.
  • R 46 represents a hydrogen atom, an alkyl group, or an aryl group.
  • R 47 represents a monovalent substituent.
  • Examples of the monovalent substituent represented by Ri 1 , Ri 2 and Ri 3 in the general formula (I-1) and the general formula (I-2) include the substituents mentioned in the section of the substituent group A. More specifically, the monovalent substituent is an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms such as methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), aryl group (preferably having 6 to 36 carbon atoms, more preferably carbon number) 6-18 aryl groups, for example, phenyl, naphthyl, sulfonamido groups), alkenyl groups (straight chain, branched chain
  • R 42 represents a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.
  • Examples of the monovalent substituent represented by R 43 include the substituents mentioned in the above-mentioned Substituent group A, and particularly preferred are a cyano group and a carbamoyl group.
  • R 44 represents a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.
  • T represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable.
  • R 44 and R 45 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.
  • R 46 represents a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably an alkyl group having 1 to 5 carbon atoms and a phenyl group.
  • Examples of the monovalent substituent represented by R 47 include the substituents mentioned in the above-mentioned Substituent Group A section, preferably a hydrogen atom, an alkyl group and an aryl group, particularly an alkyl group having 1 to 5 carbon atoms and a phenyl group. Groups are preferred.
  • Mv represents Cr or Co.
  • Rv 1 represents an oxygen atom or —COO—.
  • Rv 2 and Rv 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • v represents an integer of 0 to 4.
  • Rv 4 represents a monovalent substituent. When v is 2 or more, adjacent Rv 4 may be connected to each other to form a ring.
  • Rv 2 and Rv 3 are particularly preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • Examples of the monovalent substituent represented by Rv 4 include the substituents mentioned in the above-mentioned Substituent Group A section, particularly preferably an alkyl group, an aryl group, a nitro group, a sulfamoyl group, and a sulfo group. Most preferred are 5 alkyl groups, phenyl groups, and nitro groups.
  • the azo dyes represented by the general formula (I-1), the general formula (I-2), and the general formula (V) are preferable as the yellow dye.
  • cyanine dye a partial structure derived from a cyanine dye (cyanine compound). Details of these can be referred to the descriptions in paragraph numbers 0191 to 0201 of JP 2013-28764 A, and the contents thereof are incorporated in the present specification.
  • Subphthalocyanine Dye One embodiment of the cation having a dye structure according to the present invention is one having a subphthalocyanine dye structure. Details of these can be referred to the description of paragraph numbers 0242 to 0250 in JP 2013-28764 A, and the contents thereof are incorporated in the present specification.
  • the cation having a dye structure used in the present invention may have a squarylium dye structure. Details of these can be referred to the descriptions in paragraph numbers 0202 to 0223 of JP2013-28764A, the contents of which are incorporated herein.
  • a hydrogen atom in the dye structure may be substituted with a substituent selected from the following substituent group A unless departing from the spirit of the present invention.
  • substituent group A examples of the substituent that the dye may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and a carboxyl group.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • a linear or branched alkyl group a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms
  • a cycloalkyl group preferably substituted with 3 to 30 carbon atoms or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms
  • Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl A group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred.
  • Cycloalkenyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),
  • An aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl
  • a heterocyclic group preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom
  • a heterocyclic group having at least one hetero atom of any one of a nitrogen atom, an oxygen atom and a sulfur atom more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms
  • alkoxy group preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy
  • aryloxy group preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy
  • silyloxy group preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy
  • a heterocyclic oxy group preferably having a carbon number of 2 to 30 substituted or unsubstituted heterocyclic oxy groups , Heterocyclic portion is preferably described
  • An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituent having 2
  • amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms
  • amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-oc
  • Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino)
  • Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atom
  • alkylthio group preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio
  • arylthio group preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms
  • the heterocyclic portion described in the above is preferably, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfur Moil, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (
  • alkyl or arylsulfinyl group preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl
  • an alkyl or arylsulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl
  • alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl
  • a carbamoyl group preferably having a carbon number 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero
  • a ring azo group preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle
  • a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substitution having 3 to 30 carbon atoms) Or, an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).
  • those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups.
  • functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group.
  • methylsulfonylaminocarbonyl examples thereof include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups.
  • the counter anion may be in the same repeating unit of the dye multimer or outside the same repeating unit.
  • the counter anion is in the same repeating unit refers to a case where a cation and an anion are bonded via a covalent bond in a repeating unit having a dye structure.
  • “outside the same repeating unit” means a case other than the above. For example, it refers to the case where the cation and the anion are not bonded via a covalent bond and exist as separate compounds, or the case where the cation and the anion are contained as independent repeating units of the dye multimer.
  • the anion in the present invention is preferably a non-nucleophilic anion.
  • the non-nucleophilic anion may be an organic anion or an inorganic anion, and an organic anion is preferred.
  • Examples of the counter anion used in the present invention include known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.
  • the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
  • the first embodiment of the anion in the present invention is a case in which the counter anion is in the same repeating unit. Specifically, in the repeating unit having a dye structure, And an anion are bonded via a covalent bond.
  • the anion moiety is at least selected from —SO 3 ⁇ , —COO ⁇ , —PO 4 ⁇ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2).
  • 1 type is preferable and at least 1 sort (s) selected from the structure represented by the following general formula (A1) and the structure represented by the following general formula (A2) is more preferable.
  • the general formula (A1) is more preferably represented by the following general formula (A1-1).
  • Formula (A1-1) (In General Formula (A1-1), R 1 and R 2 each independently represent —SO 2 — or —CO—, and X 1 and X 2 each independently represent an alkylene group or an arylene group. )
  • R 1 and R 2 of the general formula (A1) in the same meaning as R 1 and R 2, and preferred ranges are also the same.
  • X 1 represents an alkylene group
  • the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • X 1 represents an arylene group
  • the number of carbon atoms in the arylene group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6.
  • X 1 has a substituent, it is preferably substituted with a fluorine atom.
  • X 2 represents an alkyl group or an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.
  • X 2 has a substituent, it is preferably substituted with a fluorine atom.
  • R 3 represents —SO 2 — or —CO—.
  • R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
  • Preferably representing the at least two R 3 ⁇ R 5 is -SO 2 - - In formula (A2), at least one of R 3 ⁇ R 5 -SO 2 more preferably represents.
  • a part of L 1 includes a portion represented by the general formula (A1).
  • the case is given as a preferred example. Specific examples in this case include (a-xt-1), (a-xt-5), and (a-xt-6) among examples of repeating units having a dye structure described later.
  • the case where the skeleton of the dye multimer used in the present invention includes the structural unit represented by the general formula (B) is also given as an example. Specific examples of this case include (B-dp-1), (B-mp-1), (B-xt-1), (B-xt-) among the examples of repeating units having a dye structure described later. 2) is exemplified.
  • the second embodiment of the anion in the present invention is a case where the counter anion is outside the same repeating unit, and the cation and the anion do not bind via a covalent bond and exist as separate molecules.
  • the anion in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a non-nucleophilic anion, and a non-nucleophilic anion is preferable.
  • the non-nucleophilic counter anion may be an organic anion or an inorganic anion, and an organic anion is preferred.
  • Examples of the counter anion used in the present invention include known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.
  • 4-n1 R a is an alkyl group having 1 to 10 carbon atoms or carbon number Represents an aryl group of 6 to 10, n1 represents 1 to 4)
  • PF n2 R P (6-n2) ⁇ R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents 1 to 6
  • AN-1 a structure represented by the following general formula (AN-1) is preferable.
  • X 1 and X 2 each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom.
  • X 1 and X 2 are bonded to each other to form a ring. It may be formed.
  • X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ⁇ 10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.
  • a structure represented by the following general formula (AN-2) is preferable.
  • X 3 , X 4 and X 5 each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
  • X 3 , X 4 and X 5 are each independently the same as X 1 and X 2 , and the preferred range is also the same.
  • the tetraarylborate anion which is a non-nucleophilic counter anion, is preferably a compound represented by the following general formula ((AN-5)).
  • AN-5 Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
  • the aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent.
  • a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferred, and a fluorine atom and a C 1-4 perfluoroalkyl group are more preferred.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently more preferably a phenyl group having a halogen atom and / or an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having fluorine. Is more preferable.
  • the non-nucleophilic counter anion is also —B (CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4.
  • Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • R a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
  • n1 is preferably 1 to 3, and more preferably 1 to 2.
  • the non-nucleophilic counter anion is further —PF 6 R P (6-n2) ⁇ (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6) It is preferable that R P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 3 carbon atoms. n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably 100 to 1,000, and more preferably 200 to 500.
  • the dye multimer of the present invention may contain only one kind of non-nucleophilic counter anion, or may contain two or more kinds.
  • non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.
  • the anion may be a multimer.
  • the multimer in this case include a multimer containing a repeating unit containing an anion and not containing a repeating unit derived from a dye structure containing a cation.
  • the repeating unit containing an anion can mention the repeating unit containing the anion described in 3rd embodiment mentioned later as a preferable example.
  • the multimer containing an anion may have a repeating unit other than the repeating unit containing an anion. As such a repeating unit, other repeating units that may be contained in the dye multimer used in the present invention to be described later are exemplified as preferred examples.
  • the anion may be present in the side chain of the dye multimer, may be present in the main chain, or has a counter anion in both the main chain and the side chain. Also good. Preferably, it is a side chain.
  • the repeating unit containing an anion include a repeating unit represented by the general formula (C) and a repeating unit represented by the general formula (D).
  • X 1 represents the main chain of the repeating unit.
  • L 1 represents a single bond or a divalent linking group.
  • Anion represents a counter anion.
  • X 1 represents the main chain of the repeating unit, and usually represents a linking group formed by a polymerization reaction, and is preferably (meth) acrylic, styrene, vinyl, etc. More preferred are (meth) acrylic and styrene, and (meth) acrylic is more preferred.
  • Two sites represented by * are repeating units.
  • L 1 represents a divalent linking group
  • an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, —CH ⁇ CH—, —O—, —S—, —C ( ⁇ O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO 2 — and a linking group obtained by combining two or more thereof are preferred.
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
  • L 1 is a single bond, an alkylene group having 1 to 10 carbon atoms (preferably — (CH 2 ) n— (n is an integer of 5 to 10), an arylene group having 6 to 12 carbon atoms (preferably phenylene group, naphthalene group) is, - NH -, - CO 2 -, - O- and -SO 2 - is a divalent linking group formed by combining two or more preferred.
  • Formula (D) (In general formula (D), L 2 and L 3 each independently represent a single bond or a divalent linking group. Anion represents the counter anion.)
  • L 2 and L 3 represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH ⁇ CH— , —O—, —S—, —C ( ⁇ O) —, —CO 2 —, —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and combinations of two or more thereof
  • the linking group is preferred.
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
  • L 2 is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group).
  • the arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
  • L 3 is preferably a group composed of a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.
  • the anion portion described in the case where the counter anion is in the same repeating unit is exemplified as a preferable anion.
  • repeating units having a dye structure that are preferably used in the present invention are shown below. Needless to say, the present invention is not limited to these examples.
  • X ⁇ represents a counter anion. Moreover, although a part of X is shown in a state where the anion structure is not dissociated, it goes without saying that the dissociated state is also included in the present invention.
  • the dye multimer of the present invention may have another functional group in the dye structure portion of the dye multimer described above. Examples of other functional groups include polymerizable groups and alkali-soluble groups.
  • the dye multimer of the present invention may contain other repeating units in addition to the repeating unit containing the dye structure described above. Other repeating units may have a functional group.
  • the repeating unit containing at least 1 sort (s) of a polymeric group and an alkali-soluble group (preferably acid group) is illustrated. That is, the dye multimer of the present invention may have other repeating units in addition to the repeating units represented by the general formulas (A) to (C).
  • One type of other repeating unit may be included in one dye multimer, or two or more types may be included.
  • the dye multimer of the present invention may have other functional groups in the dye multimer represented by the general formulas (A) to (D). Details of these will be described below.
  • the dye multimer of the present invention preferably contains a polymerizable group.
  • One type of polymerizable group may be included, or two or more types may be included.
  • the dye structure may contain a polymerizable group, or may contain other parts.
  • the dye structure preferably includes a polymerizable group. By adopting such a configuration, the heat resistance tends to be improved.
  • dye structure contain a polymeric group is also preferable.
  • the polymerizable group a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used.
  • a group containing an ethylenically unsaturated bond a cyclic ether group (epoxy group, oxetane group),
  • a methylol group and the like can be mentioned, a group containing an ethylenically unsaturated bond is particularly preferred, a (meth) acryloyl group is more preferred, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate ( More preferred is a (meth) acryloyl group.
  • the polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye multimer, and more preferably as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye multimer of the present invention is an embodiment in which the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having a polymerizable group, and the repeating contains a dye monomer. More preferably, the unit contains a repeating unit having an ethylenically unsaturated bond.
  • a method for introducing a polymerizable group (1) a method in which a dye multimer is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. Etc. Details will be described below.
  • a method of introducing a dye multimer after modifying it with a polymerizable group-containing compound As a method for introducing the dye multimer by modifying with a polymerizable group-containing compound, a known method can be used without any particular limitation. For example, (a) a method of reacting a carboxylic acid contained in a dye multimer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting a hydroxyl group or amino group of the dye multimer with an unsaturated bond-containing isocyanate compound. (C) A method of reacting an epoxy compound contained in the dye multimer with an unsaturated bond-containing carboxylic acid compound is preferable from the viewpoint of production.
  • Examples of the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid of the dye multimer with the unsaturated bond-containing epoxy compound include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxy. Examples thereof include cyclohexylmethyl acrylate and 3,4-epoxy-cyclohexylmethyl methacrylate, and glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate are particularly preferable because of excellent crosslinkability and storage stability.
  • Known conditions can be used as the reaction conditions.
  • the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the dye multimer with the unsaturated bond-containing isocyanate compound 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl atacrylate 1,1-bis (acryloyloxymethyl) ethyl isocyanate and the like, and 2-isocyanatoethyl methacrylate is preferred because of its excellent crosslinkability and storage stability.
  • Known conditions can be used as the reaction conditions.
  • any carboxylic acid compound having a known (meth) acryloyloxy group may be used. Although it can be used without particular limitation, methacrylic acid and acrylic acid are preferred, and methacrylic acid is particularly preferred because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.
  • a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced (2) As a method for copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, known methods can be used without any particular limitation.
  • D A radically polymerizable dye monomer and a radical can be used.
  • a method of copolymerizing a polymerizable group-containing compound that can be polymerized, and a method (e) a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition are preferred.
  • a radically polymerizable polymerizable group-containing compound in a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound an allyl group-containing compound (for example, (meth)) Allyl acrylate), epoxy group-containing compounds (for example, glycidyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, etc.), oxetane group-containing compounds (for example, 3-methyl-3-oxetanylmethyl (meth) ) Acrylate, etc.) and methylol group-containing compounds (for example, N- (hydroxymethyl) acrylamide etc.), and epoxy compounds and oxetane compounds are particularly preferred.
  • Known conditions can be used as the reaction conditions.
  • a method for introducing a polymerizable group a method of reacting a carboxylic acid possessed by a dye multimer, a carboxylic acid possessed by a dye multimer, and an unsaturated bond-containing epoxy compound is particularly preferable.
  • the amount of polymerizable group possessed by the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1. Particularly preferred is 0 mmol.
  • the ratio of the repeating unit containing a repeating unit having a polymerizable group in the dye multimer is, for example, preferably 5 to 50 mol, and more preferably 10 to 20 mol with respect to 100 mol of all repeating units.
  • the method for introducing the polymerizable group a method in which the carboxylic acid contained in the dye multimer, the carboxylic acid contained in the dye multimer, and the unsaturated bond-containing epoxy compound is particularly preferred.
  • repeating unit having a polymerizable group examples include the following. However, the present invention is not limited to these.
  • a dye monomer having an ethylenically unsaturated bond is preferable, among which a methacryloyl group, an acryloyl group, a styryl group, or a vinyloxy group is preferable, and a methacryloyl group.
  • An acryloyl group is more preferable, and a methacryloyl group is more preferable.
  • Alkali-soluble group of dye multimer An example of the alkali-soluble group that the dye multimer in the present invention may have is an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the alkali-soluble group (preferably an acid group) is preferably contained in the dye multimer as a repeating unit having an alkali-soluble group (acid group).
  • the acid value of the dye multimer of the present invention is preferably 0.5 to 1.50 mmol / g, preferably 0.5 to 1.0 mmol / g. More preferably.
  • the acid value of the dye multimer can be calculated from the average content of acid groups in the dye multimer, for example.
  • the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises a pigment
  • a method for introducing an alkali-soluble group into a dye multimer a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulf
  • the amount of the alkali-soluble group contained in the dye multimer is preferably from 0.3 mmol to 2.0 mmol, more preferably from 0.4 mmol to 1.5 mmol, more preferably from 0.5 mmol to 1. Particularly preferred is 0 mmol.
  • the dye multimer used in the present invention has a repeating unit having 2 to 20 unsubstituted alkyleneoxy chains in the side chain as a repeating unit containing an alkali-soluble group (hereinafter referred to as “(b) repeating unit”. May be included).
  • the number of repeating alkyleneoxy chains in the repeating single (b) position is preferably 2 to 10, more preferably 2 to 15, and even more preferably 2 to 10.
  • One alkyleneoxy chain is represented by — (CH 2 ) n O—, where n is an integer, n is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 or 3.
  • the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains may contain only one kind of alkyleneoxy chain, or may contain two or more kinds.
  • the repeating unit (b) is preferably represented by the following general formula (P).
  • General formula (P) (In general formula (P), X 1 represents a linking group formed by polymerization, L 1 represents a single bond or a divalent linking group. P represents a group containing a group consisting of repeating alkyleneoxy chains. .)
  • X 1 and L 1 in the general formula (P) have the same meanings as X 1 and L 1 in formula (A), and preferred ranges are also the same.
  • P represents a group containing a group consisting of repeating alkyleneoxy chains, more preferably a group consisting of repeating alkyleneoxy chains-terminal atom or terminal group.
  • the terminal atom or terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a hydroxyl group, a hydrogen atom, a methyl group, a phenyl group and A hydroxyl group is more preferred, and a hydrogen atom is particularly preferred.
  • the ratio of the repeating unit having a group composed of repeating 2 to 20 unsubstituted alkyleneoxy chains in the side chain is 2 to 20 mol% of all repeating units constituting the dye multimer. Preferably, 5 to 15 mol% is more preferable. Examples of the repeating unit (b) that can be used in the present invention are shown below, but it goes without saying that the present invention is not limited thereto.
  • the dye multimer used in the present invention may have at least one of the structures represented by the formulas (1) to (5) in the same molecule.
  • the structures represented by the formulas (1) to (5) function as a light stabilizer, thereby contributing to an improvement in exposure sensitivity and light resistance.
  • adhesiveness can be improved.
  • the generation of development residues can be suppressed.
  • the dye structure and the formula (1) are obtained by using a dye multimer having at least one of the dye structure and the structures represented by the formulas (1) to (5) in the same molecule.
  • the distance from the structure represented by (5) becomes closer. As a result, it is considered that exposure sensitivity and light resistance can be improved more effectively.
  • the structure represented by the formula (1) is generically called a hindered amine system.
  • the structure represented by the formula (2) is generically called a hindered phenol type.
  • the structure represented by the formula (3) is generically called a benzotriazole type.
  • the structure represented by the formula (4) is generically referred to as a hydroxybenzophenone series.
  • the structure represented by the formula (5) is generically called a triazine type.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxy radical.
  • R 2 and R 3 each independently represents an alkyl group having 1 to 18 carbon atoms.
  • R 2 and R 3 may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms.
  • “*” Represents a bond between the structure represented by the formula (1) and the polymer skeleton.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an oxy radical, preferably an alkyl group having 1 to 18 carbon atoms.
  • the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear.
  • the number of carbon atoms of the alkyl group having 1 to 18 carbon atoms is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 3, and particularly preferably 1 or 2.
  • the alkyl group having 1 to 18 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • the aryl group may have 6 to 18 carbon atoms, 6 to 12 carbon atoms, or 6 to 6 carbon atoms. Specific examples include a phenyl group.
  • R 1 in Formula (1) represents an alkyl group or aryl group having 1 to 18 carbon atoms
  • the alkyl group or aryl group having 1 to 18 carbon atoms may have a substituent or unsubstituted It may be.
  • the substituent which may have include a substituent selected from the substituent group A described above.
  • R 2 and R 3 each independently represent a methyl group or an ethyl group, and a methyl group is preferred.
  • R 2 and R 3 may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms.
  • “*” represents a bond between the structure represented by formula (1) and the polymer skeleton.
  • the bond may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the above-described dye structure directly or via a linking group.
  • “*” in formula (1) is preferably bonded to the polymer backbone directly or via a linking group.
  • “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.
  • R 4 represents the following formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group.
  • R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
  • “*” Represents a bond between the structure represented by the formula (2) and the polymer skeleton.
  • R 4 represents the above formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group, and is preferably represented by formula (2A).
  • the alkyl group and aryl group having 1 to 18 carbon atoms have the same meaning as the alkyl group and aryl group having 1 to 18 carbon atoms described for R 1 in formula (1).
  • “*” Is synonymous with the bond described in the formula (1).
  • each R 6 independently represents an alkyl group having 1 to 18 carbon atoms.
  • “*” Represents a bond between the structure represented by the formula (2A) and the structure represented by the formula (2).
  • R 6 has the same meaning as the alkyl group having 1 to 18 carbon atoms explained for R 1 in the formula (1).
  • “*” Is synonymous with the bond described in the formula (1).
  • the specific example of the structure represented by Formula (2) is shown, it is not limited to these.
  • “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.
  • R 7 represents an alkyl group having 1 to 18 carbon atoms; n1 represents an integer of 0 to 3. When n1 is 2 or 3, each R 7 may be the same or different.
  • “*” Represents a bond between the structure represented by the formula (3) and the polymer skeleton.
  • R 7 has the same meaning as the alkyl group having 1 to 18 carbon atoms explained for R 1 in the formula (1).
  • n1 represents an integer of 0 to 3, preferably an integer of 0 to 2, and preferably 0 or 1.
  • “*” is synonymous with the bond described in formula (1).
  • “*” represents a bond between the structure represented by the formula (3) and the polymer skeleton.
  • R 8 and R 9 each independently represents an alkyl group having 1 to 18 carbon atoms.
  • n2 represents an integer of 0 to 3.
  • n3 represents an integer of 0 to 4.
  • each R 8 may be the same or different.
  • n3 represents an integer of 2 to 4, each R 9 may be the same or different.
  • “*” Represents a bond between the structure represented by the formula (4) and the polymer skeleton.
  • R 8 and R 9 have the same meaning as the alkyl group having 1 to 18 carbon atoms explained for R 1 in the formula (1).
  • n2 represents an integer of 0 to 3, preferably an integer of 0 to 2, and preferably 0 or 1.
  • n3 represents an integer of 0 to 4, preferably an integer of 0 to 2, and preferably 0 or 1.
  • “*” is synonymous with the bond described in formula (1).
  • the specific example of the structure represented by Formula (4) is shown, it is not limited to these.
  • “*” represents a bond between the structure represented by the formula (4) and the polymer skeleton.
  • R 10 to R 12 each independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • n4 to n6 each independently represents an integer of 0 to 5.
  • n7 to n9 each independently represents 0 or 1, and at least one of n7 to n9 represents 1.
  • “*” Represents a bond between the structure represented by the formula (5) and the polymer skeleton.
  • R 10 in formula (5) represents an alkyl group having 1 to 18 carbon atoms, it is synonymous with the alkyl group having 1 to 18 carbon atoms described for R 1 in formula (1), and has 1 to 3 carbon atoms.
  • the alkyl group is preferably a methyl group.
  • R 10 represents an alkoxy group having 1 to 8 carbon atoms, the alkoxy group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • R 10 in Formula (5) may further have a substituent. Examples of the substituent which may have include a substituent selected from the substituent group A described above.
  • N4 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 4, and preferably 2 or 3.
  • R 10 may be the same or different.
  • R 11 in formula (5) has the same meaning as R 10 in formula (5), and the preferred range is also the same.
  • N5 in the formula (5) represents an integer of 0 to 5, preferably an integer of 1 to 3, and preferably 1 or 2.
  • R 12 in formula (5) has the same meaning as R 10 in formula (5), and the preferred range is also the same.
  • N6 in the formula (5) represents an integer of 0 to 5, preferably an integer of 0 to 3, and preferably 0 or 1.
  • each R 12 may be the same or different.
  • n7 to n9 each independently represents 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 represents 1, only n8 and n9 represent 1, or only one of n7, n8 and n9 represents 1.
  • “*” is synonymous with the bond described in formula (1).
  • the specific example of the structure represented by Formula (5) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (5) and the polymer skeleton.
  • the structural unit having at least one of the structures represented by formulas (1) to (5) possessed by the dye multimer used in the present invention is preferably represented by the following formula (E).
  • X 3 has the same meaning as X 1 in general formula (A).
  • L 4 has the same meaning as L 1 in formula (A).
  • Z 1 represents a structure represented by the above formulas (1) to (5). Specific examples of structural units having at least one of the structures represented by formulas (1) to (5) are shown below, but the present invention is not limited to these.
  • the dye multimer may not have a structural unit having at least one of the structures represented by the formulas (1) to (5), but if it has, 100 masses of all the structural units in the dye multimer. %,
  • the content of the structural unit having at least one of the structures represented by formulas (1) to (5) is preferably 0.5 to 20% by mass, and 1 to 10% by mass More preferably, the content is 1 to 5% by mass.
  • Other functional groups possessed by the dye multimer include development accelerators such as lactones, acid anhydrides, amides, —COCH 2 CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
  • the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.
  • repeating unit having an alkali-soluble group or other functional group that the dye multimer may have are shown below, but the present invention is not limited thereto.
  • the weight average molecular weight of the dye multimer is preferably 3,000 to 30,000, and more preferably 5,000 to 25,000. Further, the ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye multimer is preferably 1.0 to 2.0, preferably 1.1 to 2.0. The ratio is more preferably 1.8, and particularly preferably 1.1 to 1.5.
  • the glass transition temperature (Tg) of the dye multimer according to the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, when applying the colored composition of the present invention to the production of a color filter or the like, it becomes possible to reduce the concentration change caused by the heating process.
  • the dye multimer used in the present invention contains a repeating unit having a dye structure and another repeating unit, it is preferably a random polymer of a polymerizable compound containing a dye and another polymerizable compound.
  • a random polymer By using a random polymer, the dye structure is present randomly in the dye multimer, and the effects of the present invention are more effectively exhibited.
  • the molar extinction coefficient of the dye multimer used in the colored composition of the present invention is preferably as high as possible from the viewpoint of coloring power.
  • the reduced viscosity of the dye multimer used in the colored composition of the present invention is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, from the viewpoint of color transfer, More preferably, it is 0.0 to 7.0.
  • the reduced viscosity can be measured using, for example, an Ubbelohde viscometer. 1.0-1.8
  • the dye multimer according to the present invention is preferably a compound that is soluble in the following organic solvents.
  • the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate).
  • the dye multimer may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to content mentioned later.
  • the content of the dye multimer in the colored composition of the present invention is set in consideration of the content ratio with the pigment described later.
  • the mass ratio of the dye multimer to the pigment is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.
  • the colored composition of the present invention is preferably used for forming a colored layer of a color filter.
  • the coloring composition used in the present invention contains a polymerizable compound, and may further contain a photopolymerization initiator and a pigment.
  • the colored composition of the present invention is preferably a composition containing the dye multimer of the present invention, a polymerizable compound, an alkali-soluble resin, a photopolymerization initiator and a pigment.
  • components such as a surfactant and a solvent may be included.
  • dye multimer of this invention a polymeric compound, a photoinitiator, and a pigment is preferable. Furthermore, components such as a surfactant and a solvent may be included. Details of these will be described below.
  • the coloring composition of the present invention contains a polymerizable compound.
  • a polymerizable compound that can be cross-linked by radicals, acids, and heat can be used, and examples thereof include polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like.
  • the polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.
  • Such compound groups are widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and multimers thereof.
  • the polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.
  • examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably used in the present invention.
  • a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylene group is also preferable.
  • examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanedio
  • polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
  • fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc., and ethylenically unsaturated groups.
  • a compound having two or more functions, a cardo resin can also be used.
  • radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • n is 0 to 14, and m is 1 to 8.
  • a plurality of R and T present in one molecule may be the same or different.
  • at least one of a plurality of R is —OC ( ⁇ O) CH ⁇ CH 2 or —OC A group represented by ( ⁇ O) C (CH 3 ) ⁇ CH 2 is represented.
  • Specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-2699779. It can be suitably used in the invention.
  • dipentaerythritol triacrylate (KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (KAYARAD D-320 as commercially available products) are available as polymerizable compounds.
  • dipentaerythritol penta (meth) acrylate commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol hexa (meth) acrylate commercially available product KAYARAD DPHA; Nippon Kayaku Co., Ltd.
  • Ethyleneoxy-modified dipentaerythritol hexaacrylate commercially available product is A-DPH-12E; manufactured by Nippon Kayaku Co., Ltd.
  • oligomer types can also be used.
  • the polymerizable compound is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups.
  • non-aromatic carboxylic acid anhydride examples include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.
  • the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g.
  • the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted to fall within the above range. Is preferred.
  • polyfunctional monomer which has a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.
  • the specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).
  • each E is independently — ((CH 2 ) yCH 2 O) — or — ((CH 2 ) yCH (CH 3 ) O) —.
  • Each represents independently an integer of 0 to 10
  • each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
  • the total number of acryloyl groups and methacryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
  • the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • — ((CH 2 ) yCH 2 O) — or — ((CH 2 ) yCH (CH 3 ) O) — represents an oxygen atom side.
  • a form in which the terminal of X is bonded to X is preferred.
  • the compounds represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is ring-opened to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • polymerizable compound examples include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds.
  • polymerizable compounds include urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd., DPHA-40H (Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • cyclic ether examples include those having an epoxy group such as bisphenol A type epoxy resin, JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003.
  • JER-1055, JER-1007, JER-1009, JER-1010 manufactured by Japan Epoxy Resin Co., Ltd.
  • EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 manufactured by DIC Corporation
  • bisphenol F As type epoxy resins, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON83 EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins such as JER-152, JER-154, JER -157S70, JER-157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLONICN-740, EPICLON N-740,
  • the details of usage methods can be arbitrarily set according to the final performance design of a coloring composition.
  • a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
  • those having three or more functional groups are preferable, and further, different numbers of functional groups / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, A method of adjusting both sensitivity and strength by using a combination of vinyl ether compounds) is also effective.
  • a tri- or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the colored composition can be adjusted and an excellent pattern forming ability can be obtained.
  • the compatibility and dispersibility with other components (for example, photopolymerization initiators, dispersions, alkali-soluble resins, etc.) contained in the colored composition are also selected and used as a polymerizable compound. This is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
  • a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.
  • the content of the polymerizable compound in the colored composition of the present invention is preferably 0.1% by mass to 90% by mass, and 1.0% by mass to 60% by mass with respect to the total solid content in the colored composition. % By mass is more preferable, and 2.0% by mass to 40% by mass is particularly preferable.
  • the composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
  • the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (I).
  • Formula (I) (In the formula, n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)
  • the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
  • Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination.
  • the polyfunctional thiol content in the composition of the present invention is in the range of 0.3 to 8.9% by weight, more preferably 0.8 to 6.4% by weight, based on the total solid content excluding the solvent. It is desirable to add at. Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
  • the colored composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving sensitivity.
  • the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
  • the photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime.
  • Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like, with oxime compounds being preferred.
  • trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
  • compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, and acetophenone compounds.
  • At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound is particularly preferable.
  • the triarylimidazole compound may be a mixture with benzimidazole.
  • examples of the trihalomethyltriazine compound include the following compounds. Note that Ph is a phenyl group.
  • Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.
  • a commercially available product can be used as the trihalomethyltriazine compound, for example, TAZ-107 (manufactured by Midori Chemical Co., Ltd.) can also be used.
  • TAZ-107 manufactured by Midori Chemical Co., Ltd.
  • TAZ-107 manufactured by Midori Chemical Co., Ltd.
  • stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low.
  • an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.
  • halogenated hydrocarbon compound having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in paragraph No. 0075 of JP2013-077009A, and the like.
  • acridine derivatives are exemplified as photopolymerization initiators other than those described above.
  • Specific examples include the compounds described in paragraph No. 0076 of JP2013-077009A, and the contents thereof are incorporated in the present specification.
  • Examples of the ketone compounds include compounds described in paragraph No. 0077 of JP2013-077009A, and the contents thereof are incorporated in the present specification.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • More preferable examples of the photopolymerization initiator include oxime compounds.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.
  • oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule
  • a compound described in US Pat. No. 7,556,910 contained therein a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
  • cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744.
  • cyclic oxime compounds in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
  • the compounds described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because high sensitivity can be achieved by regenerating the active radical from the polymerization inert radical. it can.
  • oxime compounds having a specific substituent as disclosed in JP 2007-26997A and oxime compounds having a thioaryl group as disclosed in JP 2009-191061 A are particularly preferred.
  • the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general formula (OX-1).
  • the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
  • these groups may have one or more substituents.
  • the substituent mentioned above may be further substituted by another substituent.
  • substituents examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
  • a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.
  • the content of the photopolymerization initiator is preferably 0.1% by mass or more and 50% by mass or less based on the total solid content of the color composition, More preferably, they are 0.5 mass% or more and 30 mass% or less, More preferably, they are 1 mass% or more and 20 mass% or less. Within this range, better sensitivity and pattern formability can be obtained.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the colored composition of the present invention may further contain a colorant other than the above-mentioned dye multimer. Specifically, it is preferable to contain a pigment.
  • a pigment As the pigment used in the present invention, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferably used.
  • the pigment preferably has a high transmittance.
  • inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.
  • organic pigment for example, C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199; C. I. Pigment orange 36, 38, 43, 71; C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270; C. I. Pigment violet 19, 23, 32, 39; C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C. I. Pigment green 7, 36, 37, 58; C. I. Pigment brown 25, 28; C. I. Pigment black 1, 7; Etc.
  • organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of the above combinations are shown below.
  • a red pigment an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc.
  • an anthraquinone pigment C.I. I. Pigment red 177
  • perylene pigments include C.I. I. Pigment red 155, C.I. I.
  • Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.
  • the mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm. When the ratio is 100: 51 or more, the main wavelength tends to be closer to the short wavelength, and the color resolution may not be improved. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the required spectrum.
  • a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used.
  • a disazo yellow pigment e.g., a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment
  • C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83 e. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
  • the mass ratio of green pigment to yellow pigment is preferably 100: 5 to 100: 150.
  • the mass ratio is particularly preferably in the range of 100: 30 to 100: 120.
  • a phthalocyanine pigment can be used alone, or a mixture of this with a dioxazine purple pigment can be used.
  • C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
  • the mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.
  • the pigment for the black matrix carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable.
  • the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.
  • the coloring composition of the present invention preferably contains a pigment other than black, and is suitable for a blue pigment.
  • the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability.
  • the primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
  • the primary particle size of the pigment can be measured by a known method such as an electron microscope.
  • the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments.
  • C.I. I. Pigment red 177 anthraquinone pigment
  • C.I. I. Pigment red 254 diketopyrrolopyrrole pigment
  • C.I. I. Pigment green 7, 36, 58 C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment
  • C.I. I. Pigment yellow 138 quinophthalone pigment
  • C.I. I. Pigment yellow 139,185 isoindoline pigment
  • C.I. I. Pigment yellow 150 azomethine pigment
  • C.I. I. Pigment violet 23 dioxazine pigment
  • the content of the pigment is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 25%, based on all components excluding the solvent contained in the coloring composition. % By mass to 50% by mass.
  • the composition of the present invention may contain only one type of pigment or two or more types of pigment. When two or more types are included, the total amount is preferably within the above range.
  • dyes other than the above-mentioned dye multimers and pigments other than those described above may be included.
  • the chemical structure uses dyes such as pyrazole azo, anilino azo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. it can.
  • dyes such as pyrazole azo, anilino azo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. it can.
  • a pigment dispersant can be used in combination as desired.
  • pigment dispersants include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.
  • Examples of the terminal-modified polymer having an anchor site to the pigment surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like. Examples thereof include polymers having a sulfonic acid group at the terminal end described in JP-A-273191 and the like, and polymers having a partial skeleton of an organic dye and a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
  • Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, and specific examples thereof include JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, etc., JP-A-10-339949 A copolymer of a macromonomer and a nitrogen atom monomer described in JP-A-2004-37986, International Publication Pamphlet WO 2010/110491, JP-A-2003-238837, JP-A-2008-9426, JP-A Graphs having partial skeletons and heterocyclic rings of organic dyes described in JP-A-2008-81732 Type polymer, and a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication.
  • amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 has the dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the color composition using the pigment dispersion. From the viewpoint of
  • Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate having a methacryloyl group), AS-6 (polystyrene having a methacryloyl group at the end group), AN-6S (a copolymer of styrene and acrylonitrile having a methacryloyl group at the end group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd.
  • JP-A-2-27 examples thereof include a polyester-based macromonomer described in the 2009 publication.
  • a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion
  • a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is particularly preferable.
  • block polymers having an anchor site to the pigment surface block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
  • the pigment dispersant that can be used in the present invention is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate) manufactured by BYK Chemie.
  • Oligomer “Polflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (manufactured by Enomoto Kasei Co., Ltd.) Polyether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid) "manufactured by Kao Corporation Formalin polycondensate) ”,“ homogenol L-18 (polymer polycal) Acid "),” Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 86 (stearylamine acetate) ",” Solsperse 5000 (phthalocyanine derivative) "manufactured by Nippon Lubri
  • pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.
  • the pigment dispersant may be used in combination with an alkali-soluble resin together with the terminal-modified polymer, graft polymer, or block polymer having an anchor site to the pigment surface.
  • Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable.
  • An alkali-soluble resin containing is also preferred. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.
  • the total content of the pigment dispersant is preferably 1 part by weight to 80 parts by weight with respect to 100 parts by weight of the pigment, and 5 parts by weight to 70 parts by weight. More preferred is 10 parts by mass to 60 parts by mass.
  • the specific dispersion resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, among the dispersant components contained in the coloring composition.
  • the composition of the present invention may contain only one type of pigment dispersant, or two or more types of pigment dispersants. When two or more types are included, the total amount is preferably within the above range.
  • the amount used is preferably in the range of 5 to 100 parts by mass with respect to 100 parts by mass of the pigment, and 10 to 80 parts by mass. More preferred is the range of parts.
  • the amount of the pigment derivative used is preferably in the range of 1 to 30 parts by mass in terms of mass with respect to 100 parts by mass of the pigment. The range is more preferable, and the range of 5 to 15 parts by mass is particularly preferable.
  • the total content of the coloring agent and the dispersing agent component is 50% by mass or more and 90% by mass or less with respect to the total solid content constituting the coloring composition. Is more preferable, 55 mass% or more and 85 mass% or less is more preferable, and 60 mass% or more and 80 mass% or less is further more preferable.
  • the coloring composition of the present invention preferably further contains an alkali-soluble resin.
  • the molecular weight of the alkali-soluble resin is not particularly defined, but it is preferable that Mw is 5000 to 100,000. Further, Mn is preferably 1000 to 20,000.
  • the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
  • Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group.
  • the group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable.
  • These acid groups may be used alone or in combination of two or more.
  • Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (methacrylate). ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.
  • a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
  • a treatment for imparting an acid group as described later is required after the polymerization.
  • a known radical polymerization method can be applied.
  • Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
  • a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
  • examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
  • vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
  • ether dimers a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing the monomer component.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • General formula (ED2) In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description in JP 2010-168539 A can be referred to.
  • the coloring composition of this invention can form the cured coating film which was very excellent also in transparency with heat resistance.
  • the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited.
  • Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like.
  • an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is
  • ether dimer examples include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl)
  • dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.
  • These ether dimers may be only one kind or two or more kinds.
  • the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.
  • alkali-soluble resin may contain the structural unit derived from the ethylenically unsaturated monomer shown by following formula (X).
  • Formula (X) (In Formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or a benzene ring which may contain a benzene ring. And represents an alkyl group of 20. n represents an integer of 1 to 15.)
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
  • the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
  • Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • an alkali-soluble resin having a polymerizable group In order to improve the crosslinking efficiency of the colored composition in the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group.
  • an alkali-soluble resin having a polymerizable group an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful.
  • Examples of the above-described polymer containing a polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co.Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
  • an alkali-soluble resin containing these polymerizable groups an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting compound having polymerizable group, JP 2002-229207 A Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulf
  • alkali-soluble resin in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable. .
  • benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc.
  • the acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
  • the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, more preferably 2% by mass with respect to the total solid content of the coloring composition. It is ⁇ 12% by mass, and particularly preferably 3% by mass to 10% by mass.
  • the composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention is within the range that does not impair the effects of the present invention, and further includes an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic acid anhydride. It may contain other components such as products.
  • the coloring composition of the present invention may contain an organic solvent.
  • the organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but in particular, the solubility, coating property, and safety of ultraviolet absorbers, alkali-soluble resins and dispersants, etc. It is preferable to select in consideration of the properties. Moreover, when preparing the coloring composition in this invention, it is preferable that at least 2 type of organic solvent is included.
  • organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
  • Alkyl oxyacetates eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
  • alkyl 3-oxypropionate Esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
  • Oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
  • ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as Tolue And xylene are preferable.
  • ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons
  • organic solvents are preferably mixed in two or more types from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coated surface, and the like.
  • It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the content of the organic solvent in the colored composition is preferably such that the total solid content of the composition is 5% by mass to 80% by mass from the viewpoint of applicability, and 5% by mass to 60% by mass. More preferred is 10% by mass to 50% by mass.
  • the composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
  • Crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction.
  • the crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction.
  • the blending amount of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, and preferably 3 to 20% by mass based on the total solid content of the composition. More preferred.
  • the composition of the present invention may contain only one type of cross-linking agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • ⁇ Polymerization inhibitor In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
  • the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
  • the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.
  • the composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • surfactant Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability.
  • various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the coloring composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved.
  • Liquidity can be further improved. That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the coloring composition of the present invention contains a surfactant
  • the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass with respect to the total mass of the coloring composition, more preferably 0.005% by mass to 1.0% by mass.
  • the composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
  • Organic carboxylic acid, organic carboxylic anhydride may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
  • organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids.
  • aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid.
  • monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid
  • aromatic carboxylic acid examples include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond.
  • carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid
  • carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond examples of the aromatic carboxylic acid.
  • those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500 specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.
  • organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned.
  • aromatic carboxylic acid anhydride examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Of these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.
  • the amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight based on the total solid content.
  • the range is preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight.
  • the composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the coloring composition as necessary.
  • these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
  • the coloring composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.
  • the composition of the present invention may contain only one type of the above components, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the coloring composition of the present invention is prepared by mixing the aforementioned components.
  • the components constituting the colored composition may be mixed together, or may be sequentially added after each component is dissolved and dispersed in a solvent.
  • the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
  • the colored composition prepared as described above is preferably used after being filtered using a filter having a pore size of 0.01 ⁇ m to 3.0 ⁇ m, more preferably a pore size of about 0.05 ⁇ m to 0.5 ⁇ m. Can be provided.
  • the colored composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film having excellent heat resistance and color characteristics, it is suitably used for forming a colored pattern (colored layer) of a color filter. .
  • the colored composition of the present invention is used for forming a colored pattern such as a solid-state imaging device (for example, CCD, CMOS, etc.), a color filter used in an image display device such as a liquid crystal display device (LCD) or an organic EL display device. Can be suitably used. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application.
  • the cured film of the present invention is formed by curing the colored composition of the present invention.
  • Such a cured film is preferably used for a color filter.
  • the colored composition of the present invention is applied onto a support to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.
  • the pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
  • the composition of the present invention may produce a color filter by pattern formation by a so-called photolithography method, or may form a pattern by dry etching.
  • a method for producing a color filter including a step of developing and removing an unexposed portion to form a colored pattern is exemplified.
  • a step of applying a colored composition on a support to form a colored composition layer and curing to form a colored layer a photo on the colored layer
  • Production of a color filter comprising a step of forming a resist layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask A method is illustrated.
  • Step of Forming Colored Composition Layer In the step of forming the colored composition layer, the colored composition layer forming step is formed on the support by applying the colored composition of the present invention.
  • a solid-state imaging in which an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate).
  • An element substrate can be used.
  • the colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
  • a light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the substrate for the solid-state image sensor.
  • an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
  • a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like can be blended, and each of these components is derived from the components blended in the above-described composition of the present invention. It is preferable to select appropriately.
  • various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.
  • the drying (pre-baking) of the colored composition layer coated on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven or the like.
  • Exposure Step the colored composition layer formed in the colored composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thereby, a cured film is obtained.
  • radiation light
  • ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line).
  • Irradiation dose is more preferably 30mJ / cm 2 ⁇ 1500mJ / cm 2 is preferably 50mJ / cm 2 ⁇ 1000mJ / cm 2, 80mJ / cm 2 ⁇ 500mJ / cm 2 is particularly preferred.
  • the thickness of the cured film (colored film) is preferably 1.0 ⁇ m or less, more preferably 0.1 ⁇ m to 0.9 ⁇ m, and further preferably 0.2 ⁇ m to 0.8 ⁇ m. It is preferable to set the film thickness to 1.0 ⁇ m or less because high resolution and high adhesion can be obtained.
  • a cured film having a thin film thickness of 0.7 ⁇ m or less can also be suitably formed, and the obtained cured film is developed in a pattern forming process described later, thereby forming a thin film.
  • the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.
  • the developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit.
  • the development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
  • Organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001 to 10% by mass
  • An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as the developer.
  • an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • post-bake heat treatment after drying. If a multicolor coloring pattern is to be formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.
  • the post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
  • This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
  • the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as a process other than the above as needed.
  • a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.
  • the colored composition according to the present invention when used, for example, clogging of the nozzle of the coating device discharge section or the piping section, contamination due to adhesion, sedimentation, or drying of the colored composition or pigment in the coating machine may occur. is there. Therefore, in order to efficiently clean the contamination caused by the colored composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a cleaning liquid.
  • the cleaning liquids described in JP-A-2007-2101, JP-A-2007-2102, JP-A-2007-281523 and the like can also be suitably used for cleaning and removing the colored composition according to the present invention.
  • alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred. These solvents may be used alone or in combination of two or more.
  • the mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20.
  • a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) the ratio is particularly preferably 60/40.
  • a surfactant related to the present composition described above may be added to the cleaning liquid.
  • the color filter of the present invention uses the colored composition of the present invention, the color filter of the present invention can be exposed with an excellent exposure margin, and the formed colored pattern (colored pixel) is excellent in pattern shape, and the surface of the pattern is not rough. Since the residue in the developing part is suppressed, the color characteristics are excellent.
  • the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels.
  • the color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.
  • the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and particularly preferably 1.7 ⁇ m or less.
  • the solid-state imaging device of the present invention includes the above-described color filter of the present invention.
  • the configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
  • a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support.
  • light collecting means for example, a microlens, etc., the same shall apply hereinafter
  • the color filter of the present invention can be used not only for the solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices.
  • the liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
  • display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter of the present invention may be used in a color TFT liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
  • the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
  • COA Color-filter On Array
  • the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above.
  • the color filter of the present invention since a dye multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in color, so the resolution is high and the long-term durability is excellent.
  • a COA type liquid crystal display device can be provided.
  • a resin film may be provided on the color filter layer.
  • the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
  • these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
  • backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
  • the color filter according to the present invention When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED).
  • RGB-LED red, green and blue LED light sources
  • Monomer (a-1) 8.0 g, methacrylic acid 2.0 g, and 2-cyano-2-propyldodecyltrithiocarbonate 0.5 g were dissolved in cyclohexanone 20.0 g and heated to 80 ° C. in a nitrogen stream. To this, 0.1 g of 2,2′-azobis (methyl 2-methylpropionate) was added and stirred with heating for 2 hours. Further, 0.1 g of 2,2′-azobis (methyl 2-methylpropionate) was added and heated for 2 hours, and then heated at 90 ° C. for 2 hours.
  • Monomer (a-2) 8.0 g, styrene carboxylic acid 2.0 g, 2,2,6,6-tetramethylpiperidine-1-oxyl 0.5 g free radical was dissolved in cyclohexanone 8.0 g, and a nitrogen stream 140 Heated to ° C.
  • the benzoyl peroxide 0.1g was added here, and it heat-stirred for 2 hours. Further, 0.1 g of benzoyl peroxide was added and heated for 2 hours.
  • 1.0 g of glycidyl methacrylate and 0.010 g of tetrabutylammonium bromide were added and heated at 100 ° C. for 10 hours.
  • the reaction solution was dropped into a mixed solution of 100 mL of methanol and 100 mL of water, and the precipitated solid was filtered and dried to obtain 8.5 g of (A-13).
  • Pigment Blue 15: 6 Pigment Dispersion Blue Pigment Dispersion 1 was prepared as follows.
  • dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism.
  • This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration 13%) used in the coloring compositions of Examples and Comparative Examples.
  • the particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.
  • Pigment dispersion containing pigment described in the following table (pigment concentration: 13.0%) 0.615 parts ⁇ Polymerizable compound (dipentaerythritol hexaacrylate, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 0.070 parts ⁇ Glycerol propoxylate (1% cyclohexane solution) 0.048 parts
  • i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
  • exposure was performed at various exposure doses of 50 to 1200 mJ / cm 2 through an Island pattern mask having a pattern of 1.0 ⁇ m square at a wavelength of 365 nm.
  • the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film).
  • Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.
  • the silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. As described above, a monochromatic color filter having a colored pattern formed by the colored composition of the example or the comparative example was produced. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size was 1.0 ⁇ m was determined as the optimum exposure amount.
  • Performance evaluation 5-1 Light resistance-Fabrication of monochromatic color filters and evaluation of light resistance- Each colored curable composition obtained above was applied on a glass substrate using a spin coater so that the film thickness after drying was 0.6 ⁇ m, prebaked at 100 ° C. for 120 seconds, and evaluated for light resistance. A monochromatic color filter was obtained. The obtained monochromatic color filter for light resistance evaluation was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux ⁇ h). The color difference ( ⁇ E * ab value) of the monochromatic color filter before and after the xenon lamp irradiation was measured and used as an index of light resistance. Note that the smaller the ⁇ E * ab value, the better the light resistance.
  • Coating property The coating property at the time of coating each colored composition was evaluated by the following method. That is, each colored composition was applied with a spin coater so that the film thickness after drying was 0.6 ⁇ m, and observed with an optical microscope to evaluate the coating property.
  • the evaluation criteria are as follows. -Evaluation criteria- A: Application unevenness was not confirmed at all. B: Some coating unevenness was confirmed. C: Many coating unevenness was confirmed.
  • Patterned Coloring Composition Applying Dry Etching Method The following components were mixed and dissolved to obtain colored compositions of Examples 37 to 72 and Comparative Examples 3 to 4.
  • -Cyclohexanone 1.133 parts-Dye multimer (compound described in the following table) 0.040 parts as solid content-Blue pigment dispersion liquid (pigment concentration 13.0%) 0.615 parts-Polymerizable compound (EHPE -3150 (Daicel Chemical Industries, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct)) 0.070 parts glycerol propoxylate (1% cyclohexane solution) 0.048 parts
  • each colored composition was evaluated by the following method. That is, each colored composition was applied with a spin coater so that the film thickness after drying was 0.6 ⁇ m, and observed with an optical microscope to evaluate the coating property.
  • the evaluation criteria are as follows. -Evaluation criteria- A: Application unevenness was not confirmed at all. B: Some coating unevenness was confirmed. C: Many coating unevenness was confirmed.
  • Example 45 In Example 1, the polymerizable compound was changed to the same mass of A-DPH-12E (manufactured by Nippon Kayaku Co., Ltd., ethyleneoxy-modified dipentaerythritol hexaacrylate), and other tests were performed in the same manner as in Example 1. As a result, the same preferable results as in Example 1 were obtained.
  • A-DPH-12E manufactured by Nippon Kayaku Co., Ltd., ethyleneoxy-modified dipentaerythritol hexaacrylate

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