WO2020071041A1 - Color material dispersion, colored resin composition and cured product thereof, color filter, and display device - Google Patents

Color material dispersion, colored resin composition and cured product thereof, color filter, and display device

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Publication number
WO2020071041A1
WO2020071041A1 PCT/JP2019/034743 JP2019034743W WO2020071041A1 WO 2020071041 A1 WO2020071041 A1 WO 2020071041A1 JP 2019034743 W JP2019034743 W JP 2019034743W WO 2020071041 A1 WO2020071041 A1 WO 2020071041A1
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WIPO (PCT)
Prior art keywords
group
substituent
mass
general formula
integer
Prior art date
Application number
PCT/JP2019/034743
Other languages
French (fr)
Japanese (ja)
Inventor
知亜紀 大友
政人 岡田
教弘 小倉
陽平 伊藤
はるな 和田
Original Assignee
株式会社Ｄｎｐファインケミカル
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 株式会社Ｄｎｐファインケミカル, 大日本印刷株式会社 filed Critical 株式会社Ｄｎｐファインケミカル
Priority to JP2020550223A priority Critical patent/JP7346435B2/en
Priority to CN201980065116.4A priority patent/CN112805338B/en
Publication of WO2020071041A1 publication Critical patent/WO2020071041A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00—Lakes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a colorant dispersion, a colored resin composition and a cured product thereof, a color filter, and a display device.
  • Color filters are used in these liquid crystal display devices and organic light emitting display devices.
  • a color image of a liquid crystal display device light that has passed through a color filter is directly colored into the color of each pixel constituting the color filter, and light of those colors is combined to form a color image.
  • an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used.
  • a color filter is used for color adjustment and the like.
  • the color filter is generally formed on the substrate and the substrate, and is formed on the substrate so as to partition each coloring pattern, including a coloring layer including three primary color coloring patterns of red, green, and blue.
  • a light-shielding portion As a method for forming such a colored layer, there is known a method in which a colored resin composition obtained by adding a curable binder component or the like to a coloring material dispersion liquid in which a coloring material is dispersed is applied to a substrate and cured. In order to stably obtain a high-contrast colored layer, the colorant dispersion liquid is required to have good dispersibility and storage stability of the colorant.
  • Patent Document 1 discloses a color filter or the like using a specific coloring material containing a divalent or more cation and a divalent or more anion in which a plurality of dye skeletons are crosslinked by a crosslinking group. It is described that the coloring material has excellent heat resistance, and that a color filter using the coloring material has high contrast, excellent solvent resistance, and excellent electrical reliability.
  • Patent Document 2 discloses a combination of a coloring material, a polymer having a structural unit having a specific acidic phosphorus compound group, and at least two solvents of a relatively high polarity solvent and a relatively low polarity solvent as a solvent. Color material dispersions are disclosed. It is described that the colorant dispersion liquid has excellent dispersibility and storage stability, and can form a coating film having high contrast even after long-term storage, and having excellent heat resistance and solvent resistance.
  • Patent Document 2 discloses that in Example 17 and Comparative Examples 25 and 26, a rake color material corresponding to the specific color material of Patent Document 1 and a commercially available Pigment Blue 15: 6 were mixed at a mass ratio of 90:10. And a colorant dispersion in which the colorant is dispersed by using either a polymer having a structural unit having a specific acid phosphorus structure or a basic dispersant.
  • Patent Document 2 when a lake color material such as the specific color material of Patent Document 1 is mixed with a phthalocyanine pigment such as Pigment Blue 15: 6 which is widely distributed in the market, If the content of the phthalocyanine pigment is more than 10 parts by mass with respect to the total of 100 parts by mass of the lake color material and the phthalocyanine pigment, the dispersibility and the storage stability are significantly deteriorated. However, it was difficult to produce a colored resin composition by mixing the specific lake colorant and the phthalocyanine pigment in a desired range. Further, with the colored layer of the related art as described in Patent Document 2, the substrate adhesion and the uniformity of the coating film are still insufficient, and further improvement in the substrate adhesion and the uniformity of the coating film is required. Was.
  • the present invention has been made based on the above findings, and has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range, and has excellent substrate adhesion and coating properties.
  • a coloring material dispersion liquid capable of forming a colored layer with improved film uniformity, a colored resin composition, a color filter having the colored layer, and a display device using the color filter and having excellent display characteristics. The purpose is to do.
  • the coloring material dispersion according to the present invention is a coloring material dispersion containing a coloring material, an acidic dispersant, and a solvent,
  • the color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2).
  • Phthalocyanine pigments included in the acidic dispersant.
  • the acidic dispersant includes a polymer having at least one selected from structural units represented by the following general formula (I).
  • the colored resin composition according to the present invention is a colored resin composition containing a coloring material, an acidic dispersant, a binder component, and a solvent,
  • the color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2).
  • Phthalocyanine pigments included in the acidic dispersant.
  • the acidic dispersant includes a polymer having at least one selected from the structural units represented by the general formula (I).
  • the present invention provides a cured product of the colored resin composition according to the present invention.
  • the present invention is a color filter comprising at least a substrate and a coloring layer provided on the substrate, wherein at least one of the coloring layers contains a coloring material and an acidic dispersant, and the coloring material is A phthalocyanine pigment which has been subjected to a basic treatment with at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2)
  • a color filter, wherein the acidic dispersant comprises a polymer having at least one selected from the structural units represented by the general formula (I).
  • the present invention provides a display device having the color filter according to the present invention.
  • a colored layer having excellent dispersibility and storage stability, and having improved substrate adhesion and coating film uniformity is formed.
  • a possible color material dispersion, a colored resin composition, a color filter including the colored layer, and a display device having excellent display characteristics using the color filter can be provided.
  • FIG. 1 is a schematic diagram showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention.
  • FIG. 3 is a schematic view showing another example of the display device of the present invention.
  • light includes electromagnetic waves having wavelengths in the visible and invisible regions, and furthermore, radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 ⁇ m or less and an electron beam.
  • (meth) acryl represents each of acryl and methacryl
  • (meth) acrylate represents each of acrylate and methacrylate.
  • “to”, which indicates a numerical range is used to mean that the numerical values described before and after the numerical value range are included as a lower limit and an upper limit.
  • the colorant dispersion liquid is a colorant dispersion containing a colorant, an acidic dispersant, and a solvent,
  • the color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2).
  • Phthalocyanine pigments The acidic dispersant includes a polymer having at least one selected from structural units represented by the following general formula (I).
  • A is an a-valent organic group in which the carbon atom directly bonded to N has no ⁇ bond, and the organic group has a saturated aliphatic carbon at least at the terminal directly bonded to N.
  • B c- represents a c-valent polyacid anion.
  • R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may combine to form a ring structure, and R vi and R vii each independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group.
  • .Ar 1 2 may have a substituent divalent aromatic group represents a group I represent.
  • R i ⁇ R vii and Ar 1 there are a plurality of may each be the same or different.
  • a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more.
  • e is 0 or 1, and when e is 0, no bond exists.
  • f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less.
  • a plurality of e, f, and g may be the same or different.
  • R I ⁇ R VI are each independently a hydrogen atom, which may have an alkyl group or a substituted group which may have a substituent aryl group, R I and R II , R III and R IV , or R V and R VI may combine to form a ring structure, wherein R VII and R VIII each independently represent an alkyl group or a substituent which may have a substituent; alkoxy group which may have, .Ar 2 represents a halogen atom or a cyano group represents an aromatic heterocyclic group which may have a substituent, plural R I ⁇ R VIII and Ar 2 E m- represents an m-valent polyacid anion. m represents an integer of 2 or more.
  • j is 0 or 1, and when j is 0, no bond exists.
  • k and l represent an integer of 0 or more and 4 or less, and k + j and 1 + j are 0 or more and 4 or less.
  • a plurality of j, k and l may be the same or different.
  • L 1 is a direct bond or a divalent linking group
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a hydroxyl group, a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , — [(CH 2 ) y1 —O] z1 —R 5 , or —O—R 6 is a monovalent group
  • R 6 is a hydrocarbon group ,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , -C (R 7 ) (R 8 ) -C ( R 9 ) (R 10 ) —OH or a monovalent group represented by —CH 2 —C (R 11 ) (R 12 ) —CH 2 —OH.
  • R 3 and R 4 are each independently a hydrogen atom or a methyl group
  • R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having at least one selected from an ether bond and an ester bond. Yes, R 7 and R 9 may combine with each other to form a ring structure.
  • the cyclic structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon having one or more types selected from an ether bond and an ester bond. It is a hydrogen group.
  • the hydrocarbon group may have a substituent.
  • X represents a hydrogen atom or an organic cation. x1 is an integer of 1 to 18; y1 is an integer of 1 to 5; z1 is an integer of 1 to 18; )
  • the colorant dispersion according to the embodiment of the present invention has excellent dispersibility and storage stability even when a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, and has excellent substrate adhesion and coating film uniformity. It is possible to form a colored layer with improved properties. Further, according to the colorant dispersion according to the embodiment of the present invention, even when a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, the dispersibility and storage stability are excellent, and the substrate adhesion is improved. A colored resin composition capable of forming a colored layer with improved coating uniformity can be obtained.
  • a phthalocyanine pigment such as Pigment Blue 15: 6, which is widely distributed in the market, is selected from the structural units represented by the general formula (I) as a dispersant, as shown in Comparative Example 4 described below.
  • a polymer having at least one kind was used, dispersibility was poor and storage stability was poor.
  • a polymer having at least one selected from the structural units represented by the general formula (I) is used as a dispersant, and a lake color material is mixed with a phthalocyanine pigment that is widely distributed in the market, As shown in Comparative Example 5 described below, even if the content of the phthalocyanine pigment is slightly increased, the dispersibility and storage stability are significantly deteriorated. Therefore, the content of the phthalocyanine pigment cannot be increased.
  • a base is added to at least one kind of lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2).
  • a predetermined lake by combining the phthalocyanine pigment having been subjected to the acid treatment and using, as a dispersant, an acidic dispersant containing a polymer having at least one selected from the structural units represented by the general formula (I).
  • the colorant and the phthalocyanine pigment are mixed in a desired range, a colorant dispersion having excellent dispersibility and storage stability can be obtained.
  • the phthalocyanine pigment subjected to the basic treatment is used in combination, the dispersibility and the storage stability are improved because of the cationic group derived from the basic compound present on the surface of the phthalocyanine pigment, and the acid group of the acidic dispersant. This is presumed to be because the adsorption effect of the compound becomes particularly strong.
  • the lake coloring material is also a salt-forming compound, it is presumed that the lake coloring material has a strong adsorptive action with the acidic group of the acidic dispersant.
  • both the lake color material and the basic-treated phthalocyanine pigment are well coated with a dispersant, it is presumed that they are excellent in dispersibility and storage stability even when mixed in a desired range.
  • a phthalocyanine pigment which has been subjected to a basic treatment to at least one kind of lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2)
  • an acidic dispersant containing a polymer having at least one selected from the structural units represented by formula (I) as a dispersant whereby substrate adhesion and coating film uniformity are improved.
  • An improved colored layer can be formed.
  • the phthalocyanine pigment which has been subjected to the basic treatment has a strong adsorptive action with the acidic group of the acidic dispersant, and the pigment surface is uniformly coated with the acidic dispersant.
  • the improved viscosity of the colorant dispersion and the resin composition is improved, and the fluidity of the resin composition is improved, so that it becomes easier to produce a uniform coating film, and that the uniformity of the coating film may have improved. Presumed.
  • the dispersant has an acidic group such as a phosphoric acid group or a carboxylic acid group
  • the dispersing agent is easily bonded not only to the color material surface but also to a polar group on the substrate surface (for example, a Si—OH group on the glass substrate surface). It is estimated that the adhesion of the substrate was improved.
  • the coloring material dispersion according to the present invention contains at least a coloring material, an acidic dispersant, and a solvent, and further contains other components as necessary, as long as the effect is not impaired. Is also good.
  • each component of such a colorant dispersion will be described in detail in order.
  • the coloring material includes at least one kind of lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2); And a phthalocyanine pigment that has been subjected to a sexual treatment.
  • the rake coloring material used in the present invention is at least one rake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2). is there.
  • the coloring material represented by the general formula (1) contains a divalent or higher valent anion and a divalent or higher cation, in the aggregate of the coloring material, the anion and the cation are simply one molecule to one molecule. Since a plurality of molecules can form a molecular aggregate through ionic bond instead of ionic bond, the apparent molecular weight is significantly increased as compared with the molecular weight of a conventional lake pigment. Due to the formation of such molecular aggregates, the cohesive force in the solid state is further increased, thermal motion is reduced, dissociation of ion pairs and decomposition of the cation part can be suppressed, and it is estimated that discoloration is less likely than conventional lake pigments Is done.
  • a in the general formula (1) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a ⁇ bond, and the organic group is saturated at least at a terminal directly bonded to N.
  • the organic group has a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N, and may include a hetero atom such as O, S, or N in a carbon chain; Alternatively, it represents an aromatic group having an aliphatic hydrocarbon group at a terminal directly bonded to N and optionally containing a hetero atom such as O, S, or N in a carbon chain. Since the carbon atom directly bonded to N does not have a ⁇ bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A or other coloring portions, and are not affected by the monomer. Similar colors can be retained.
  • At least the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is a straight-chain, branched, or cyclic group unless the terminal carbon atom directly bonded to N has a ⁇ bond.
  • carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and O, S, and N are contained in the carbon chain. Is also good.
  • a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom and the like.
  • the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to at least N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N. Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the rigidity of the skeleton.
  • Examples of the cyclic aliphatic hydrocarbon group include groups containing cyclohexane, cyclopentane, norbornane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, adamantane, and the like.
  • Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring.
  • A is a divalent organic group, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms or an aromatic group having two substituted alkylene groups having 1 to 20 carbon atoms such as a xylylene group. And the like.
  • A has two or more cyclic aliphatic hydrocarbon groups and has a terminal directly bonded to N in view of improving heat resistance while achieving both robustness and freedom of molecular movement.
  • Is preferably an aliphatic hydrocarbon group which has a saturated aliphatic hydrocarbon group and may contain O, S and N in the carbon chain.
  • the group is more preferably a group, and particularly preferably has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.
  • the two or more cyclic aliphatic hydrocarbon groups may be the same or different, and for example, include the same cyclic aliphatic hydrocarbon groups as described above, and among them, cyclohexane and cyclopentane are preferred.
  • A is preferably a substituent represented by the following general formula (1a).
  • R xi represents an alkyl group having 1 to 4 carbon atoms as a substituent or an alkylene group having 1 to 3 carbon atoms which may have an alkoxy group having 1 to 4 carbon atoms.
  • R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p is an integer of 1 to 3 and q and r are each independently to .
  • R xi an integer of 0 to 4, if R xii, R xiii and r there are multiple, the plurality of R xi, R xii, R xiii and r may being the same or different .
  • R xi be an alkylene group having 1 to 3 carbon atoms in R xi because it is excellent in both fastness and thermal motion of the color-developing portion and heat resistance is improved.
  • Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group. Among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
  • R xii and R xiii the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are the same as the substituents that R xi may have.
  • the number of cyclohexane (cyclohexylene group) is preferably 2 or more, that is, p is 1 or more and 3 or less from the viewpoint of heat resistance. Is more preferable.
  • the number of substituents R xii and R xiii of the cyclohexylene group is not particularly limited, but is preferably 1 or more and 3 or less, and preferably 1 or more and 2 or less from the viewpoint of heat resistance. Is more preferred. That is, q and r are preferably integers of 1 or more and 3 or less, and q and r are preferably integers of 1 or more and 2 or less.
  • linking group A includes the following, but are not limited thereto.
  • the alkyl group in R i to R v is not particularly limited.
  • a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms may be mentioned.
  • a linear or branched alkyl group having 1 to 8 carbon atoms may be mentioned.
  • From 5 to 5 are straight-chain or branched alkyl groups from the viewpoint of luminance and heat resistance, and the alkyl group in R i to R v is an ethyl group or a methyl group.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and an alkoxy group.
  • the substituted alkyl group includes an aralkyl group such as a benzyl group And the like.
  • the aryl group in R i to R v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent which the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group and the like.
  • R i to R v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a bond between R ii and R iii , or R iv and R v from the viewpoint of chemical stability.
  • At least one of R ii to R v is preferably a cycloalkyl group which may have a substituent or an aryl group which may have a substituent.
  • R ii to R v has a cycloalkyl group or an aryl group, intermolecular interaction due to steric hindrance is reduced, so that the effect of the coloring site on heat can be suppressed. Considered excellent.
  • At least one of R ii to R v is preferably a substituent represented by the following general formula (1b) or the following general formula (1c).
  • R xiv , R xv , and R xvi each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent. Represents a good alkoxy group having 1 to 4 carbon atoms.
  • R xvii , R xviii , and R xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent. Represents a good alkoxy group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R xiv , R xv , R xvi , R xvii , R xviii , and R xix include a methyl group, an ethyl group, a propyl group, and a butyl group. Or may have a branch.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
  • Examples of the substituent which the alkyl group and the alkoxy group may have include a halogen atom and a hydroxyl group.
  • R xiv , R xv , and R xvi has 1 to 4 carbon atoms which may have a substituent from the viewpoint of heat resistance.
  • R xvii , R xviii , and R xix has 1 to 4 carbon atoms which may have a substituent from the viewpoint of heat resistance. It is preferably an alkyl group or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, wherein at least one of R xvii and R xviii has 1 carbon atom which may have a substituent More preferably, it is an alkyl group having 4 to 4 or less, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
  • substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include, but are not limited to, the following.
  • R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group.
  • the alkyl group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably, there is.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched.
  • the substituent that the alkyl group may have is not particularly limited, but examples include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • the alkoxy group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. More preferably, it is a group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
  • the substituent that the alkoxy group may have is not particularly limited, but examples include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
  • examples of the halogen atom in R vi and R vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the substitution numbers of R vi and R vii that is, f and g each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less.
  • a plurality of f and g may be the same or different.
  • R vi and R vii may be substituted at any position of a triarylmethane skeleton or an aromatic ring having a resonance structure in a xanthene skeleton.
  • -NR ii R iii or -NR iv is preferable. It is preferably substituted at the meta position based on the substitution position of the amino group represented by R v .
  • the divalent aromatic group in Ar 1 is not particularly limited.
  • the aromatic group in Ar 1 may be a heterocyclic group in addition to an aromatic hydrocarbon group having a carbon ring.
  • the aromatic hydrocarbon in the aromatic hydrocarbon group include, in addition to a benzene ring, a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, a tetralin ring, an indene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring; biphenyl, terphenyl, Examples include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene.
  • the chain polycyclic hydrocarbon may have O, S, and N in a chain skeleton such as diphenyl ether.
  • examples of the heterocycle in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; Condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline and quinoxaline.
  • These aromatic groups may further have, as substituents, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted by these, and the like.
  • a plurality of R i to R vii and Ar 1 in one molecule may be the same or different.
  • a desired color can be adjusted by a combination of R i to R vii and Ar 1 .
  • the valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more.
  • This lake color material has excellent heat resistance because the valence a of the cation is 2 or more, and it is particularly preferable that the valence a of the cation is 3 or more.
  • the upper limit of a is not particularly limited, a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
  • the cation represented by the general formula (A) has a molecular weight of preferably 1200 or more, and more preferably 1300 or more, from the viewpoint that the cation has excellent heat resistance and color change upon heating is easily suppressed.
  • the anion part (B c ⁇ ) is a c-valent polyacid anion and a divalent or more anion from the viewpoint of high luminance and excellent heat resistance.
  • the polyoxometalate anion in which a plurality of oxoacids are condensed, isopoly acid anion (M m O n) heteropoly acid anion be a c- (X l M m O n ) may be a c-.
  • M represents a poly atom
  • X represents a hetero atom
  • m represents a composition ratio of a poly atom
  • n represents a composition ratio of an oxygen atom.
  • the poly atom M include Mo, W, V, Ti, and Nb.
  • the hetero atom X include Si, P, As, S, Fe, and Co.
  • a counter cation such as Na + or H + may be partially contained.
  • a polyacid containing at least one element selected from tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of excellent heat resistance.
  • a polyacid include tungstate ion [W 10 O 32 ] 4 ⁇ , molybdate ion [Mo 6 O 19 ] 2- , which is an isopoly acid, and phosphotungstate ion [heteropolyacid], PW 12 O 40 ] 3 ⁇ , [P 2 W 18 O 62 ] 6 ⁇ , silicotungstate ion [SiW 12 O 40 ] 4 ⁇ , phosphomolybdate ion [PMo 12 O 40 ] 3 ⁇ , silicomolybdate ion [ SiMo 12 O 40] 4-, phosphate tongue strike molybdate [PW 12-s Mo s O 40] 3- (s is 1 to 11 integer), [P 2 W 18- t Mo t O 62] 6- (t is 1 or 17 an integer),
  • the polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above from the viewpoint of heat resistance and availability of raw materials. ) Is more preferable. Furthermore, it is heat-resistant that any one of a phosphorus tungstomolybdate ion [PW 10 Mo 2 O 40 ] 3 ⁇ , [PW 11 Mo 1 O 40 ] 3 ⁇ , and a phosphotungstate ion [PW 12 O 40 ] 3 ⁇ It is more preferable from the viewpoint of properties.
  • ⁇ ⁇ ⁇ ⁇ b in the general formula (1) represents the number of cations
  • d represents the number of anions in the molecular aggregate
  • b and d represent an integer of 1 or more.
  • b is 2 or more
  • a plurality of cations in the molecular association may be used alone or in combination of two or more.
  • d is 2 or more
  • a plurality of anions in the molecular aggregate may be used alone or in combination of two or more.
  • E in the general formula (1) is an integer of 0 or 1, and when e is 0, no bond exists.
  • a plurality of e may be the same or different.
  • the lake color material represented by the general formula (1) used in the present invention a material containing at least a triarylmethane skeleton is suitably used.
  • the lake color material represented by the general formula (1) can be prepared with reference to, for example, WO2012 / 144520 pamphlet and WO2018 / 003706 pamphlet.
  • R I ⁇ R VI are each independently a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R I R II , R III and R IV , or R V and R VI may combine to form a ring structure.
  • R I to R VI may be the same as R i to R v in the general formula (1), respectively.
  • R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. It may be the same as R vi and R vii in the general formula (1) described above.
  • Ar 2 represents an aromatic heterocyclic group which may have a substituent, said Ar 2 is of Ar 1 in the general formula (1) described above, aromatic It may be the same as the group heterocyclic group.
  • Em- represents an m-valent polyacid anion.
  • the m-valent polyacid anion is the same as the above-mentioned c-valent polyacid anion of the general formula (1). Good.
  • m represents the number of cations and the number of anions, and represents an integer of 2 or more.
  • the plurality of cations in the general formula (2) may be used alone or in combination of two or more.
  • the anions may be used alone or in combination of two or more.
  • j is 0 or 1, and when j is 0, no bond exists.
  • J in the general formula (2) may be the same as e in the general formula (1).
  • k and l in the general formula (2) may be the same as f and g in the general formula (1).
  • the lake color material represented by the general formula (2) can be prepared, for example, with reference to JP-A-2017-16099.
  • the basic-treated phthalocyanine pigment used in the present invention refers to a phthalocyanine pigment having a structure derived from a basic compound.
  • a phthalocyanine pigment having a structure derived from a basic compound for example, a phthalocyanine pigment containing a basic compound such as a colorant derivative having a basic site can be mentioned as a preferable one.
  • the phthalocyanine pigment used in the basic treatment at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) Since it is used in combination with a phthalocyanine pigment, a blue phthalocyanine pigment is preferable, and a copper phthalocyanine pigment is preferable because it has relatively excellent luminance.
  • the copper phthalocyanine pigment used in the basic treatment may be a crude copper phthalocyanine pigment or a copper phthalocyanine pigment having a crystal structure such as ⁇ -type, ⁇ -type, ⁇ -type, or ⁇ -type.
  • the copper phthalocyanine pigments used in the basic treatment among others, from the viewpoint of excellent dispersion stability, selected from the group consisting of copper phthalocyanine pigments having an ⁇ -type crystal structure and copper phthalocyanine pigments having a ⁇ -type crystal structure Preferably, at least one kind is used.
  • a colorant derivative having a basic site or a colorless compound derivative having a basic site is suitably used for the basic treatment.
  • the term "having a basic site” includes an embodiment having a basic group as a substituent, an embodiment in which an acidic group and a basic compound form a salt in the substituent, and the like.
  • the basic site of the colorant derivative or the colorless compound derivative in the present invention include an amino group, an ammonium sulfonate, or a sulfonamide group having an amino group, an amide group having an amino group, and a basic heterocyclic ring. And the like.
  • the basic site of the coloring material derivative may be included in a mode in which a hydrogen atom of the coloring material is substituted with the basic site, or the basic site may be included in the coloring material via a linking group. May be included in a substituted mode.
  • the coloring material is substituted with the basic site via a linking group include, for example, the coloring material being substituted with a hydrocarbon group having 1 to 20 carbon atoms or a substituent having a hydrocarbon group.
  • An embodiment in which a hydrogen atom of a hydrogen group is substituted at the basic site is mentioned.
  • the mode of the basic site of the derivative of the colorless compound may be the same as the mode of the basic site of the colorant derivative.
  • the amino group is represented by —NR a R b , wherein R a and R b each independently represent a hydrogen atom or a carbon number of 1 to 30 which may be substituted by —NR a ′ R b ′.
  • R a ′ and R b ′ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • Examples of the sulfonic acid ammonium salt, -SO 3 - ⁇ NHR c R d is represented by R e +, wherein R c, R d, and R e are each independently a hydrogen atom, optionally substituted with an amino group And a hydrocarbon group having 1 to 30 carbon atoms.
  • sulfonamide groups having an amino group a group represented by —SO 2 NH— (CH 2 ) m —NR f R g (where R f and R g are each independently a hydrogen atom And a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with the amino group, or a basic heterocyclic ring which is bonded to an adjacent nitrogen atom together with each other, and m is an integer of 1 to 15 Is preferable from the viewpoint of dispersibility of the coloring material.
  • amide group having an amino group a group represented by —CONH— (CH 2 ) m ′ —NR j R k (where R j and R k are each independently a hydrogen atom, A hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with an amino group, or a group bonded to each other to form a basic heterocyclic ring with an adjacent nitrogen atom, and m 'is an integer of 1 to 15 Is preferable from the viewpoint of dispersibility of the coloring material.
  • the hydrocarbon group having 1 to 30 carbon atoms includes: Examples thereof include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group, and a combination thereof. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples include a t-butyl group, an n-hexyl group, and a benzyl group.
  • R a , R b , R a ′ , R b ′ , R c , R d , R e , R f , R g , R j , and R k each independently represent a hydrogen atom or a C 1-25 alkyl group; It is preferably a hydrocarbon group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or Even more preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms.
  • m and m 'each represent an integer of 1 to 15, preferably 2 to 8, and particularly preferably 3 to 6.
  • the structure in which a basic heterocyclic ring is formed together with an adjacent nitrogen atom by bonding to each other may further include a nitrogen, oxygen, or sulfur atom in the heterocyclic ring.
  • Good examples include morpholine, piperidine, pyridine, triazine, thiazole and the like.
  • the basic heterocyclic group as the basic site include a morpholino group, a piperidino group, a pyridino group, and a triazino group.
  • the basic site where the derivative has, among others, from the viewpoint of easily interact with acidic dispersing agent, a sulfonic acid ammonium salt, or sulfonamide group having an amino group are preferable, among them, the -SO 2 NH- (CH 2) m -NR f R g group represented by is preferable.
  • the derivative may have at least one basic site per colorant or one molecule of the colorless compound, and is not particularly limited, but may have one or two basic sites from the viewpoint of colorant dispersibility. preferable.
  • the position where the basic site of the derivative is substituted with a coloring material or a colorless compound is not particularly limited.
  • the coloring material used for the coloring material derivative having a basic site a known coloring material can be appropriately selected and used, but it is preferable that the coloring material has a structure that is easily adsorbed to the phthalocyanine pigment used for the basic treatment, and is the same. Alternatively, it is preferable to have a similar dye skeleton or a structure that easily interacts. Further, a coloring material which does not impair the tint of the phthalocyanine pigment used in the basic treatment is preferable.
  • a blue coloring material derivative is particularly preferable.
  • a coating solution by mixing the color material with an appropriate binder component and solvent, apply it on a transparent substrate, and dry it. And harden it.
  • a binder component a non-curable thermoplastic resin composition may be used, or a photo-curable (photosensitive) or thermo-curable resin composition, as long as a transparent coating film capable of performing color measurement can be formed. May be used.
  • a composition containing only a blue coloring material as a coloring material
  • a solid content other than the coloring material used in the resin composition of Example 1 described later can be used as the binder component.
  • a colorant dispersion may be prepared.
  • a colorant dispersion and a colored resin composition are respectively prepared in the same manner as in Example 1 described below, and when the optical performance of Examples described later is evaluated.
  • a cured film may be produced in the same manner as the cured film described above.
  • a transparent coating film capable of performing colorimetry including a binder component for example, a film having a thickness of 2.0 ⁇ m and a transmittance of a spectral transmittance spectrum in a range of 380 nm to 780 nm of 95% or more is a standard. Can be.
  • the spectral transmittance spectrum can be measured using a spectrophotometer (for example, Olympus microspectrophotometer OSP-SP200).
  • a spectrophotometer for example, Olympus microspectrophotometer OSP-SP200.
  • OSP-SP200 Olympus microspectrophotometer
  • a phthalocyanine-based colorant for example, Olympus microspectrophotometer OSP-SP200
  • a triarylmethane-based colorant for example, an anthraquinone-based colorant, a naphthol-based colorant, a benzimidazolone-based colorant, or the like
  • the phthalocyanine-based coloring materials include copper phthalocyanines such as Pigment Blue (PB) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, and PB75, which are represented by color indexes. , PB79 and the like.
  • PB Pigment Blue
  • PB15 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, and PB75, which are represented by color indexes. , PB79 and the like.
  • a phthalocyanine-based coloring material having the same skeleton as the phthalocyanine pigment used in the basic treatment as the coloring material used in the coloring material derivative having a basic moiety.
  • copper phthalocyanine is preferably used as the blue color material used in the color material derivative having a basic site in terms of improving dispersibility and luminance.
  • the colorless compound used for the derivative of the colorless compound having a basic moiety is a compound in which the color of the phthalocyanine pigment does not change before and after the basic treatment even when the phthalocyanine pigment is subjected to basic treatment using the derivative of the colorless compound. It can be.
  • the color measurement of the phthalocyanine pigment before and after the basic treatment can be performed in the same manner as in the case of the blue color material. Specifically, using the phthalocyanine pigments before and after the basic treatment, respectively, a colorant dispersion liquid and a colored resin composition are respectively prepared in the same manner as in Example 1 described below, and the optical performance of Examples described later is evaluated. Each of the cured films is produced in the same manner as the cured film at that time.
  • the chromaticity of each cured film was measured by the method described in Examples described later, and the chromaticity (L 0 , a 0 , b 0 ) of the cured film containing the phthalocyanine pigment before the basic treatment and the chromaticity after the basic treatment were measured.
  • the colorless compound used for the derivative of the colorless compound having a basic moiety for example, an organic compound having an absorption maximum in a wavelength region of 400 nm or less can be mentioned, and can be appropriately selected and used.
  • the colorless compound preferably has a structure that easily adsorbs to the phthalocyanine pigment used in the basic treatment, and preferably has a structure that easily interacts with the phthalocyanine pigment.
  • a condensed ring compound such as a naphthalene-based compound or a triazine-based compound or an aromatic polycyclic compound in which a plurality of aromatic rings are bonded can be used.
  • Examples of the triazine-based aromatic polycyclic compound include a structure in which a triazine ring is substituted with three substituents having an aromatic hydrocarbon group such as a phenylamino group. Above all, it is preferable to use a triazine-based aromatic polycyclic compound from the viewpoint of improving dispersibility and luminance.
  • the coloring material derivative having a basic site can be produced by a conventionally known method.
  • it can be produced by a method of sulfonating a coloring material and then forming a salt with ammonia or an organic amine, or a method of sulfonamidating a substituent of the coloring material.
  • a coloring material is added to concentrated sulfuric acid or fuming sulfuric acid, and heated to perform sulfonation.
  • the reaction solution is poured into a large amount of ice water, and the precipitated sulfonated derivative is separated by filtration with a filter press or the like and washed with water.
  • the obtained water paste of the sulfonated derivative is redispersed in a large amount of water and neutralized with a basic compound.
  • a method of salt formation with an organic amine may be used.
  • a coloring material derivative having a powdery basic site can be obtained.
  • organic amine used for sulfonamidation of a coloring material derivative having a basic moiety or formation of an organic amine salt include methylamine, ethylamine, n-propylamine, isopropylamine, and n-butylamine.
  • a phthalocyanine pigment having a structure derived from a basic compound for example, as a method of preparing a phthalocyanine pigment containing a colorant derivative having a basic moiety, for example, a colorant derivative having a basic moiety, and a phthalocyanine pigment
  • a method of further mixing a colorant derivative having a basic site is used.
  • a ball mill, a vibration mill, an attritor, or the like can be used as the dry pulverizer, and the pulverization temperature can be freely set at 20 to 130 ° C.
  • a method of preparing a phthalocyanine pigment containing a colorant derivative having a basic site a colorant derivative having a basic site, a phthalocyanine pigment, and a water-soluble inorganic salt such as sodium chloride, calcium chloride, and ammonium sulfate.
  • a water-soluble organic solvent such as a glycol-based organic solvent is mixed and kneaded with a kneader-type polishing machine by a solvent salt milling method.
  • the content of the colorant derivative having a basic site or a derivative of a colorless compound is from the viewpoint of dispersibility and storage stability. It is preferably at least 0.5 part by mass, more preferably at least 3 parts by mass, still more preferably at least 5 parts by mass, and even more preferably at least 8 parts by mass with respect to parts by mass. preferable.
  • the content of the colorant derivative having a basic moiety or the derivative of a colorless compound is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, based on 100 parts by mass of the phthalocyanine pigment, from the viewpoint of excellent luminance. More preferably, it is even more preferably 30 parts by mass or less.
  • the fact that the phthalocyanine pigment has been subjected to basic treatment can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, and a combination thereof. More specifically, for example, after washing the basic-treated phthalocyanine pigment with an alcoholic solvent such as methanol, ethanol, or isopropanol, or a solvent such as N-methylpyrrolidone, the washed phthalocyanine pigment is subjected to mass spectrometry. It can be confirmed by detecting a peak derived from a structure derived from a desired basic compound such as a coloring material derivative having a sexual site.
  • the coloring material used in the present invention is at least one lake color selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2) as an essential component.
  • a material and a phthalocyanine pigment which has been subjected to a basic treatment are used, but other color materials may be used in combination in order to adjust the color tone within a range that does not impair the effects of the present invention.
  • known pigments, dyes, lake color materials, and the like can be used alone or in combination of two or more.
  • blue color materials other blue color materials, purple color materials, and red color materials are preferably used, but are not limited thereto.
  • blue color materials a known organic blue pigment different from the phthalocyanine pigment, a color material represented by the general formula (1), and a triarylmethane different from the color material represented by the general formula (2) Rake color materials.
  • a purple coloring material C.I. I.
  • Known organic violet pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and the like.
  • red to reddish purple colorant include a xanthene dye, a colorant represented by the general formula (1), and a lake colorant of a xanthene dye different from the colorant represented by the general formula (2).
  • each lake colorant selected from the group consisting of the colorant represented by the general formula (1) and the colorant represented by the general formula (2); It is preferable that each content ratio with the phthalocyanine pigment subjected to the basic treatment, and further when the other color material is used, be a content ratio used in a colored resin composition described later. Specifically, it is preferable to use the following content ratio.
  • the coloring resin composition can be produced by appropriately mixing two or more kinds of the coloring material dispersion liquids, the coloring material dispersion liquid may be used without using the content ratio used in the coloring resin composition described later.
  • the colorant dispersion of the present invention contains at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1) and the colorant represented by the general formula (2).
  • the amount is the total content of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) and the phthalocyanine pigment. 20% by mass or more and 85% by mass or less with respect to the desired line width while suppressing the chromaticity change of the colored layer after the high-temperature heating step (post-baking) in the color filter manufacturing step and improving the luminance. This is preferable in that a pattern can be formed.
  • the inventors of the present invention have found that when an attempt is made to form a blue colored layer using only a phthalocyanine pigment, a designed colored layer may not be formed. This is because the blue phthalocyanine pigment absorbs around 300 nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, so that the photopolymerization reaction does not proceed sufficiently and insufficient curing inside the colored layer occurs during exposure. It is estimated that On the other hand, by using the specific lake color material in combination with the specific ratio in the phthalocyanine pigment in the specific ratio, the specific lake color material hardly absorbs a wavelength of about 300 nm.
  • the content of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is the same as that of the general formula ( With respect to the total content of the phthalocyanine pigment and at least one lake color material selected from the group consisting of the color material represented by 1) and the color material represented by the general formula (2), It is preferably at least 30% by mass, more preferably at least 40% by mass, from the viewpoint of easiness of patterning at a line width of, and, on the other hand, at most 80% by mass, from the viewpoint of heat resistance. Is preferably 75% by mass or less, more preferably 75% by mass or less, and from the viewpoint of further improving the substrate adhesion, and from the viewpoint of improving the developability when the photosensitive resin composition is used, 55% by mass or less. Even more preferred.
  • a phthalocyanine pigment and a colorant other than the colorant represented by the general formula (1) are added to the colorant as long as the effects of the present invention are not impaired.
  • the total content of the phthalocyanine pigment and the coloring material represented by the general formula (1) is preferably 70% by mass or more and 100% by mass or less based on the total amount of the coloring material, The content is more preferably from 80% by mass to 100% by mass, further preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass.
  • the average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can form a desired color when the coloring layer of the color filter is used, and is different depending on the type of coloring material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle size of the coloring material is in the above range, a display device including a color filter manufactured using the coloring material dispersion of the present invention can have high contrast and high quality. .
  • the average dispersed particle size of the colorant in the colorant dispersion varies depending on the type of the colorant used, but is preferably in the range of 10 nm to 150 nm, and more preferably in the range of 15 nm to 60 nm. More preferred.
  • the average dispersion particle size of the colorant in the colorant dispersion is the dispersion particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, which is measured by a laser light scattering particle size distribution meter. It is.
  • the measurement of the particle size by the laser light scattering particle size distribution meter is performed by appropriately diluting the color material dispersion liquid with a solvent used for the color material dispersion liquid to a concentration measurable by the laser light scattering particle size distribution meter (for example, 1000 times). And the like, and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.).
  • the average distribution particle size is a volume average particle size.
  • the content of the colorant is not particularly limited.
  • the content of the coloring material is 5% by mass or more and 80% by mass or less, more preferably 8% by mass or more and 70% by mass or less based on the total solid content in the coloring material dispersion.
  • the amount of the solid content in the coloring material dispersion is 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 75% by mass. It is preferable to mix them in the following ratio.
  • the solid content is all other than the above-mentioned solvent, and includes monomers and the like dissolved in the solvent.
  • the acidic dispersant used in the present invention includes a polymer having at least one selected from the structural units represented by the general formula (I).
  • a polymer having at least one selected from the structural units represented by the general formula (I) is used as the acidic dispersant, the dispersibility and heat resistance of the lake color material are improved, and the lake after heating is improved. It is possible to suppress a change in the chromaticity of the coloring material, improve the dispersibility and storage stability of the phthalocyanine pigment, and form a colored layer with improved substrate adhesion and coating uniformity.
  • the heat resistance of the skeleton is higher than that of a polyether or polyester polymer.
  • active oxygen such as peroxy radical (hydrogen abstraction or substitution reaction). It is estimated that the suppression of the rake color material (oxidation deterioration) is suppressed.
  • L 1 is a direct bond or a divalent linking group.
  • the bond L 1 is directly, phosphorus atom, means that attached directly to a carbon atom of the main chain without passing through a linking group.
  • the divalent linking group for L 1 is not particularly limited as long as the carbon atom in the main chain skeleton can be linked to a phosphorus atom.
  • Examples of the divalent linking group for L 1 include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, —NHCOO— groups, ether groups (—O— groups), thioether groups (—S— groups), combinations thereof, and the like.
  • the direction of the bond of the divalent linking group is arbitrary. That is, when -CONH- is contained in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain. May be -CO on the side of a phosphorus atom in the side chain.
  • L 1 in the general formula (I) is preferably a divalent linking group containing a —CONH— group or a —COO— group from the viewpoint of dispersibility.
  • L 1 is a divalent linking group containing a —COO— group
  • L 1 is a —COO-L 1 ′ -group (where L 1 ′ is a carbon atom which may have a hydroxyl group.
  • the alkylene group having 1 to 8 carbon atoms in L 1 ′ may be linear, branched or cyclic, and includes, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, It is a butylene group, various pentylene groups, various hexylene groups, various octylene groups, and the like, and a part of hydrogen may be substituted by a hydroxyl group.
  • x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less
  • y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably Is 2 or 3.
  • z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.
  • w is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less.
  • L 1 in the general formula (I) include, for example, —COO—CH 2 CH (OH) CH 2 —O—, —COO—CH 2 CH 2 —O—CH 2 CH (OH) CH 2 -O -, - COO-CH 2 C (CH 2 CH 3) (CH 2 OH) CH 2 -O- or the like including without being limited thereto.
  • Examples of the hydrocarbon group for R 2 include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group.
  • the alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic.
  • the alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic.
  • Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group.
  • the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of reactivity of the obtained polymer.
  • Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent.
  • the carbon number of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
  • Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 14 carbon atoms.
  • the alkyl group or alkenyl group may have a substituent, and examples of the substituent include a halogen atom such as F, Cl, and Br, and a nitro group.
  • Examples of the substituent for the aromatic ring such as the aryl group or the aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom. Can be mentioned. The preferred carbon number does not include the carbon number of the substituent.
  • x1 is said x
  • y1 is said y
  • z1 are as defined above z.
  • Examples of the hydrocarbon group for R 5 to R 12 include the same as the hydrocarbon group for R 2 described above.
  • the hydrocarbon group is monovalent, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group are mentioned.
  • the hydrocarbon group is divalent, an alkylene group, an alkenylene group, an arylene group, and a combination thereof are used. The group of is mentioned.
  • the number of carbon atoms forming the ring structure is preferably 5 or more and 8 or less, and is preferably 6, that is, a 6-membered ring. More preferably, a cyclohexane ring is formed.
  • the hydrocarbon group or the hydrocarbon group having at least one kind selected from an ether bond and an ester bond is selected from the groups represented by R 7 , R 8 , R 9 , R 10 , R 11, and R 12 . It can be similar to the one.
  • R 2 is a hydroxyl group, a hydrocarbon group,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[ (CH 2 ) y1 —O] is preferably a monovalent group represented by z1 —R 5 or —OR 6 , and has a hydroxyl group, a methyl group, an ethyl group, a vinyl group, or a substituent.
  • Groups, vinyl groups, methyl groups and hydroxyl groups are more preferred.
  • R 2 is a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , or — [(CH 2 ) y1 —O ] it is preferably a monovalent group represented by z1 -R 5. It is presumed that when the compound has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is difficult to be hydrolyzed, so that a resin layer having excellent alkali resistance can be formed.
  • X represents a hydrogen atom or an organic cation.
  • the organic cation refers to a cation moiety containing a carbon atom.
  • Examples of the organic cation include an imidazolium cation, a pyridinium cation, an aminium cation, a piperidinium cation, a pyrrolidinium cation, an ammonium cation such as a tetraalkylammonium cation and a trialkylammonium cation, and a sulfonium cation such as a trialkylsulfonium cation.
  • a phosphonium cation such as a tetraalkylphosphonium cation.
  • a protonated nitrogen-containing organic cation is preferable in terms of dispersibility and alkali developability.
  • the organic cation has an ethylenically unsaturated double bond, it is preferable in that it can impart curability.
  • the structural unit represented by the general formula (I) may be contained alone in the polymer, or may be contained in two or more kinds.
  • X may include both a structural unit of a hydrogen atom and X as a structural unit of an organic cation. In the case of including both of the structural units, it is sufficient that good dispersibility and dispersion stability are exhibited, and there is no particular limitation. Is preferably from 0 to 50 mol% based on the total number of structural units represented by
  • the method for synthesizing the polymer having at least one selected from the structural units represented by the general formula (I) is not particularly limited.
  • the polymer having at least one selected from the structural units represented by the general formula (I) can be synthesized with reference to, for example, JP-A-2017-2191.
  • the polymer having at least one selected from the structural units represented by the general formula (I) is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in a side chain and an acidic phosphorus compound. It is preferable that at least a part of the acidic phosphorus compound group is a polymer that may form a salt.
  • the polymer having at least one selected from the structural units represented by Formula (I) preferably further has a solvent affinity site from the viewpoint of dispersibility.
  • a block copolymer having at least one selected from the structural units represented by the general formula (I) and a structural unit represented by the following general formula (III) It is excellent in dispersibility and storage stability, and is preferable because a high-contrast coating film can be formed even after long-term storage.
  • L 2 is a direct bond or a divalent linking group
  • R 21 is a hydrogen atom or a methyl group
  • Polymer is a polymer chain having a structural unit represented by the following general formula (IV).
  • R 22 is a hydrogen atom or a methyl group
  • R 23 is a hydrocarbon group,-[CH (R 24 ) -CH (R 25 ) -O] x2 -R 26 ,-[(CH 2) y2 -O] z2 -R 26 , - [CO- (CH 2) y2 -O] z2 -R 26, -CO-O-R 26 ' or a monovalent represented by -O-CO-R 26
  • R 24 and R 25 are each independently a hydrogen atom or a methyl group
  • R 26 is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 27
  • R 24 and R 25 are each independently a hydrogen
  • the hydrocarbon group may have a substituent.
  • x2 and x2 ' represent an integer of 1 to 18;
  • y2 and y2' represent an integer of 1 to 5;
  • R 31 is a hydrogen atom or a methyl group
  • R 32 is a hydrocarbon group,-[CH (R 33 ) -CH (R 34 ) -O] x3 -R 35 ,-[( CH 2 ) y3 —O] z3 —R 35 , — [CO— (CH 2 ) y3 —O] z3 —R 35 , monovalent represented by —CO— OR 36 or —O—CO—R 37
  • a group, R 33 and R 34 each independently represent a hydrogen atom or a methyl group
  • R 35 represents a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 38
  • R 36 is a hydrocarbon group,-[CH (R 33 ) -CH (R 34 ) -O] x4 -R 35 ,-[(CH 2 ) y4 -O] z4 -R 35 ,
  • n shows the integer of 5 or more and 200 or less.
  • x3 and x4 each represent an integer of 1 to 18;
  • y3 and y4 each represent an integer of 1 to 5;
  • z3 and z4 each represent an integer of 1 to 18;
  • L 2 is a direct bond or a divalent linking group.
  • L The divalent linking group for 2, connecting carbon atom with a polymer chain derived from an ethylenically unsaturated double bond, if possible, is not particularly limited. Examples of the divalent linking group for L 2, for example, those similar to the divalent linking group for the L 1 and the like.
  • Polymer represents a polymer chain having a structural unit represented by the general formula (IV).
  • the hydrocarbon group for R 32 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, or an aryl group having 2 to 18 carbon atoms. Is preferred. These include, for example, those similar to the of R 2.
  • R 35 is preferably a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO or —CH 2 COOR 38
  • R 36 is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R 33 ) -CH (R 34 ) -O] x4 -R 35 ,-[(CH 2 ) y4 -O] z4 -R 35, - [CO- (CH 2) y4 -O] 1 monovalent group is preferably represented by z4 -R 35.
  • R 37 represents an alkyl group having 1 to 18 carbon atoms
  • R 38 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Examples of the alkyl group, aralkyl group, and aryl group having 1 to 18 carbon atoms in R 35 and R 36 include those similar to R 2 described above.
  • As the alkyl group of R 37 and R 38 those similar to the aforementioned R 2 can be mentioned.
  • R 35 , R 36 , R 37 and R 38 are groups having an aromatic ring, the aromatic ring may further have a substituent.
  • substituents examples include a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkenyl group, a nitro group, and a halogen atom such as F, Cl, or Br. .
  • the preferred carbon number does not include the carbon number of the substituent.
  • R 32 and R 36 is x3 and x4 and the x, the y3 and y4 and the y, the z3 and z4 is the same as the z.
  • R 32 , R 35 , R 36 , R 37 and R 38 may further include an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group as long as the dispersing performance and the like of the graft copolymer are not hindered. It may be substituted by a substituent such as an isocyanate group or a hydrogen bond forming group. Alternatively, after a graft copolymer having these substituents is synthesized, a compound having a polymerizable group and a functional group that reacts with the substituent may be reacted to add a polymerizable group.
  • adding a polymerizable group by reacting glycidyl (meth) acrylate with a graft copolymer having a carboxyl group or reacting hydroxyethyl (meth) acrylate with a graft copolymer having an isocyanate group.
  • a polymerizable group by reacting glycidyl (meth) acrylate with a graft copolymer having a carboxyl group or reacting hydroxyethyl (meth) acrylate with a graft copolymer having an isocyanate group.
  • the polymer chain contained in the structural unit represented by the general formula (IV) includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl Those having structural units derived from (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinylcyclohexane and the like are preferable. However, it is not
  • the R 32 and R 36 are appropriately selected according to the organic solvent used in the colorant dispersion.
  • the organic solvent uses an organic solvent such as an ether alcohol acetate system, an ether system, and an ester system that are generally used as an organic solvent of the colorant dispersion, a methyl group, an ethyl group, Groups, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl and the like.
  • the reason for setting the R 32 and R 36 in this manner is that the structural unit containing the R 32 and R 36 has solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and This is because the dispersibility and the stability of the particles of the coloring material or the like can be made particularly excellent when the salt portion has a high adsorptivity to the particles of the coloring material or the like.
  • the weight average molecular weight Mw of the polymer chain in Polymer is preferably in the range of 500 or more and 15000 or less, more preferably in the range of 1000 or more and 8000 or less.
  • a sufficient steric repulsion effect as a dispersant can be maintained, and an increase in time required for dispersing particles such as a coloring material due to the steric effect can also be suppressed.
  • the solubility of the polymer chain in Polymer at 23 ° C. in an organic solvent used in combination is preferably 50 (g / 100 g solvent) or more.
  • the polymer chain may be a homopolymer or a copolymer. Further, the polymer chain contained in the structural unit represented by the general formula (II) may be used alone or as a mixture of two or more kinds in the graft copolymer.
  • the total amount of the structural units represented by the general formula (I) is 3% by mass or more and 80% by mass or less with respect to all the structural units of the graft copolymer. It is more preferably from 70% by mass to 70% by mass, further preferably from 20% by mass to 60% by mass.
  • the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity site with the particles in the graft copolymer becomes appropriate, and the organic solvent Since a decrease in solubility in water can be suppressed, the adsorptivity to particles such as coloring materials becomes good, and excellent dispersibility and dispersion stability can be obtained.
  • the constitutional unit represented by the general formula (II) is preferably contained in a proportion of 20% by mass or more and 97% by mass or less with respect to all the constitutional units of the graft copolymer, and 25% by mass or less. % To 95% by mass, more preferably 40% to 90% by mass.
  • the content ratio of the structural unit is such that a graft copolymer having at least one type selected from the structural units represented by the general formula (I) and the structural unit represented by the general formula (II) is synthesized. It is calculated from the charged amount at the time.
  • the mass average molecular weight Mw of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and more preferably in the range of 5,000 to 300,000. Is more preferable. When the content is within the above range, particles such as a coloring material can be uniformly dispersed. In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography).
  • the measurement was performed using Tosoh's HLC-8220GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol / l of lithium bromide was added, and the polystyrene standard for the calibration curve was Mw: 8 ⁇ 10 5 (F-80 ), Mw: 4 ⁇ 10 5 (F-40), Mw: 2 ⁇ 10 5 (F-20), Mw: 1 ⁇ 10 5 (F-10), Mw: 4 ⁇ 10 4 (F-4), Mw: 2 ⁇ 10 4 (F-2), Mw: 5 ⁇ 10 3 (A-5000), Mw: 2.5 ⁇ 10 3 (A-2500), Mw: 1 ⁇ 10 3 (A-1000), Mw: 5 ⁇ 10 2 (A-500) (manufactured by Tosoh) and two measurement columns TSK-GEL ALPHA-M (manufactured by Tosoh).
  • the graft copolymer used in the embodiment of the present invention has other structural units in addition to the structural units represented by the general formula (I) and the general formula (II). May be.
  • An ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer or the like which derives at least one selected from the structural units represented by the general formula (I) is appropriately selected and copolymerized, and the other structural units are Can be introduced.
  • Block copolymer In the block portion including at least one selected from the structural units represented by the general formula (I), it is preferable that a total of three or more structural units represented by the general formula (I) are included. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferable to include 3 to 200, more preferably 3 to 50, and still more preferably 3 to 30. Is more preferred. At least one selected from the structural units represented by the general formula (I) may function as a coloring material affinity site, and may be composed of one type or may include two or more types of structural units. You may go out. When two or more types of structural units are included, two or more types of structural units may be randomly arranged in a block portion including at least one type selected from the structural units represented by the general formula (I).
  • the total content of the structural units represented by the general formula (I) may be 5% by mass or more and 80% by mass or less based on all the structural units of the block copolymer. It is more preferably from 10% by mass to 70% by mass, and still more preferably from 20% by mass to 60% by mass. If it is within the above range, the ratio of the affinity site with the particles in the block copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed, so that the adsorptivity to the particles such as the coloring material becomes good, Excellent dispersibility and dispersion stability are obtained.
  • the acidic phosphorus compound group of the block copolymer can be stably localized around the coloring material, a color filter excellent in heat resistance and contrast can be obtained.
  • the content ratio of the structural unit is calculated from the charged amount at the time of synthesizing the block copolymer.
  • the block copolymer has a block portion containing the structural unit represented by the general formula (III), the affinity for the solvent is improved, the dispersibility and the dispersion stability of the coloring material are improved, and the heat resistance is improved. The properties are good and the NMP resistance is excellent.
  • R 23 is a hydrocarbon group,-[CH (R 24 ) -CH (R 25 ) -O] x2 -R 26 ,-[(CH 2 ) y2 -O] z2 -R 26 , — [CO— (CH 2 ) y2 —O] z2 —R 26 , —CO— OR 26 ′ or —O—CO—R 26 ′′ .
  • the hydrocarbon group for R 23 it may be similar to that shown in the R 2.
  • R 26 is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 27
  • R 12 ′ is a hydrocarbon group, — [CH ( R 24 ) -CH (R 25 ) -O] x2 ' -R 26 ,-[(CH 2 ) y2' -O] z2 ' -R 26 ,-[CO- (CH 2 ) y2' -O] z2 '
  • a monovalent group represented by —R 26 , R 26 ′′ is an alkyl group having 1 to 18 carbon atoms
  • R 27 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • hydrocarbon group may have a substituent.
  • the hydrocarbon group for R 26 can be the same as that for R 2 .
  • 'In, x2 and x2' the R 23 and R 26 and the x, y2 and y2 'are said y, z2 and z2' are the same as defined above z.
  • R 23 in the structural unit represented by the general formula (III) may be the same as or different from each other.
  • R 23 and R 26 ' are each an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group as long as the dispersibility of the block copolymer is not hindered. May be substituted with a substituent such as an isocyanate group or a hydrogen bond-forming group, or after the synthesis of the block copolymer, by reacting with the compound having the substituent to add the substituent. Is also good.
  • a compound having a polymerizable group and a functional group that reacts with the substituent may be reacted to add a polymerizable group.
  • adding a polymerizable group by reacting (meth) acrylic acid with a block copolymer having a glycidyl group or reacting hydroxyethyl (meth) acrylate with a block copolymer having an isocyanate group.
  • a polymerizable group by reacting (meth) acrylic acid with a block copolymer having a glycidyl group or reacting hydroxyethyl (meth) acrylate with a block copolymer having an isocyanate group.
  • the number of structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, but the solvent-affinity site and the colorant-affinity site work effectively, and the colorant dispersion liquid From the viewpoint of improving dispersibility, it is preferably from 10 to 200, more preferably from 20 to 100, and even more preferably from 30 to 80.
  • the content of the structural unit represented by the general formula (III) is preferably 30% by mass or more and 95% by mass or less based on all the structural units of the block copolymer. More preferably, the content is 40% by mass or more and 90% by mass or less. In addition, the content ratio of the structural unit is calculated from the charged amount at the time of synthesizing the block copolymer.
  • the block part containing the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity site, and the structural unit represented by the general formula (III) is composed of one kind. Or two or more types of constituent units.
  • the structural unit represented by the general formula (III) includes two or more types of structural units
  • the block unit including the structural unit represented by the general formula (III) has two types.
  • the above constituent units may be randomly arranged.
  • the ratio m / n of the number m and the number n of the structural units of the block unit including the structural unit represented by the general formula (III) is preferably in the range of 0.01 or more and 1 or less, and 0 It is more preferably in the range of from 1 to 0.7 in view of the dispersibility and dispersion stability of the coloring material.
  • a block part containing at least one selected from the structural units represented by the general formula (I) and a block part containing a structural unit represented by the general formula (III) It is not particularly limited as long as it can disperse the coloring material stably, and the block portion including at least one selected from the structural units represented by the general formula (I) is preferably used as the block unit. It is preferable that the polymer is bonded to only one end of the polymer because it has excellent interaction with the coloring material and can effectively suppress aggregation of the dispersants.
  • the mass average molecular weight of the block copolymer is not particularly limited, but it is preferable that the weight average molecular weight is 2500 or more and 500,000 or less, and 3,000 or more and 400,000 or less, from the viewpoint of excellent dispersibility and excellent heat resistance. More preferably, it is more preferably 6,000 or more and 300,000 or less.
  • the acid value of the polymer having at least one selected from the structural units represented by the general formula (I) is preferably 20 mgKOH / g or more from the viewpoint of the dispersibility and storage stability of the coloring material. It is more preferably at least 30 mgKOH / g, and even more preferably at least 40 mgKOH / g.
  • the acid value of the polymer having at least one selected from the structural units represented by the general formula (I) is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g. Or less, more preferably 100 mgKOH / g or less.
  • the acid value refers to the number of mg of potassium hydroxide required for neutralizing the acid component contained in 1 g of a sample, and can be measured according to JIS K 0070: 1992.
  • the colorant dispersion of the present invention may further contain another acidic dispersant different from the polymer having at least one selected from the structural units represented by the general formula (I).
  • Other acidic dispersants include dispersants having an acidic group.
  • examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. It is preferable from the viewpoint of excellent dispersibility.
  • the acid value of the other acidic dispersant is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of excellent dispersibility.
  • the acid value of the other acidic dispersant is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less, and further preferably 180 mgKOH / g or less from the viewpoint of suppressing the development residue. .
  • the use of another acidic dispersant in combination with a polymer having at least one selected from the structural units represented by formula (I) improves the suppression of development residues.
  • a polymer dispersant having a carboxy group is preferable, and among them, when used in combination with a polymer having at least one selected from the structural units represented by the general formula (I), From the point that the suppression of the residue is improved and the uniformity of the coating film is improved, the structure derived from the A block including the structural unit derived from the carboxy group-containing ethylenically unsaturated monomer and the structure derived from the alkyl (meth) acrylate ester It is preferable to further include a block copolymer containing a B block containing a unit.
  • Block copolymer containing A block containing a constitutional unit derived from a carboxy group-containing ethylenically unsaturated monomer and B block containing a constitutional unit derived from an alkyl (meth) acrylate a block copolymer including an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth) acrylate ester is simply referred to as a “carboxy group-containing block”.
  • Copolymer ".
  • the A block is a polymer block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer.
  • Examples of the carboxy group-containing ethylenically unsaturated monomer used in the A block include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate and 4- (meth) acrylic acid.
  • Examples thereof include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride with hydroxyalkyl (meth) acrylate such as hydroxybutyl, and vinyl monomers having a carboxy group such as vinylbenzoic acid.
  • the constitutional unit derived from the ethylenically unsaturated monomer refers to a constitutional unit in which a radically polymerizable carbon-carbon double bond of the ethylenically unsaturated monomer has become a carbon-carbon single bond.
  • each structural unit may be included in the A block in any mode such as random copolymerization or block copolymerization. It is preferably contained in the form of a copolymer.
  • the constituent unit derived from the carboxy group-containing ethylenically unsaturated monomer is preferably 40% by mass or more, more preferably 70% by mass or more, based on all the constituent units of the A block. It is even more preferable that the polymer block is composed of only a structural unit derived from the contained ethylenically unsaturated monomer.
  • the A block may be composed of only a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer, or a carboxy group-containing ethylenically unsaturated monomer as long as the acidity of the A block is stronger than that of the B block. May contain structural units derived from different ethylenically unsaturated monomers.
  • the A block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer, the content is preferably 60% by mass or less based on all the structural units of the A block. It is more preferable that the content be not more than mass%.
  • Examples of the ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer include structural units used for a B block described later.
  • the content of the A block is preferably 5% by mass or more, and more preferably 10% by mass or more, based on all the structural units of the block copolymer. , 95% by mass or less, more preferably 40% by mass or less.
  • the B block is a polymer block containing a structural unit derived from an alkyl (meth) acrylate.
  • the (meth) acrylic acid alkyl ester monomer used for the B block may be the same as the (meth) acrylic acid alkyl ester monomer used for the polymer chain contained in the structural unit represented by the general formula (IV). , Or a mixture of two or more.
  • the B block may contain a structural unit derived from another ethylenically unsaturated monomer in addition to the structural unit derived from the alkyl (meth) acrylate. Examples of the structural unit derived from the other ethylenically unsaturated monomer include structural units different from the structural unit derived from the alkyl (meth) acrylate among the structural units represented by the general formula (III).
  • each structural unit may be included in the B block in any mode such as random copolymerization or block copolymerization. It is preferably contained in the form of a copolymer.
  • the B block may be formed of a copolymer of a structural unit composed of the b1 block and a structural unit composed of the b2 block.
  • the structural unit derived from the ethylenically unsaturated monomer having an acidic group is preferably 10% by mass or less, more preferably 5% by mass or less, based on all the structural units of the B block. It is more preferred that the content be not more than mass%. In the present invention, it is even more preferable that the B block is a polymer block containing no structural unit derived from an ethylenically unsaturated monomer having an acidic group.
  • the carboxy group-containing block copolymer may be an AB block copolymer or a BAB block copolymer.
  • the block copolymer is a BAB block copolymer
  • the content ratio of each of the two B blocks is adjusted within a range of (50:50) to (70:30) in terms of mass from the viewpoint of dispersibility. Is preferred.
  • the acid value of the carboxy group-containing block copolymer is preferably in the range of 30 mgKOH / g to 250 mgKOH / g from the viewpoint of dispersibility, so that the acid value of the block copolymer falls within this range.
  • a block preferably contain a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer.
  • the acid value is preferably at least 50 mgKOH / g, more preferably at least 70 mgKOH / g.
  • the acid value is preferably at most 200 mgKOH / g, more preferably at most 150 mgKOH / g.
  • the weight average molecular weight (Mw) of the carboxy group-containing block copolymer is preferably 5,000 or more and 100,000 or less from the viewpoint of dispersibility. Mw is more preferably 8,000 or more, and even more preferably 10,000 or more. Mw is more preferably 80,000 or less, and even more preferably 70,000 or less.
  • the molecular weight distribution of the carboxy group-containing block copolymer is preferably less than 2, more preferably less than 1.5, even more preferably less than 1.3.
  • the molecular weight distribution is determined by (weight average molecular weight (Mw)) / (number average molecular weight (Mn)). The larger the molecular weight distribution, the smaller the molecular weight or the higher the molecular weight compared to the molecular weight of the designed polymer, and the lower the molecular weight distribution because the tendency to deteriorate the dispersibility of the coloring material is included. Is more preferred.
  • the method for producing the carboxy group-containing block copolymer a conventionally known method for producing a block copolymer can be appropriately selected and used. From the viewpoint of easily producing a polymer having a uniform composition, it is preferable to use a living polymerization method.
  • a living polymerization method a method using an organic acid catalyst and a silyl-based initiator (GTP method), a method using a transition metal catalyst ( (ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), and a method using an organic tellurium compound (TERP method).
  • ⁇ Content of acidic dispersant> As the acidic dispersant, when a polymer having at least one selected from the structural units represented by the general formula (I) is used in combination with another acidic dispersant different from the above-described general formula (I), The content ratio of the polymer having at least one selected from the structural units represented by (I) and another acidic dispersant different from the polymer can be appropriately selected and used. Above all, the mass ratio of the polymer having at least one selected from the structural units represented by the general formula (I) to another acidic dispersant different from the polymer is included in the coloring material.
  • the content of the polymer having at least one selected from the structural units represented by the general formula (I) in the acidic dispersant is represented by the general formula (I).
  • the total content of the polymer having at least one selected from the structural units and another acidic dispersant different from the polymer is preferably 20% by mass or more and 85% by mass or less, and the dispersibility and the development residue suppression. It is preferable from the point of view.
  • the content of the acidic dispersant in the colorant dispersion may be appropriately adjusted, but from the viewpoint of dispersibility and storage stability, the content is preferably 5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the colorant. More preferably, it is more than 20 parts by mass and not more than 70 parts by mass.
  • the content of the acidic dispersant in the colorant dispersion is preferably 3% by mass or more and 45% by mass or less, more preferably 3% by mass or less, based on the total solid content in the colorant dispersion, from the viewpoint of dispersibility and dispersion stability. It is more preferable to mix at a ratio of 5% by mass or more and 35% by mass or less.
  • the solvent used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the colorant dispersion and can dissolve or disperse these components.
  • the solvents can be used alone or in combination of two or more.
  • Specific examples of the solvent include, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxy ethanol and ethoxyethoxy ethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl buty
  • Glycol acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate, butyl carbitol acetate (BCA) and carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether and ethylene glycol mono Ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Glycol ether solvents such as tyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl
  • glycol ether acetate solvents examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, and ethyl ethoxypropionate.
  • BCA butyl carbitol acetate
  • Ethyl lactate, and 3-methoxybutyl acetate are preferred in view of solubility of other components and suitability for application.
  • the colorant dispersion of the present invention preferably contains the above solvent in a range of usually 55% by mass or more and 95% by mass or less based on the total amount of the colorant dispersion containing the solvent. It is preferably in the range of from 70% by mass to 90% by mass, and more preferably in the range of from 70% by mass to 88% by mass. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. On the other hand, if the amount of the solvent is too large, the concentration of the coloring material may decrease, and it may be difficult to achieve the target chromaticity coordinates.
  • the colorant dispersion of the present invention may further contain a dispersion assisting resin and other components, if necessary, as long as the effects of the present invention are not impaired.
  • the dispersion assisting resin include an alkali-soluble resin exemplified by a colored resin composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, stabilizing the dispersion, and reducing the amount of the dispersant due to the effect of stabilizing the dispersion in some cases.
  • Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cissing agent, an antioxidant, an anti-agglomerating agent, and an ultraviolet absorber. And the like.
  • the colorant dispersion of the present invention is used as a preliminary preparation for preparing a colored resin composition described below. That is, the colorant dispersion liquid is P / V (mass of the colorant component in the composition) / (mass of the colorant component in the composition) which is preliminarily prepared in the stage before preparing the colorant resin composition described below. It is a colorant dispersion having a high (solid content mass) ratio. Specifically, the ratio of (mass of coloring material component in composition) / (mass of solid content other than coloring material component in composition) is usually 1.0 or more.
  • the method for producing a colorant dispersion is not particularly limited as long as the colorant can be obtained by dispersing the colorant in a solvent with the dispersant.
  • the method for producing a colorant dispersion according to the present invention includes a step of preparing the colorant, a step of preparing the dispersant, and dispersing the colorant in a solvent in the presence of the dispersant. And a process.
  • a solvent in the presence of the dispersant, two or more color materials may be co-dispersed, or one or more color materials may be dispersed or co-dispersed, and then two or more color material dispersions may be mixed.
  • the colorant dispersion of the present invention may be obtained.
  • at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is mixed in a solvent with the general formula (
  • a colorant dispersion a dispersed in the presence of a polymer having at least one selected from the structural units represented by I) is prepared.
  • the coloring material can be dispersed using a conventionally known dispersing machine.
  • the dispersing machine include a roll mill such as a two-roller and a three-roller, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a bead mill such as a continuous disk type bead mill, and a continuous annular type bead mill.
  • the bead diameter used is preferably from 0.03 mm to 3.0 mm, more preferably from 0.05 to 2.0 mm.
  • the colored resin composition according to the present invention is a colored resin composition containing a coloring material, an acidic dispersant, a binder component, and a solvent,
  • the color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2).
  • Phthalocyanine pigments is a colored resin composition containing a polymer having at least one selected from the structural units represented by the general formula (I).
  • the colored resin composition of the present invention has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range by the same action as described in the above-described color material dispersion, In addition, there is an effect that a colored layer having improved substrate adhesion and coating film uniformity can be formed.
  • the colored resin composition of the present invention contains at least a coloring material, a dispersant, a binder component, and a solvent, and may further contain other components as long as the effects of the present invention are not impaired. Good thing.
  • each component contained in the colored resin composition of the present invention will be described, but the colorant, dispersant, and solvent are the same as those described in the colorant dispersion of the present invention. Is omitted.
  • each component of the colored resin composition of the present invention will be described in detail in order.
  • the colored resin composition of the present invention contains a binder component in order to impart film formability and adhesion to a surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component.
  • the curable binder component is not particularly limited, and a curable binder component used for forming a coloring layer of a conventionally known color filter can be appropriately used.
  • the curable binder component for example, visible light, ultraviolet light, a photocurable binder component containing a photocurable resin that can be polymerized and cured by an electron beam, or a thermosetting resin that can be polymerized and cured by heating What contains a thermosetting binder component can be used.
  • a photosensitive binder component having alkali developability is preferably used.
  • a thermosetting binder component may be further used as the photosensitive binder component.
  • the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component.
  • the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitizing component.
  • the negative photosensitive binder component a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
  • the colored resin composition according to the present invention is preferably a negative photosensitive binder component in that a pattern can be easily formed by a photolithography method using an existing process.
  • the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.
  • the alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those soluble in an alkali developer used for pattern formation.
  • the alkali-soluble resin can be used as a guide when the acid value is 40 mgKOH / g or more.
  • the preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, for example, an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. And an epoxy (meth) acrylate resin having a carboxy group.
  • those having a carboxy group on the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group on the side chain are particularly preferable.
  • the alkali-soluble resins are cross-linked with each other, or the photopolymerizable compound such as the alkali-soluble resin and a polyfunctional monomer. Can be formed.
  • the film strength of the cured film is further improved to improve the development resistance, and the heat shrinkage of the cured film is suppressed, so that the adhesion to the substrate becomes excellent.
  • the method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to the carboxy group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Or a method in which a structural unit having a hydroxyl group is introduced into a copolymer, and a compound having an isocyanate group and an ethylenic double bond in a molecule is added to introduce a ethylenic double bond into a side chain. And the like.
  • a compound having both an epoxy group and an ethylenic double bond in the molecule such as glycidyl (meth) acrylate
  • the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer.
  • a hydrocarbon ring which is a bulky group
  • shrinkage during curing is suppressed, separation from the substrate is eased, and substrate adhesion is improved.
  • a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a combination thereof.
  • the hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher valent group.
  • hydrocarbon ring examples include aliphatic such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane.
  • Hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and cardo structures (9,9-diarylfluorene) ); Groups in which some of these groups are substituted with substituents.
  • substituents include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.
  • the heat resistance and adhesion of the colored layer are improved, and the luminance of the obtained colored layer is preferably improved.
  • the curability of the colored layer is improved, the fading of the coloring material is suppressed, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.
  • Acrylic resins such as an acrylic copolymer having a structural unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group include, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
  • the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride
  • ⁇ -carboxy-polycaprolactone Mono (meth) acrylates can also be used.
  • an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of the carboxy group.
  • (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.
  • the alkali-soluble resin in the present invention is a carboxy group-containing copolymer such as an acrylic copolymer or a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring.
  • a carboxy group-containing such as an acrylic copolymer or a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. More preferably, it is a copolymer.
  • Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (Meth) acrylate, styrene, and the like, and cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from meth) acrylate, benzyl (meth) acrylate, and styrene.
  • the carboxy group-containing copolymer may further contain other structural units such as a structural unit having an ester group, such as methyl (meth) acrylate and ethyl (meth) acrylate.
  • a structural unit having an ester group such as methyl (meth) acrylate and ethyl (meth) acrylate.
  • the constituent unit having an ester group not only functions as a component for suppressing alkali solubility of the colored resin composition, but also functions as a component for improving solubility in a solvent and further improving solvent resolubility.
  • the carboxy group-containing copolymer can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.
  • the charged amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of monomers, from the viewpoint of obtaining a good pattern.
  • the amount of the carboxy group-containing ethylenically unsaturated monomer to be added is preferably 50% by mass or less, and more preferably 40% by mass or less based on the total amount of the monomers, from the viewpoint of suppressing film roughness on the pattern surface after development. More preferably, there is.
  • the compound having an ionic double bond is preferably from 10% by mass to 95% by mass, and more preferably from 15% by mass to 90% by mass, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer. More preferred.
  • the preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the binder function after curing is improved, and when it is 50,000 or less, pattern formation becomes good at the time of development with an alkali developing solution.
  • the epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
  • the epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known compounds and used.
  • the epoxy (meth) acrylate resin having a carboxy group also preferably has the above-mentioned hydrocarbon ring in the molecule. Among them, those containing a cardo structure improve the curability of the coloring layer and reduce the fading of the coloring material. This is preferred because it suppresses the coloration and increases the residual film ratio of the colored layer.
  • Epoxy (meth) acrylate resins having a carboxy group may be used alone or in combination of two or more.
  • an alkali-soluble resin having an acid value of 30 mgKOH / g or more.
  • the alkali-soluble resin preferably has an acid value of 40 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer and adhesion to a substrate. It is preferably from 50 mgKOH / g to 280 mgKOH / g.
  • the ethylenically unsaturated bond equivalent has the effect of improving the film strength of the cured film, improving the development resistance, and improving the adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance and adhesion are excellent. Further, if it is 100 or more, the ratio of the other structural unit such as the structural unit having a carboxy group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developing unit is excellent in developing property and heat resistance. I have.
  • the ethylenically unsaturated bond equivalent is a mass average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
  • Ethylenically unsaturated bond equivalent (g / mol) W (g) / M (mol) (In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)
  • the ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with a test method for element number as described in JIS K 0070: 1992. It may be calculated.
  • the alkali-soluble resin used in the colored resin composition may be used singly or in combination of two or more, and the content thereof is not particularly limited, but the solid content of the colored resin composition is not particularly limited.
  • the alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 8% by mass to 40% by mass, based on the total amount. When the content of the alkali-soluble resin is equal to or more than the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is equal to or less than the above upper limit, film roughness or chipping of a pattern during development. Can be suppressed.
  • the photopolymerizable compound used in the colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and usually, a compound having two or more ethylenically unsaturated double bonds is preferably used.
  • a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
  • Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include, for example, those described in JP-A-2013-029832.
  • polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.
  • the photopolymerizable compound should have at least three (trifunctional) polymerizable double bonds. Preference is given to poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof.
  • a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate is preferable because the fading of the lake color material is easily suppressed and the luminance after post-baking is easily improved.
  • the content of the photopolymerizable compound used in the colored resin composition is not particularly limited, but the photopolymerizable compound is preferably 5% by mass or more and 60% by mass or less based on the total solid content of the colored resin composition. More preferably, it is in the range of 10% by mass to 50% by mass.
  • the content of the photopolymerizable compound is equal to or more than the lower limit, the photocuring proceeds sufficiently, the exposed portion can suppress elution at the time of development, and when the content of the photopolymerizable compound is equal to or less than the upper limit. Alkaline developability is sufficient.
  • the photoinitiator used in the colored resin composition of the present invention is not particularly limited, and one or a combination of two or more of conventionally known initiators can be used.
  • the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthones, and the like. be able to.
  • the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethyl benzoin.
  • Biimidazoles such as benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Halomethyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- -Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one eg, Irgacure 907, manufactured by BASF
  • 2-benzyl-2- (dimethylamino) -1- 4-Morpholinophenyl) -1-butanone
  • 4,4′-bis (diethylamino) benzophenone eg, Hicure ABP, manufactured by Kawaguchi Pharmaceutical
  • diethylthioxanthone are preferably used.
  • the photoinitiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity.
  • an oxime ester-based photoinitiator By using an oxime ester-based photoinitiator, when a fine line pattern is formed, variation in in-plane line width is easily suppressed. Furthermore, by using an oxime ester-based photoinitiator, development resistance tends to be improved, and the effect of suppressing the occurrence of water stain tends to be increased.
  • water stain means that when a component that enhances alkali developability is used, traces of water stain occur after rinsing with pure water after alkali development.
  • Oxime ester photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, It can be appropriately selected from oxime ester-based photoinitiators described in JP-A-2013-041153 and the like.
  • Irgacure OXE-01 manufactured by BASF having a carbazole skeleton
  • Adeka Arculs NCI-831 manufactured by ADEKA
  • TR-PBG-304 manufactured by Changshu Strong Electronics New Materials
  • Adeka having a diphenylsulfide skeleton Arkles NCI-930 ADEKA
  • TR-PBG-345 TR-PBG-3057
  • TR-PBG-365 having a fluorene skeleton
  • SPI-04 manufactured by Sanyo
  • an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving luminance. It is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
  • the use of two or more oxime ester-based photoinitiators can be achieved by appropriately selecting and combining two or more oxime ester compounds having different sensitivities, thereby maintaining a good sensitivity and a line width at the time of pattern formation. It is preferable because the development resistance and the luminance can be easily improved, and the effect of suppressing the occurrence of water stain is high.
  • the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton increases heat resistance. This is preferable because the luminance is easily improved.
  • the radical moves to an unexposed portion after radical generation. Therefore, when patterning the colored layer and simultaneously forming the desired micro holes in the colored layer, the unexposed portion peripheral portion is formed without fluctuation while maintaining the shape of the unexposed portion inside the exposed portion. It was difficult.
  • an oxime ester-based photoinitiator having a fluorene skeleton is used in the combination of the coloring materials of the present invention, there is an advantage that, when the coloring layer is patterned, desired micropores are easily formed in the coloring layer at the same time. is there.
  • the brightness and the sensitivity can be easily improved without greatly reducing the sensitivity.
  • the colored resin composition of the present invention may be used, for example, to form a colored layer on a TFT substrate in order to form a reflective color filter, It is also suitable for use in forming a through-hole for conduction in a semiconductor device.
  • “brilliance” refers to a problem that the dimensional accuracy is deteriorated due to non-uniform straight lines or curves at the pattern end.
  • the ⁇ -aminoacetophenone-based photoinitiator in combination with the oxime ester-based photoinitiator from the viewpoints of suppressing water stain and improving sensitivity. Since a photoinitiator having a tertiary amine structure such as ⁇ -aminoacetophenone has a tertiary amine structure which is an oxygen quencher in the molecule, the radical generated from the initiator is hardly deactivated by oxygen, and the sensitivity is high. It is because it can improve.
  • a thioxanthone photoinitiator with an oxime ester photoinitiator from the viewpoint of sensitivity adjustment, suppressing water stain, and improving development resistance.
  • the combination of a system photoinitiator is preferable in that the luminance and development resistance are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stain is high, and the development resistance is improved.
  • the total content of the photoinitiator used in the colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 0.1 to the total solid content of the colored resin composition. It is in the range of 1% by mass to 12.0% by mass, more preferably in the range of 1.0% by mass to 8.0% by mass.
  • the photocuring proceeds sufficiently to prevent the exposed portion from being eluted during development, while when the content is equal to or less than the upper limit, yellowing of the obtained colored layer is increased and the luminance is increased. Can be suppressed from decreasing.
  • the colored resin composition according to the present invention further contains an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the coloring material, and improving luminance.
  • the colored resin composition according to the present invention contains an antioxidant in combination with an oxime ester-based photoinitiator, whereby excessive radicals in the micropores are formed without impairing the curability when forming the micropores in the cured film. Since the chain reaction can be controlled, micropores having a desired shape can be formed more easily.
  • the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones.
  • the antioxidant include, for example, a hindered phenol antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a hydrazine antioxidant, and the like. It is preferable to use a hindered phenolic antioxidant from the viewpoint of improving the shape of the pores and the pores. It may be a latent antioxidant as described in WO 2014/021023.
  • hindered phenolic antioxidants examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3 , 5-Di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6'-thiobis (2-tert-butyl-4-methylphenol (Trade name: Irganox 1081, manufactured by BASF), 3,5-di -tert- buty
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
  • the content of the antioxidant is preferably 0.1% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more, based on the total solid content in the colored resin composition. More preferably, the content is 5.0 mass% or less. If it is at least the above lower limit, it is excellent in heat resistance and light resistance. On the other hand, when the content is equal to or less than the above upper limit, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.
  • the content of the antioxidant is 1 part by mass based on 100 parts by mass of the total amount of the oxime ester-based photoinitiator.
  • the content is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and even more preferably 5 parts by mass or more and 65 parts by mass or less. Within the above range, the effect of the above combination is excellent.
  • the colored resin composition of the present invention may contain various additives as necessary.
  • the additives include a mercapto compound, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
  • Specific examples of the surfactant and the plasticizer include, for example, those described in JP-A-2013-029832.
  • the total content of the coloring material is preferably from 3% by mass to 65% by mass, more preferably from 4% by mass to 60% by mass, based on the total solid content of the colored resin composition. If it is at least the above lower limit, the colored layer when the colored resin composition is applied to a predetermined thickness (usually 1.0 ⁇ m or more and 5.0 ⁇ m or less) will have a sufficient color density. When the content is equal to or less than the above upper limit, a colored layer having excellent storage stability, sufficient hardness and adhesion to a substrate can be obtained.
  • the content of the coloring material is preferably 15% by mass or more and 65% by mass or less, more preferably 25% by mass or more, based on the total solid content of the colored resin composition. It is preferable to mix at a ratio of 60% by mass or less.
  • the total content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, 1% by mass or more based on the total solid content of the colored resin composition 40 mass% or less can be used. Furthermore, it is preferable to mix at a ratio of 2% by mass or more and 30% by mass or less, particularly preferably 3% by mass or more and 25% by mass or less, based on the total solid content of the colored resin composition.
  • the content of the dispersant is preferably 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more, based on the total solid content of the colored resin composition. It is preferable to mix at a ratio of 20% by mass or less.
  • the total content of the binder component is preferably from 5% by mass to 90% by mass, and more preferably from 10% by mass to 80% by mass, based on the total solid content of the colored resin composition.
  • the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass, based on the total amount of the colored resin composition containing the solvent. More preferred. When the content of the solvent is within the above range, excellent coating properties can be obtained.
  • the P / V ratio ((mass of coloring material component in the composition) / (mass of solid content other than the coloring material component in the composition) ratio) is different from that of the blue colored resin composition.
  • the P / V ratio is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of desired color development.
  • it is preferably 0.65 or less, more preferably 0.50 or less, and even more preferably 0.45 or less.
  • the method for producing the colored resin composition of the present invention is not particularly limited.
  • a binder component and, if necessary, other components are added to the colorant dispersion of the present invention, and using a known mixing means. It can be obtained by mixing.
  • a colorant dispersion of each colorant is prepared, and each colorant dispersion, a binder component, and other components as necessary, using known mixing means. It can be obtained by mixing.
  • the colored resin composition of the present invention has excellent dispersibility and storage stability even when a predetermined lake coloring material and a phthalocyanine pigment are mixed in a desired range, and has improved substrate adhesion and coating uniformity. Since it can form a layer, it is suitably used for color filters.
  • the cured product according to the present invention is a cured product of the colored resin composition according to the present invention.
  • the cured product according to the present invention can be appropriately selected and produced according to the curability of the binder component.
  • a photosensitive binder component it is obtained by forming a coating film of the colored resin composition according to the present invention, drying the coating film, exposing, and developing as necessary.
  • a method of forming a coating film, exposing, and developing for example, a method similar to a method used in forming a colored layer included in a color filter according to the present invention described later can be used.
  • a coating film of the colored resin composition according to the present invention is applied by patterning as necessary, and after drying the coating film, heating is performed.
  • the cured product according to the present invention has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range, and has improved substrate adhesion and coating film uniformity. This is suitably used as a coloring layer of a color filter.
  • the color filter according to the present invention is a color filter including at least a transparent substrate and a coloring layer provided on the transparent substrate, at least one of the coloring layers, a coloring material, an acidic dispersant, wherein the colorant comprises at least one lake colorant selected from the group consisting of a colorant represented by the general formula (1) and a colorant represented by the general formula (2), and a base A phthalocyanine pigment that has been subjected to a sexual treatment, and wherein the acidic dispersant contains a polymer having at least one selected from the structural units represented by the general formula (I).
  • At least one of the coloring layers includes a coloring material and an acidic dispersant
  • the coloring material includes a coloring material represented by the general formula (1) and a coloring material represented by the general formula (2).
  • FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention.
  • a color filter 10 of the present invention has a transparent substrate 1, a light shielding portion 2, and a coloring layer 3.
  • At least one of the coloring layers used in the color filter of the present invention includes a coloring material and an acidic dispersant, and the coloring material includes the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2).
  • the coloring material includes the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2).
  • the colored layer contains a polymer having at least one selected from structural units.
  • the coloring layer is usually formed in an opening of a light-shielding portion on a transparent substrate described later, and usually includes a coloring pattern of three or more colors.
  • the arrangement of the coloring layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. Further, the width, the area, and the like of the coloring layer can be arbitrarily set.
  • the thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but is usually preferably in the range of 1 ⁇ m to 5 ⁇ m.
  • the colored layer can be formed by the following method.
  • the coloring layer used in the color filter contains the coloring material described above, an acidic dispersant, a solvent, and a binder component, and the coloring material is represented by the general formula (1) and the coloring material described above. It comprises at least one lake colorant selected from the group consisting of the colorants represented by the formula (2) and a phthalocyanine pigment which has been subjected to a basic treatment, wherein the acidic dispersant is represented by the general formula (I) It is preferably formed using a colored resin composition containing a polymer having at least one selected from the structural units represented, and is preferably a cured product of the colored resin composition.
  • the colored resin composition is applied to a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method to form a wet coating film.
  • an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method to form a wet coating film.
  • an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method to form a wet coating film.
  • an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method to form a wet coating film.
  • the exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like. Further, heat treatment may be performed after the exposure in order to accelerate the polymerization reaction.
  • the heating conditions are appropriately selected depending on the mixing ratio of each component in the coloring resin composition to be used, the thickness of the coating film, and the like.
  • the coating film is formed in a desired pattern by performing development processing using a developing solution and dissolving and removing the unexposed portions.
  • a developing solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used.
  • An appropriate amount of a surfactant or the like may be added to this alkaline solution.
  • a general method can be adopted as a developing method.
  • the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer.
  • a heat treatment may be performed to sufficiently cure the coating film.
  • the heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
  • the light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and may be the same as that used as a light-shielding portion in a general color filter.
  • the pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape.
  • the light shielding portion may be a thin metal film of chromium or the like by a sputtering method, a vacuum evaporation method, or the like.
  • the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder.
  • the thickness of the light-shielding portion is set at about 0.2 ⁇ m or more and 0.4 ⁇ m or less for a metal thin film, and about 0.5 ⁇ m or more and 2 ⁇ m or less for a black pigment dispersed or dissolved in a binder resin. Is set by
  • the transparent substrate is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, synthetic quartz plate or the like, or a flexible resin film, an optical resin plate, a flexible glass or the like having flexibility or flexibility. A transparent flexible material may be used.
  • the transparent substrate used for such a color filter usually has a polar group on the surface. From the viewpoint that the substrate adhesion of the colored resin composition of the present invention is improved, the transparent substrate is preferably a substrate containing silicon dioxide, such as quartz glass, non-alkali glass, and synthetic quartz plate.
  • the thickness of the transparent substrate is not particularly limited, a thickness of, for example, about 50 ⁇ m or more and 1 mm or less can be used depending on the use of the color filter.
  • the color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, a columnar spacer, and the like, in addition to the transparent substrate, the light-shielding portion, and the coloring layer. May be done.
  • the color filter of the present invention is not limited to the above-described configuration, and a known configuration generally used for a color filter can be appropriately selected and used.
  • a display device includes the color filter according to the present invention.
  • the configuration of the display device is not particularly limited and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.
  • a liquid crystal display device includes the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
  • a liquid crystal display device of the present invention will be described with reference to the drawings.
  • FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device.
  • the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
  • the configuration of the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may be a configuration generally known as a liquid crystal display device using a color filter.
  • the driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be adopted.
  • Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
  • the counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention and the like.
  • a method for forming the liquid crystal layer a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
  • An organic light emitting display device includes the above-described color filter according to the present invention and an organic light emitting body. Such an organic light emitting display device of the present invention will be described with reference to the drawings.
  • FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of the organic light emitting display device.
  • the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80.
  • An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic luminous body 80.
  • a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. And a method of bonding the organic light emitting body 80 formed on another substrate to the inorganic oxide film 60.
  • the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting body 80 known structures can be appropriately used.
  • the organic light-emitting display device 100 manufactured in this manner is applicable to, for example, a passive drive organic EL display and an active drive organic EL display.
  • the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3, but may have a structure generally known as an organic light emitting display device using a color filter.
  • the acid value was determined by a method according to JIS K 0070: 1992.
  • the weight average molecular weight (Mw) was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
  • C.I. I. Pigment Blue 15: 6 ( ⁇ -type copper phthalocyanine pigment, DIC FASTOGEN BLUE A510) and 5 parts by weight of the blue coloring material derivative 1 having a basic site are 1.5 hours at 60 ° C. with an attritor. Dry pulverized. This pulverized product was further mixed with 5 parts by mass of the blue coloring material derivative 1 having a basic site to obtain a basic-treated phthalocyanine pigment 1, which is an objective basic-treated phthalocyanine pigment. .
  • a basic treated phthalocyanine pigment 3 was obtained in the same manner as in Synthesis Example 3 except that the blue colored material derivative 1 was used instead of the blue colored material derivative 1 in the synthesis of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. .
  • a basic treated phthalocyanine pigment 4 was obtained in the same manner as in Synthesis Example 3 except that the blue coloring material derivative 3 was used instead of the blue coloring material derivative 1 in the synthesis of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. .
  • Synthesis Example 7 Synthesis of acidic dispersant A1 (polymer having at least one selected from structural units represented by formula (I)))
  • Synthesis of Macromonomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated PGMEA) was placed in a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was charged and heated to a temperature of 90 ° C. while stirring under a nitrogen stream.
  • PGMEA propylene glycol monomethyl ether acetate
  • the reaction solution was cooled to 80 ° C., 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol And 10 parts by mass of PGMEA, and stirred for 3 hours to obtain a 49.5% by mass solution of the macromonomer MM-1.
  • the obtained macromonomer MM-1 had a weight average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.
  • the obtained graft copolymer A1 had a mass average molecular weight (Mw) of 10,570, a number average molecular weight (Mn) of 4,370, and a molecular weight distribution (Mw / Mn) of 2.42.
  • a combined (acidic dispersant A1) solution (solid content: 25.0% by mass) was obtained.
  • the progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and 1 H-NMR measurement (confirmed that the peak derived from epoxy had disappeared).
  • the acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.
  • Synthesis Example 8 Synthesis of acidic dispersant A2 (a polymer having at least one selected from structural units represented by formula (I)))
  • Block Copolymer A2 Referring to Synthesis Example 6 described in Japanese Patent No. 5889525, 50 parts by mass of methyl methacrylate (MMA), 30 parts by mass of n-butyl methacrylate (BMA), benzyl methacrylate A 40% by mass PGMEA solution of a diblock copolymer having (BzMA) 20 parts by mass and glycidyl methacrylate (GMA) 25 parts by mass was obtained.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • GMA glycidyl methacrylate
  • the obtained block copolymer A2 had a weight average molecular weight (Mw) of 9470, a number average molecular weight (Mn) of 7880, and a molecular weight distribution (Mw / Mn) of 1.20.
  • a polymer (acid dispersant A2) solution solid content 25% by mass) was obtained.
  • the progress of the esterification reaction between GMA and PPA of the block copolymer A2 was confirmed by acid value measurement and 1 H-NMR measurement.
  • the acid value of the obtained acidic dispersant A2 was 65 mgKOH / g.
  • Acid dispersant B1 (a block copolymer including an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth) acrylate). Synthesis) With reference to Example 1 described in International Publication WO 2016/1328643, a block of 20 parts by mass of MMA and 40 parts by mass of BMA, a block of 20 parts by mass of acrylic acid (MAA) and 20 parts by mass of BMA, and 20 parts by mass of MMA and 40 parts by mass of BMA A triblock copolymer having the following blocks was synthesized. The obtained block copolymer had a weight average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Acid dispersant B2 (a block copolymer including an A block including a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block including a structural unit derived from an alkyl (meth) acrylate). Synthesis) Except that the monomer charging ratio was changed to the following composition, a block of MMA 30 parts by mass, 40 parts by mass of BMA, a block of 10 parts by mass of acrylic acid (MAA), a block of 20 parts by mass of BMA, and 20 parts by mass of MMA And a block of 40 parts by mass of BMA were synthesized.
  • the obtained block copolymer had a weight average molecular weight (Mw) of 15,500, a molecular weight distribution (Mw / Mn) of 1.35, and an acid value of 80 mgKOH / g.
  • Example 1 Colorant dispersion B1 (1-1) Preparation of Coloring Material Dispersion B1a1 of Lake Coloring Material 1 10 parts by mass of Lake Coloring Material 1 of Synthesis Example 1 and 20 parts by mass of Acid Dispersant A1 Solution of Synthesis Example 7 (5.0 mass of effective solids) Parts), 7.5 parts by mass of the alkali-soluble resin A of Synthesis Example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA, and the mixture was preliminarily prepared using a paint shaker (made by Asada Iron Works). Dispersion was performed with 2 mm zirconia beads for 1 hour and further with 0.1 mm zirconia beads for 4 hours to obtain a colorant dispersion B1a1.
  • Colored resin composition B1 Color material dispersion B1 16.7 parts by mass, photosensitive binder component CR-1 of Preparation Example 1 24.0 parts by mass, surfactant Megafac R08MH (manufactured by DIC) 0.3 part by mass, PGMEA 59.0 parts by mass was mixed to obtain a colored resin composition B1 of Example 1.
  • Examples 2 to 13 (1) Colorant dispersions B2 to B13 Except that the mixing ratio of the color material dispersion B1a1 and the color material dispersion B1b1 was changed so that the color material ratio (mass ratio) shown in Table 1 was obtained, the color material dispersion was obtained in the same manner as in Example 1. B2 to B13 were prepared. (2) Colored resin compositions B2 to B13 Colored resin compositions B2 to B13 were obtained in the same manner as in Example 1 except that the colorant dispersions B2 to B13 were used instead of the colorant dispersion B1.
  • Example 14 to 21 Colorant dispersions B14 to B21 A colorant dispersion B1a1 was obtained in the same manner as in (1-1) of Example 1. A colorant dispersion B2a1 was obtained in the same manner as in (1-1) of Example 1, except that the rake colorant 2 of Synthesis Example 2 was used instead of the rake colorant 1 of Synthesis Example 1. Further, in the same manner as in (1-1) of Example 1, except that the acidic dispersant A2 solution of Synthesis Example 8 was used instead of the acidic dispersant A1 solution of Synthesis Example 7, the coloring material dispersion B1a2 was prepared in the same manner. Obtained.
  • a colorant dispersion B1b1 was obtained in the same manner as in (1-2) of Example 1.
  • the colorant dispersion B2b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 2 of Synthesis Example 4 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained.
  • the colorant dispersion B3b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 3 of Synthesis Example 5 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained.
  • a colorant dispersion B4b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 4 of Synthesis Example 6 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained. Further, in the same manner as in (1-2) of Example 1, except that the acidic dispersant B2 solution of Synthesis Example 10 was used instead of the acidic dispersant B1 solution of Synthesis Example 9, the coloring material dispersion B1b2 was prepared in the same manner. Obtained.
  • Example 22 Colorant dispersion B22 5.0 parts by mass of the lake color material 1 of Synthesis Example 1, 1 part by mass of the basic treated phthalocyanine pigment of Synthesis Example 3, and 20 parts by mass of the acidic dispersant A1 solution of Synthesis Example 7 (effective solid content: 5. 0 parts by mass), 7.5 parts by mass of the alkali-soluble resin A of Synthesis Example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA, and mixed with a paint shaker (made by Asada Tekko).
  • Example 23 and 24 (1) Colorant dispersions B23 to B24 Coloring material dispersions B23 to B24 were prepared in the same manner as in Example 22, except that the content ratio of the coloring material and the type of the rake coloring material were changed as shown in Table 2. (2) Colored resin composition B23 to B24 Colored resin compositions B23 to B24 were obtained in the same manner as in Example 1 except that the colorant dispersions B23 to B24 were used instead of the colorant dispersion B1.
  • Colorant dispersions CB1 and CB5 In Example 22, in place of the basic-treated phthalocyanine pigment 1, a commercially available Pigment Blue 15: 6 (manufactured by DIC, FASTOGEN BLUE A510) was used, and the content ratio of the coloring material was changed as shown in Table 2. In the same manner as in Example 22, colorant dispersions CB1 and CB5 were prepared. (2) Colored resin compositions CB1 and CB5 Colored resin compositions CB1 and CB5 were obtained in the same manner as in Example 1 except that the colorant dispersions CB1 and CB5 were used instead of the colorant dispersion B1.
  • Colorant dispersion CB2 In Comparative Example 1, a colorant dispersion CB2 was prepared in the same manner as in Comparative Example 1 except that the acidic dispersant A1 solution of Synthesis Example 7 was changed to the basic dispersant 1 solution of Synthesis Example 11. did. (2) Colored resin composition CB2 A colored resin composition CB2 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid CB2 was used instead of the coloring material dispersion liquid B1.
  • Colorant dispersion CB3 A colorant dispersion CB3 was prepared in the same manner as in Example 22 except that the basic treated phthalocyanine pigment 1 was not used and the lake colorant 110 of Synthesis Example 1 was used in an amount of 10 parts by mass.
  • Colored resin composition CB3 A colored resin composition CB3 was obtained in the same manner as in Example 1, except that the coloring material dispersion liquid CB3 was used instead of the coloring material dispersion liquid B1.
  • Colorant dispersion CB4 Example 22 Example 22 was repeated except that the lake color material 1 and the basic phthalocyanine pigment 1 of Synthesis Example 1 were not used, and 10 parts by mass of a commercially available Pigment Blue 15: 6 (FASTOGEN BLUE A510 manufactured by DIC) was used. In the same manner as in the above, a colorant dispersion CB4 was prepared.
  • Colored resin composition CB4 A colored resin composition CB4 was obtained in the same manner as in Example 1, except that the coloring material dispersion liquid CB4 was used instead of the coloring material dispersion liquid B1.
  • Substrate adhesion evaluation criteria There is no peeling of any grid A: There is a place where the cured film is peeled along the cut line, but there is no place where the whole grid is peeled B: There is a place where the whole grid is peeled, Exclusive area of peeling is less than 25% C: There is a place where the entire grid is peeled off, and the exclusive area of peeling is 25% or more
  • Ultraviolet light of 60 mJ / cm 2 was irradiated using an ultrahigh pressure mercury lamp through a photomask pattern having a pattern (a pattern for evaluating micropores) on which a chromium mask was arranged. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous solution of potassium hydroxide as an alkaline developer, and was post-baked in a 230 ° C. clean oven for 30 minutes.
  • Line width shift value ( ⁇ m) measured line width ( ⁇ m) ⁇ 95 ( ⁇ m)
  • ⁇ Eab ⁇ (L 1 ⁇ L 0 ) 2 + (a 1 ⁇ a 0 ) 2 + (b 1 ⁇ b 0 ) 2 ⁇ 1/2 ( ⁇ Eab evaluation criteria)
  • lens cleaner trade name: Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.
  • the degree of coloring of the lens cleaner was visually observed.
  • the color material ratio is a ratio when the total color material amount is 100
  • the dispersant ratio is a ratio when the total dispersant amount is 100.
  • Comparative Examples 1 and 5 in which a commercially available phthalocyanine pigment not subjected to basic treatment was used as the phthalocyanine pigment, the dispersibility and storage stability deteriorated only by slightly increasing the content of the phthalocyanine pigment. It was shown that. Furthermore, in Comparative Examples 1 and 5 in which a commercially available phthalocyanine pigment that had not been subjected to a basic treatment was used as the phthalocyanine pigment, the substrate adhesion and the coating film uniformity were inferior to those of the examples.
  • Comparative Example 2 in which a commercially available phthalocyanine pigment that had not been subjected to basic treatment was used as the phthalocyanine pigment and a basic dispersant was used as the dispersant, the dispersibility and storage stability of the coloring material were poor, and the adhesion to the substrate was poor. The film uniformity was poor, and the developability, chromaticity change after heating and development residue were also poor. In Comparative Example 3 using only the lake coloring material without using the phthalocyanine pigment, the dispersibility was poor, and the substrate adhesion and the coating film uniformity were poor as compared with the examples.
  • Comparative Example 4 in which only a commercially available phthalocyanine pigment not subjected to basic treatment was dispersed with a polymer having at least one selected from the structural units represented by the general formula (I), the initial viscosity was too high. And no evaluable coating film was formed.
  • the content of the lake color material is 20% by mass or more and 85% by mass or less with respect to the total content of the lake color material and the phthalocyanine pigment. It was shown that this is preferable because the line width shift is suppressed while a chromaticity change after the high-temperature heating step is suppressed, and a pattern can be formed with a desired line width.
  • the acidic dispersant was found to be composed of an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and an alkyl (meth) acrylate-derived ester. It was shown that when a block copolymer containing a B block containing a structural unit was further contained, the suppression of development residue was improved.

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Abstract

Provided is a color material dispersion which has excellent dispersibility and high storage stability even in the case where a definite lake color material and a phthalocyanine pigment are mixed at a ratio within a desired range and which is capable of forming a colored layer showing improved adhesion to a substrate and enhanced coating film uniformity. The color material dispersion comprises a color material, an acidic dispersant and a solvent, wherein the color material comprises a specific lake color material and a basic treated phthalocyanine pigment and the acidic dispersant comprises a polymer having a specific acidic phosphorus compound group and a salt thereof.

Description

色材分散液、着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置Colorant dispersion, colored resin composition and cured product thereof, color filter, and display device
　本発明は、色材分散液、着色樹脂組成物及びその硬化物、カラーフィルタ、並びに表示装置に関する。 The present invention relates to a colorant dispersion, a colored resin composition and a cured product thereof, a color filter, and a display device.
　近年、パーソナルコンピューターの発達、特に携帯用パーソナルコンピューターの発達に伴って、液晶ディスプレイの需要が増加している。モバイルディスプレイ（携帯電話、スマートフォン、タブレットＰＣ）の普及率も高まっており、益々液晶ディスプレイの市場は拡大する状況にある。また、最近においては、自発光により視認性が高い有機ＥＬディスプレイのような有機発光表示装置も、次世代画像表示装置として注目されている。これらの画像表示装置の性能においては、コントラストや色再現性の向上といったさらなる高画質化が望まれている。 In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has attracted attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility is desired.
　これらの液晶表示装置や有機発光表示装置には、カラーフィルタが用いられる。例えば液晶表示装置のカラー画像の形成は、カラーフィルタを通過した光がそのままカラーフィルタを構成する各画素の色に着色されて、それらの色の光が合成されてカラー画像を形成する。その際の光源としては、従来の冷陰極管のほか、白色発光の有機発光素子や白色発光の無機発光素子が利用される場合がある。また、有機発光表示装置では、色調整などのためにカラーフィルタを用いる。 カ ラ ー Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light that has passed through a color filter is directly colored into the color of each pixel constituting the color filter, and light of those colors is combined to form a color image. As a light source at this time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In the organic light emitting display device, a color filter is used for color adjustment and the like.
　近年の傾向として、画像表示装置の省電力化が求められており、バックライトの利用効率を向上させるためにカラーフィルタの高輝度化が特に求められている。特にモバイルディスプレイ（携帯電話、スマートフォン、タブレットＰＣ）では大きな課題である。 In recent years, there has been a demand for power saving of image display devices, and in particular, there has been a demand for higher brightness of color filters in order to improve the use efficiency of backlights. In particular, this is a major problem for mobile displays (mobile phones, smartphones, tablet PCs).
　ここで、カラーフィルタは、一般的に、基板と、基板上に形成され、赤、緑、青の三原色の着色パターンを含む着色層と、各着色パターンを区画するように基板上に形成された遮光部とを有している。
　このような着色層の形成方法として、色材を分散させた色材分散液に硬化性バインダー成分等を添加した着色樹脂組成物を基材に塗布し硬化する方法などが知られている。
　色材分散液は、高コントラストな着色層を安定して得るために、色材の分散性や保存安定性が求められている。また、カラーフィルタの高コントラスト化や高輝度化の要求に伴って、色材として、微細化した顔料を使用したり、より高透過率な染料やレーキ色材を使用する検討が行われている。このような色材分散液から得られた着色層は、顔料のみを使用した場合よりも製造工程における各種耐性が劣る場合があった。 Here, the color filter is generally formed on the substrate and the substrate, and is formed on the substrate so as to partition each coloring pattern, including a coloring layer including three primary color coloring patterns of red, green, and blue. A light-shielding portion.
As a method for forming such a colored layer, there is known a method in which a colored resin composition obtained by adding a curable binder component or the like to a coloring material dispersion liquid in which a coloring material is dispersed is applied to a substrate and cured.
In order to stably obtain a high-contrast colored layer, the colorant dispersion liquid is required to have good dispersibility and storage stability of the colorant. Also, with the demand for higher contrast and higher brightness of color filters, studies have been made to use finer pigments as coloring materials or to use dyes and lake coloring materials with higher transmittance. . The coloring layer obtained from such a coloring material dispersion liquid was sometimes inferior to various resistances in the production process as compared with the case where only the pigment was used.
　特許文献１には、複数の染料骨格が架橋基によって架橋された２価以上のカチオンと、２価以上のアニオンを含む特定の色材を用いたカラーフィルタ等が開示されている。上記色材は耐熱性に優れており、当該色材を用いたカラーフィルタは高コントラストで、耐溶剤性及び電気信頼性に優れていると記載されている。 Patent Document 1 discloses a color filter or the like using a specific coloring material containing a divalent or more cation and a divalent or more anion in which a plurality of dye skeletons are crosslinked by a crosslinking group. It is described that the coloring material has excellent heat resistance, and that a color filter using the coloring material has high contrast, excellent solvent resistance, and excellent electrical reliability.
　特許文献２には、色材と、特定の酸性リン化合物基を有する構成単位を有する重合体と、溶剤として比較的極性の高い溶剤と比較的極性の低い溶剤の少なくとも２種の溶剤とを組み合わせた色材分散液が開示されている。上記色材分散液は、分散性及び保存安定性に優れ、長期保管後であっても高コントラストで、耐熱性及び耐溶剤性に優れた塗膜を形成可能であると記載されている。また、特許文献２には、実施例１７と比較例２５及び２６において、特許文献１の特定の色材に相当するレーキ色材と、市販のピグメントブルー１５：６とを、質量比９０：１０で混合して色材として用い、特定の酸リン構造を有する構成単位を有する重合体か、塩基性分散剤のいずれかによって前記色材を分散させた色材分散液が記載されている。 Patent Document 2 discloses a combination of a coloring material, a polymer having a structural unit having a specific acidic phosphorus compound group, and at least two solvents of a relatively high polarity solvent and a relatively low polarity solvent as a solvent. Color material dispersions are disclosed. It is described that the colorant dispersion liquid has excellent dispersibility and storage stability, and can form a coating film having high contrast even after long-term storage, and having excellent heat resistance and solvent resistance. Patent Document 2 discloses that in Example 17 and Comparative Examples 25 and 26, a rake color material corresponding to the specific color material of Patent Document 1 and a commercially available Pigment Blue 15: 6 were mixed at a mass ratio of 90:10. And a colorant dispersion in which the colorant is dispersed by using either a polymer having a structural unit having a specific acid phosphorus structure or a basic dispersant.
国際公開第２０１２／１４４５２１号International Publication No. 2012/144521 特開２０１７－２１９１号JP 2017-2191A
　しかしながら特許文献１の特定の色材を用いても、顔料に比べると耐熱性が劣るため、カラーフィルタ製造工程における高温加熱（ポストベーク）後に、色度が変化し易く、また、最終的に得られる着色層の輝度は未だ十分ではなく、更なる向上が求められている。
　本発明者らは、高温加熱後の色度変化を抑制したり、最終的に得られる着色層の輝度を向上させるために、特許文献１の特定の色材のようなレーキ色材と、顔料とを混合して用いることを考えた。しかしながら、特許文献２のように、特許文献１の特定の色材のようなレーキ色材と、市販で多く流通しているピグメントブルー１５：６のようなフタロシアニン顔料とを混合する場合に、前記レーキ色材とフタロシアニン顔料の合計１００質量部に対して、フタロシアニン顔料の含有量を１０質量部よりも多くしようとすると、分散性や保存安定性が著しく悪くなるため、フタロシアニン顔料の含有量を多くできず、前記特定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合して着色樹脂組成物を製造することは困難であった。
　また、特許文献２に記載されているような従来技術の着色層では、基板密着性と塗膜均一性が未だ不十分であり、更なる基板密着性と塗膜均一性の向上が求められていた。 However, even when the specific color material of Patent Document 1 is used, the heat resistance is inferior to that of the pigment, so that the chromaticity easily changes after high-temperature heating (post-baking) in the color filter manufacturing process, and the color filter is finally obtained. The brightness of the colored layer obtained is not yet sufficient, and further improvement is required.
In order to suppress the change in chromaticity after heating at a high temperature or to improve the luminance of a finally obtained colored layer, the inventors have proposed a rake color material such as a specific color material of Patent Document 1 and a pigment. Was considered to be used as a mixture. However, as described in Patent Document 2, when a lake color material such as the specific color material of Patent Document 1 is mixed with a phthalocyanine pigment such as Pigment Blue 15: 6 which is widely distributed in the market, If the content of the phthalocyanine pigment is more than 10 parts by mass with respect to the total of 100 parts by mass of the lake color material and the phthalocyanine pigment, the dispersibility and the storage stability are significantly deteriorated. However, it was difficult to produce a colored resin composition by mixing the specific lake colorant and the phthalocyanine pigment in a desired range.
Further, with the colored layer of the related art as described in Patent Document 2, the substrate adhesion and the uniformity of the coating film are still insufficient, and further improvement in the substrate adhesion and the uniformity of the coating film is required. Was.
　本発明は、上記の知見に基づいてなされたものであり、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能な色材分散液、及び着色樹脂組成物、及び前記着色層を備えたカラーフィルタ、及び、当該カラーフィルタを用いた表示特性に優れた表示装置を提供することを目的とする。 The present invention has been made based on the above findings, and has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range, and has excellent substrate adhesion and coating properties. Provided are a coloring material dispersion liquid capable of forming a colored layer with improved film uniformity, a colored resin composition, a color filter having the colored layer, and a display device using the color filter and having excellent display characteristics. The purpose is to do.
　本発明に係る色材分散液は、色材と、酸性分散剤と、溶剤とを含有する色材分散液であって、
　前記色材が、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
　前記酸性分散剤が、下記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む。 The coloring material dispersion according to the present invention is a coloring material dispersion containing a coloring material, an acidic dispersant, and a solvent,
The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2). Phthalocyanine pigments,
The acidic dispersant includes a polymer having at least one selected from structural units represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000010
 （一般式（１）中、各符号は後述のとおりである。）
Figure JPOXMLDOC01-appb-C000010
 (In the general formula (1), each symbol is as described below.)
Figure JPOXMLDOC01-appb-C000011
 （一般式（２）中、各符号は後述のとおりである。）
Figure JPOXMLDOC01-appb-C000011
 (In the general formula (2), each symbol is as described below.)
Figure JPOXMLDOC01-appb-C000012
 （一般式（Ｉ）中、各符号は後述のとおりである。）
Figure JPOXMLDOC01-appb-C000012
 (In the general formula (I), each symbol is as described below.)
　本発明に係る着色樹脂組成物は、色材と、酸性分散剤と、バインダー成分と、溶剤とを含有する着色樹脂組成物であって、
　前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
　前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む。 The colored resin composition according to the present invention is a colored resin composition containing a coloring material, an acidic dispersant, a binder component, and a solvent,
The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2). Phthalocyanine pigments,
The acidic dispersant includes a polymer having at least one selected from the structural units represented by the general formula (I).
　本発明は、前記本発明に係る着色樹脂組成物の硬化物を提供する。
　本発明は、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、前記着色層の少なくとも一つが、色材と、酸性分散剤とを含み、前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、カラーフィルタを提供する。 The present invention provides a cured product of the colored resin composition according to the present invention.
The present invention is a color filter comprising at least a substrate and a coloring layer provided on the substrate, wherein at least one of the coloring layers contains a coloring material and an acidic dispersant, and the coloring material is A phthalocyanine pigment which has been subjected to a basic treatment with at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) A color filter, wherein the acidic dispersant comprises a polymer having at least one selected from the structural units represented by the general formula (I).
　本発明は、前記本発明に係るカラーフィルタを有する表示装置を提供する。 The present invention provides a display device having the color filter according to the present invention.
　本発明によれば、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能な色材分散液、及び着色樹脂組成物、及び前記着色層を備えたカラーフィルタ、及び、当該カラーフィルタを用いた表示特性に優れた表示装置を提供することができる。 According to the present invention, even when a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, a colored layer having excellent dispersibility and storage stability, and having improved substrate adhesion and coating film uniformity is formed. A possible color material dispersion, a colored resin composition, a color filter including the colored layer, and a display device having excellent display characteristics using the color filter can be provided.
図１は、本発明のカラーフィルタの一例を示す概略図である。FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. 図２は、本発明の表示装置の一例を示す概略図である。FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention. 図３は、本発明の表示装置の他の一例を示す概略図である。FIG. 3 is a schematic view showing another example of the display device of the present invention.
　以下、本発明に係る色材分散液、着色樹脂組成物、カラーフィルタ、表示装置について、順に詳細に説明する。
　なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長５μｍ以下の電磁波、及び電子線のことをいう。
　本発明において（メタ）アクリルとは、アクリル及びメタクリルの各々を表し、（メタ）アクリレートとは、アクリレート及びメタクリレートの各々を表す。
　また、本明細書において数値範囲を示す「～」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。 Hereinafter, the colorant dispersion, the colored resin composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and furthermore, radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In this specification, “to”, which indicates a numerical range, is used to mean that the numerical values described before and after the numerical value range are included as a lower limit and an upper limit.
Ｉ．色材分散液
　本発明に係る色材分散液は、色材と、酸性分散剤と、溶剤とを含有する色材分散液であって、
　前記色材が、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
　前記酸性分散剤が、下記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む。 I. Colorant dispersion liquid The colorant dispersion according to the present invention is a colorant dispersion containing a colorant, an acidic dispersant, and a solvent,
The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2). Phthalocyanine pigments,
The acidic dispersant includes a polymer having at least one selected from structural units represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000013
 （一般式（１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000013
 (In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group has a saturated aliphatic carbon at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may have a hetero atom in the carbon chain, and B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may combine to form a ring structure, and R vi and R vii each independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. .Ar 1 2 may have a substituent divalent aromatic group represents a group I represent. R i ~ R vii and Ar 1 there are a plurality of may each be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f, and g may be the same or different. )
Figure JPOXMLDOC01-appb-C000014
 （一般式（２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000014
 (In the general formula (2) represents R I ~ R VI are each independently a hydrogen atom, which may have an alkyl group or a substituted group which may have a substituent aryl group, R I and R II , R III and R IV , or R V and R VI may combine to form a ring structure, wherein R VII and R VIII each independently represent an alkyl group or a substituent which may have a substituent; alkoxy group which may have, .Ar 2 represents a halogen atom or a cyano group represents an aromatic heterocyclic group which may have a substituent, plural R I ~ R VIII and Ar 2 E m- represents an m-valent polyacid anion.
m represents an integer of 2 or more. j is 0 or 1, and when j is 0, no bond exists. k and l represent an integer of 0 or more and 4 or less, and k + j and 1 + j are 0 or more and 4 or less. A plurality of j, k and l may be the same or different. )
Figure JPOXMLDOC01-appb-C000015
 （一般式（Ｉ）中、Ｌ１は、直接結合又は２価の連結基、Ｒ１は、水素原子又はメチル基、Ｒ２は、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であり、Ｒ６は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、－Ｃ（Ｒ７）（Ｒ８）－Ｃ（Ｒ９）（Ｒ１０）－ＯＨ、又は、－ＣＨ２－Ｃ（Ｒ１１）（Ｒ１２）－ＣＨ２－ＯＨで示される１価の基である。
　Ｒ３及びＲ４は、それぞれ独立に水素原子又はメチル基であり、Ｒ５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ、－ＣＯ－ＣＨ＝ＣＨ２、－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２又は－ＣＨ２ＣＯＯＲ１３で示される１価の基であり、Ｒ１３は水素原子又は炭素数が１個以上５個以下のアルキル基である。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２は、それぞれ独立に、水素原子、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基であり、Ｒ７及びＲ９は、互いに結合して環構造を形成してもよい。上記環状構造を形成した場合、当該環状構造が更に置換基Ｒ１４を有していてもよく、Ｒ１４は、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基である。前記炭化水素基は、置換基を有していてもよい。Ｘは、水素原子又は有機カチオンを表す。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。）
Figure JPOXMLDOC01-appb-C000015
 (In the general formula (I), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydroxyl group, a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , — [(CH 2 ) y1 —O] z1 —R 5 , or —O—R 6 is a monovalent group, and R 6 is a hydrocarbon group ,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , -C (R 7 ) (R 8 ) -C ( R 9 ) (R 10 ) —OH or a monovalent group represented by —CH 2 —C (R 11 ) (R 12 ) —CH 2 —OH.
R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is a hydrogen atom, a hydrocarbon group, —CHO, —CH 2 CHO, —CO—CH ＝ CH 2 , —CO—C ( CH 3 ) = CH 2 or —CH 2 COOR 13 is a monovalent group, and R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having at least one selected from an ether bond and an ester bond. Yes, R 7 and R 9 may combine with each other to form a ring structure. When the above-mentioned cyclic structure is formed, the cyclic structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon having one or more types selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 to 18; y1 is an integer of 1 to 5; z1 is an integer of 1 to 18; )
　本発明の実施形態に係る色材分散液は、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能である。また、本発明の実施形態に係る色材分散液によれば、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能な着色樹脂組成物を得ることができる。 The colorant dispersion according to the embodiment of the present invention has excellent dispersibility and storage stability even when a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, and has excellent substrate adhesion and coating film uniformity. It is possible to form a colored layer with improved properties. Further, according to the colorant dispersion according to the embodiment of the present invention, even when a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, the dispersibility and storage stability are excellent, and the substrate adhesion is improved. A colored resin composition capable of forming a colored layer with improved coating uniformity can be obtained.
　市販で多く流通しているピグメントブルー１５：６のようなフタロシアニン顔料は、後述する比較例４でも示されるように、分散剤として、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を用いると、分散性が悪く、また保存安定性も悪かった。分散剤として、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を用い、レーキ色材と、市販で多く流通しているフタロシアニン顔料とを混合する場合、後述する比較例５でも示されるように、フタロシアニン顔料の含有量を少し増加しただけで分散性や保存安定性が著しく悪くなるため、フタロシアニン顔料の含有量を多くできず、特許文献１の特定の色材のようなレーキ色材とフタロシアニン顔料とを所望の範囲で混合して着色樹脂組成物を製造することは困難であった。
　それに対して、本発明では、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材に、塩基性処理されたフタロシアニン顔料を組み合わせ、且つ、分散剤として前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む酸性分散剤を用いることにより、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れた色材分散液を得ることができる。塩基性処理されたフタロシアニン顔料を組み合わせて用いると、分散性と保存安定性が優れるようになるのは、フタロシアニン顔料の表面に存在する塩基性化合物由来のカチオン部によって、酸性分散剤の酸性基との吸着作用が特に強くなるからと推定される。また、前記レーキ色材も造塩化合物であることから酸性分散剤の酸性基との吸着作用が強いと推定される。前記レーキ色材及び前記塩基性処理されたフタロシアニン顔料が共に、良好に分散剤で被覆されるため、所望の範囲で混合しても分散性と保存安定性に優れると推定される。
　また、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材に、塩基性処理されたフタロシアニン顔料を組み合わせ、且つ、分散剤として前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む酸性分散剤を用いることにより、基板密着性と塗膜均一性が向上した着色層を形成可能である。この作用としては、中でも特に、前記塩基性処理されたフタロシアニン顔料が、酸性分散剤の酸性基と吸着作用が強くて顔料表面が均一に酸性分散剤で被覆されることにより、色材分散性が向上して色材分散液や樹脂組成物が低粘度化し、樹脂組成物の流動性が良好になることから均一な塗膜を作製し易くなり、塗膜の均一性も向上したのではないかと推定される。また、分散剤がリン酸基やカルボン酸基等の酸性基を有することで、色材表面だけでなく、基板表面の極性基（例えば、ガラス基板表面のＳｉ－ＯＨ基）とも結合しやすくなることで基板密着性が向上したと推定される。 A phthalocyanine pigment such as Pigment Blue 15: 6, which is widely distributed in the market, is selected from the structural units represented by the general formula (I) as a dispersant, as shown in Comparative Example 4 described below. When a polymer having at least one kind was used, dispersibility was poor and storage stability was poor. When a polymer having at least one selected from the structural units represented by the general formula (I) is used as a dispersant, and a lake color material is mixed with a phthalocyanine pigment that is widely distributed in the market, As shown in Comparative Example 5 described below, even if the content of the phthalocyanine pigment is slightly increased, the dispersibility and storage stability are significantly deteriorated. Therefore, the content of the phthalocyanine pigment cannot be increased. It has been difficult to produce a colored resin composition by mixing a lake color material such as a color material and a phthalocyanine pigment in a desired range.
On the other hand, in the present invention, a base is added to at least one kind of lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2). A predetermined lake by combining the phthalocyanine pigment having been subjected to the acid treatment and using, as a dispersant, an acidic dispersant containing a polymer having at least one selected from the structural units represented by the general formula (I). Even if the colorant and the phthalocyanine pigment are mixed in a desired range, a colorant dispersion having excellent dispersibility and storage stability can be obtained. When the phthalocyanine pigment subjected to the basic treatment is used in combination, the dispersibility and the storage stability are improved because of the cationic group derived from the basic compound present on the surface of the phthalocyanine pigment, and the acid group of the acidic dispersant. This is presumed to be because the adsorption effect of the compound becomes particularly strong. Further, since the lake coloring material is also a salt-forming compound, it is presumed that the lake coloring material has a strong adsorptive action with the acidic group of the acidic dispersant. Since both the lake color material and the basic-treated phthalocyanine pigment are well coated with a dispersant, it is presumed that they are excellent in dispersibility and storage stability even when mixed in a desired range.
Further, a phthalocyanine pigment which has been subjected to a basic treatment to at least one kind of lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2) And the use of an acidic dispersant containing a polymer having at least one selected from the structural units represented by formula (I) as a dispersant, whereby substrate adhesion and coating film uniformity are improved. An improved colored layer can be formed. As this action, among others, the phthalocyanine pigment which has been subjected to the basic treatment has a strong adsorptive action with the acidic group of the acidic dispersant, and the pigment surface is uniformly coated with the acidic dispersant. The improved viscosity of the colorant dispersion and the resin composition is improved, and the fluidity of the resin composition is improved, so that it becomes easier to produce a uniform coating film, and that the uniformity of the coating film may have improved. Presumed. Further, when the dispersant has an acidic group such as a phosphoric acid group or a carboxylic acid group, the dispersing agent is easily bonded not only to the color material surface but also to a polar group on the substrate surface (for example, a Si—OH group on the glass substrate surface). It is estimated that the adhesion of the substrate was improved.
　本発明に係る色材分散液は、少なくとも、色材と、酸性分散剤と、溶剤とを含有するものであり、効果が損なわれない範囲で、必要に応じて更に他の成分を含有してもよいものである。
　以下、このような色材分散液の各成分について順に詳細に説明する。 The coloring material dispersion according to the present invention contains at least a coloring material, an acidic dispersant, and a solvent, and further contains other components as necessary, as long as the effect is not impaired. Is also good.
Hereinafter, each component of such a colorant dispersion will be described in detail in order.
［色材］
　本発明において、色材は、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含むことを特徴とする。 [Color material]
In the present invention, the coloring material includes at least one kind of lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2); And a phthalocyanine pigment that has been subjected to a sexual treatment.
＜前記レーキ色材＞
　本発明において用いられるレーキ色材は、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材である。 <Rake color material>
The rake coloring material used in the present invention is at least one rake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2). is there.
　前記一般式（１）で表される色材は、２価以上のアニオンと、２価以上のカチオンとを含むため、当該色材の凝集体においては、アニオンとカチオンが単に１分子対１分子でイオン結合しているのではなく、イオン結合を介して複数の分子が会合する分子会合体を形成し得ることから、見かけの分子量が、従来のレーキ顔料の分子量に比べて格段に増大する。このような分子会合体の形成により固体状態での凝集力がより高まり、熱運動を低下させ、イオン対の解離やカチオン部の分解を抑制でき、従来のレーキ顔料に比べて退色し難いと推定される。 Since the coloring material represented by the general formula (1) contains a divalent or higher valent anion and a divalent or higher cation, in the aggregate of the coloring material, the anion and the cation are simply one molecule to one molecule. Since a plurality of molecules can form a molecular aggregate through ionic bond instead of ionic bond, the apparent molecular weight is significantly increased as compared with the molecular weight of a conventional lake pigment. Due to the formation of such molecular aggregates, the cohesive force in the solid state is further increased, thermal motion is reduced, dissociation of ion pairs and decomposition of the cation part can be suppressed, and it is estimated that discoloration is less likely than conventional lake pigments Is done.
　前記一般式（１）におけるＡは、Ｎ（窒素原子）と直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ（酸素原子）、Ｓ（硫黄原子）、Ｎ（窒素原子）等のヘテロ原子が含まれていてもよいものである。すなわち、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎ等のヘテロ原子が含まれてもよい脂肪族炭化水素基、又は、Ｎと直接結合する末端に脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎ等のヘテロ原子が含まれてもよい芳香族基を表す。Ｎと直接結合する炭素原子がπ結合を有しないため、カチオン性の発色部位が有する色調や透過率等の色特性は、連結基Ａや他の発色部位の影響を受けず、単量体と同様の色を保持することができる。 A in the general formula (1) is an a-valent organic group in which a carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at a terminal directly bonded to N. Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and includes O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in a carbon chain. May be included. That is, the organic group has a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N, and may include a hetero atom such as O, S, or N in a carbon chain; Alternatively, it represents an aromatic group having an aliphatic hydrocarbon group at a terminal directly bonded to N and optionally containing a hetero atom such as O, S, or N in a carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A or other coloring portions, and are not affected by the monomer. Similar colors can be retained.
  Ａにおいて、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基は、Ｎと直接結合する末端の炭素原子がπ結合を有しなければ、直鎖、分岐又は環状のいずれであってもよく、末端以外の炭素原子が不飽和結合を有していてもよく、置換基を有していてもよく、炭素鎖中に、Ｏ、Ｓ、Ｎが含まれていてもよい。例えば、カルボニル基、カルボキシ基、オキシカルボニル基、アミド基等が含まれていてもよく、水素原子が更にハロゲン原子等に置換されていてもよい。
  また、Ａにおいて上記脂肪族炭化水素基を有する芳香族基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基を有する、単環又は多環芳香族基が挙げられ、置換基を有していてもよく、Ｏ、Ｓ、Ｎが含まれる複素環であってもよい。
  中でも、骨格の堅牢性の点から、Ａは、環状の脂肪族炭化水素基又は芳香族基を含むことが好ましい。
　環状の脂肪族炭化水素基としては、シクロヘキサン、シクロペンタン、ノルボルナン、ビシクロ［２．２．２］オクタン、トリシクロ［５．２．１．０２，６］デカン、アダマンタンを含む基等が挙げられる。また、芳香族基としては、例えば、ベンゼン環、ナフタレン環を含む基等が挙げられる。例えば、Ａが２価の有機基の場合、炭素数１～２０の直鎖、分岐、又は環状のアルキレン基や、キシリレン基等の炭素数１～２０のアルキレン基を２個置換した芳香族基等が挙げられる。 In A, at least the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is a straight-chain, branched, or cyclic group unless the terminal carbon atom directly bonded to N has a π bond. And carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and O, S, and N are contained in the carbon chain. Is also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom and the like.
In A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to at least N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the rigidity of the skeleton.
Examples of the cyclic aliphatic hydrocarbon group include groups containing cyclohexane, cyclopentane, norbornane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, adamantane, and the like. . Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring. For example, when A is a divalent organic group, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms or an aromatic group having two substituted alkylene groups having 1 to 20 carbon atoms such as a xylylene group. And the like.
　本発明においては、堅牢性と、分子運動の自由度を両立して、耐熱性を向上する点から、Ａが、２個以上の環状脂肪族炭化水素基を有し、Ｎと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基であることが好ましい。Ａは、２個以上のシクロアルキレン基を有し、Ｎと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基であることがより好ましく、中でも、２個以上の環状脂肪族炭化水素基が直鎖又は分岐の脂肪族炭化水素基で連結した構造を有することが更に好ましい。
　２個以上ある環状脂肪族炭化水素基は、それぞれ同一であっても異なっていてもよく、例えば、前記環状の脂肪族炭化水素基と同様のものが挙げられ、中でもシクロヘキサン、シクロペンタンが好ましい。 In the present invention, A has two or more cyclic aliphatic hydrocarbon groups and has a terminal directly bonded to N in view of improving heat resistance while achieving both robustness and freedom of molecular movement. Is preferably an aliphatic hydrocarbon group which has a saturated aliphatic hydrocarbon group and may contain O, S and N in the carbon chain. A has two or more cycloalkylene groups, has a saturated aliphatic hydrocarbon group at a terminal directly bonded to N, and may contain O, S, and N in the carbon chain. The group is more preferably a group, and particularly preferably has a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.
The two or more cyclic aliphatic hydrocarbon groups may be the same or different, and for example, include the same cyclic aliphatic hydrocarbon groups as described above, and among them, cyclohexane and cyclopentane are preferred.
　本発明においては、耐熱性の点から、中でも、前記Ａが、下記一般式（１ａ）で表される置換基であることが好ましい。 に お い て In the present invention, from the viewpoint of heat resistance, A is preferably a substituent represented by the following general formula (1a).
Figure JPOXMLDOC01-appb-C000016
 （一般式（１ａ）中、Ｒｘｉは置換基として炭素数１以上４以下のアルキル基、又は炭素数１以上４以下のアルコキシ基を有してもよい炭素数１以上３以下のアルキレン基を表し、Ｒｘｉｉ及びＲｘｉｉｉは各々独立に炭素数１以上４以下のアルキル基、又は炭素数１以上４以下のアルコキシ基を表し、ｐは１以上３以下の整数を、ｑ及びｒは各々独立に０以上４以下の整数を表す。Ｒｘｉ、Ｒｘｉｉ、Ｒｘｉｉｉ及びｒが複数ある場合、当該複数あるＲｘｉ、Ｒｘｉｉ、Ｒｘｉｉｉ及びｒは互いに同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000016
 (In the general formula (1a), R xi represents an alkyl group having 1 to 4 carbon atoms as a substituent or an alkylene group having 1 to 3 carbon atoms which may have an alkoxy group having 1 to 4 carbon atoms. R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p is an integer of 1 to 3 and q and r are each independently to .R xi an integer of 0 to 4, if R xii, R xiii and r there are multiple, the plurality of R xi, R xii, R xiii and r may being the same or different .)
　堅牢性と、発色部位の熱運動との両立に優れ、耐熱性が向上する点から、Ｒｘｉにおける炭素数１以上３以下のアルキレン基であることが好ましい。このようなアルキレン基としては、メチレン基、エチレン基、プロピレン基等が挙げられ、中でもメチレン基又はエチレン基が好ましく、メチレン基がより好ましい。
　炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。
　また、炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。 It is preferable that R xi be an alkylene group having 1 to 3 carbon atoms in R xi because it is excellent in both fastness and thermal motion of the color-developing portion and heat resistance is improved. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group. Among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched.
Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
　Ｒｘｉｉ及びＲｘｉｉｉにおける、炭素数１以上４以下のアルキル基、及び、炭素数１以上４以下のアルコキシ基は、前記Ｒｘｉが有してもよい置換基と同様のものが挙げられる。 In R xii and R xiii , the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are the same as the substituents that R xi may have.
　一般式（１ａ）において、シクロヘキサン（シクロヘキシレン基）は２個以上４個以下、即ち、ｐが１以上３以下であることが、耐熱性の点から好ましく、中でもｐが１以上２以下であることがより好ましい。
　またシクロヘキシレン基が有する置換基Ｒｘｉｉ及びＲｘｉｉｉの置換数は、特に限定されないが、耐熱性の点から、１個以上３個以下であることが好ましく、１個以上２個以下であることがより好ましい。即ちｑ及びｒが１以上３以下の整数であることが好ましく、ｑ及びｒが１以上２以下の整数であることが好ましい。 In the general formula (1a), the number of cyclohexane (cyclohexylene group) is preferably 2 or more, that is, p is 1 or more and 3 or less from the viewpoint of heat resistance. Is more preferable.
The number of substituents R xii and R xiii of the cyclohexylene group is not particularly limited, but is preferably 1 or more and 3 or less, and preferably 1 or more and 2 or less from the viewpoint of heat resistance. Is more preferred. That is, q and r are preferably integers of 1 or more and 3 or less, and q and r are preferably integers of 1 or more and 2 or less.
　このような連結基Ａの好適な具体例としては、以下のものが挙げられるが、これらに限定されるものではない。 好 適 Preferable specific examples of such a linking group A include the following, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　Ｒｉ～Ｒｖにおけるアルキル基は、特に限定されない。例えば、炭素数１～２０の直鎖、分岐状又は環状のアルキル基等が挙げられ、中でも、炭素数が１～８の直鎖又は分岐のアルキル基であることが挙げられ、炭素数が１～５の直鎖又は分岐のアルキル基であることが、輝度及び耐熱性の点から挙げられ、Ｒｉ～Ｒｖにおけるアルキル基がエチル基又はメチル基であることが挙げられる。アルキル基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられ、置換されたアルキル基としては、ベンジル基のようなアラルキル基等が挙げられる。
　Ｒｉ～Ｒｖにおけるアリール基は、特に限定されない。例えば、フェニル基、ナフチル基等が挙げられる。アリール基が有してもよい置換基としては、例えばアルキル基、ハロゲン原子、アルコキシ基、水酸基等が挙げられる。
　中でも化学的安定性の点からＲｉ～Ｒｖとしては、各々独立に、水素原子、炭素数１～５のアルキル基、フェニル基、又は、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合してピロリジン環、ピペリジン環、モルホリン環を形成していることが好ましい。 The alkyl group in R i to R v is not particularly limited. For example, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms may be mentioned. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms may be mentioned. From 5 to 5 are straight-chain or branched alkyl groups from the viewpoint of luminance and heat resistance, and the alkyl group in R i to R v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and an alkoxy group. The substituted alkyl group includes an aralkyl group such as a benzyl group And the like.
The aryl group in R i to R v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent which the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group and the like.
Among them, R i to R v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a bond between R ii and R iii , or R iv and R v from the viewpoint of chemical stability. To form a pyrrolidine ring, a piperidine ring, and a morpholine ring.
　耐熱性の点からは、Ｒｉｉ～Ｒｖのうち少なくとも一つが、置換基を有してもよいシクロアルキル基、又は、置換基を有していてもよいアリール基であることが好ましい。Ｒｉｉ～Ｒｖのうち少なくとも一つが、シクロアルキル基、又は、アリール基を有することにより、立体障害による分子間相互作用が低減するため、発色部位の熱に対する影響を抑制できるため、耐熱性に優れていると考えられる。 From the viewpoint of heat resistance, at least one of R ii to R v is preferably a cycloalkyl group which may have a substituent or an aryl group which may have a substituent. When at least one of R ii to R v has a cycloalkyl group or an aryl group, intermolecular interaction due to steric hindrance is reduced, so that the effect of the coloring site on heat can be suppressed. Considered excellent.
　耐熱性の点からは、Ｒｉｉ～Ｒｖのうち少なくとも一つが、下記一般式（１ｂ）又は、下記一般式（１ｃ）で表される置換基であることが好ましい。 From the viewpoint of heat resistance, at least one of R ii to R v is preferably a substituent represented by the following general formula (1b) or the following general formula (1c).
Figure JPOXMLDOC01-appb-C000018
 （一般式（１ｂ）中、Ｒｘｉｖ、Ｒｘｖ、及びＲｘｖｉは各々独立に水素原子、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基を表す。）
Figure JPOXMLDOC01-appb-C000018
 (In the general formula (1b), R xiv , R xv , and R xvi each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent. Represents a good alkoxy group having 1 to 4 carbon atoms.)
Figure JPOXMLDOC01-appb-C000019
 （一般式（１ｃ）中、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘは各々独立に水素原子、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基を表す。）
Figure JPOXMLDOC01-appb-C000019
 (In the general formula (1c), R xvii , R xviii , and R xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent. Represents a good alkoxy group having 1 to 4 carbon atoms.)
　Ｒｘｉｖ、Ｒｘｖ、Ｒｘｖｉ、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘにおける炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。また、炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。
　前記アルキル基及びアルコキシ基が有してもよい置換基としては、ハロゲン原子、水酸基等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms in R xiv , R xv , R xvi , R xvii , R xviii , and R xix include a methyl group, an ethyl group, a propyl group, and a butyl group. Or may have a branch. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.
Examples of the substituent which the alkyl group and the alkoxy group may have include a halogen atom and a hydroxyl group.
　前記一般式（１ｂ）で表される置換基を有する場合、耐熱性の点から、Ｒｘｉｖ、Ｒｘｖ、及びＲｘｖｉの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることが好ましく、Ｒｘｉｖ及びＲｘｖの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることがより好ましい。 When it has a substituent represented by the general formula (1b), at least one of R xiv , R xv , and R xvi has 1 to 4 carbon atoms which may have a substituent from the viewpoint of heat resistance. Is preferably an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and at least one of R xiv and R xv has 1 or more carbon atoms which may have a substituent More preferably, it is an alkyl group having 4 or less or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
　また前記一般式（１ｃ）で表される置換基を有する場合、耐熱性の点から、Ｒｘｖｉｉ、Ｒｘｖｉｉｉ、及びＲｘｉｘの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることが好ましく、Ｒｘｖｉｉ及びＲｘｖｉｉｉの少なくとも一つが、置換基を有してもよい炭素数１以上４以下のアルキル基、又は置換基を有してもよい炭素数１以上４以下のアルコキシ基であることがより好ましい。 When the compound has a substituent represented by the general formula (1c), at least one of R xvii , R xviii , and R xix has 1 to 4 carbon atoms which may have a substituent from the viewpoint of heat resistance. It is preferably an alkyl group or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, wherein at least one of R xvii and R xviii has 1 carbon atom which may have a substituent More preferably, it is an alkyl group having 4 to 4 or less, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
　一般式（１ｂ）で表される置換基、及び、一般式（１ｃ）で表される置換基の好適な具体例としては、以下のものが挙げられるが、これらに限定されるものではない。 Preferable specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include, but are not limited to, the following.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　Ｒｖｉ及びＲｖｉｉは各々独立に置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ｒｖｉ及びＲｖｉｉにおけるアルキル基としては、特に限定されないが、炭素数が１以上８以下の直鎖、又は分岐を有するアルキル基であることが好ましく、炭素数が１以上４以下のアルキル基であることがより好ましい。炭素数１以上４以下のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基が挙げられ、直鎖状であっても分岐を有していてもよい。アルキル基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。
　また、Ｒｖｉ及びＲｖｉｉにおけるアルコキシ基としては、特に限定されないが、炭素数が１以上８以下の直鎖、又は分岐を有するアルコキシ基であることが好ましく、炭素数が１以上４以下のアルコキシ基であることがより好ましい。炭素数１以上４以下のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、直鎖状であっても分岐を有していてもよい。アルコキシ基が有してもよい置換基としては、特に限定されないが、例えば、アリール基、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。
　Ｒｖｉ及びＲｖｉｉにおけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　Ｒｖｉ及びＲｖｉｉの置換数、即ち、ｆ及びｇはそれぞれ独立に０以上４以下の整数を表し、中でも０以上２以下であることが好ましく、０以上１以下であることがより好ましい。複数あるｆ及びｇはそれぞれ同一であっても異なっていてもよい。
　また、Ｒｖｉ及びＲｖｉｉは、トリアリールメタン骨格、又は、キサンテン骨格内の共鳴構造を有する芳香環のいずれの部位に置換されていてもよいが、中でも、－ＮＲｉｉＲｉｉｉ又は－ＮＲｉｖＲｖで表されるアミノ基の置換位置を基準にメタ位に置換されていることが好ましい。 R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably, there is. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, and may be linear or branched. The substituent that the alkyl group may have is not particularly limited, but examples include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
The alkoxy group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, but examples include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
Examples of the halogen atom in R vi and R vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The substitution numbers of R vi and R vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. A plurality of f and g may be the same or different.
Further, R vi and R vii may be substituted at any position of a triarylmethane skeleton or an aromatic ring having a resonance structure in a xanthene skeleton. Among them, -NR ii R iii or -NR iv is preferable. It is preferably substituted at the meta position based on the substitution position of the amino group represented by R v .
　Ａｒ１における２価の芳香族基は特に限定されない。Ａｒ１における芳香族基は、炭素環からなる芳香族炭化水素基の他、複素環基であってもよい。芳香族炭化水素基における芳香族炭化水素としては、ベンゼン環の他、ナフタレン環、テトラリン環、インデン環、フルオレン環、アントラセン環、フェナントレン環等の縮合多環芳香族炭化水素；ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環式炭化水素が挙げられる。当該鎖状多環式炭化水素においては、ジフェニルエーテル等のように鎖状骨格中にＯ、Ｓ、Ｎを有していてもよい。一方、複素環基における複素環としては、フラン、チオフェン、ピロール、オキサゾール、チアゾール、イミダゾール、ピラゾール等の５員複素環；ピラン、ピロン、ピリジン、ピロン、ピリダジン、ピリミジン、ピラジン等の６員複素環；ベンゾフラン、チオナフテン、インドール、カルバゾール、クマリン、ベンゾ－ピロン、キノリン、イソキノリン、アクリジン、フタラジン、キナゾリン、キノキサリン等の縮合多環式複素環が挙げられる。これらの芳香族基は更に置換基として、アルキル基、アルコキシ基、水酸基、ハロゲン原子、及び、これらで置換されていても良いフェニル基等を有していてもよい。 The divalent aromatic group in Ar 1 is not particularly limited. The aromatic group in Ar 1 may be a heterocyclic group in addition to an aromatic hydrocarbon group having a carbon ring. Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include, in addition to a benzene ring, a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, a tetralin ring, an indene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring; biphenyl, terphenyl, Examples include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in a chain skeleton such as diphenyl ether. On the other hand, examples of the heterocycle in the heterocyclic group include 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; Condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline and quinoxaline. These aromatic groups may further have, as substituents, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted by these, and the like.
　１分子内に複数あるＲｉ～Ｒｖｉｉ及びＡｒ１は、同一であっても異なっていてもよい。Ｒｉ～Ｒｖｉｉ及びＡｒ１の組み合わせにより、所望の色に調整することができる。 A plurality of R i to R vii and Ar 1 in one molecule may be the same or different. A desired color can be adjusted by a combination of R i to R vii and Ar 1 .
  Ａにおける価数ａは、カチオンを構成する発色性カチオン部位の数であり、ａは２以上の整数である。このレーキ色材においては、カチオンの価数ａが２以上であるため、耐熱性に優れており、中でも、カチオンの価数ａが３以上であることが好ましい。ａの上限は特に限定されないが、製造の容易性の点から、ａが４以下であることが好ましく、３以下であることがより好ましい。 The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. This lake color material has excellent heat resistance because the valence a of the cation is 2 or more, and it is particularly preferable that the valence a of the cation is 3 or more. Although the upper limit of a is not particularly limited, a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
　一般式（Ａ）で表されるカチオンは、耐熱性に優れ、加熱時の色変化が抑制され易い点から、分子量が１２００以上であることが好ましく、１３００以上であることが好ましい。 カ チ オ ン The cation represented by the general formula (A) has a molecular weight of preferably 1200 or more, and more preferably 1300 or more, from the viewpoint that the cation has excellent heat resistance and color change upon heating is easily suppressed.
  一般式（１）で表される色材において、アニオン部（Ｂｃ－）は、高輝度で耐熱性に優れる点から、ｃ価のポリ酸アニオンであって、２価以上のアニオンである。 In the coloring material represented by the general formula (1), the anion part (B c− ) is a c-valent polyacid anion and a divalent or more anion from the viewpoint of high luminance and excellent heat resistance.
　複数のオキソ酸が縮合したポリ酸アニオンとしては、イソポリ酸アニオン（ＭｍＯｎ）ｃ－であってもヘテロポリ酸アニオン（ＸｌＭｍＯｎ）ｃ－であってもよい。上記イオン式中、Ｍはポリ原子、Ｘはヘテロ原子、ｍはポリ原子の組成比、ｎは酸素原子の組成比を表す。ポリ原子Ｍとしては、例えば、Ｍｏ、Ｗ、Ｖ、Ｔｉ、Ｎｂ等が挙げられる。またヘテロ原子Ｘとしては、例えば、Ｓｉ、Ｐ、Ａｓ、Ｓ、Ｆｅ、Ｃｏ等が挙げられる。また、一部にＮａ＋やＨ＋等の対カチオンが含まれていてもよい。
　中でも、耐熱性に優れる点から、タングステン（Ｗ）及びモリブデン（Ｍｏ）より選択される１種以上の元素を有するポリ酸であることが好ましい。
　このようなポリ酸としては、例えば、イソポリ酸である、タングステン酸イオン［Ｗ１０Ｏ３２］４－、モリブデン酸イオン［Ｍｏ６Ｏ１９］２－や、ヘテロポリ酸である、リンタングステン酸イオン［ＰＷ１２Ｏ４０］３－、［Ｐ２Ｗ１８Ｏ６２］６－、ケイタングステン酸イオン［ＳｉＷ１２Ｏ４０］４－、リンモリブデン酸イオン［ＰＭｏ１２Ｏ４０］３－、ケイモリブデン酸イオン［ＳｉＭｏ１２Ｏ４０］４－、リンタングストモリブデン酸イオン［ＰＷ１２－ｓＭｏｓＯ４０］３－（ｓは１以上１１以下の整数）、［Ｐ２Ｗ１８－ｔＭｏｔＯ６２］６－（ｔは１以上１７以下の整数）、ケイタングストモリブデン酸イオン［ＳｉＷ１２－ｕＭｏｕＯ４０］４－（ｕは１以上１１以下の整数）等が挙げられる。タングステン（Ｗ）及びモリブデン（Ｍｏ）の少なくとも１種を含むポリ酸としては、耐熱性の点、及び原料入手の容易さの点から、上記の中でもヘテロポリ酸であることが好ましく、更にリン（Ｐ）を含むヘテロポリ酸であることがより好ましい。
　さらに、リンタングストモリブデン酸イオン［ＰＷ１０Ｍｏ２Ｏ４０］３－、［ＰＷ１１Ｍｏ１Ｏ４０］３－、リンタングステン酸イオン［ＰＷ１２Ｏ４０］３－、のいずれかであることが耐熱性の点からさらに好ましい。 The polyoxometalate anion in which a plurality of oxoacids are condensed, isopoly acid anion (M m O n) heteropoly acid anion be a c- (X l M m O n ) may be a c-. In the above formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, and n represents a composition ratio of an oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co. Further, a counter cation such as Na + or H + may be partially contained.
Among them, a polyacid containing at least one element selected from tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of excellent heat resistance.
Examples of such a polyacid include tungstate ion [W 10 O 32 ] 4− , molybdate ion [Mo 6 O 19 ] 2- , which is an isopoly acid, and phosphotungstate ion [heteropolyacid], PW 12 O 40 ] 3− , [P 2 W 18 O 62 ] 6− , silicotungstate ion [SiW 12 O 40 ] 4− , phosphomolybdate ion [PMo 12 O 40 ] 3− , silicomolybdate ion [ SiMo 12 O 40] 4-, phosphate tongue strike molybdate [PW 12-s Mo s O 40] 3- (s is 1 to 11 integer), [P 2 W 18- t Mo t O 62] 6- (t is 1 or 17 an integer), Keita ring strike molybdate [SiW 12-u Mo u O 40] 4- (u is 1 or more 11 or more And the like is an integer), and the like. The polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above from the viewpoint of heat resistance and availability of raw materials. ) Is more preferable.
Furthermore, it is heat-resistant that any one of a phosphorus tungstomolybdate ion [PW 10 Mo 2 O 40 ] 3− , [PW 11 Mo 1 O 40 ] 3− , and a phosphotungstate ion [PW 12 O 40 ] 3− It is more preferable from the viewpoint of properties.
  一般式（１）におけるｂはカチオンの数を、ｄは分子会合体中のアニオンの数を示し、ｂ及びｄは１以上の整数を表す。ｂが２以上の場合、分子会合体中に複数あるカチオンは、１種単独であっても、２種以上が組み合わされていてもよい。また、ｄが２以上の場合、分子会合体中に複数あるアニオンは、１種単独であっても、２種以上が組み合わされていてもよい。 に お け る b in the general formula (1) represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular association may be used alone or in combination of two or more. When d is 2 or more, a plurality of anions in the molecular aggregate may be used alone or in combination of two or more.
  一般式（１）におけるｅは、０又は１の整数であり、ｅが０のとき結合は存在しない。ｅ＝０はトリアリールメタン骨格を表し、ｅ＝１はキサンテン骨格を表す。複数あるｅは同一であっても異なっていてもよい。本発明に用いられる一般式（１）で表されるレーキ色材においては、少なくともトリアリールメタン骨格を含むものが好適に用いられる。
  なお、一般式（１）で表されるレーキ色材としては、例えば、国際公開第２０１２／１４４５２０号パンフレット、国際公開第２０１８／００３７０６号パンフレットを参考にして調製することができる。 E in the general formula (1) is an integer of 0 or 1, and when e is 0, no bond exists. e = 0 represents a triarylmethane skeleton, and e = 1 represents a xanthene skeleton. A plurality of e may be the same or different. As the lake color material represented by the general formula (1) used in the present invention, a material containing at least a triarylmethane skeleton is suitably used.
In addition, the lake color material represented by the general formula (1) can be prepared with reference to, for example, WO2012 / 144520 pamphlet and WO2018 / 003706 pamphlet.
　一方、一般式（２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよいものである。ＲＩ～ＲＶＩは各々、前述の一般式（１）のＲｉ～Ｒｖと同様であって良い。
　一般式（２）中、ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表すが、これらも前述の一般式（１）のＲｖｉ及びＲｖｉｉと同様であって良い。
　一般式（２）中、Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表すが、当該Ａｒ２は、前述の一般式（１）のＡｒ１のうち、芳香族複素環基と同様であって良い。
　また、一般式（２）中、Ｅｍ－はｍ価のポリ酸アニオンを表すが、当該ｍ価のポリ酸アニオンは、前述の一般式（１）のｃ価のポリ酸アニオンと同様であって良い。 On the other hand, represents the general formula (2), R I ~ R VI are each independently a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, and R I R II , R III and R IV , or R V and R VI may combine to form a ring structure. R I to R VI may be the same as R i to R v in the general formula (1), respectively.
In the general formula (2), R VII and R VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. It may be the same as R vi and R vii in the general formula (1) described above.
In the general formula (2), Ar 2 represents an aromatic heterocyclic group which may have a substituent, said Ar 2 is of Ar 1 in the general formula (1) described above, aromatic It may be the same as the group heterocyclic group.
In the general formula (2), Em- represents an m-valent polyacid anion. The m-valent polyacid anion is the same as the above-mentioned c-valent polyacid anion of the general formula (1). Good.
　一般式（２）中、ｍは、カチオンの数及びアニオンの数を示し、２以上の整数を表す。一般式（２）中に複数あるカチオンは、１種単独であっても、２種以上が組み合わされていてもよい。また、アニオンについても、１種単独であっても、２種以上が組み合わされていてもよい。
　一般式（２）中、ｊは０又は１であり、ｊが０のとき結合は存在しない。一般式（２）中のｊは、前述の一般式（１）のｅと同様であって良い。また、一般式（２）中のｋ及びｌは、前述の一般式（１）のｆ及びｇと同様であって良い。
　なお、一般式（２）で表されるレーキ色材としては、例えば、特開２０１７－１６０９９号公報を参考にして調製することができる。 In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. The plurality of cations in the general formula (2) may be used alone or in combination of two or more. Further, the anions may be used alone or in combination of two or more.
In the general formula (2), j is 0 or 1, and when j is 0, no bond exists. J in the general formula (2) may be the same as e in the general formula (1). Further, k and l in the general formula (2) may be the same as f and g in the general formula (1).
The lake color material represented by the general formula (2) can be prepared, for example, with reference to JP-A-2017-16099.
＜塩基性処理されたフタロシアニン顔料＞
　本発明で用いられる塩基性処理されたフタロシアニン顔料は、塩基性化合物に由来する構造を有するフタロシアニン顔料をいう。
　塩基性化合物に由来する構造を有するフタロシアニン顔料としては、例えば、塩基性部位を有する色材誘導体等の塩基性化合物を含むフタロシアニン顔料が好適なものとして挙げられる。 <Basically treated phthalocyanine pigment>
The basic-treated phthalocyanine pigment used in the present invention refers to a phthalocyanine pigment having a structure derived from a basic compound.
As a phthalocyanine pigment having a structure derived from a basic compound, for example, a phthalocyanine pigment containing a basic compound such as a colorant derivative having a basic site can be mentioned as a preferable one.
  塩基性処理に用いられるフタロシアニン顔料としては、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と組み合わせて用いられることから、青色フタロシアニン顔料であることが好ましく、比較的輝度に優れる点から、銅フタロシアニン顔料が好ましい。塩基性処理に用いられる銅フタロシアニン顔料としては、粗製銅フタロシアニン顔料であっても良いし、α型、β型、γ型、ε型などの結晶構造を有する銅フタロシアニン顔料であっても良い。塩基性処理に用いられる銅フタロシアニン顔料としては、中でも、分散安定性に優れる点から、ε型の結晶構造を有する銅フタロシアニン顔料、及びβ型の結晶構造を有する銅フタロシアニン顔料よりなる群から選択される１種以上であることが好ましい。 As the phthalocyanine pigment used in the basic treatment, at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) Since it is used in combination with a phthalocyanine pigment, a blue phthalocyanine pigment is preferable, and a copper phthalocyanine pigment is preferable because it has relatively excellent luminance. The copper phthalocyanine pigment used in the basic treatment may be a crude copper phthalocyanine pigment or a copper phthalocyanine pigment having a crystal structure such as α-type, β-type, γ-type, or ε-type. Among the copper phthalocyanine pigments used in the basic treatment, among others, from the viewpoint of excellent dispersion stability, selected from the group consisting of copper phthalocyanine pigments having an ε-type crystal structure and copper phthalocyanine pigments having a β-type crystal structure Preferably, at least one kind is used.
　本発明において塩基性処理には、塩基性部位を有する色材誘導体や、塩基性部位を有する無色化合物の誘導体が好適に用いられる。
　本発明において、塩基性部位を有するとは、置換基として塩基性基を有する態様、置換基において酸性基と塩基性化合物とが塩形成している態様等が挙げられる。
　本発明で色材誘導体又は無色化合物の誘導体が有する塩基性部位としては、例えば、アミノ基、スルホン酸アンモニウム塩、又は、アミノ基を有するスルホンアミド基、アミノ基を有するアミド基、塩基性複素環基等が挙げられる。
　本発明で色材誘導体が有する塩基性部位は、色材の水素原子が前記塩基性部位で置換されている態様で含まれていても良いし、色材に連結基を介して前記塩基性部位が置換されている態様で含まれていても良い。色材に連結基を介して前記塩基性部位が置換されている態様としては、例えば、色材に炭素数１～２０の炭化水素基や、炭化水素基を有する置換基が置換され、当該炭化水素基の水素原子が前記塩基性部位で置換されている態様が挙げられる。無色化合物の誘導体の塩基性部位の態様も、色材誘導体の塩基性部位の態様と同様であって良い。 In the present invention, a colorant derivative having a basic site or a colorless compound derivative having a basic site is suitably used for the basic treatment.
In the present invention, the term "having a basic site" includes an embodiment having a basic group as a substituent, an embodiment in which an acidic group and a basic compound form a salt in the substituent, and the like.
Examples of the basic site of the colorant derivative or the colorless compound derivative in the present invention include an amino group, an ammonium sulfonate, or a sulfonamide group having an amino group, an amide group having an amino group, and a basic heterocyclic ring. And the like.
In the present invention, the basic site of the coloring material derivative may be included in a mode in which a hydrogen atom of the coloring material is substituted with the basic site, or the basic site may be included in the coloring material via a linking group. May be included in a substituted mode. Examples of an embodiment in which the coloring material is substituted with the basic site via a linking group include, for example, the coloring material being substituted with a hydrocarbon group having 1 to 20 carbon atoms or a substituent having a hydrocarbon group. An embodiment in which a hydrogen atom of a hydrogen group is substituted at the basic site is mentioned. The mode of the basic site of the derivative of the colorless compound may be the same as the mode of the basic site of the colorant derivative.
　前記アミノ基としては、－ＮＲａＲｂで表され、ここでＲａ及びＲｂはそれぞれ独立に、水素原子、又は－ＮＲａ’Ｒｂ’で置換されていても良い炭素数１～３０の炭化水素基が挙げられ、Ｒａ’及びＲｂ’はそれぞれ独立に、水素原子、又は炭素数１～３０の炭化水素基が挙げられる。 The amino group is represented by —NR a R b , wherein R a and R b each independently represent a hydrogen atom or a carbon number of 1 to 30 which may be substituted by —NR a ′ R b ′. R a ′ and R b ′ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
　前記スルホン酸アンモニウム塩としては、－ＳＯ３ －・ＮＨＲｃＲｄＲｅ＋で表され、ここでＲｃ、Ｒｄ、及びＲｅはそれぞれ独立に、水素原子、前記アミノ基で置換されていても良い炭素数１～３０の炭化水素基が挙げられる。
　前記アミノ基を有するスルホンアミド基としては、中でも、－ＳＯ２ＮＨ－（ＣＨ２）ｍ－ＮＲｆＲｇで表される基（ここで、Ｒｆ、及びＲｇはそれぞれ独立に、水素原子、前記アミノ基で置換されていても良い炭素数１～３０の炭化水素基、又は、互いに結合して隣接する窒素原子と共に塩基性複素環を形成したものを示し、ｍは１～１５の整数を示す）であることが、色材分散性の点から好ましい。
　前記アミノ基を有するアミド基としては、中でも、－ＣＯＮＨ－（ＣＨ２）ｍ’－ＮＲｊＲｋで表される基（ここで、Ｒｊ、及びＲｋはそれぞれ独立に、水素原子、前記アミノ基で置換されていても良い炭素数１～３０の炭化水素基、又は、互いに結合して隣接する窒素原子と共に塩基性複素環を形成したものを示し、ｍ’は１～１５の整数を示す）であることが、色材分散性の点から好ましい。 Examples of the sulfonic acid ammonium salt, -SO 3 - · NHR c R d is represented by R e +, wherein R c, R d, and R e are each independently a hydrogen atom, optionally substituted with an amino group And a hydrocarbon group having 1 to 30 carbon atoms.
Among the sulfonamide groups having an amino group, a group represented by —SO 2 NH— (CH 2 ) m —NR f R g (where R f and R g are each independently a hydrogen atom And a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with the amino group, or a basic heterocyclic ring which is bonded to an adjacent nitrogen atom together with each other, and m is an integer of 1 to 15 Is preferable from the viewpoint of dispersibility of the coloring material.
As the amide group having an amino group, a group represented by —CONH— (CH 2 ) m ′ —NR j R k (where R j and R k are each independently a hydrogen atom, A hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with an amino group, or a group bonded to each other to form a basic heterocyclic ring with an adjacent nitrogen atom, and m 'is an integer of 1 to 15 Is preferable from the viewpoint of dispersibility of the coloring material.
　前記Ｒａ、Ｒｂ、Ｒａ’、Ｒｂ’、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇ、Ｒｊ、及びＲｋにおいて、炭素数１～３０の炭化水素基としては、炭素数１～３０の脂肪族炭化水素基、芳香族炭化水素基、及びこれらの組み合わせが挙げられ、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ヘキシル基、ベンジル基等が挙げられる。
　前記Ｒａ、Ｒｂ、Ｒａ’、Ｒｂ’、Ｒｃ、Ｒｄ、Ｒｅ、Ｒｆ、Ｒｇ、Ｒｊ、及びＲｋはそれぞれ独立に、水素原子又は炭素数１～２５の炭化水素基であることが好ましく、水素原子又は炭素数１～２０の炭化水素基であることがより好ましく、水素原子又は炭素数１～１０の炭化水素基であることがより好ましく、水素原子又は直鎖状或いは分岐状の炭素数１～６のアルキル基であることがより更に好ましい。
　前記ｍ及びｍ’は１～１５の整数を示すが、中でも２～８が好ましく、特に３～６が好ましい。
　また、Ｒｆ、Ｒｇ、Ｒｊ及びＲｋにおいて、互いに結合して隣接する窒素原子と共に塩基性複素環を形成した構造は、複素環に更に窒素、酸素、若しくは硫黄原子を含んでいても良く、例えば、モルホリン、ピペリジン、ピリジン、トリアジン、チアゾール等が挙げられる。
　また、塩基性部位としての前記塩基性複素環基としては、モルホリノ基、ピペリジノ基、ピリジノ基、トリアジノ基等が挙げられる。 In R a , R b , R a ′ , R b ′ , R c , R d , R e , R f , R g , R j and R k , the hydrocarbon group having 1 to 30 carbon atoms includes: Examples thereof include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group, and a combination thereof. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples include a t-butyl group, an n-hexyl group, and a benzyl group.
R a , R b , R a ′ , R b ′ , R c , R d , R e , R f , R g , R j , and R k each independently represent a hydrogen atom or a C 1-25 alkyl group; It is preferably a hydrocarbon group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or Even more preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms.
The above m and m 'each represent an integer of 1 to 15, preferably 2 to 8, and particularly preferably 3 to 6.
In R f , R g , R j, and R k , the structure in which a basic heterocyclic ring is formed together with an adjacent nitrogen atom by bonding to each other may further include a nitrogen, oxygen, or sulfur atom in the heterocyclic ring. Good examples include morpholine, piperidine, pyridine, triazine, thiazole and the like.
Examples of the basic heterocyclic group as the basic site include a morpholino group, a piperidino group, a pyridino group, and a triazino group.
　前記誘導体が有する塩基性部位としては、中でも、酸性分散剤と相互作用しやすい点から、スルホン酸アンモニウム塩、又は、アミノ基を有するスルホンアミド基が好ましく、中でも、前記－ＳＯ２ＮＨ－（ＣＨ２）ｍ－ＮＲｆＲｇで表される基であることが好ましい。
　また、前記誘導体が有する塩基性部位は、色材又は無色化合物１分子に対して少なくとも１個有すれば良く、特に限定されないが、色材分散性の点から、１個又は２個有することが好ましい。前記誘導体が有する塩基性部位が色材又は無色化合物に置換されている位置は特に限定されない。 The basic site where the derivative has, among others, from the viewpoint of easily interact with acidic dispersing agent, a sulfonic acid ammonium salt, or sulfonamide group having an amino group are preferable, among them, the -SO 2 NH- (CH 2) m -NR f R g group represented by is preferable.
The derivative may have at least one basic site per colorant or one molecule of the colorless compound, and is not particularly limited, but may have one or two basic sites from the viewpoint of colorant dispersibility. preferable. The position where the basic site of the derivative is substituted with a coloring material or a colorless compound is not particularly limited.
　塩基性部位を有する色材誘導体に用いられる色材は、公知の色材を適宜選択して用いることができるが、塩基性処理に用いられるフタロシアニン顔料と吸着し易い構造を有することが好ましく、同一又は類似の色素骨格や、相互作用し易い構造を有することが好ましい。また、塩基性処理に用いられるフタロシアニン顔料の色味を損なわない色材が好ましい。 As the coloring material used for the coloring material derivative having a basic site, a known coloring material can be appropriately selected and used, but it is preferable that the coloring material has a structure that is easily adsorbed to the phthalocyanine pigment used for the basic treatment, and is the same. Alternatively, it is preferable to have a similar dye skeleton or a structure that easily interacts. Further, a coloring material which does not impair the tint of the phthalocyanine pigment used in the basic treatment is preferable.
　塩基性部位を有する色材誘導体としては、中でも青色色材誘導体であることが好ましい。
　塩基性部位を有する色材誘導体に用いられる青色色材とは、Ｐ／Ｖ比（（組成物中の色材全質量）／（組成物中の色材以外の固形分全質量）比）＝０．２で２．５μｍの塗膜を形成し分光透過率スペクトルを測定した場合に、４２０ｎｍ透過率が２０％以上且つ５２０ｎｍ透過率が１０％以上且つ５８０ｎｍ透過率が１０％未満の色材が用いられる。
　色材を単体で塗膜化して測色するためには、色材に適当なバインダー成分及び溶剤を配合して塗工液を調製し、透明基板上に塗工して乾燥し、必要に応じて硬化させればよい。バインダー成分としては、測色を行い得る透明な塗膜を形成できる限り、非硬化性の熱可塑性樹脂組成物を用いても良いし、光硬化性（感光性）又は熱硬化性の樹脂組成物を用いても良い。また、後述する本発明の着色樹脂組成物において、色材として青色色材のみ含有する組成物を用いることで、色材として青色色材のみ含有する塗膜を形成し、測色を行うこともできる。具体的には例えば、後述の実施例１の樹脂組成物に用いられた色材以外の固形分を、バインダー成分とすることができる。必要に応じて、色材分散液を調製しても良く、後述の実施例１と同様にして色材分散液と着色樹脂組成物を各々調製し、後述の実施例の光学性能を評価する際の硬化膜と同様にして、硬化膜を作製しても良い。
　バインダー成分を含む、測色を行い得る透明な塗膜としては、例えば、膜厚２．０μｍで、３８０ｎｍ以上７８０ｎｍ以下における分光透過率スペクトルの透過率が９５％以上であることを目安にすることができる。
　なお、分光透過率スペクトルは、分光測定装置（例えば、オリンパス製　顕微分光光度計　ＯＳＰ－ＳＰ２００）を用いて測定することができる。
　塩基性部位を有する色材誘導体に用いられる青色色材としては、フタロシアニン系色材、トリアリールメタン系色材、アンスラキノン系色材、ナフトール系色材、ベンズイミダゾロン系色材等を用いることができるが、色味や耐熱性の点からフタロシアニン系色材を用いることが好ましい。フタロシアニン系色材としては、カラーインデックスで示されるピグメントブルー（ＰＢ）１５、ＰＢ１５：１、ＰＢ１５：２、ＰＢ１５：３、ＰＢ１５：４、ＰＢ１５：５、ＰＢ１５：６などの銅フタロシアニン、ＰＢ１６、ＰＢ７５、ＰＢ７９などが挙げられる。
　中でも、分散性と輝度が向上する点から、塩基性部位を有する色材誘導体に用いられる色材としては、塩基性処理に用いられるフタロシアニン顔料と同じ骨格を有するフタロシアニン系色材を用いることが好ましい。
　また、中でも、分散性と輝度が向上する点から塩基性部位を有する色材誘導体に用いられる青色色材としては、銅フタロシアニンを用いることが好ましい。 As the coloring material derivative having a basic site, a blue coloring material derivative is particularly preferable.
The blue color material used for the color material derivative having a basic moiety is defined as P / V ratio ((total mass of color material in composition) / (total mass of solids other than color material in composition) ratio) = When a coating film having a thickness of 0.2 μm and a thickness of 2.5 μm was formed and the spectral transmittance spectrum was measured, a coloring material having a transmittance of 420 nm of 20% or more, a transmittance of 520 nm of 10% or more, and a transmittance of 580 nm of less than 10% was found. Used.
In order to measure the color by coating the color material alone, prepare a coating solution by mixing the color material with an appropriate binder component and solvent, apply it on a transparent substrate, and dry it. And harden it. As the binder component, a non-curable thermoplastic resin composition may be used, or a photo-curable (photosensitive) or thermo-curable resin composition, as long as a transparent coating film capable of performing color measurement can be formed. May be used. Further, in the colored resin composition of the present invention described below, by using a composition containing only a blue coloring material as a coloring material, it is also possible to form a coating film containing only a blue coloring material as a coloring material and perform colorimetry. it can. Specifically, for example, a solid content other than the coloring material used in the resin composition of Example 1 described later can be used as the binder component. If necessary, a colorant dispersion may be prepared. When a colorant dispersion and a colored resin composition are respectively prepared in the same manner as in Example 1 described below, and when the optical performance of Examples described later is evaluated. A cured film may be produced in the same manner as the cured film described above.
As a transparent coating film capable of performing colorimetry including a binder component, for example, a film having a thickness of 2.0 μm and a transmittance of a spectral transmittance spectrum in a range of 380 nm to 780 nm of 95% or more is a standard. Can be.
The spectral transmittance spectrum can be measured using a spectrophotometer (for example, Olympus microspectrophotometer OSP-SP200).
As the blue colorant used for the colorant derivative having a basic moiety, a phthalocyanine-based colorant, a triarylmethane-based colorant, an anthraquinone-based colorant, a naphthol-based colorant, a benzimidazolone-based colorant, or the like is used. However, it is preferable to use a phthalocyanine-based coloring material from the viewpoint of color and heat resistance. Examples of the phthalocyanine-based coloring materials include copper phthalocyanines such as Pigment Blue (PB) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, and PB75, which are represented by color indexes. , PB79 and the like.
Among them, from the viewpoint of improving dispersibility and luminance, it is preferable to use a phthalocyanine-based coloring material having the same skeleton as the phthalocyanine pigment used in the basic treatment, as the coloring material used in the coloring material derivative having a basic moiety. .
In particular, copper phthalocyanine is preferably used as the blue color material used in the color material derivative having a basic site in terms of improving dispersibility and luminance.
　塩基性部位を有する無色化合物の誘導体に用いられる無色化合物は、フタロシアニン顔料に、当該無色化合物の誘導体を用いて塩基性処理しても、塩基性処理前後でフタロシアニン顔料の色が変化しない化合物を目安とすることができる。塩基性処理前後のフタロシアニン顔料の測色は、前記青色色材の場合と同様に行うことができる。具体的には、塩基性処理前後のフタロシアニン顔料を各々用いて、後述の実施例１と同様にして色材分散液と着色樹脂組成物を各々調製し、後述の実施例の光学性能を評価する際の硬化膜と同様にして、硬化膜を各々作製する。後述の実施例に記載の方法により各硬化膜の色度を測定し、塩基性処理前のフタロシアニン顔料を含有する硬化膜の色度（Ｌ０、ａ０、ｂ０）と塩基性処理後のフタロシアニン顔料を含有する硬化膜の色度（Ｌ１、ａ１、ｂ１）の色差ΔＥａｂ＝｛（Ｌ１－Ｌ０）２＋（ａ１－ａ０）２＋（ｂ１－ｂ０）２｝１／２が、１０未満の場合には色が変化しないとする。 The colorless compound used for the derivative of the colorless compound having a basic moiety is a compound in which the color of the phthalocyanine pigment does not change before and after the basic treatment even when the phthalocyanine pigment is subjected to basic treatment using the derivative of the colorless compound. It can be. The color measurement of the phthalocyanine pigment before and after the basic treatment can be performed in the same manner as in the case of the blue color material. Specifically, using the phthalocyanine pigments before and after the basic treatment, respectively, a colorant dispersion liquid and a colored resin composition are respectively prepared in the same manner as in Example 1 described below, and the optical performance of Examples described later is evaluated. Each of the cured films is produced in the same manner as the cured film at that time. The chromaticity of each cured film was measured by the method described in Examples described later, and the chromaticity (L 0 , a 0 , b 0 ) of the cured film containing the phthalocyanine pigment before the basic treatment and the chromaticity after the basic treatment were measured. Color difference ΔEab of chromaticity (L 1 , a 1 , b 1 ) of cured film containing phthalocyanine pigment ΔEab = ｛(L 1 -L 0 ) 2 + (a 1 -a 0 ) 2 + (b 1 -b 0 ) If 2 ｝ 1/2 is less than 10, the color does not change.
　塩基性部位を有する無色化合物の誘導体に用いられる無色化合物としては、例えば４００ｎｍ以下の波長領域に吸収極大をもつ有機化合物が挙げられ、適宜選択して用いることができる。当該無色化合物は、塩基性処理に用いられるフタロシアニン顔料と吸着し易い構造を有することが好ましく、相互作用し易い構造を有することが好ましい。当該無色化合物としては、例えばナフタレン系、トリアジン系等の縮合環化合物や複数の芳香族環が結合している芳香族多環化合物を用いることができる。トリアジン系の芳香族多環化合物としては、例えば、トリアジン環に、フェニルアミノ基等の芳香族炭化水素基を有する置換基が３つ置換された構造が挙げられる。中でも、分散性と輝度が向上する点からトリアジン系の芳香族多環化合物を用いることが好ましい。 無色 As the colorless compound used for the derivative of the colorless compound having a basic moiety, for example, an organic compound having an absorption maximum in a wavelength region of 400 nm or less can be mentioned, and can be appropriately selected and used. The colorless compound preferably has a structure that easily adsorbs to the phthalocyanine pigment used in the basic treatment, and preferably has a structure that easily interacts with the phthalocyanine pigment. As the colorless compound, for example, a condensed ring compound such as a naphthalene-based compound or a triazine-based compound or an aromatic polycyclic compound in which a plurality of aromatic rings are bonded can be used. Examples of the triazine-based aromatic polycyclic compound include a structure in which a triazine ring is substituted with three substituents having an aromatic hydrocarbon group such as a phenylamino group. Above all, it is preferable to use a triazine-based aromatic polycyclic compound from the viewpoint of improving dispersibility and luminance.
　塩基性部位を有する色材誘導体は、従来公知の方法により製造することができる。例えば、色材をスルホン化した後に、アンモニアや有機アミンで塩形成させる方法、又は、色材の置換基をスルホンアミド化する方法により製造することができる。
　具体的には例えば、濃硫酸または発煙硫酸中に色材を添加し、加熱してスルホン化を行う。次いで、この反応溶液を大量の氷水中へ注入して析出するスルホン化誘導体をフィルタープレス等で濾別、水洗する。得られたスルホン化誘導体の水ペーストを多量の水へ再分散し、塩基性化合物により中和、より具体的にはｐＨが７になるまでアンモニア又は有機アミン水溶液を添加して、スルホン酸をアンモニア又は有機アミンで造塩する方法が挙げられる。この後、濾別、水洗、乾燥、粉砕の工程を経て、粉末状の塩基性部位を有する色材誘導体を得ることができる。 The coloring material derivative having a basic site can be produced by a conventionally known method. For example, it can be produced by a method of sulfonating a coloring material and then forming a salt with ammonia or an organic amine, or a method of sulfonamidating a substituent of the coloring material.
Specifically, for example, a coloring material is added to concentrated sulfuric acid or fuming sulfuric acid, and heated to perform sulfonation. Next, the reaction solution is poured into a large amount of ice water, and the precipitated sulfonated derivative is separated by filtration with a filter press or the like and washed with water. The obtained water paste of the sulfonated derivative is redispersed in a large amount of water and neutralized with a basic compound. Alternatively, a method of salt formation with an organic amine may be used. Thereafter, through the steps of filtration, washing, drying, and pulverization, a coloring material derivative having a powdery basic site can be obtained.
　塩基性部位を有する色材誘導体のスルホンアミド化又は有機アミン塩を形成する際に用いられる有機アミンとしては、具体的には例えば、メチルアミン、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、第２ブチルアミン、第３ブチルアミン、イソブチルアミン、ジメチルアミン、ジエチルアミン、ジｎ－プロピルアミン、ジイソプロピルアミン、エチルメチルアミン、ｎ－プロピルメチルアミン、イソプロピルメチルアミン、１，１，７，７－テトラメチル－１，４，７－トリアザヘプタン、１，１，７，７－テトラエチル－１，４，７－トリアザヘプタン、１，１，７，７－テトラプロピル－１，４，７－トリアザヘプタン、１，１，７，７－テトライソプロピル－１，４，７－トリアザヘプタン、１，１，７，７－テトラブチル－１，４，７－トリアザヘプタン、１，１－ジメチル－１，５－ジアザペンタン、１，１－ジエチル－１，５－ジアザペンタン、１，１－ジイソプロピル－１，５－ジアザペンタン、１，１－ジブチル－１，５－ジアザペンタン等が挙げられるが、これらに限定されるものではない。
　塩基性部位を有する無色化合物の誘導体も、塩基性部位を有する色材誘導体と同様に、従来公知の方法により製造することができる。 Specific examples of the organic amine used for sulfonamidation of a coloring material derivative having a basic moiety or formation of an organic amine salt include methylamine, ethylamine, n-propylamine, isopropylamine, and n-butylamine. , Sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, ethylmethylamine, n-propylmethylamine, isopropylmethylamine, 1,1,7,7-tetramethyl -1,4,7-triazaheptane, 1,1,7,7-tetraethyl-1,4,7-triazaheptane, 1,1,7,7-tetrapropyl-1,4,7-triaza Heptane, 1,1,7,7-tetraisopropyl-1,4,7-triazaheptane, 1,1 7,7-tetrabutyl-1,4,7-triazaheptane, 1,1-dimethyl-1,5-diazapentane, 1,1-diethyl-1,5-diazapentane, 1,1-diisopropyl-1,5- Examples include, but are not limited to, diazapentane and 1,1-dibutyl-1,5-diazapentane.
The derivative of the colorless compound having a basic moiety can be produced by a conventionally known method, similarly to the colorant derivative having a basic moiety.
　塩基性化合物に由来する構造を有するフタロシアニン顔料として、例えば、塩基性部位を有する色材誘導体を含むフタロシアニン顔料を調製する方法としては、例えば、塩基性部位を有する色材誘導体と、フタロシアニン顔料とを乾式粉砕後、更に塩基性部位を有する色材誘導体を混合する方法が挙げられる。この場合乾式粉砕機としてはボールミル、振動ミル、アトライター等が使用でき、粉砕温度は２０～１３０℃で自由に設定できる。
　また、塩基性部位を有する色材誘導体を含むフタロシアニン顔料を調製する方法としては、塩基性部位を有する色材誘導体と、フタロシアニン顔料と、塩化ナトリウム、塩化カルシウム、硫酸アンモニウム等の水溶性の無機塩と、グリコール系有機溶剤等の水溶性の有機溶剤を混合し、ソルベントソルトミリング法でニーダータイプの研磨機により混練りする方法等が挙げられる。
　色材分散前に予め、塩基性処理されたフタロシアニン顔料を調製乃至準備し、色材を分散することにより、色材分散性を向上することができる。 As a phthalocyanine pigment having a structure derived from a basic compound, for example, as a method of preparing a phthalocyanine pigment containing a colorant derivative having a basic moiety, for example, a colorant derivative having a basic moiety, and a phthalocyanine pigment After the dry pulverization, a method of further mixing a colorant derivative having a basic site is used. In this case, a ball mill, a vibration mill, an attritor, or the like can be used as the dry pulverizer, and the pulverization temperature can be freely set at 20 to 130 ° C.
Further, as a method of preparing a phthalocyanine pigment containing a colorant derivative having a basic site, a colorant derivative having a basic site, a phthalocyanine pigment, and a water-soluble inorganic salt such as sodium chloride, calcium chloride, and ammonium sulfate. And a method in which a water-soluble organic solvent such as a glycol-based organic solvent is mixed and kneaded with a kneader-type polishing machine by a solvent salt milling method.
By preparing or preparing a phthalocyanine pigment which has been subjected to a basic treatment before dispersing the coloring material, and dispersing the coloring material, the dispersibility of the coloring material can be improved.
　塩基性部位を有する色材誘導体又は無色化合物の誘導体を含むフタロシアニン顔料において、塩基性部位を有する色材誘導体又は無色化合物の誘導体の含有量は、分散性及び保存安定性の点から、フタロシアニン顔料１００質量部に対して、０．５質量部以上であることが好ましく、３質量部以上であることがより好ましく、５質量部以上であることが更に好ましく、８質量部以上であることがより更に好ましい。一方、塩基性部位を有する色材誘導体又は無色化合物の誘導体の含有量は、輝度に優れる点から、フタロシアニン顔料１００質量部に対して、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３０質量部以下であることが更に好ましい。 In a phthalocyanine pigment containing a colorant derivative having a basic site or a derivative of a colorless compound, the content of the colorant derivative having a basic site or a derivative of a colorless compound is from the viewpoint of dispersibility and storage stability. It is preferably at least 0.5 part by mass, more preferably at least 3 parts by mass, still more preferably at least 5 parts by mass, and even more preferably at least 8 parts by mass with respect to parts by mass. preferable. On the other hand, the content of the colorant derivative having a basic moiety or the derivative of a colorless compound is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, based on 100 parts by mass of the phthalocyanine pigment, from the viewpoint of excellent luminance. More preferably, it is even more preferably 30 parts by mass or less.
　塩基性処理されたフタロシアニン顔料であることは、例えば、質量分析、元素分析、表面分析、電位差滴定、及びこれらの組み合わせを用いて適宜分析することができる。より具体的には例えば、塩基性処理されたフタロシアニン顔料を、メタノール、エタノール、イソプロパノール等のアルコール系溶剤やＮ－メチルピロリドン等の溶剤で洗浄した後に、洗浄後のフタロシアニン顔料を質量分析し、塩基性部位を有する色材誘導体等所望の塩基性化合物に由来する構造由来のピークが検出されることにより確認できる。 The fact that the phthalocyanine pigment has been subjected to basic treatment can be appropriately analyzed using, for example, mass spectrometry, elemental analysis, surface analysis, potentiometric titration, and a combination thereof. More specifically, for example, after washing the basic-treated phthalocyanine pigment with an alcoholic solvent such as methanol, ethanol, or isopropanol, or a solvent such as N-methylpyrrolidone, the washed phthalocyanine pigment is subjected to mass spectrometry. It can be confirmed by detecting a peak derived from a structure derived from a desired basic compound such as a coloring material derivative having a sexual site.
＜他の色材＞
　本発明に用いられる色材は、必須成分として前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含むが、本発明の効果を損なわない範囲で、色調を調整するために、更に他の色材を組み合わせて用いてもよい。
　他の色材としては公知の顔料、染料、レーキ色材等を、単独で又は２種以上混合して用いることができる。 <Other color materials>
The coloring material used in the present invention is at least one lake color selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2) as an essential component. A material and a phthalocyanine pigment which has been subjected to a basic treatment are used, but other color materials may be used in combination in order to adjust the color tone within a range that does not impair the effects of the present invention.
As other color materials, known pigments, dyes, lake color materials, and the like can be used alone or in combination of two or more.
　他の色材としては、中でも他の青色色材、紫色色材、赤色色材が好ましく用いられるがこれらに限定されるものではない。
　他の青色色材として、前記フタロシアニン顔料とは異なる公知の有機青色顔料、前記一般式（１）で表される色材及び前記一般式（２）で表される色材とは異なるトリアリールメタン系レーキ色材等。
　紫色色材として、Ｃ．Ｉ．ピグメントバイオレット１、１４、１５、１９、２３、２９、３２、３３、３６、３７、３８等の公知の有機紫色顔料。
　赤色乃至赤紫色色材として、キサンテン染料及び前記一般式（１）で表される色材及び前記一般式（２）で表される色材とは異なるキサンテン系染料のレーキ色材等。 As other color materials, other blue color materials, purple color materials, and red color materials are preferably used, but are not limited thereto.
As other blue color materials, a known organic blue pigment different from the phthalocyanine pigment, a color material represented by the general formula (1), and a triarylmethane different from the color material represented by the general formula (2) Rake color materials.
As a purple coloring material, C.I. I. Known organic violet pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and the like.
Examples of the red to reddish purple colorant include a xanthene dye, a colorant represented by the general formula (1), and a lake colorant of a xanthene dye different from the colorant represented by the general formula (2).
＜色材の含有割合＞
　本発明の色材分散液において、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料との各含有割合、更にその他の色材を用いる場合の含有割合は、後述の着色樹脂組成物で用いられる含有割合とすることが好ましい。具体的には以下の含有割合で用いられることが好ましい。但し、色材分散液は、適宜２種以上混合して用いて、着色樹脂組成物を製造することができるため、後述の着色樹脂組成物で用いられる含有割合としなくても用いることもできる。 <Color material content>
In the colorant dispersion of the present invention, at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1) and the colorant represented by the general formula (2); It is preferable that each content ratio with the phthalocyanine pigment subjected to the basic treatment, and further when the other color material is used, be a content ratio used in a colored resin composition described later. Specifically, it is preferable to use the following content ratio. However, since the coloring resin composition can be produced by appropriately mixing two or more kinds of the coloring material dispersion liquids, the coloring material dispersion liquid may be used without using the content ratio used in the coloring resin composition described later.
　本発明の色材分散液において、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有量は、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下であることが、カラーフィルタ製造工程における高温加熱工程（ポストベーク）後の着色層の色度変化を抑制し、輝度を向上させながら、所望の線幅でパターンを形成可能な点から好ましい。
　本発明者らは、フタロシアニン顔料のみを用いて青色着色層を形成しようとすると、設計通りの着色層が形成されない場合があるとの知見を得た。これは、青色フタロシアニン顔料は、光開始剤の吸収波長（ラジカル発生波長）である３００ｎｍ前後を吸収してしまうため、光重合反応が十分に進まず、露光時に着色層内部の硬化不足が発生していると推定される。それに対して、フタロシアニン顔料に、前記特定のレーキ色材を、前記特定の割合で組み合わせて用いることにより、前記特定のレーキ色材が３００ｎｍ前後の波長を吸収し難いことから、ネガ型感光性バインダー成分を組み合わせて青色着色層用の感光性着色樹脂組成物としても、露光時に着色層内部の硬化不足が生じ難く、所望の線幅でパターンを形成し易くなると推定される。
　更に、フタロシアニン顔料に、前記特定の一般式（１）で表される色材を、特定の割合で組み合わせて用いることにより、前記特定の一般式（１）で表される色材による色度変化を抑制しつつ、透過率を向上でき、カラーフィルタ製造工程における高温加熱（ポストベーク）後に最終的に得られる着色層の輝度を向上させることが出来ると推定される。 The colorant dispersion of the present invention contains at least one lake colorant selected from the group consisting of the colorant represented by the general formula (1) and the colorant represented by the general formula (2). The amount is the total content of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) and the phthalocyanine pigment. 20% by mass or more and 85% by mass or less with respect to the desired line width while suppressing the chromaticity change of the colored layer after the high-temperature heating step (post-baking) in the color filter manufacturing step and improving the luminance. This is preferable in that a pattern can be formed.
The inventors of the present invention have found that when an attempt is made to form a blue colored layer using only a phthalocyanine pigment, a designed colored layer may not be formed. This is because the blue phthalocyanine pigment absorbs around 300 nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, so that the photopolymerization reaction does not proceed sufficiently and insufficient curing inside the colored layer occurs during exposure. It is estimated that On the other hand, by using the specific lake color material in combination with the specific ratio in the phthalocyanine pigment in the specific ratio, the specific lake color material hardly absorbs a wavelength of about 300 nm. It is presumed that even when a photosensitive colored resin composition for a blue colored layer is formed by combining the components, insufficient curing inside the colored layer hardly occurs at the time of exposure, and a pattern can be easily formed with a desired line width.
Further, by using the phthalocyanine pigment in combination with the color material represented by the specific general formula (1) at a specific ratio, the chromaticity change due to the color material represented by the specific general formula (1) is obtained. It is presumed that the transmittance can be improved while suppressing the brightness, and the luminance of the coloring layer finally obtained after high-temperature heating (post-baking) in the color filter manufacturing process can be improved.
　中でも、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有量が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材及び前記フタロシアニン顔料の合計含有量に対して、輝度と所望の線幅でのパターニングの容易性の点から、３０質量％以上であることが好ましく、更に４０質量％以上であることが好ましく、一方で、耐熱性の点から、８０質量％以下であることが好ましく、更に７５質量％以下であることが好ましく、基板密着性がより向上する点から、また感光性樹脂組成物にした場合の現像性が向上する点から、５５質量％以下であることがより更に好ましい。 Above all, the content of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is the same as that of the general formula ( With respect to the total content of the phthalocyanine pigment and at least one lake color material selected from the group consisting of the color material represented by 1) and the color material represented by the general formula (2), It is preferably at least 30% by mass, more preferably at least 40% by mass, from the viewpoint of easiness of patterning at a line width of, and, on the other hand, at most 80% by mass, from the viewpoint of heat resistance. Is preferably 75% by mass or less, more preferably 75% by mass or less, and from the viewpoint of further improving the substrate adhesion, and from the viewpoint of improving the developability when the photosensitive resin composition is used, 55% by mass or less. Even more preferred.
　また、本発明の色材分散液においては、本発明の効果が損なわれない範囲で、色材中に、フタロシアニン顔料及び前記一般式（１）で表される色材以外の他の色材を更に含んでいても良いが、フタロシアニン顔料及び前記一般式（１）で表される色材の合計含有量は、色材全量に対して、７０質量％以上１００質量％以下であることが好ましく、８０質量％以上１００質量％以下であることが更に好ましく、９０質量％以上１００質量％以下であることが更に好ましく、９５質量％以上１００質量％以下であることがより更に好ましい。 In the colorant dispersion of the present invention, a phthalocyanine pigment and a colorant other than the colorant represented by the general formula (1) are added to the colorant as long as the effects of the present invention are not impaired. Although it may further include, the total content of the phthalocyanine pigment and the coloring material represented by the general formula (1) is preferably 70% by mass or more and 100% by mass or less based on the total amount of the coloring material, The content is more preferably from 80% by mass to 100% by mass, further preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass.
　本発明に用いられる色材の平均一次粒径としては、カラーフィルタの着色層とした場合に、所望の発色が可能なものであればよく、特に限定されず、用いる色材の種類によっても異なるが、１０ｎｍ以上１００ｎｍ以下の範囲内であることが好ましく、１５ｎｍ以上６０ｎｍ以下であることがより好ましい。色材の平均一次粒径が上記範囲であることにより、本発明の色材分散液を用いて製造されたカラーフィルタを備えた表示装置を高コントラストで、かつ高品質なものとすることができる。 The average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can form a desired color when the coloring layer of the color filter is used, and is different depending on the type of coloring material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle size of the coloring material is in the above range, a display device including a color filter manufactured using the coloring material dispersion of the present invention can have high contrast and high quality. .
　また、色材分散液中の色材の平均分散粒径は、用いる色材の種類によっても異なるが、１０ｎｍ以上１５０ｎｍの範囲内であることが好ましく、１５ｎｍ以上６０ｎｍ以下の範囲内であることがより好ましい。
　色材分散液中の色材の平均分散粒径は、少なくとも溶剤を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、色材分散液に用いられている溶剤で、色材分散液をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈（例えば、１０００倍など）し、レーザー光散乱粒度分布計（例えば、日機装社製ナノトラック粒度分布測定装置ＵＰＡ－ＥＸ１５０）を用いて動的光散乱法により２３℃にて測定することができる。ここでの平均分布粒径は、体積平均粒径である。 The average dispersed particle size of the colorant in the colorant dispersion varies depending on the type of the colorant used, but is preferably in the range of 10 nm to 150 nm, and more preferably in the range of 15 nm to 60 nm. More preferred.
The average dispersion particle size of the colorant in the colorant dispersion is the dispersion particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, which is measured by a laser light scattering particle size distribution meter. It is. The measurement of the particle size by the laser light scattering particle size distribution meter is performed by appropriately diluting the color material dispersion liquid with a solvent used for the color material dispersion liquid to a concentration measurable by the laser light scattering particle size distribution meter (for example, 1000 times). And the like, and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). Here, the average distribution particle size is a volume average particle size.
　本発明の色材分散液において、色材の含有量は、特に限定されない。色材の含有量は、分散性及び分散安定性の点から、色材分散液中の固形分全量に対して、５質量％以上８０質量％以下、より好ましくは８質量％以上７０質量％以下の割合で配合することが好ましい。
　特に色材濃度が高い塗膜乃至着色層を形成する場合には、色材分散液中の固形分全量に対して、３０質量％以上８０質量％以下、より好ましくは４０質量％以上７５質量％以下の割合で配合することが好ましい。
　尚、本発明において固形分は、上述した溶剤以外のもの全てであり、溶剤中に溶解しているモノマー等も含まれる。 In the colorant dispersion of the present invention, the content of the colorant is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is 5% by mass or more and 80% by mass or less, more preferably 8% by mass or more and 70% by mass or less based on the total solid content in the coloring material dispersion. Is preferably blended at a ratio of
In particular, when forming a coating film or a colored layer having a high coloring material concentration, the amount of the solid content in the coloring material dispersion is 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 75% by mass. It is preferable to mix them in the following ratio.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers and the like dissolved in the solvent.
［酸性分散剤］
　本発明に用いられる酸性分散剤は、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む。
　酸性分散剤として、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を用いると、前記レーキ色材の分散性と耐熱性を向上し、加熱後のレーキ色材の色度変化を抑制可能であり、且つ、前記フタロシアニン顔料の分散性及び保存安定性を向上し、基板密着性と塗膜均一性が向上した着色層を形成可能である。
　前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体はエチレン性不飽和モノマー重合体であるため、ポリエーテル系やポリエステル系重合体と比較して骨格の耐熱性が高く、且つ、当該重合体中に複数存在する酸性リン化合物基（－Ｐ（＝Ｏ）（－Ｒ２）（ＯＨ））及びその塩（－Ｐ（＝Ｏ）（－Ｒ２）（Ｏ－Ｘ＋））が、微粒子化された色材の表面に対する吸着力が強いものと推定される。また、色材表面が酸性リン化合物基及びその塩の少なくとも一種で被覆された状態になると、パーオキシラジカルなどの活性酸素によるレーキ色材の色素骨格への攻撃（水素引き抜きや置換反応など）が抑制され、レーキ色材の劣化（酸化劣化）が抑制されると推定される。 [Acid dispersant]
The acidic dispersant used in the present invention includes a polymer having at least one selected from the structural units represented by the general formula (I).
When a polymer having at least one selected from the structural units represented by the general formula (I) is used as the acidic dispersant, the dispersibility and heat resistance of the lake color material are improved, and the lake after heating is improved. It is possible to suppress a change in the chromaticity of the coloring material, improve the dispersibility and storage stability of the phthalocyanine pigment, and form a colored layer with improved substrate adhesion and coating uniformity.
Since the polymer having at least one selected from the structural units represented by the general formula (I) is an ethylenically unsaturated monomer polymer, the heat resistance of the skeleton is higher than that of a polyether or polyester polymer. Acidic phosphorus compound groups (—P (＝ O) (— R 2 ) (OH)) and their salts (—P (＝ O) (— R 2 ) ( O − X + )) is presumed to have strong adsorption power to the surface of the finely divided color material. In addition, when the surface of the coloring material is coated with at least one of an acidic phosphorus compound group and a salt thereof, attack on the dye skeleton of the lake coloring material by active oxygen such as peroxy radical (hydrogen abstraction or substitution reaction). It is estimated that the suppression of the rake color material (oxidation deterioration) is suppressed.
＜前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体＞
　一般式（Ｉ）において、Ｌ１は、直接結合又は２価の連結基である。ここでＬ１が直接結合とは、リン原子が、連結基を介することなく主鎖骨格の炭素原子に直接結合していることを意味する。
　Ｌ１における２価の連結基としては、主鎖骨格の炭素原子と、リン原子とを連結可能であれば、特に制限はない。Ｌ１における２価の連結基としては、例えば、直鎖、分岐又は環状のアルキレン基、水酸基を有する、直鎖、分岐又は環状のアルキレン基、アリーレン基、－ＣＯＮＨ－基、－ＣＯＯ－基、－ＮＨＣＯＯ－基、エーテル基（－Ｏ－基）、チオエーテル基（－Ｓ－基）、及びこれらの組み合わせ等が挙げられる。なお、本発明において、２価の連結基の結合の向きは任意である。すなわち、２価の連結基に－ＣＯＮＨ－が含まれる場合、－ＣＯが主鎖の炭素原子側で－ＮＨが側鎖のリン原子側であっても良いし、反対に、－ＮＨが主鎖の炭素原子側で－ＣＯが側鎖のリン原子側であっても良い。 <Polymer having at least one selected from structural units represented by formula (I)>
In the general formula (I), L 1 is a direct bond or a divalent linking group. Here, the bond L 1 is directly, phosphorus atom, means that attached directly to a carbon atom of the main chain without passing through a linking group.
The divalent linking group for L 1 is not particularly limited as long as the carbon atom in the main chain skeleton can be linked to a phosphorus atom. Examples of the divalent linking group for L 1 include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, —NHCOO— groups, ether groups (—O— groups), thioether groups (—S— groups), combinations thereof, and the like. In the present invention, the direction of the bond of the divalent linking group is arbitrary. That is, when -CONH- is contained in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain. May be -CO on the side of a phosphorus atom in the side chain.
　中でも、分散性の点から、一般式（Ｉ）におけるＬ１は、－ＣＯＮＨ－基、又は、－ＣＯＯ－基を含む２価の連結基であることが好ましい。
　例えば、Ｌ１が－ＣＯＯ－基を含む２価の連結基である場合、Ｌ１が、－ＣＯＯ－Ｌ１’－基（ここで、Ｌ１’は、水酸基を有していても良い炭素数が１個以上８個以下のアルキレン基、－［ＣＨ（ＲＬ１１）－ＣＨ（ＲＬ１２）－Ｏ］ｘ－、又は－［（ＣＨ２）ｙ－Ｏ］ｚ－（ＣＨ２）ｙ－Ｏ－、－［ＣＨ（ＲＬ１３）］ｗ－Ｏ－、であり、ＲＬ１１、ＲＬ１２及びＲＬ１３は、それぞれ独立に水素原子、メチル基、又は水酸基である。ｘは１以上１８以下の整数、ｙは１以上５以下の整数、ｚは１以上１８以下の整数、ｗは１以上１８以下の整数を表す。）であることが好ましい。 Among them, L 1 in the general formula (I) is preferably a divalent linking group containing a —CONH— group or a —COO— group from the viewpoint of dispersibility.
For example, when L 1 is a divalent linking group containing a —COO— group, L 1 is a —COO-L 1 ′ -group (where L 1 ′ is a carbon atom which may have a hydroxyl group. An alkylene group having from 1 to 8 alkyl groups,-[CH (R L11 ) -CH (R L12 ) -O] x- , or-[(CH 2 ) y -O] z- (CH 2 ) y- O—, — [CH (R L13 )] w —O—, and R L11 , R L12 and R L13 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and x is 1 or more and 18 or less. An integer, y is an integer of 1 to 5; z is an integer of 1 to 18; and w is an integer of 1 to 18).
　Ｌ１’における炭素数が１個以上８個以下のアルキレン基は、直鎖状、分岐状、又は環状のいずれであってもよく、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、各種ブチレン基、各種ペンチレン基、各種へキシレン基、各種オクチレン基などであり、一部の水素が水酸基に置換されていても良い。
　ｘは１以上１８以下の整数、好ましくは１以上４以下の整数、より好ましくは１以上２以下の整数であり、ｙは１以上５以下の整数、好ましくは１以上４以下の整数、より好ましくは２又は３である。ｚは１以上１８以下の整数、好ましくは１以上４以下の整数、より好ましくは１以上２以下の整数である。ｗは１以上１８以下の整数、好ましくは１以上４以下の整数である。 The alkylene group having 1 to 8 carbon atoms in L 1 ′ may be linear, branched or cyclic, and includes, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, It is a butylene group, various pentylene groups, various hexylene groups, various octylene groups, and the like, and a part of hydrogen may be substituted by a hydroxyl group.
x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably Is 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less.
　一般式（Ｉ）におけるＬ１の好適な具体例としては、例えば、－ＣＯＯ－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－Ｏ－、－ＣＯＯ－ＣＨ２ＣＨ２－Ｏ－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－Ｏ－、－ＣＯＯ－ＣＨ２Ｃ（ＣＨ２ＣＨ３）（ＣＨ２ＯＨ）ＣＨ２－Ｏ－等が挙げられるが、これらに限定されるものではない。 Preferable specific examples of L 1 in the general formula (I) include, for example, —COO—CH 2 CH (OH) CH 2 —O—, —COO—CH 2 CH 2 —O—CH 2 CH (OH) CH 2 -O -, - COO-CH 2 C (CH 2 CH 3) (CH 2 OH) CH 2 -O- or the like including without being limited thereto.
　Ｒ２における炭化水素基としては、例えば、炭素数が１個以上１８個以下のアルキル基、炭素数が２個以上１８個以下のアルケニル基、アラルキル基、及びアリール基などが挙げられる。
　前記炭素数が１個以上１８個以下のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、シクロペンチル基、シクロヘキシル基、ボルニル基、イソボルニル基、ジシクロペンタニル基、アダマンチル基、低級アルキル基置換アダマンチル基などを挙げることができる。
　前記炭素数が２個以上１８個以下のアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。このようなアルケニル基としては、例えばビニル基、アリル基、プロペニル基などを挙げることができる。アルケニル基の二重結合の位置には限定はないが、得られたポリマーの反応性の点からは、アルケニル基の末端に二重結合があることが好ましい。
　アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられ、更に置換基を有していてもよい。アリール基の炭素数は、６個以上２４個以下が好ましく、更に６個以上１２個以下が好ましい。
　また、アラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられ、更に置換基を有していてもよい。アラルキル基の炭素数は、７個以上２０個以下が好ましく、更に７個以上１４個以下が好ましい。
　前記アルキル基やアルケニル基は置換基を有していても良く、当該置換基としては、Ｆ、Ｃｌ、Ｂｒなどのハロゲン原子、ニトロ基等が挙げられる。
　また、前記アリール基やアラルキル基等の芳香環の置換基としては、炭素数が１個以上４個以下の直鎖状、分岐状のアルキル基の他、アルケニル基、ニトロ基、ハロゲン原子などを挙げることができる。
　なお、前記好ましい炭素数には、置換基の炭素数は含まれない。
　前記Ｒ２において、ｘ１は前記ｘと、ｙ１は前記ｙと、ｚ１は前記ｚと同様である。
　Ｒ５～Ｒ１２における炭化水素基としては、例えば、前記Ｒ２における炭化水素基と同様のものが挙げられる。 Examples of the hydrocarbon group for R 2 include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl Groups, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, adamantyl, lower alkyl-substituted adamantyl and the like.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of reactivity of the obtained polymer.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. The carbon number of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 14 carbon atoms.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include a halogen atom such as F, Cl, and Br, and a nitro group.
Examples of the substituent for the aromatic ring such as the aryl group or the aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom. Can be mentioned.
The preferred carbon number does not include the carbon number of the substituent.
In the R 2, x1 is said x, y1 is said y, z1 are as defined above z.
Examples of the hydrocarbon group for R 5 to R 12 include the same as the hydrocarbon group for R 2 described above.
　Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２における、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基とは、－Ｒ’－Ｏ－Ｒ”、－Ｒ’－（Ｃ＝Ｏ）－Ｏ－Ｒ”、又は－Ｒ’－Ｏ－（Ｃ＝Ｏ）－Ｒ”（Ｒ’及びＲ”は、炭化水素基、又は、炭化水素基をエーテル結合及びエステル結合の少なくとも１つで結合した基）で表される基である。１つの基の中に、エーテル結合及びエステル結合を２つ以上有していてもよい。炭化水素基が１価の場合としては、アルキル基、アルケニル基、アラルキル基、アリール基が挙げられ、炭化水素基が２価の場合としては、アルキレン基、アルケニレン基、アリーレン基、及びこれらの組み合わせの基が挙げられる。 In R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , the hydrocarbon group having at least one kind selected from an ether bond and an ester bond refers to —R′—OR ″, —R '-(C = O) -OR "or -R'-O- (C = O) -R"(R' and R "represent a hydrocarbon group or an ether bond and an ester of a hydrocarbon group. (A group bonded by at least one bond). One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group are mentioned. When the hydrocarbon group is divalent, an alkylene group, an alkenylene group, an arylene group, and a combination thereof are used. The group of is mentioned.
　Ｒ７とＲ９が結合して環構造を形成する場合、環構造を形成する炭素数は、５個以上８個以下であることが好ましく、６であること、即ち６員環であることがより好ましく、シクロヘキサン環を形成することが好ましい。
　置換基Ｒ１４における、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基は、前記Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２におけるものと同様のものとすることができる。 When R 7 and R 9 are combined to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 or more and 8 or less, and is preferably 6, that is, a 6-membered ring. More preferably, a cyclohexane ring is formed.
In the substituent R 14 , the hydrocarbon group or the hydrocarbon group having at least one kind selected from an ether bond and an ester bond is selected from the groups represented by R 7 , R 8 , R 9 , R 10 , R 11, and R 12 . It can be similar to the one.
　分散される粒子の分散性及び分散安定性に優れる点から、前記Ｒ２が、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であることが好ましく、水酸基、メチル基、エチル基、ビニル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基、Ｒ３及びＲ４がそれぞれ独立に水素原子又はメチル基であり、Ｒ５が－ＣＯ－ＣＨ＝ＣＨ２又は－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２であるものがより好ましく、中でも、Ｒ２が、置換基を有していてもよいアリール基、ビニル基、メチル基及び水酸基がより好ましい。 In view of excellent dispersibility and dispersion stability of the dispersed particles, R 2 is a hydroxyl group, a hydrocarbon group,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[ (CH 2 ) y1 —O] is preferably a monovalent group represented by z1 —R 5 or —OR 6 , and has a hydroxyl group, a methyl group, an ethyl group, a vinyl group, or a substituent. An aryl group or an aralkyl group, a vinyl group, an allyl group,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , Or a monovalent group represented by —OR 6 , R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is —CO—CH ＝ CH 2 or —CO—C (CH 3 ) = CH 2 is more preferable, and among them, R 2 is an aryl which may have a substituent. Groups, vinyl groups, methyl groups and hydroxyl groups are more preferred.
　また、耐アルカリ性が向上する点から、Ｒ２は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、又は、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５で示される１価の基であることが好ましい。リン原子に炭素原子が直接結合した構造を有する場合には、加水分解され難いため耐アルカリ性に優れた樹脂層を形成可能と推定される。中でも、Ｒ２は、メチル基、エチル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、又は、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５で示される１価の基、Ｒ３及びＲ４がそれぞれ独立に水素原子又はメチル基であり、Ｒ５が－ＣＯ－ＣＨ＝ＣＨ２又は－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２であるものが耐アルカリ性に優れ、且つ、分散される粒子の分散性及び分散安定性に優れる点から好ましい。中でも、Ｒ２は、置換基を有していてもよいアリール基が分散性の点からより好ましい。 In addition, from the viewpoint of improving alkali resistance, R 2 is a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , or — [(CH 2 ) y1 —O ] it is preferably a monovalent group represented by z1 -R 5. It is presumed that when the compound has a structure in which a carbon atom is directly bonded to a phosphorus atom, it is difficult to be hydrolyzed, so that a resin layer having excellent alkali resistance can be formed. Among them, R 2 represents a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 or a monovalent group represented by — [(CH 2 ) y1 —O] z1 —R 5 , R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is —CO Those in which -CH = CH 2 or -CO-C (CH 3 ) = CH 2 are preferable because they have excellent alkali resistance and excellent dispersibility and dispersion stability of dispersed particles. Among them, R 2 is more preferably an aryl group which may have a substituent, from the viewpoint of dispersibility.
　また、一般式（Ｉ）において、Ｘは、水素原子又は有機カチオンを表す。有機カチオンとは、カチオン部分に炭素原子を含むものをいう。有機カチオンとしては、例えば、イミダゾリウムカチオン、ピリジニウムカチオン、アミニジウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、テトラアルキルアンモニウムカチオン及びトリアルキルアンモニウムカチオン等のアンモニウムカチオン、トリアルキルスルホニウムカチオン等のスルホニウムカチオン、テトラアルキルホスホニウムカチオン等のホスホニウムカチオン等が挙げられる。中でも、プロトン化された含窒素有機カチオンであることが、分散性とアルカリ現像性の点から好ましい。
　中でも、有機カチオンがエチレン性不飽和二重結合を有する場合には、硬化性を付与することができる点から好ましい。 In the general formula (I), X represents a hydrogen atom or an organic cation. The organic cation refers to a cation moiety containing a carbon atom. Examples of the organic cation include an imidazolium cation, a pyridinium cation, an aminium cation, a piperidinium cation, a pyrrolidinium cation, an ammonium cation such as a tetraalkylammonium cation and a trialkylammonium cation, and a sulfonium cation such as a trialkylsulfonium cation. And a phosphonium cation such as a tetraalkylphosphonium cation. Among them, a protonated nitrogen-containing organic cation is preferable in terms of dispersibility and alkali developability.
Above all, when the organic cation has an ethylenically unsaturated double bond, it is preferable in that it can impart curability.
　一般式（Ｉ）で表される構成単位は、重合体中に、１種類単独で含まれていても良く、２種以上含まれていても良い。 構成 The structural unit represented by the general formula (I) may be contained alone in the polymer, or may be contained in two or more kinds.
　重合体において、一般式（Ｉ）で表される構成単位のうち、Ｘが水素原子の構成単位と、Ｘが有機カチオンの構成単位の両方の構成単位を含んでいてもよい。当該両方の構成単位を含む場合、良好な分散性、及び分散安定性が発揮されるのであればよく、特に制限はないが、Ｘが有機カチオンの構成単位数の割合は、一般式（Ｉ）で表される構成単位の合計の構成単位数に対して０以上５０モル％以下であることが好ましい。 In the polymer, among the structural units represented by the general formula (I), X may include both a structural unit of a hydrogen atom and X as a structural unit of an organic cation. In the case of including both of the structural units, it is sufficient that good dispersibility and dispersion stability are exhibited, and there is no particular limitation. Is preferably from 0 to 50 mol% based on the total number of structural units represented by
　一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体の合成方法は特に限定されない。一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体は、例えば、特開２０１７－２１９１号公報を参照して合成することができる。一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体は、エポキシ基及び環状エーテル基の少なくとも一方を側鎖に有する重合体と、酸性リン化合物との反応生成物であって、酸性リン化合物基の少なくとも一部が塩を形成していてもよい重合体であることが好ましい。 方法 The method for synthesizing the polymer having at least one selected from the structural units represented by the general formula (I) is not particularly limited. The polymer having at least one selected from the structural units represented by the general formula (I) can be synthesized with reference to, for example, JP-A-2017-2191. The polymer having at least one selected from the structural units represented by the general formula (I) is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in a side chain and an acidic phosphorus compound. It is preferable that at least a part of the acidic phosphorus compound group is a polymer that may form a salt.
　本発明の実施形態において一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体は、分散性の点から更に溶剤親和性部位を有することが好ましい。このような重合体としては、中でも、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種と、下記一般式（ＩＩ）で表される構成単位とを有するグラフト共重合体であるか、又は、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種と、下記一般式（ＩＩＩ）で表される構成単位とを有するブロック共重合体であることが、分散性、及び保存安定性に優れ、長期保管後であっても高コントラストな塗膜を形成可能な点から好ましい。 に お い て In the embodiment of the present invention, the polymer having at least one selected from the structural units represented by Formula (I) preferably further has a solvent affinity site from the viewpoint of dispersibility. Among such polymers, among others, a graft copolymer having at least one selected from the structural units represented by the general formula (I) and a structural unit represented by the following general formula (II) Or a block copolymer having at least one selected from the structural units represented by the general formula (I) and a structural unit represented by the following general formula (III). It is excellent in dispersibility and storage stability, and is preferable because a high-contrast coating film can be formed even after long-term storage.
Figure JPOXMLDOC01-appb-C000021
 （一般式（ＩＩ）中、Ｌ２は、直接結合又は２価の連結基、Ｒ２１は、水素原子又はメチル基、Ｐｏｌｙｍｅｒは、下記一般式（ＩＶ）で表される構成単位を有するポリマー鎖を表す。
　一般式（ＩＩＩ）中、Ｒ２２は、水素原子又はメチル基、Ｒ２３は、炭化水素基、－［ＣＨ（Ｒ２４）－ＣＨ（Ｒ２５）－Ｏ］ｘ２－Ｒ２６、－［（ＣＨ２）ｙ２－Ｏ］ｚ２－Ｒ２６、－［ＣＯ－（ＣＨ２）ｙ２－Ｏ］ｚ２－Ｒ２６、－ＣＯ－Ｏ－Ｒ２６’又は－Ｏ－ＣＯ－Ｒ２６”で示される１価の基、Ｒ２４及びＲ２５は、それぞれ独立に水素原子又はメチル基、Ｒ２６は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ又は－ＣＨ２ＣＯＯＲ２７で示される１価の基であり、Ｒ２６’は、炭化水素基、－［ＣＨ（Ｒ２４）－ＣＨ（Ｒ２５）－Ｏ］ｘ２’－Ｒ２６、－［（ＣＨ２）ｙ２’－Ｏ］ｚ２’－Ｒ２６、－［ＣＯ－（ＣＨ２）ｙ２’－Ｏ］ｚ２’－Ｒ２６で示される１価の基であり、Ｒ２６”は炭素数が１個以上１８個以下のアルキル基、Ｒ２７は水素原子又は炭素数が１個以上５個以下のアルキル基である。前記炭化水素基は、置換基を有していてもよい。
　ｘ２及びｘ２’は１以上１８以下の整数、ｙ２及びｙ２’は１以上５以下の整数、ｚ２及びｚ２’は１以上１８以下の整数を示す。）
Figure JPOXMLDOC01-appb-C000021
 (In the general formula (II), L 2 is a direct bond or a divalent linking group, R 21 is a hydrogen atom or a methyl group, and Polymer is a polymer chain having a structural unit represented by the following general formula (IV). Represents
In the general formula (III), R 22 is a hydrogen atom or a methyl group, R 23 is a hydrocarbon group,-[CH (R 24 ) -CH (R 25 ) -O] x2 -R 26 ,-[(CH 2) y2 -O] z2 -R 26 , - [CO- (CH 2) y2 -O] z2 -R 26, -CO-O-R 26 ' or a monovalent represented by -O-CO-R 26 " R 24 and R 25 are each independently a hydrogen atom or a methyl group; R 26 is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 27 And R 26 ' is a hydrocarbon group,-[CH (R 24 ) -CH (R 25 ) -O] x2' -R 26 ,-[(CH 2 ) y2 ' -O] z2' -R 26 , - [CO- (CH 2) y2 is a monovalent group represented by '-O] z2' -R 26, R 2 "Is an alkyl group having 1 or more 18 or less alkyl groups, R 27 is a hydrogen atom or a carbon number of 5 or less one or more carbon. The hydrocarbon group may have a substituent.
x2 and x2 'represent an integer of 1 to 18; y2 and y2' represent an integer of 1 to 5; z2 and z2 'represent an integer of 1 to 18; )
Figure JPOXMLDOC01-appb-C000022
 （一般式（ＩＶ）中、Ｒ３１は水素原子又はメチル基であり、Ｒ３２は炭化水素基、－［ＣＨ（Ｒ３３）－ＣＨ（Ｒ３４）－Ｏ］ｘ３－Ｒ３５、－［（ＣＨ２）ｙ３－Ｏ］ｚ３－Ｒ３５、－［ＣＯ－（ＣＨ２）ｙ３－Ｏ］ｚ３－Ｒ３５、－ＣＯ－Ｏ－Ｒ３６又は－Ｏ－ＣＯ－Ｒ３７で示される１価の基、Ｒ３３及びＲ３４は、それぞれ独立に水素原子又はメチル基、Ｒ３５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ又は－ＣＨ２ＣＯＯＲ３８で示される１価の基、Ｒ３６は、炭化水素基、－［ＣＨ（Ｒ３３）－ＣＨ（Ｒ３４）－Ｏ］ｘ４－Ｒ３５、－［（ＣＨ２）ｙ４－Ｏ］ｚ４－Ｒ３５、－［ＣＯ－（ＣＨ２）ｙ４－Ｏ］ｚ４－Ｒ３５で示される１価の基、Ｒ３７は炭素数が１個以上１８個以下のアルキル基、Ｒ３８は水素原子又は炭素数が１個以上５個以下のアルキル基であり、前記炭化水素基は、置換基を有していてもよい。
　ｎは５以上２００以下の整数を示す。ｘ３及びｘ４は１以上１８以下の整数、ｙ３及びｙ４は１以上５以下の整数、ｚ３及びｚ４は１以上１８以下の整数を示す。）
Figure JPOXMLDOC01-appb-C000022
 (In the general formula (IV), R 31 is a hydrogen atom or a methyl group, R 32 is a hydrocarbon group,-[CH (R 33 ) -CH (R 34 ) -O] x3 -R 35 ,-[( CH 2 ) y3 —O] z3 —R 35 , — [CO— (CH 2 ) y3 —O] z3 —R 35 , monovalent represented by —CO— OR 36 or —O—CO—R 37 A group, R 33 and R 34 each independently represent a hydrogen atom or a methyl group, R 35 represents a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 38 ; R 36 is a hydrocarbon group,-[CH (R 33 ) -CH (R 34 ) -O] x4 -R 35 ,-[(CH 2 ) y4 -O] z4 -R 35 ,-[CO- (CH 2) y4 -O] 1 monovalent group represented by z4 -R 35, R 37 is one or more carbon atoms The upper 18 or less alkyl groups and R 38 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have a substituent.
n shows the integer of 5 or more and 200 or less. x3 and x4 each represent an integer of 1 to 18; y3 and y4 each represent an integer of 1 to 5; z3 and z4 each represent an integer of 1 to 18; )
（グラフト共重合体）
　前記一般式（ＩＩ）において、Ｌ２は、直接結合又は２価の連結基である。Ｌ２における２価の連結基としては、エチレン性不飽和二重結合由来の炭素原子とポリマー鎖を連結可能であれば、特に制限はない。Ｌ２における２価の連結基としては、例えば、前記Ｌ１における２価の連結基と同様のものが挙げられる。 (Graft copolymer)
In the general formula (II), L 2 is a direct bond or a divalent linking group. L The divalent linking group for 2, connecting carbon atom with a polymer chain derived from an ethylenically unsaturated double bond, if possible, is not particularly limited. Examples of the divalent linking group for L 2, for example, those similar to the divalent linking group for the L 1 and the like.
　前記一般式（ＩＩ）において、Ｐｏｌｙｍｅｒは、前記一般式（ＩＶ）で表される構成単位を有するポリマー鎖を表す。
　式（ＩＶ）中、Ｒ３２における炭化水素基としては、炭素数が１個以上１８個以下のアルキル基、炭素数が２個以上１８個以下のアルケニル基、アラルキル基、又はアリール基であることが好ましい。これらは、例えば、前記のＲ２と同様のものが挙げられる。 In the general formula (II), Polymer represents a polymer chain having a structural unit represented by the general formula (IV).
In the formula (IV), the hydrocarbon group for R 32 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, or an aryl group having 2 to 18 carbon atoms. Is preferred. These include, for example, those similar to the of R 2.
　Ｒ３５は、水素原子、あるいは炭素数が１個以上１８個以下のアルキル基、アラルキル基、アリール基、－ＣＨＯ、－ＣＨ２ＣＨＯ又は－ＣＨ２ＣＯＯＲ３８で示される１価の基が好ましく、Ｒ３６は、炭素数が１個以上１８個以下のアルキル基、アラルキル基、アリール基、－［ＣＨ（Ｒ３３）－ＣＨ（Ｒ３４）－Ｏ］ｘ４－Ｒ３５、－［（ＣＨ２）ｙ４－Ｏ］ｚ４－Ｒ３５、－［ＣＯ－（ＣＨ２）ｙ４－Ｏ］ｚ４－Ｒ３５で示される１価の基が好ましい。Ｒ３７は、炭素数が１個以上１８個以下のアルキル基であり、Ｒ３８は水素原子又は炭素数が１個以上５個以下のアルキル基を示す。
　前記Ｒ３５及びＲ３６のうちの炭素数が１個以上１８個以下のアルキル基、アラルキル基、アリール基は、前記のＲ２と同様のものが挙げられる。
　前記Ｒ３７及びＲ３８のうちのアルキル基は、前記のＲ２と同様のものが挙げられる。
　前記Ｒ３５、Ｒ３６、Ｒ３７及びＲ３８が、芳香環を有する基である場合、当該芳香環はさらに置換基を有していてもよい。当該置換基としては、例えば炭素数が１個以上５個以下の直鎖状、分岐状、環状のアルキル基の他、アルケニル基、ニトロ基、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子などが挙げられる。
　なお、前記好ましい炭素数には、置換基の炭素数は含まれない。
　前記Ｒ３２及びＲ３６において、ｘ３及びｘ４は前記ｘと、ｙ３及びｙ４は前記ｙと、ｚ３及びｚ４は前記ｚと同様である。 R 35 is preferably a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO or —CH 2 COOR 38 , R 36 is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group,-[CH (R 33 ) -CH (R 34 ) -O] x4 -R 35 ,-[(CH 2 ) y4 -O] z4 -R 35, - [CO- (CH 2) y4 -O] 1 monovalent group is preferably represented by z4 -R 35. R 37 represents an alkyl group having 1 to 18 carbon atoms, and R 38 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Examples of the alkyl group, aralkyl group, and aryl group having 1 to 18 carbon atoms in R 35 and R 36 include those similar to R 2 described above.
As the alkyl group of R 37 and R 38 , those similar to the aforementioned R 2 can be mentioned.
When R 35 , R 36 , R 37 and R 38 are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms, an alkenyl group, a nitro group, and a halogen atom such as F, Cl, or Br. .
The preferred carbon number does not include the carbon number of the substituent.
In the R 32 and R 36, is x3 and x4 and the x, the y3 and y4 and the y, the z3 and z4 is the same as the z.
　さらに、前記Ｒ３２、Ｒ３５、Ｒ３６、Ｒ３７及びＲ３８は、前記グラフト共重合体の分散性能等を妨げない範囲で、更に、アルコキシ基、水酸基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基、水素結合形成基等の置換基によって置換されたものとしてもよい。また、これらの置換基を有するグラフト共重合体を合成した後に、当該置換基と反応する官能基と重合性基とを有する化合物を反応させて、重合性基を付加したものとしてもよい。例えば、カルボキシル基を有するグラフト共重合体にグリシジル（メタ）アクリレートを反応させたり、イソシアネート基を有するグラフト共重合体にヒドロキシエチル（メタ）アクリレートを反応させたりして、重合性基を付加することができる。 Further, the aforementioned R 32 , R 35 , R 36 , R 37 and R 38 may further include an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group as long as the dispersing performance and the like of the graft copolymer are not hindered. It may be substituted by a substituent such as an isocyanate group or a hydrogen bond forming group. Alternatively, after a graft copolymer having these substituents is synthesized, a compound having a polymerizable group and a functional group that reacts with the substituent may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting glycidyl (meth) acrylate with a graft copolymer having a carboxyl group or reacting hydroxyethyl (meth) acrylate with a graft copolymer having an isocyanate group. Can be.
　一般式（ＩＶ）で表される構成単位に含まれるポリマー鎖は、前記した構成単位の中でもメチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、スチレン、α－メチルスチレン、ビニルシクロヘキサンなど由来の構成単位を有するものが好ましい。しかしながら、これらに限定されるものではない。 The polymer chain contained in the structural unit represented by the general formula (IV) includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl Those having structural units derived from (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, α-methylstyrene, vinylcyclohexane and the like are preferable. However, it is not limited to these.
　本発明の実施形態において、前記Ｒ３２及びＲ３６としては、中でも、後述する有機溶剤との溶解性に優れたものを用いることが好ましく、色材分散液に使用する有機溶剤に合わせて適宜選択されれば良い。具体的には、例えば前記有機溶剤が、色材分散液の有機溶剤として一般的に使用されているエーテルアルコールアセテート系、エーテル系、エステル系などの有機溶剤を用いる場合には、メチル基、エチル基、イソブチル基、ｎ－ブチル基、２－エチルヘキシル基、２－エトキシエチル基、シクロヘキシル基、ベンジル基等が好ましい。
　ここで、前記Ｒ３２及びＲ３６をこのように設定する理由は、前記Ｒ３２及びＲ３６を含む構成単位が、前記有機溶剤に対して溶解性を有し、前記モノマーの酸性リン化合物基及びその塩の部位が色材等の粒子に対して高い吸着性を有するものであることにより、色材等の粒子の分散性、及び安定性を特に優れたものとすることができるからである。 In the embodiment of the present invention, it is preferable to use, as the R 32 and R 36 , those having excellent solubility with an organic solvent described below, and are appropriately selected according to the organic solvent used in the colorant dispersion. Just do it. Specifically, for example, when the organic solvent uses an organic solvent such as an ether alcohol acetate system, an ether system, and an ester system that are generally used as an organic solvent of the colorant dispersion, a methyl group, an ethyl group, Groups, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl and the like.
Here, the reason for setting the R 32 and R 36 in this manner is that the structural unit containing the R 32 and R 36 has solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and This is because the dispersibility and the stability of the particles of the coloring material or the like can be made particularly excellent when the salt portion has a high adsorptivity to the particles of the coloring material or the like.
　Ｐｏｌｙｍｅｒにおけるポリマー鎖の質量平均分子量Ｍｗは、５００以上１５０００以下の範囲内であることが好ましく、１０００以上８０００以下の範囲内であることがより好ましい。前記範囲であることにより、分散剤としての十分な立体反発効果を保持できるとともに、立体効果による色材等の粒子の分散に要する時間の増大を抑制することもできる。 質量 The weight average molecular weight Mw of the polymer chain in Polymer is preferably in the range of 500 or more and 15000 or less, more preferably in the range of 1000 or more and 8000 or less. When the content is within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and an increase in time required for dispersing particles such as a coloring material due to the steric effect can also be suppressed.
　また、Ｐｏｌｙｍｅｒにおけるポリマー鎖は、目安として、組み合わせて用いられる有機溶剤に対して、２３℃における溶解度が５０（ｇ／１００ｇ溶剤）以上であることが好ましい。 Further, as a guide, the solubility of the polymer chain in Polymer at 23 ° C. in an organic solvent used in combination is preferably 50 (g / 100 g solvent) or more.
　前記ポリマー鎖は、単独重合体でもよく、共重合体であってもよい。また、一般式（ＩＩ）で表される構成単位に含まれるポリマー鎖は、グラフト共重合体において、１種単独でも良く、２種以上混合していても良い。 The polymer chain may be a homopolymer or a copolymer. Further, the polymer chain contained in the structural unit represented by the general formula (II) may be used alone or as a mixture of two or more kinds in the graft copolymer.
　前記グラフト共重合体の全構成単位に対して、前記一般式（Ｉ）で表される構成単位は、その合計が３質量％以上８０質量％以下の割合で含まれていることが好ましく、１０質量％以上７０質量％以下がより好ましく、２０質量％以上６０質量％以下がさらに好ましい。グラフト共重合体中の一般式（Ｉ）で表される構成単位の合計含有量が前記範囲内にあれば、グラフト共重合体中の粒子との親和性部位の割合が適切となり、かつ有機溶剤に対する溶解性の低下を抑制できるので、色材等の粒子に対する吸着性が良好となり、優れた分散性、及び分散安定性が得られる。また、前記グラフト共重合体の酸性リン化合物基が色材周辺に安定的に局在化することができるため、耐熱性やコントラストに優れたカラーフィルタが得られる。
　一方、前記グラフト共重合体の全構成単位に対して、前記一般式（ＩＩ）で表される構成単位は、２０質量％以上９７質量％以下の割合で含まれていることが好ましく、２５質量％以上９５質量％以下がより好ましく、４０質量％以上９０質量％以下がさらに好ましい。
　なお、前記構成単位の含有割合は、一般式（Ｉ）で表される構成単位から選択される少なくとも１種、及び一般式（ＩＩ）で表される構成単位を有するグラフト共重合体を合成する際の仕込み量から算出される。 It is preferable that the total amount of the structural units represented by the general formula (I) is 3% by mass or more and 80% by mass or less with respect to all the structural units of the graft copolymer. It is more preferably from 70% by mass to 70% by mass, further preferably from 20% by mass to 60% by mass. When the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity site with the particles in the graft copolymer becomes appropriate, and the organic solvent Since a decrease in solubility in water can be suppressed, the adsorptivity to particles such as coloring materials becomes good, and excellent dispersibility and dispersion stability can be obtained. Further, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the coloring material, a color filter having excellent heat resistance and contrast can be obtained.
On the other hand, the constitutional unit represented by the general formula (II) is preferably contained in a proportion of 20% by mass or more and 97% by mass or less with respect to all the constitutional units of the graft copolymer, and 25% by mass or less. % To 95% by mass, more preferably 40% to 90% by mass.
The content ratio of the structural unit is such that a graft copolymer having at least one type selected from the structural units represented by the general formula (I) and the structural unit represented by the general formula (II) is synthesized. It is calculated from the charged amount at the time.
　また、前記グラフト共重合体の質量平均分子量Ｍｗは、１０００以上５０００００以下の範囲内であることが好ましく、３０００以上４０００００以下の範囲内であることがより好ましく、５０００以上３０００００以下の範囲内であることがさらに好ましい。前記範囲であることにより、色材等の粒子を均一に分散させることができる。
　なお、本発明において質量平均分子量Ｍｗは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定された値である。測定は、東ソー製のＨＬＣ－８２２０ＧＰＣを用い、溶出溶剤を０．０１モル／リットルの臭化リチウムを添加したＮ－メチルピロリドンとし、校正曲線用ポリスチレンスタンダードをＭｗ：８×１０５（Ｆ－８０）、Ｍｗ：４×１０５（Ｆ－４０）、Ｍｗ：２×１０５（Ｆ－２０）、Ｍｗ：１×１０５（Ｆ－１０）、Ｍｗ：４×１０４（Ｆ－４）、Ｍｗ：２×１０４（Ｆ－２）、Ｍｗ：５×１０３（Ａ－５０００）、Ｍｗ：２．５×１０３（Ａ－２５００）、Ｍｗ：１×１０３（Ａ－１０００）、Ｍｗ：５×１０２（Ａ－５００）（以上、東ソー製）とし、測定カラムをＴＳＫ－ＧＥＬ　ＡＬＰＨＡ－Ｍ×２本（東ソー製）として行われたものである。 The mass average molecular weight Mw of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and more preferably in the range of 5,000 to 300,000. Is more preferable. When the content is within the above range, particles such as a coloring material can be uniformly dispersed.
In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement was performed using Tosoh's HLC-8220GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol / l of lithium bromide was added, and the polystyrene standard for the calibration curve was Mw: 8 × 10 5 (F-80 ), Mw: 4 × 10 5 (F-40), Mw: 2 × 10 5 (F-20), Mw: 1 × 10 5 (F-10), Mw: 4 × 10 4 (F-4), Mw: 2 × 10 4 (F-2), Mw: 5 × 10 3 (A-5000), Mw: 2.5 × 10 3 (A-2500), Mw: 1 × 10 3 (A-1000), Mw: 5 × 10 2 (A-500) (manufactured by Tosoh) and two measurement columns TSK-GEL ALPHA-M (manufactured by Tosoh).
　本発明の実施形態に用いられる前記グラフト共重合体は、前記一般式（Ｉ）で表される構成単位及び前記一般式（ＩＩ）で表される構成単位以外に、更に他の構成単位を有していても良い。前記一般式（Ｉ）で表される構成単位から選択される少なくとも一種を誘導するエチレン不飽和モノマー等と共重合可能な、エチレン不飽和モノマーを適宜選択して共重合し、他の構成単位を導入することができる。 The graft copolymer used in the embodiment of the present invention has other structural units in addition to the structural units represented by the general formula (I) and the general formula (II). May be. An ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer or the like which derives at least one selected from the structural units represented by the general formula (I) is appropriately selected and copolymerized, and the other structural units are Can be introduced.
（ブロック共重合体）
　一般式（Ｉ）で表される構成単位から選択される少なくとも一種を含むブロック部中、一般式（Ｉ）で表される構成単位は、合計で、３個以上含まれることが好ましい。中でも、分散性を良好なものとし、耐熱性を向上する点から、３個以上２００個以下含むことが好ましく、３個以上５０個以下含むことがより好ましく、更に３個以上３０個以下含むことがより好ましい。
　一般式（Ｉ）で表される構成単位から選択される少なくとも一種は、色材親和性部位として機能すれば良く、１種からなるものであっても良いし、２種以上の構成単位を含んでいてもよい。２種以上の構成単位を含む場合には、一般式（Ｉ）で表される構成単位から選択される少なくとも一種を含むブロック部内は２種以上の構成単位がランダムに配列していてもよい。 (Block copolymer)
In the block portion including at least one selected from the structural units represented by the general formula (I), it is preferable that a total of three or more structural units represented by the general formula (I) are included. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferable to include 3 to 200, more preferably 3 to 50, and still more preferably 3 to 30. Is more preferred.
At least one selected from the structural units represented by the general formula (I) may function as a coloring material affinity site, and may be composed of one type or may include two or more types of structural units. You may go out. When two or more types of structural units are included, two or more types of structural units may be randomly arranged in a block portion including at least one type selected from the structural units represented by the general formula (I).
　前記ブロック共重合体中、一般式（Ｉ）で表される構成単位の合計の含有割合は、前記ブロック共重合体の全構成単位に対して、５質量％以上８０質量％以下であることが好ましく、１０質量％以上７０質量％以下であることがより好ましく、２０質量％以上６０質量％以下であることがさらに好ましい。
　前記範囲内にあれば、ブロック共重合体中の粒子との親和性部位の割合が適切となり、かつ有機溶剤に対する溶解性の低下を抑制できるので、色材等の粒子に対する吸着性が良好となり、優れた分散性、及び分散安定性が得られる。また、前記ブロック共重合体の酸性リン化合物基が色材周辺に安定的に局在化することができるため、耐熱性やコントラストに優れたカラーフィルタが得られる。
　なお、前記構成単位の含有割合は、前記ブロック共重合体を合成する際の仕込み量から算出される。 In the block copolymer, the total content of the structural units represented by the general formula (I) may be 5% by mass or more and 80% by mass or less based on all the structural units of the block copolymer. It is more preferably from 10% by mass to 70% by mass, and still more preferably from 20% by mass to 60% by mass.
If it is within the above range, the ratio of the affinity site with the particles in the block copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed, so that the adsorptivity to the particles such as the coloring material becomes good, Excellent dispersibility and dispersion stability are obtained. Further, since the acidic phosphorus compound group of the block copolymer can be stably localized around the coloring material, a color filter excellent in heat resistance and contrast can be obtained.
In addition, the content ratio of the structural unit is calculated from the charged amount at the time of synthesizing the block copolymer.
　前記ブロック共重合体は、前記一般式（ＩＩＩ）で表される構成単位を含むブロック部を有することにより、溶剤親和性を良好にし、色材の分散性及び分散安定性が良好で、且つ耐熱性も良好で、更に耐ＮＭＰ性に優れたものとなる。 Since the block copolymer has a block portion containing the structural unit represented by the general formula (III), the affinity for the solvent is improved, the dispersibility and the dispersion stability of the coloring material are improved, and the heat resistance is improved. The properties are good and the NMP resistance is excellent.
　一般式（ＩＩＩ）において、Ｒ２３は、炭化水素基、－［ＣＨ（Ｒ２４）－ＣＨ（Ｒ２５）－Ｏ］ｘ２－Ｒ２６、－［（ＣＨ２）ｙ２－Ｏ］ｚ２－Ｒ２６、－［ＣＯ－（ＣＨ２）ｙ２－Ｏ］ｚ２－Ｒ２６、－ＣＯ－Ｏ－Ｒ２６’又は－Ｏ－ＣＯ－Ｒ２６”で示される１価の基である。
　Ｒ２３における炭化水素基としては、前記Ｒ２で示したものと同様のものとすることができる。 In the general formula (III), R 23 is a hydrocarbon group,-[CH (R 24 ) -CH (R 25 ) -O] x2 -R 26 ,-[(CH 2 ) y2 -O] z2 -R 26 , — [CO— (CH 2 ) y2 —O] z2 —R 26 , —CO— OR 26 ′ or —O—CO—R 26 ″ .
As the hydrocarbon group for R 23, it may be similar to that shown in the R 2.
　また、前記Ｒ２６は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ又は－ＣＨ２ＣＯＯＲ２７で示される１価の基であり、Ｒ１２’は、炭化水素基、－［ＣＨ（Ｒ２４）－ＣＨ（Ｒ２５）－Ｏ］ｘ２’－Ｒ２６、－［（ＣＨ２）ｙ２’－Ｏ］ｚ２’－Ｒ２６、－［ＣＯ－（ＣＨ２）ｙ２’－Ｏ］ｚ２’－Ｒ２６で示される１価の基であり、Ｒ２６”は炭素数が１個以上１８個以下のアルキル基、Ｒ２７は水素原子又は炭素数が１個以上５個以下のアルキル基であり、前記炭化水素基は、置換基を有していてもよい。
　前記Ｒ２６における炭化水素基は、前記Ｒ２で示したものと同様のものとすることができる。
　前記Ｒ２３及びＲ２６’において、ｘ２及びｘ２’は前記ｘと、ｙ２及びｙ２’は前記ｙと、ｚ２及びｚ２’は前記ｚと同様である。
　また、前記一般式（ＩＩＩ）で表される構成単位中のＲ２３は、互いに同一であってもよいし、異なるものであってもよい。 R 26 is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH 2 CHO or —CH 2 COOR 27 , and R 12 ′ is a hydrocarbon group, — [CH ( R 24 ) -CH (R 25 ) -O] x2 ' -R 26 ,-[(CH 2 ) y2' -O] z2 ' -R 26 ,-[CO- (CH 2 ) y2' -O] z2 ' A monovalent group represented by —R 26 , R 26 ″ is an alkyl group having 1 to 18 carbon atoms, and R 27 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. And the hydrocarbon group may have a substituent.
The hydrocarbon group for R 26 can be the same as that for R 2 .
'In, x2 and x2' the R 23 and R 26 and the x, y2 and y2 'are said y, z2 and z2' are the same as defined above z.
Further, R 23 in the structural unit represented by the general formula (III) may be the same as or different from each other.
　前記Ｒ２３及びＲ２６’としては、中でも、後述する溶剤との溶解性に優れたものを用いることが好ましく、例えば、前記Ｒ３２及びＲ３６と同様のものが挙げられる。
　また、前記Ｒ２３、Ｒ２６、Ｒ２６’、Ｒ２６’’及びＲ２７は、前記ブロック共重合体の分散性能等を妨げない範囲で、アルコキシ基、水酸基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基、水素結合形成基等の置換基によって置換されたものとしてもよく、また、前記ブロック共重合体の合成後に、前記置換基を有する化合物と反応させて、前記置換基を付加させてもよい。また、これらの置換基を有するブロック共重合体を合成した後に、当該置換基と反応する官能基と重合性基とを有する化合物を反応させて、重合性基を付加したものとしてもよい。例えば、グリシジル基を有するブロック共重合体に（メタ）アクリル酸を反応させたり、イソシアネート基を有するブロック共重合体にヒドロキシエチル（メタ）アクリレートを反応させたりして、重合性基を付加することができる。 Examples of R 23 and R 26 ', among others, it is preferable to use those having excellent solubility in a solvent to be described later, for example, it includes the same as the above-mentioned R 32 and R 36.
R 23 , R 26 , R 26 ′ , R 26 ″ and R 27 are each an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group as long as the dispersibility of the block copolymer is not hindered. May be substituted with a substituent such as an isocyanate group or a hydrogen bond-forming group, or after the synthesis of the block copolymer, by reacting with the compound having the substituent to add the substituent. Is also good. Alternatively, after a block copolymer having these substituents is synthesized, a compound having a polymerizable group and a functional group that reacts with the substituent may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting (meth) acrylic acid with a block copolymer having a glycidyl group or reacting hydroxyethyl (meth) acrylate with a block copolymer having an isocyanate group. Can be.
　一般式（ＩＩＩ）で表される構成単位を含むブロック部を構成する構成単位の数は特に限定されないが、溶剤親和性部位と色材親和性部位が効果的に作用し、色材分散液の分散性を向上する点から、１０以上２００以下であることが好ましく、２０以上１００以下であることがより好ましく、更に３０以上８０以下であることがより好ましい。 The number of structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, but the solvent-affinity site and the colorant-affinity site work effectively, and the colorant dispersion liquid From the viewpoint of improving dispersibility, it is preferably from 10 to 200, more preferably from 20 to 100, and even more preferably from 30 to 80.
　前記ブロック共重合体中、一般式（ＩＩＩ）で表される構成単位の含有割合は、前記ブロック共重合体の全構成単位に対して、３０質量％以上９５質量％以下であることが好ましく、４０質量％以上９０質量％以下であることがより好ましい。
　なお、前記構成単位の含有割合は、前記ブロック共重合体を合成する際の仕込み量から算出される。 In the block copolymer, the content of the structural unit represented by the general formula (III) is preferably 30% by mass or more and 95% by mass or less based on all the structural units of the block copolymer. More preferably, the content is 40% by mass or more and 90% by mass or less.
In addition, the content ratio of the structural unit is calculated from the charged amount at the time of synthesizing the block copolymer.
　一般式（ＩＩＩ）で表される構成単位を含むブロック部は、溶剤親和性部位として機能するように選択されれば良く、一般式（ＩＩＩ）で表される構成単位は１種からなるものであっても良いし、２種以上の構成単位を含んでいてもよい。本発明の実施形態においては、一般式（ＩＩＩ）で表される構成単位が２種以上の構成単位を含む場合に、前記一般式（ＩＩＩ）で表される構成単位を含むブロック部内は２種以上の構成単位がランダムに配列していてもよい。 The block part containing the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity site, and the structural unit represented by the general formula (III) is composed of one kind. Or two or more types of constituent units. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more types of structural units, the block unit including the structural unit represented by the general formula (III) has two types. The above constituent units may be randomly arranged.
　分散剤として用いられるブロック共重合体において、一般式（Ｉ）で表される構成単位及び一般式（Ｉ’）で表される構成単位から選択される少なくとも一種を含むブロック部の構成単位のユニット数ｍと、一般式（ＩＩＩ）で表される構成単位を含むブロック部の構成単位のユニット数ｎの比率ｍ／ｎとしては、０．０１以上１以下の範囲内であることが好ましく、０．１以上０．７以下の範囲内であることが、色材の分散性、分散安定性の点からより好ましい。 In the block copolymer used as a dispersant, a unit of a structural unit of a block portion including at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I ′) The ratio m / n of the number m and the number n of the structural units of the block unit including the structural unit represented by the general formula (III) is preferably in the range of 0.01 or more and 1 or less, and 0 It is more preferably in the range of from 1 to 0.7 in view of the dispersibility and dispersion stability of the coloring material.
　前記ブロック共重合体の結合順としては、前記一般式（Ｉ）で表される構成単位から選択される少なくとも一種を含むブロック部及び一般式（ＩＩＩ）で表される構成単位を含むブロック部を有し、色材を安定に分散することができるものであればよく、特に限定されないが、前記一般式（Ｉ）で表される構成単位から選択される少なくとも一種を含むブロック部が前記ブロック共重合体の一端のみに結合したものであることが、色材との相互作用に優れ、分散剤同士の凝集を効果的に抑えることができる点から好ましい。 As the bonding order of the block copolymer, a block part containing at least one selected from the structural units represented by the general formula (I) and a block part containing a structural unit represented by the general formula (III) It is not particularly limited as long as it can disperse the coloring material stably, and the block portion including at least one selected from the structural units represented by the general formula (I) is preferably used as the block unit. It is preferable that the polymer is bonded to only one end of the polymer because it has excellent interaction with the coloring material and can effectively suppress aggregation of the dispersants.
　前記ブロック共重合体の質量平均分子量は、特に限定されないが、分散性を良好なものとし、耐熱性に優れる点から、２５００以上５０００００以下であることが好ましく、３０００以上４０００００以下であることがより好ましく、更に６０００以上３０００００以下であることがより好ましい。 The mass average molecular weight of the block copolymer is not particularly limited, but it is preferable that the weight average molecular weight is 2500 or more and 500,000 or less, and 3,000 or more and 400,000 or less, from the viewpoint of excellent dispersibility and excellent heat resistance. More preferably, it is more preferably 6,000 or more and 300,000 or less.
　前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体の酸価は、前記色材の分散性及び保存安定性の点から、２０ｍｇＫＯＨ／ｇ以上であることが好ましく、３０ｍｇＫＯＨ／ｇ以上であることがより好ましく、４０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。一方で、現像性に優れる点から、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体の酸価は１５０ｍｇＫＯＨ／ｇ以下であることが好ましく、１２０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１００ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。
　なお、本発明において酸価は、試料１ｇ中に含まれる酸成分を中和するのに要する水酸化カリウムのｍｇ数をいい、ＪＩＳ　Ｋ　００７０：１９９２に従って測定することができる。 The acid value of the polymer having at least one selected from the structural units represented by the general formula (I) is preferably 20 mgKOH / g or more from the viewpoint of the dispersibility and storage stability of the coloring material. It is more preferably at least 30 mgKOH / g, and even more preferably at least 40 mgKOH / g. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having at least one selected from the structural units represented by the general formula (I) is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g. Or less, more preferably 100 mgKOH / g or less.
In the present invention, the acid value refers to the number of mg of potassium hydroxide required for neutralizing the acid component contained in 1 g of a sample, and can be measured according to JIS K 0070: 1992.
＜その他の酸性分散剤＞
　本発明の色材分散液において、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体とは異なる、その他の酸性分散剤が、更に含まれていても良い。
　その他の酸性分散剤としては、酸性基を有する分散剤が挙げられる。ここで酸性基としては、例えば、カルボキシ基、スルホン酸基、若しくはリン酸基等が挙げられるが、その他の酸性分散剤の分散剤に含まれる酸性基としては、中でもカルボキシ基であることが、分散性に優れる点から好ましい。 <Other acidic dispersants>
The colorant dispersion of the present invention may further contain another acidic dispersant different from the polymer having at least one selected from the structural units represented by the general formula (I). .
Other acidic dispersants include dispersants having an acidic group. Here, examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. It is preferable from the viewpoint of excellent dispersibility.
　その他の酸性分散剤の酸価は、分散性に優れる点から、４０ｍｇＫＯＨ／ｇ以上であることが好ましく、５０ｍｇＫＯＨ／ｇ以上であることがより好ましく、７０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。一方で、現像残渣抑制の点から、その他の酸性分散剤の酸価は２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１９０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１８０ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。 (4) The acid value of the other acidic dispersant is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of excellent dispersibility. On the other hand, the acid value of the other acidic dispersant is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less, and further preferably 180 mgKOH / g or less from the viewpoint of suppressing the development residue. .
　本発明において、その他の酸性分散剤としては、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体と組み合わせて用いることにより、現像残渣の抑制性が向上する点から、カルボキシ基を有する高分子分散剤であることが好ましく、中でも、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体と組み合わせて用いることにより、現像残渣の抑制性が向上し、且つ、塗膜の均一性がより良好になる点から、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含むことが好ましい。 In the present invention, the use of another acidic dispersant in combination with a polymer having at least one selected from the structural units represented by formula (I) improves the suppression of development residues. From the viewpoint, a polymer dispersant having a carboxy group is preferable, and among them, when used in combination with a polymer having at least one selected from the structural units represented by the general formula (I), From the point that the suppression of the residue is improved and the uniformity of the coating film is improved, the structure derived from the A block including the structural unit derived from the carboxy group-containing ethylenically unsaturated monomer and the structure derived from the alkyl (meth) acrylate ester It is preferable to further include a block copolymer containing a B block containing a unit.
（カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体）
　以下、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、単に、「カルボキシ基含有ブロック共重合体」という場合がある。
｛Ａブロック｝
　Ａブロックは、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むポリマーブロックである。
　Ａブロックに用いられるカルボキシ基含有エチレン不飽和モノマーとしては、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、（メタ）アクリル酸２－ヒドロキシエチルや（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキルに無水マレイン酸、無水コハク酸、無水フタル酸等の酸無水物を反応させたモノマー、ビニル安息香酸等のカルボキシ基を有するビニルモノマー等が挙げられる。
　なお、エチレン性不飽和モノマー由来の構成単位とは、エチレン性不飽和モノマーのラジカル重合可能な炭素－炭素二重結合が炭素－炭素単結合になった構成単位をいう。 (Block copolymer containing A block containing a constitutional unit derived from a carboxy group-containing ethylenically unsaturated monomer and B block containing a constitutional unit derived from an alkyl (meth) acrylate)
Hereinafter, a block copolymer including an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth) acrylate ester is simply referred to as a “carboxy group-containing block”. Copolymer ".
｛A block｝
The A block is a polymer block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer.
Examples of the carboxy group-containing ethylenically unsaturated monomer used in the A block include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate and 4- (meth) acrylic acid. Examples thereof include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride with hydroxyalkyl (meth) acrylate such as hydroxybutyl, and vinyl monomers having a carboxy group such as vinylbenzoic acid.
The constitutional unit derived from the ethylenically unsaturated monomer refers to a constitutional unit in which a radically polymerizable carbon-carbon double bond of the ethylenically unsaturated monomer has become a carbon-carbon single bond.
　Ａブロックにおいて２種以上の構成単位が含まれる場合は、各構成単位はＡブロック内において、ランダム共重合、ブロック共重合等の何れの態様で含まれていてもよく、均一性の観点からランダム共重合の態様で含有されていることが好ましい。 When two or more types of structural units are included in the A block, each structural unit may be included in the A block in any mode such as random copolymerization or block copolymerization. It is preferably contained in the form of a copolymer.
　Ａブロックは、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位が、Ａブロックの全構成単位に対して４０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位のみから構成されているポリマーブロックであることがより更に好ましい。 In the A block, the constituent unit derived from the carboxy group-containing ethylenically unsaturated monomer is preferably 40% by mass or more, more preferably 70% by mass or more, based on all the constituent units of the A block. It is even more preferable that the polymer block is composed of only a structural unit derived from the contained ethylenically unsaturated monomer.
　Ａブロックは、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位のみから構成されていてもよいし、ＢブロックよりもＡブロックの酸性度が強くなる範囲において、カルボキシ基含有エチレン性不飽和モノマーとは異なるエチレン性不飽和モノマーに由来する構成単位が含まれていてもよい。Ａブロックにカルボキシ基含有エチレン性不飽和モノマーとは異なるエチレン性不飽和モノマーに由来する構成単位を含む場合は、Ａブロックの全構成単位に対して、６０質量％以下にすることが好ましく、３０質量％以下にすることがより好ましい。前記カルボキシ基含有エチレン性不飽和モノマーとは異なるエチレン性不飽和モノマーとしては、後述するＢブロックに用いられる構成単位が挙げられる。 The A block may be composed of only a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer, or a carboxy group-containing ethylenically unsaturated monomer as long as the acidity of the A block is stronger than that of the B block. May contain structural units derived from different ethylenically unsaturated monomers. When the A block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer, the content is preferably 60% by mass or less based on all the structural units of the A block. It is more preferable that the content be not more than mass%. Examples of the ethylenically unsaturated monomer different from the carboxy group-containing ethylenically unsaturated monomer include structural units used for a B block described later.
　Ａブロックの含有量は、分散性及び分散安定性の点から、ブロック共重合体の全構成単位に対して５質量％以上であることが好ましく、１０質量％以上であることが好ましく、一方で、９５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。 From the viewpoint of dispersibility and dispersion stability, the content of the A block is preferably 5% by mass or more, and more preferably 10% by mass or more, based on all the structural units of the block copolymer. , 95% by mass or less, more preferably 40% by mass or less.
｛Ｂブロック｝
　Ｂブロックは、（メタ）アクリル酸アルキルエステル由来の構成単位を含むポリマーブロックである。
　Ｂブロックに用いられる（メタ）アクリル酸アルキルエステルモノマーとしては、前記一般式（ＩＶ）で表される構成単位に含まれるポリマー鎖に用いられる（メタ）アクリル酸アルキルエステルモノマーと同様であって良く、１種又は２種以上混合して使用される。
　Ｂブロックには、（メタ）アクリル酸アルキルエステル由来の構成単位の他に、他のエチレン性不飽和モノマー由来の構成単位を含んでいても良い。他のエチレン性不飽和モノマー由来の構成単位としては、前記一般式（ＩＩＩ）で表される構成単位のうち、（メタ）アクリル酸アルキルエステル由来の構成単位とは異なる構成単位が挙げられる。 ｛B block｝
The B block is a polymer block containing a structural unit derived from an alkyl (meth) acrylate.
The (meth) acrylic acid alkyl ester monomer used for the B block may be the same as the (meth) acrylic acid alkyl ester monomer used for the polymer chain contained in the structural unit represented by the general formula (IV). , Or a mixture of two or more.
The B block may contain a structural unit derived from another ethylenically unsaturated monomer in addition to the structural unit derived from the alkyl (meth) acrylate. Examples of the structural unit derived from the other ethylenically unsaturated monomer include structural units different from the structural unit derived from the alkyl (meth) acrylate among the structural units represented by the general formula (III).
　Ｂブロックにおいて２種以上の構成単位が含まれる場合は、各構成単位はＢブロック内において、ランダム共重合、ブロック共重合等の何れの態様で含まれていてもよく、均一性の観点からランダム共重合の態様で含有されていることが好ましい。例えば、Ｂブロックが、ｂ１ブロックからなる構成単位とｂ２ブロックからなる構成単位との共重合体により形成されていてもよい。 When two or more types of structural units are included in the B block, each structural unit may be included in the B block in any mode such as random copolymerization or block copolymerization. It is preferably contained in the form of a copolymer. For example, the B block may be formed of a copolymer of a structural unit composed of the b1 block and a structural unit composed of the b2 block.
　Ｂブロックは、酸性基を有するエチレン性不飽和モノマー由来の構成単位が、Ｂブロックの全構成単位に対して１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、２質量％以下であることがさらに好ましい。本発明において、Ｂブロックは、酸性基を有するエチレン性不飽和モノマー由来の構成単位を含まないポリマーブロックであることがより更に好ましい。 In the B block, the structural unit derived from the ethylenically unsaturated monomer having an acidic group is preferably 10% by mass or less, more preferably 5% by mass or less, based on all the structural units of the B block. It is more preferred that the content be not more than mass%. In the present invention, it is even more preferable that the B block is a polymer block containing no structural unit derived from an ethylenically unsaturated monomer having an acidic group.
　前記カルボキシ基含有ブロック共重合体は、ＡＢブロック共重合体であっても良いし、ＢＡＢブロック共重合体であっても良い。ブロック共重合体がＢＡＢブロック共重合体である場合の２つのＢブロックの互いの含有比率は、分散性の点から、質量比で（５０：５０）～（７０：３０）の範囲内で調整することが好ましい。 The carboxy group-containing block copolymer may be an AB block copolymer or a BAB block copolymer. When the block copolymer is a BAB block copolymer, the content ratio of each of the two B blocks is adjusted within a range of (50:50) to (70:30) in terms of mass from the viewpoint of dispersibility. Is preferred.
　前記カルボキシ基含有ブロック共重合体の酸価は、分散性の点から、３０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下の範囲内であることが好ましく、ブロック共重合体の酸価がこの範囲になるように、Ａブロックにカルボキシ基含有エチレン性不飽和モノマー由来の構成単位が含まれることが好ましい。酸価は５０ｍｇＫＯＨ／ｇ以上であることが好ましく、７０ｍｇＫＯＨ／ｇ以上であることがより好ましい。酸価は２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。 The acid value of the carboxy group-containing block copolymer is preferably in the range of 30 mgKOH / g to 250 mgKOH / g from the viewpoint of dispersibility, so that the acid value of the block copolymer falls within this range. And A block preferably contain a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer. The acid value is preferably at least 50 mgKOH / g, more preferably at least 70 mgKOH / g. The acid value is preferably at most 200 mgKOH / g, more preferably at most 150 mgKOH / g.
　前記カルボキシ基含有ブロック共重合体の質量平均分子量（Ｍｗ）は、分散性の点から、５，０００以上１００，０００以下であることが好ましい。Ｍｗは８，０００以上であることがより好ましく、１０，０００以上であることがさらに好ましい。Ｍｗは８０，０００以下であることがより好ましく、７０，０００以下であることがさらに好ましい。 質量 The weight average molecular weight (Mw) of the carboxy group-containing block copolymer is preferably 5,000 or more and 100,000 or less from the viewpoint of dispersibility. Mw is more preferably 8,000 or more, and even more preferably 10,000 or more. Mw is more preferably 80,000 or less, and even more preferably 70,000 or less.
　前記カルボキシ基含有ブロック共重合体の分子量分布は、２未満であることが好ましく、１．５未満であることがより好ましく、１．３未満であることがさらに好ましい。なお、本発明において、分子量分布とは（質量平均分子量（Ｍｗ））／（数平均分子量（Ｍｎ））によって求められるものである。分子量分布が大きいほど、設計したポリマーの分子量に比べて、分子量の小さいものや、分子量の大きいものが含まれることになり、色材の分散性を悪くする傾向があることから、分子量分布が小さい方が好ましい。 分子 The molecular weight distribution of the carboxy group-containing block copolymer is preferably less than 2, more preferably less than 1.5, even more preferably less than 1.3. In the present invention, the molecular weight distribution is determined by (weight average molecular weight (Mw)) / (number average molecular weight (Mn)). The larger the molecular weight distribution, the smaller the molecular weight or the higher the molecular weight compared to the molecular weight of the designed polymer, and the lower the molecular weight distribution because the tendency to deteriorate the dispersibility of the coloring material is included. Is more preferred.
　前記カルボキシ基含有ブロック共重合体の製造方法としては、従来公知のブロック共重合体の製造方法を適宜選択して用いることができる。均一な組成のポリマーが製造しやすい点から、リビング重合法を用いることが好ましく、リビング重合法としては、有機酸触媒とシリル系開始剤を用いる方法（ＧＴＰ法）、遷移金属触媒を用いる方法（ＡＴＲＰ法）、硫黄系の可逆的連鎖移動剤を用いる方法（ＲＡＦＴ法）、有機テルル化合物を用いる方法（ＴＥＲＰ法）等の方法が挙げられる。 As the method for producing the carboxy group-containing block copolymer, a conventionally known method for producing a block copolymer can be appropriately selected and used. From the viewpoint of easily producing a polymer having a uniform composition, it is preferable to use a living polymerization method. As the living polymerization method, a method using an organic acid catalyst and a silyl-based initiator (GTP method), a method using a transition metal catalyst ( (ATRP method), a method using a sulfur-based reversible chain transfer agent (RAFT method), and a method using an organic tellurium compound (TERP method).
　＜酸性分散剤の含有割合＞
　酸性分散剤として、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体と、当該重合体は異なるその他の酸性分散剤とを組み合わせて用いる場合、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体と、当該重合体とは異なるその他の酸性分散剤との含有割合は、適宜選択して用いることができる。中でも、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体と、当該重合体とは異なるその他の酸性分散剤との質量比は、色材中に含まれる前記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料との質量比と同様になるように用いることが、分散性と現像残渣抑制の点から好ましい。
　すなわち、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材の含有量が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下である場合、酸性分散剤における前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体の含有量は、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体及び当該重合体とは異なるその他の酸性分散剤の合計含有量に対して２０質量％以上８５質量％以下であることが分散性と現像残渣抑制の点から好ましい。 <Content of acidic dispersant>
As the acidic dispersant, when a polymer having at least one selected from the structural units represented by the general formula (I) is used in combination with another acidic dispersant different from the above-described general formula (I), The content ratio of the polymer having at least one selected from the structural units represented by (I) and another acidic dispersant different from the polymer can be appropriately selected and used. Above all, the mass ratio of the polymer having at least one selected from the structural units represented by the general formula (I) to another acidic dispersant different from the polymer is included in the coloring material. A phthalocyanine pigment which has been subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the general formula (1) and a color material represented by the following general formula (2): It is preferable to use it in the same manner as the mass ratio in terms of dispersibility and suppression of development residue.
That is, the content of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is determined by the general formula ( 20% by mass or more based on the total content of at least one lake colorant selected from the group consisting of the colorant represented by 1) and the colorant represented by the general formula (2) and the phthalocyanine pigment. When the content is 85% by mass or less, the content of the polymer having at least one selected from the structural units represented by the general formula (I) in the acidic dispersant is represented by the general formula (I). The total content of the polymer having at least one selected from the structural units and another acidic dispersant different from the polymer is preferably 20% by mass or more and 85% by mass or less, and the dispersibility and the development residue suppression. It is preferable from the point of view.
　色材分散液において酸性分散剤の含有割合は適宜調整すればよいが、分散性及び保存安定性の点から、色材１００質量部に対して、５質量部以上８０質量部以下とすることが好ましく、２０質量部以上７０質量部以下とすることがより好ましい。
　また、色材分散液において酸性分散剤の含有量は、分散性及び分散安定性の点から、色材分散液中の固形分全量に対して、３質量％以上４５質量％以下、より好ましくは５質量％以上３５質量％以下の割合で配合することがより好ましい。 The content of the acidic dispersant in the colorant dispersion may be appropriately adjusted, but from the viewpoint of dispersibility and storage stability, the content is preferably 5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the colorant. More preferably, it is more than 20 parts by mass and not more than 70 parts by mass.
The content of the acidic dispersant in the colorant dispersion is preferably 3% by mass or more and 45% by mass or less, more preferably 3% by mass or less, based on the total solid content in the colorant dispersion, from the viewpoint of dispersibility and dispersion stability. It is more preferable to mix at a ratio of 5% by mass or more and 35% by mass or less.
［溶剤］
　本発明に用いられる溶剤としては、色材分散液中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは２種以上組み合わせて使用することができる。
　溶剤の具体例としては、例えば、メチルアルコール、エチルアルコール、Ｎ－プロピルアルコール、ｉ－プロピルアルコール、メトキシアルコール、エトキシアルコールなどのアルコール系溶剤；メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤；酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、乳酸エチル、ヒドロキシプロピオン酸メチル、ヒドロキシプロピオン酸エチル、ｎ－ブチルアセテート、イソブチルアセテート、酪酸イソブチル、酪酸ｎ－ブチル、乳酸エチル、シクロヘキサノールアセテートなどのエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、２－ヘプタノンなどのケトン系溶剤；メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－３－メチル－１－ブチルアセテート、３－メトキシブチルアセテート、エトキシエチルアセテートなどのグリコールエーテルアセテート系溶剤；メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、ブチルカルビトールアセテート（ＢＣＡ）、カルビトールアセテートなどのカルビトールアセテート系溶剤；プロピレングリコールジアセテート、１，３－ブチレングリコールジアセテート等のジアセテート類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテルなどのグリコールエーテル系溶剤；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドンなどの非プロトン性アミド溶剤；γ－ブチロラクトンなどのラクトン系溶剤；テトラヒドロフランなどの環状エーテル系溶剤；ベンゼン、トルエン、キシレン、ナフタレンなどの不飽和炭化水素系溶剤；Ｎ－ヘプタン、Ｎ－ヘキサン、Ｎ－オクタンなどの飽和炭化水素系溶剤；トルエン、キシレン等の芳香族炭化水素類などの有機溶剤が挙げられる。これらの溶剤の中ではグリコールエーテルアセテート系溶剤、カルビトールアセテート系溶剤、グリコールエーテル系溶剤、エステル系溶剤が他の成分の溶解性の点で好適に用いられる。中でも、本発明に用いる溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ブチルカルビトールアセテート（ＢＣＡ）、カルビトールアセテート、３－メトキシ－３－メチル－１－ブチルアセテート、エトキシプロピオン酸エチル、乳酸エチル、及び、３－メトキシブチルアセテートよりなる群から選択される１種以上であることが、他の成分の溶解性や塗布適性の点から好ましい。 [solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the colorant dispersion and can dissolve or disperse these components. The solvents can be used alone or in combination of two or more.
Specific examples of the solvent include, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxy ethanol and ethoxyethoxy ethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Glycol acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate, butyl carbitol acetate (BCA) and carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether and ethylene glycol mono Ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Glycol ether solvents such as tyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; γ- Lactone solvents such as butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; Organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in view of solubility of other components. Among them, solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, and ethyl ethoxypropionate. , Ethyl lactate, and 3-methoxybutyl acetate are preferred in view of solubility of other components and suitability for application.
　本発明の色材分散液は、以上のような溶剤を、当該溶剤を含む色材分散液全量に対して、通常、５５質量％以上９５質量％以下の範囲内であることが好ましく、中でも６５質量％以上９０質量％以下の範囲内であることが好ましく、７０質量％以上８８質量％以下の範囲内であることがより好ましい。溶剤が少なすぎると、粘度が上昇し、分散性が低下しやすい。また、溶剤が多すぎると、色材濃度が低下し、目標とする色度座標に達成することが困難な場合がある。 The colorant dispersion of the present invention preferably contains the above solvent in a range of usually 55% by mass or more and 95% by mass or less based on the total amount of the colorant dispersion containing the solvent. It is preferably in the range of from 70% by mass to 90% by mass, and more preferably in the range of from 70% by mass to 88% by mass. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. On the other hand, if the amount of the solvent is too large, the concentration of the coloring material may decrease, and it may be difficult to achieve the target chromaticity coordinates.
［その他の成分］
　本発明の色材分散液には、本発明の効果が損なわれない限り、更に必要に応じて、分散補助樹脂、その他の成分を配合してもよい。
　分散補助樹脂としては、例えば後述する着色樹脂組成物で例示されるアルカリ可溶性樹脂が挙げられる。アルカリ可溶性樹脂の立体障害によって色材粒子同士が接触しにくくなり、分散安定化することやその分散安定化効果によって分散剤を減らす効果がある場合がある。
　また、その他の成分としては、例えば、濡れ性向上のための界面活性剤、密着性向上のためのシランカップリング剤、消泡剤、ハジキ防止剤、酸化防止剤、凝集防止剤、紫外線吸収剤などが挙げられる。 [Other ingredients]
The colorant dispersion of the present invention may further contain a dispersion assisting resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion assisting resin include an alkali-soluble resin exemplified by a colored resin composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, stabilizing the dispersion, and reducing the amount of the dispersant due to the effect of stabilizing the dispersion in some cases.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cissing agent, an antioxidant, an anti-agglomerating agent, and an ultraviolet absorber. And the like.
　本発明の色材分散液は、後述する着色樹脂組成物を調製するための予備調製物として用いられる。すなわち、色材分散液とは、後述の着色樹脂組成物を調製する前段階において予備調製される、Ｐ／Ｖ（組成物中の色材成分質量）／（組成物中の色材成分以外の固形分質量）比の高い色材分散液である。具体的には、（組成物中の色材成分質量）／（組成物中の色材成分以外の固形分質量）比は通常１．０以上である。色材分散液と、後述する各成分とを混合することにより、分散性に優れた用着色樹脂組成物を調製することができる。 色 The colorant dispersion of the present invention is used as a preliminary preparation for preparing a colored resin composition described below. That is, the colorant dispersion liquid is P / V (mass of the colorant component in the composition) / (mass of the colorant component in the composition) which is preliminarily prepared in the stage before preparing the colorant resin composition described below. It is a colorant dispersion having a high (solid content mass) ratio. Specifically, the ratio of (mass of coloring material component in composition) / (mass of solid content other than coloring material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and each of the components described below, a colored resin composition having excellent dispersibility can be prepared.
［色材分散液の製造方法］
　本発明において、色材分散液の製造方法は、前記色材が、前記分散剤により、溶剤中に分散された色材分散液が得られる方法であれば特に限定されない。
　例えば、本発明に係る色材分散液の製造方法は、前記色材を準備する工程と、前記分散剤を準備する工程と、溶剤中、前記分散剤の存在下で、前記色材を分散する工程とを有するものが挙げられる。溶剤中、前記分散剤の存在下で、２種以上の色材を共分散しても良いし、１種以上の色材を分散乃至共分散した後、２種以上の色材分散液を混合することにより本発明の色材分散液を得ても良い。
　中でも、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材を、溶剤中、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体の存在下で分散させた色材分散液ａを調製し、一方で、前記塩基性処理されたフタロシアニン顔料を、溶剤中、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体の存在下で分散させた色材分散液ｂを調製し、前記色材分散液ａと前記色材分散液ｂとを混合することにより、本発明の色材分散液を製造することが、色材の分散性、保存安定性、基板密着性及び塗膜の均一性が良好になり易い点から好ましい。 [Method for producing colorant dispersion]
In the present invention, the method for producing a colorant dispersion is not particularly limited as long as the colorant can be obtained by dispersing the colorant in a solvent with the dispersant.
For example, the method for producing a colorant dispersion according to the present invention includes a step of preparing the colorant, a step of preparing the dispersant, and dispersing the colorant in a solvent in the presence of the dispersant. And a process. In a solvent, in the presence of the dispersant, two or more color materials may be co-dispersed, or one or more color materials may be dispersed or co-dispersed, and then two or more color material dispersions may be mixed. Then, the colorant dispersion of the present invention may be obtained.
Above all, at least one kind of lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2) is mixed in a solvent with the general formula ( A colorant dispersion a dispersed in the presence of a polymer having at least one selected from the structural units represented by I) is prepared. A color material dispersed in the presence of a block copolymer including a block A containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a block B containing a structural unit derived from an alkyl (meth) acrylate. By preparing the liquid b and mixing the color material dispersion a and the color material dispersion b, the color material dispersion of the present invention can be produced. Good adhesion and uniformity of coating film Ri from the viewpoint easy.
　上記製造方法において色材は、従来公知の分散機を用いて分散することができる。
　分散機の具体例としては、２本ロール、３本ロール等のロールミル、ボールミル、振動ボールミル等のボールミル、ペイントコンディショナー、連続ディスク型ビーズミル、連続アニュラー型ビーズミル等のビーズミルが挙げられる。ビーズミルの好ましい分散条件として、使用するビーズ径は０．０３ｍｍ以上３．０ｍｍ以下が好ましく、より好ましくは０．０５以上２．０ｍｍ以下である。 In the above production method, the coloring material can be dispersed using a conventionally known dispersing machine.
Specific examples of the dispersing machine include a roll mill such as a two-roller and a three-roller, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a bead mill such as a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably from 0.03 mm to 3.0 mm, more preferably from 0.05 to 2.0 mm.
ＩＩ．着色樹脂組成物
　本発明に係る着色樹脂組成物は、色材と、酸性分散剤と、バインダー成分と、溶剤とを含有する着色樹脂組成物であって、
　前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
　前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、着色樹脂組成物であることを特徴とする。 II. Colored resin composition The colored resin composition according to the present invention is a colored resin composition containing a coloring material, an acidic dispersant, a binder component, and a solvent,
The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2). Phthalocyanine pigments,
The acidic dispersant is a colored resin composition containing a polymer having at least one selected from the structural units represented by the general formula (I).
　本発明の着色樹脂組成物は、前述の色材分散液における説明と同様の作用によって、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能であるという効果を有する。 The colored resin composition of the present invention has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range by the same action as described in the above-described color material dispersion, In addition, there is an effect that a colored layer having improved substrate adhesion and coating film uniformity can be formed.
　本発明の着色樹脂組成物は、色材と、分散剤と、バインダー成分と、溶剤とを少なくとも含有するものであり、本発明の効果を損なわない範囲で、更に他の成分を含有してもよいものである。以下、本発明の着色樹脂組成物に含まれる各成分について説明するが、色材、分散剤、及び溶剤については、上記本発明の色材分散液において説明したものと同様であるので、ここでの説明は省略する。
　以下、このような本発明の着色樹脂組成物の各成分について、順に詳細に説明する。 The colored resin composition of the present invention contains at least a coloring material, a dispersant, a binder component, and a solvent, and may further contain other components as long as the effects of the present invention are not impaired. Good thing. Hereinafter, each component contained in the colored resin composition of the present invention will be described, but the colorant, dispersant, and solvent are the same as those described in the colorant dispersion of the present invention. Is omitted.
Hereinafter, each component of the colored resin composition of the present invention will be described in detail in order.
［バインダー成分］
　本発明の着色樹脂組成物は、成膜性や被塗工面に対する密着性を付与するためにバインダー成分を含有する。塗膜に充分な硬度を付与するために、硬化性バインダー成分を含有することが好ましい。硬化性バインダー成分としては、特に限定されず、従来公知のカラーフィルタの着色層を形成するのに用いられる硬化性バインダー成分を適宜用いることができる。
　硬化性バインダー成分としては、例えば、可視光線、紫外線、電子線等により重合硬化させることができる光硬化性樹脂を含む光硬化性バインダー成分や、加熱により重合硬化させることができる熱硬化性樹脂を含む熱硬化性バインダー成分を含むものを用いることができる。 [Binder component]
The colored resin composition of the present invention contains a binder component in order to impart film formability and adhesion to a surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. The curable binder component is not particularly limited, and a curable binder component used for forming a coloring layer of a conventionally known color filter can be appropriately used.
As the curable binder component, for example, visible light, ultraviolet light, a photocurable binder component containing a photocurable resin that can be polymerized and cured by an electron beam, or a thermosetting resin that can be polymerized and cured by heating What contains a thermosetting binder component can be used.
　着色層を形成する際にフォトリソグラフィー工程を用いる場合には、アルカリ現像性を有する感光性バインダー成分が好適に用いられる。なお、感光性バインダー成分に、熱硬化性バインダー成分を更に用いてもよい。
　感光性バインダー成分としては、ポジ型感光性バインダー成分とネガ型感光性バインダー成分が挙げられる。ポジ型感光性バインダー成分としては、例えば、アルカリ可溶性樹脂と、感光性付与成分としてｏ－キノンジアジド基含有化合物とを含んだ系等が挙げられる。 When a photolithography step is used to form the colored layer, a photosensitive binder component having alkali developability is preferably used. Note that a thermosetting binder component may be further used as the photosensitive binder component.
Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitizing component.
　一方、ネガ型感光性バインダー成分としては、アルカリ可溶性樹脂と、多官能モノマーと、光開始剤を少なくとも含有する系が好適に用いられる。
　本発明に係る着色樹脂組成物においては、ネガ型感光性バインダー成分であることが、フォトリソグラフィー法によって既存のプロセスを用いて簡便にパターンを形成できる点から好ましい。
　以下、ネガ型感光性バインダー成分を構成する、アルカリ可溶性樹脂と、多官能モノマーと、光開始剤について、具体的に説明する。 On the other hand, as the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
The colored resin composition according to the present invention is preferably a negative photosensitive binder component in that a pattern can be easily formed by a photolithography method using an existing process.
Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.
＜アルカリ可溶性樹脂＞
　本発明におけるアルカリ可溶性樹脂は酸性基を有するものであり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
　本発明において、アルカリ可溶性樹脂とは、酸価が４０ｍｇＫＯＨ／ｇ以上であることを目安にすることができる。
　本発明における好ましいアルカリ可溶性樹脂は、酸性基、通常カルボキシ基を有する樹脂であり、具体的には、例えば、カルボキシ基を有するアクリル系共重合体及びカルボキシ基を有するスチレン－アクリル系共重合体等のアクリル系樹脂、カルボキシ基を有するエポキシ（メタ）アクリレート樹脂等が挙げられる。 <Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and can be appropriately selected from those soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be used as a guide when the acid value is 40 mgKOH / g or more.
The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, for example, an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. And an epoxy (meth) acrylate resin having a carboxy group.
　これらの中で特に好ましいものは、側鎖にカルボキシ基を有するとともに、さらに側鎖にエチレン性不飽和基等の光重合性官能基を有するものである。光重合性官能基を含有する場合には、カラーフィルタ製造時における樹脂組成物の硬化工程において、当該アルカリ可溶性樹脂同士、乃至、当該アルカリ可溶性樹脂と多官能モノマー等の光重合性化合物が架橋結合を形成し得る。硬化膜の膜強度がより向上して現像耐性が向上し、また、硬化膜の熱収縮が抑制されて基板との密着性に優れるようになる。
　アルカリ可溶性樹脂中に、エチレン性二重結合を導入する方法は、従来公知の方法から適宜選択すればよい。例えば、アルカリ可溶性樹脂が有するカルボキシ基に、分子内にエポキシ基とエチレン性二重結合とを併せ持つ化合物、例えばグリシジル（メタ）アクリレート等を付加させ、側鎖にエチレン性二重結合を導入する方法や、水酸基を有する構成単位を共重合体に導入しておいて、分子内にイソシアネート基とエチレン性二重結合とを備えた化合物を付加させ、側鎖にエチレン性二重結合を導入する方法などが挙げられる。 Among these, those having a carboxy group on the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group on the side chain are particularly preferable. In the case of containing a photopolymerizable functional group, in the curing step of the resin composition during the production of a color filter, the alkali-soluble resins are cross-linked with each other, or the photopolymerizable compound such as the alkali-soluble resin and a polyfunctional monomer. Can be formed. The film strength of the cured film is further improved to improve the development resistance, and the heat shrinkage of the cured film is suppressed, so that the adhesion to the substrate becomes excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to the carboxy group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Or a method in which a structural unit having a hydroxyl group is introduced into a copolymer, and a compound having an isocyanate group and an ethylenic double bond in a molecule is added to introduce a ethylenic double bond into a side chain. And the like.
　また、アルカリ可溶性樹脂は、着色層の密着性が優れる点から、更に炭化水素環を有することが好ましい。アルカリ可溶性樹脂に嵩高い基である、炭化水素環を有することにより硬化時の収縮が抑制され、基板との間の剥離が緩和し、基板密着性が向上する。
　このような炭化水素環としては、置換基を有していてもよい脂肪族炭化水素環、置換基を有していてもよい芳香族炭化水素環、及びこれらの組み合わせが挙げられ、炭化水素環がアルキル基、カルボニル基、カルボキシ基、オキシカルボニル基、アミド基、水酸基、ニトロ基、アミノ基、ハロゲン原子等の置換基を有していてもよい。
　炭化水素環は、１価の基として含まれていても良いし、２価以上の基として含まれていても良い。 Further, the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, separation from the substrate is eased, and substrate adhesion is improved.
Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a combination thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, and a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher valent group.
　炭化水素環の具体例としては、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、ノルボルナン、イソボルナン、トリシクロ［５．２．１．０（２，６）］デカン（ジシクロペンタン）、アダマンタン等の脂肪族炭化水素環；ベンゼン、ナフタレン、アントラセン、フェナントレン、フルオレン等の芳香族炭化水素環；ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環や、カルド構造（９，９－ジアリールフルオレン）；これらの基の一部が置換基によって置換された基等が挙げられる。
　上記置換基としては、アルキル基、シクロアルキル基、アルキルシクロアルキル基、水酸基、カルボニル基、ニトロ基、アミノ基、ハロゲン原子等が挙げられる。 Specific examples of the hydrocarbon ring include aliphatic such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Hydrocarbon rings; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and cardo structures (9,9-diarylfluorene) ); Groups in which some of these groups are substituted with substituents.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.
　炭化水素環として、脂肪族炭化水素環を含む場合には、着色層の耐熱性や密着性が向上すると共に、得られた着色層の輝度が向上する点から好ましい。
　また、前記カルド構造を含む場合には、着色層の硬化性が向上し、色材の退色を抑制し、耐溶剤性（ＮＭＰ膨潤抑制）が向上する点から特に好ましい。 When an aliphatic hydrocarbon ring is contained as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the luminance of the obtained colored layer is preferably improved.
In addition, when the cardo structure is included, the curability of the colored layer is improved, the fading of the coloring material is suppressed, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.
　カルボキシ基を有する構成単位を有するアクリル系共重合体、及びカルボキシ基を有するスチレン－アクリル系共重合体等のアクリル系樹脂は、例えば、カルボキシ基含有エチレン性不飽和モノマー、及び必要に応じて共重合可能なその他のモノマーを、公知の方法により（共）重合して得られた（共）重合体である。
　カルボキシ基含有エチレン性不飽和モノマーとしては、例えば、（メタ）アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、２－ヒドロキシエチル（メタ）アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。中でも、共重合性やコスト、溶解性、ガラス転移温度などの点から（メタ）アクリル酸が特に好ましい。 Acrylic resins such as an acrylic copolymer having a structural unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group include, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Can be An addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride; ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of the carboxy group. Among them, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.
　本発明におけるアルカリ可溶性樹脂は、カルボキシ基を有する構成単位と、炭化水素環を有する構成単位とを有するアクリル系共重合体及びスチレン－アクリル系共重合体等のカルボキシ基含有共重合体であることが好ましく、カルボキシ基を有する構成単位と、炭化水素環を有する構成単位と、エチレン性二重結合を有する構成単位とを有するアクリル系共重合体及びスチレン－アクリル系共重合体等のカルボキシ基含有共重合体であることがより好ましい。 The alkali-soluble resin in the present invention is a carboxy group-containing copolymer such as an acrylic copolymer or a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring. And a carboxy group-containing such as an acrylic copolymer or a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. More preferably, it is a copolymer.
　炭化水素環を有するエチレン性不飽和モノマーとしては、例えば、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、スチレンなどが挙げられ、現像後の着色層の断面形状が加熱処理においても維持される効果が大きい点から、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ベンジル（メタ）アクリレート、及びスチレンから選択される少なくとも１種を用いることが好ましい。 Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (Meth) acrylate, styrene, and the like, and cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from meth) acrylate, benzyl (meth) acrylate, and styrene.
　当該カルボキシ基含有共重合体は、更にメチル（メタ）アクリレート、エチル（メタ）アクリレート等、エステル基を有する構成単位等の他の構成単位を含有していてもよい。エステル基を有する構成単位は、着色樹脂組成物のアルカリ可溶性を抑制する成分として機能するだけでなく、溶剤に対する溶解性、さらには溶剤再溶解性を向上させる成分としても機能する。 The carboxy group-containing copolymer may further contain other structural units such as a structural unit having an ester group, such as methyl (meth) acrylate and ethyl (meth) acrylate. The constituent unit having an ester group not only functions as a component for suppressing alkali solubility of the colored resin composition, but also functions as a component for improving solubility in a solvent and further improving solvent resolubility.
　当該カルボキシ基含有共重合体は、各構成単位の仕込み量を適宜調整することにより、所望の性能を有するアルカリ可溶性樹脂とすることができる。
　カルボキシ基含有エチレン性不飽和モノマーの仕込み量は、良好なパターンが得られる点から、モノマー全量に対して５質量％以上であることが好ましく、１０質量％以上であることがより好ましい。一方、現像後のパターン表面の膜荒れ等を抑制する点から、カルボキシ基含有エチレン性不飽和モノマーの仕込み量は、モノマー全量に対して５０質量％以下であることが好ましく、４０質量％以下であることがより好ましい。 The carboxy group-containing copolymer can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.
The charged amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxy group-containing ethylenically unsaturated monomer to be added is preferably 50% by mass or less, and more preferably 40% by mass or less based on the total amount of the monomers, from the viewpoint of suppressing film roughness on the pattern surface after development. More preferably, there is.
　また、アルカリ可溶性樹脂としてより好ましく用いられる、エチレン性二重結合を有する構成単位とを有するアクリル系共重合体及びスチレン－アクリル系共重合体等のカルボキシ基含有共重合体において、エポキシ基とエチレン性二重結合とを併せ持つ化合物はカルボキシ基含有エチレン性不飽和モノマーの仕込み量に対して、１０質量％以上９５質量％以下であることが好ましく、１５質量％以上９０質量％以下であることがより好ましい。 Further, in an acrylic copolymer having a structural unit having an ethylenic double bond and a carboxy group-containing copolymer such as a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylene The compound having an ionic double bond is preferably from 10% by mass to 95% by mass, and more preferably from 15% by mass to 90% by mass, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer. More preferred.
　カルボキシ基含有共重合体の好ましい質量平均分子量（Ｍｗ）は、好ましくは１，０００～５０，０００の範囲であり、さらに好ましくは３，０００～２０，０００である。１，０００以上では硬化後のバインダー機能が向上し、５０，０００以下だとアルカリ現像液による現像時に、パターン形成が良好となる。 The preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the binder function after curing is improved, and when it is 50,000 or less, pattern formation becomes good at the time of development with an alkali developing solution.
　カルボキシ基を有するエポキシ（メタ）アクリレート樹脂としては、特に限定されるものではないが、エポキシ化合物と不飽和基含有モノカルボン酸との反応物を酸無水物と反応させて得られるエポキシ（メタ）アクリレート化合物が適している。
　エポキシ化合物、不飽和基含有モノカルボン酸、及び酸無水物は、公知のものの中から適宜選択して用いることができる。
　カルボキシ基を有するエポキシ（メタ）アクリレート樹脂としても、分子内に、前記炭化水素環を有することが好ましく、中でも、カルド構造を含むものが、着色層の硬化性が向上し、色材の退色を抑制し、また着色層の残膜率が高くなる点から好ましい。
　カルボキシ基を有するエポキシ（メタ）アクリレート樹脂は、それぞれ１種単独で使用してもよいし、二種以上を併用してもよい。 The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known compounds and used.
The epoxy (meth) acrylate resin having a carboxy group also preferably has the above-mentioned hydrocarbon ring in the molecule. Among them, those containing a cardo structure improve the curability of the coloring layer and reduce the fading of the coloring material. This is preferred because it suppresses the coloration and increases the residual film ratio of the colored layer.
Epoxy (meth) acrylate resins having a carboxy group may be used alone or in combination of two or more.
　アルカリ可溶性樹脂は、現像液に用いるアルカリ水溶液に対する現像性（溶解性）の点から、酸価が３０ｍｇＫＯＨ／ｇ以上のものを選択して用いることが好ましい。アルカリ可溶性樹脂は、現像液に用いるアルカリ水溶液に対する現像性（溶解性）の点、及び基板への密着性の点から、酸価が４０ｍｇＫＯＨ／ｇ以上３００ｍｇＫＯＨ／ｇ以下であることが好ましく、中でも、５０ｍｇＫＯＨ／ｇ以上２８０ｍｇＫＯＨ／ｇ以下であることが好ましい。 From the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer, it is preferable to select and use an alkali-soluble resin having an acid value of 30 mgKOH / g or more. The alkali-soluble resin preferably has an acid value of 40 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer and adhesion to a substrate. It is preferably from 50 mgKOH / g to 280 mgKOH / g.
　アルカリ可溶性樹脂の側鎖にエチレン性不飽和基を有する場合のエチレン性不飽和結合当量は、硬化膜の膜強度が向上して現像耐性が向上し、基板との密着性に優れるといった効果を得る点から、１００～２０００の範囲であることが好ましく、特に、１４０～１５００の範囲であることが好ましい。該エチレン性不飽和結合当量が、２０００以下であれば現像耐性や密着性に優れている。また、１００以上であれば、前記カルボキシ基を有する構成単位や、炭化水素環を有する構成単位などの他の構成単位の割合を相対的に増やすことができるため、現像性や耐熱性に優れている。
　ここで、エチレン性不飽和結合当量とは、上記アルカリ可溶性樹脂におけるエチレン性不飽和結合１モル当りの質量平均分子量のことであり、下記数式（１）で表される。 In the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent has the effect of improving the film strength of the cured film, improving the development resistance, and improving the adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance and adhesion are excellent. Further, if it is 100 or more, the ratio of the other structural unit such as the structural unit having a carboxy group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developing unit is excellent in developing property and heat resistance. I have.
Here, the ethylenically unsaturated bond equivalent is a mass average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
数式（１）
　　エチレン性不飽和結合当量（ｇ／ｍｏｌ）＝Ｗ（ｇ）／Ｍ（ｍｏｌ）
（数式（１）中、Ｗは、アルカリ可溶性樹脂の質量（ｇ）を表し、Ｍはアルカリ可溶性樹脂Ｗ（ｇ）中に含まれるエチレン性二重結合のモル数（ｍｏｌ）を表す。） Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)
　上記エチレン性不飽和結合当量は、例えば、ＪＩＳ　Ｋ　００７０：１９９２に記載のよう素価の試験方法に準拠して、アルカリ可溶性樹脂１ｇあたりに含まれるエチレン性二重結合の数を測定することにより算出してもよい。 The ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with a test method for element number as described in JIS K 0070: 1992. It may be calculated.
　着色樹脂組成物において用いられるアルカリ可溶性樹脂は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよく、その含有量としては特に制限はないが、着色樹脂組成物の固形分全量に対してアルカリ可溶性樹脂は好ましくは５質量％以上６０質量％以下、さらに好ましくは８質量％以上４０質量％以下の範囲内である。アルカリ可溶性樹脂の含有量が上記下限値以上であると、充分なアルカリ現像性が得られ、また、アルカリ可溶性樹脂の含有量が上記上限値以下であると、現像時に膜荒れやパターンの欠けを抑制できる。 The alkali-soluble resin used in the colored resin composition may be used singly or in combination of two or more, and the content thereof is not particularly limited, but the solid content of the colored resin composition is not particularly limited. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 8% by mass to 40% by mass, based on the total amount. When the content of the alkali-soluble resin is equal to or more than the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is equal to or less than the above upper limit, film roughness or chipping of a pattern during development. Can be suppressed.
＜光重合性化合物＞
　着色樹脂組成物において用いられる光重合性化合物は、光開始剤によって重合可能なものであればよく、特に限定されず、通常、エチレン性不飽和二重結合を２つ以上有する化合物が好適に用いられ、特にアクリロイル基又はメタクリロイル基を２つ以上有する、多官能（メタ）アクリレートであることが好ましい。
　このような多官能（メタ）アクリレートとしては、従来公知のものの中から適宜選択して用いればよい。具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のもの等が挙げられる。 <Photopolymerizable compound>
The photopolymerizable compound used in the colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and usually, a compound having two or more ethylenically unsaturated double bonds is preferably used. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include, for example, those described in JP-A-2013-029832.
　これらの多官能（メタ）アクリレートは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。また、本発明の着色樹脂組成物に優れた光硬化性（高感度）が要求される場合には、光重合性化合物が、重合可能な二重結合を３つ（三官能）以上有するものであるものが好ましく、３価以上の多価アルコールのポリ（メタ）アクリレート類やそれらのジカルボン酸変性物が好ましく、具体的には、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートのコハク酸変性物、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートのコハク酸変性物、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（２－（メタ）アクリロイルオキシエチル）ホスフェート等が好ましい。トリ（２－（メタ）アクリロイルオキシエチル）ホスフェートのようなリン原子含有多官能（メタ）アクリレートを用いると、レーキ色材の退色が抑制されやすく、ポストベーク後の輝度を向上させやすい点から好ましい。 は One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. When excellent photocurability (high sensitivity) is required for the colored resin composition of the present invention, the photopolymerizable compound should have at least three (trifunctional) polymerizable double bonds. Preference is given to poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Succinic acid-modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid of dipentaerythritol penta (meth) acrylate Acid-modified product, dipentaerythritol hexa Meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate and the like are preferable. The use of a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate is preferable because the fading of the lake color material is easily suppressed and the luminance after post-baking is easily improved. .
　着色樹脂組成物において用いられる上記光重合性化合物の含有量は、特に制限はないが、着色樹脂組成物の固形分全量に対して光重合性化合物は好ましくは５質量％以上６０質量％以下、さらに好ましくは１０質量％以上５０質量％以下の範囲内である。光重合性化合物の含有量が上記下限値以上であると十分に光硬化が進み、露光部分が現像時の溶出を抑制でき、また、光重合性化合物の含有量が上記上限値以下であるとアルカリ現像性が十分である。 The content of the photopolymerizable compound used in the colored resin composition is not particularly limited, but the photopolymerizable compound is preferably 5% by mass or more and 60% by mass or less based on the total solid content of the colored resin composition. More preferably, it is in the range of 10% by mass to 50% by mass. When the content of the photopolymerizable compound is equal to or more than the lower limit, the photocuring proceeds sufficiently, the exposed portion can suppress elution at the time of development, and when the content of the photopolymerizable compound is equal to or less than the upper limit. Alkaline developability is sufficient.
＜光開始剤＞
　本発明の着色樹脂組成物において用いられる光開始剤としては、特に制限はなく、従来知られている各種開始剤の中から、１種又は２種以上を組み合わせて用いることができる。
　光開始剤としては、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α－アミノケトン、ビイミダゾール類、Ｎ，Ｎ－ジメチルアミノベンゾフェノン、ハロメチル－Ｓ－トリアジン系化合物、チオキサントン等を挙げることができる。光開始剤の具体例としては、ベンゾフェノン、４，４’－ビスジエチルアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン等の芳香族ケトン類、ベンゾインメチルエーテル等のベンゾインエーテル類、エチルベンゾイン等のベンゾイン、２－（ｏ－クロロフェニル）－４，５－フェニルイミダゾール２量体等のビイミダゾール類、２－トリクロロメチル－５－（ｐ－メトキシスチリル）－１，３，４－オキサジアゾール等のハロメチルオキサジアゾール化合物、２－（４－ブトキシ－ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン等のハロメチル－Ｓ－トリアジン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパノン、１，２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１，１－ヒドロキシ－シクロヘキシル－フェニルケトン、ベンジル、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－ベンゾイル－４’－メチルジフェニルサルファイド、ベンジルメチルケタール、ジメチルアミノベンゾエート、ｐ－ジメチルアミノ安息香酸イソアミル、２－ｎ－ブトキシエチル－４－ジメチルアミノベンゾエート、２－クロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、４－ベンゾイル－メチルジフェニルサルファイド、１－ヒドロキシ－シクロヘキシル－フェニルケトン、２－ベンジル－２－（ジメチルアミノ）－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン、α－ジメトキシ－α－フェニルアセトフェノン、フェニルビス（２，４，６－トリメチルベンゾイル）フォスフィンオキサイド、２－メチル－１－［４－（メチルチオ）フェニル］－２－（４－モルフォリニル）－１－プロパノンなどが挙げられる。
　中でも、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（例えばイルガキュア９０７、ＢＡＳＦ社製）、２－ベンジル－２－（ジメチルアミノ）－１－（４－モルフォリノフェニル）－１－ブタノン（例えばイルガキュア３６９、ＢＡＳＦ社製）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン（例えば、ハイキュアＡＢＰ、川口薬品製）、ジエチルチオキサントンが好ましく用いられる。更に２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オンのようなα－アミノアセトフェノン系光開始剤とジエチルチオキサントンのようなチオキサントン系光開始剤を組み合わせることが感度調整、水染みを抑制し、現像耐性が向上する点から好ましい。 <Photo initiator>
The photoinitiator used in the colored resin composition of the present invention is not particularly limited, and one or a combination of two or more of conventionally known initiators can be used.
Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthones, and the like. be able to. Specific examples of the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethyl benzoin. Biimidazoles such as benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Halomethyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- -Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl Thioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1 [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone , Α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1 -Propanone and the like.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (eg, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- ( 4-Morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (eg, Hicure ABP, manufactured by Kawaguchi Pharmaceutical), and diethylthioxanthone are preferably used. Combining an α-aminoacetophenone-based photoinitiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone-based photoinitiator such as diethylthioxanthone Is preferred from the viewpoints of sensitivity adjustment, suppression of water stain, and improvement of development resistance.
　本発明において、光開始剤は、感度を向上させる観点から、中でも、オキシムエステル系光開始剤を含むことが好ましい。オキシムエステル系光開始剤を用いることにより、細線パターンを形成する際に、面内の線幅のばらつきが抑制され易い。更に、オキシムエステル系光開始剤を用いることにより、現像耐性が向上し、水染み発生抑制効果が高くなる傾向がある。なお、水染みとは、アルカリ現像性を高くする成分を用いると、アルカリ現像後、純水でリンスした後に、水が染みたような跡が発生することをいう。このような水染みは、ポストベーク後に消えるので製品としては問題がないが、現像後にパターニング面の外観検査において、ムラ異常として検出されてしまい、正常品と異常品の区別がつかないという問題が生じる。そのため、外観検査において検査装置の検査感度を下げると、結果として最終的なカラーフィルタ製品の歩留まり低下を引き起こし、問題となる。
　当該オキシムエステル系光開始剤としては、分解物による着色樹脂組成物の汚染や装置の汚染を低減する点から、中でも、芳香環を有するものが好ましく、芳香環を含む縮合環を有するものがより好ましく、ベンゼン環とヘテロ環を含む縮合環を有することがさらに好ましい。
　オキシムエステル系光開始剤としては、１，２－オクタジオン－１－［４－（フェニルチオ）－、２－（ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（ｏ－アセチルオキシム）、特開２０００－８００６８号公報、特開２００１－２３３８４２号公報、特表２０１０－５２７３３９、特表２０１０－５２７３３８、特開２０１３－０４１１５３等に記載のオキシムエステル系光開始剤の中から適宜選択できる。市販品として、カルバゾール骨格を有するイルガキュアＯＸＥ－０１（ＢＡＳＦ製）、アデカアークルズＮＣＩ－８３１（ＡＤＥＫＡ社製）、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料社製）、ジフェニルスルフィド骨格を有するアデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）、ＴＲ－ＰＢＧ－３４５、ＴＲ－ＰＢＧ－３０５７（以上、常州強力電子新材料社製）、フルオレン骨格を有するＴＲ－ＰＢＧ－３６５（常州強力電子新材料社製）、ＳＰＩ－０４（三養製）などを用いても良い。特にジフェニルスルフィド骨格又はフルオレン骨格を有するオキシムエステル系光開始剤を用いることが輝度を向上させる点から好ましい。またカルバゾール骨格を有するオキシムエステル系光開始剤を用いることは感度の高い点から好ましい。
　またオキシムエステル系光開始剤を２種類以上併用することは、感度の異なる２種以上のオキシムエステル化合物を適宜選択して組み合わせることにより、良好な感度を維持しつつ、パターン形成の際の線幅を調整することができ、更に、現像耐性や輝度が向上しやすく、水染み発生抑制効果が高い点で好ましい。特にジフェニルスルフィド骨格を有するオキシムエステル系光開始剤２種類の併用又は、ジフェニルスルフィド骨格を有するオキシムエステル系光開始剤とフルオレン骨格を有するオキシムエステル系光開始剤を併用することは耐熱性が高くなり、輝度が向上し易い点から好ましい。 In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity. By using an oxime ester-based photoinitiator, when a fine line pattern is formed, variation in in-plane line width is easily suppressed. Furthermore, by using an oxime ester-based photoinitiator, development resistance tends to be improved, and the effect of suppressing the occurrence of water stain tends to be increased. The term “water stain” means that when a component that enhances alkali developability is used, traces of water stain occur after rinsing with pure water after alkali development. Such a water stain disappears after post-baking, so there is no problem as a product.However, in the appearance inspection of the patterning surface after development, it is detected as unevenness abnormality, and there is a problem that a normal product and an abnormal product cannot be distinguished. Occurs. Therefore, when the inspection sensitivity of the inspection device is reduced in the appearance inspection, the yield of the final color filter product is reduced, which is a problem.
As the oxime ester photoinitiator, those having an aromatic ring are preferable, and those having a condensed ring containing an aromatic ring are more preferable, from the viewpoint of reducing the contamination of the colored resin composition and the contamination of the device by the decomposition product. More preferably, it has a condensed ring containing a benzene ring and a hetero ring.
Oxime ester photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, It can be appropriately selected from oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. As commercially available products, Irgacure OXE-01 (manufactured by BASF) having a carbazole skeleton, Adeka Arculs NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changshu Strong Electronics New Materials), and Adeka having a diphenylsulfide skeleton Arkles NCI-930 (ADEKA), TR-PBG-345, TR-PBG-3057 (Changzhou Power Electronics New Materials), TR-PBG-365 having a fluorene skeleton (Changzhou Power Electronics New Materials) And SPI-04 (manufactured by Sanyo) and the like may be used. In particular, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving luminance. It is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
The use of two or more oxime ester-based photoinitiators can be achieved by appropriately selecting and combining two or more oxime ester compounds having different sensitivities, thereby maintaining a good sensitivity and a line width at the time of pattern formation. It is preferable because the development resistance and the luminance can be easily improved, and the effect of suppressing the occurrence of water stain is high. In particular, the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton increases heat resistance. This is preferable because the luminance is easily improved.
　なお、少ない露光量でパターニングするために高感度な光開始剤を使用する場合、ラジカル発生後、未露光部までラジカルが移動してしまう。そのため、着色層をパターニングする際に、同時に着色層に所望の微小孔を形成する際に、露光部分の内部にある未露光部の形状を保ちつつ、かつ未露光部周辺部をビリツキなく形成することは困難であった。それに対して、本発明の色材の組み合わせに、フルオレン骨格を有するオキシムエステル系光開始剤を用いると、着色層をパターニングする際に、同時に着色層に所望の微小孔を形成し易いというメリットがある。中でも、フルオレン骨格を有するオキシムエステル系光開始剤と、フェニルスルフィド骨格を有するオキシムエステル系光開始剤とを併用すると、輝度、及び感度を大きく低下させることなく、微小孔の形状を向上しやすい点から好ましい。着色層に所望の微小孔を形成しやすい場合には、本発明の着色樹脂組成物は、例えば、反射型カラーフィルタを形成するために、ＴＦＴ基板上に着色層を形成し、同時に当該着色層に導通のためのスルーホールを形成する用途にも適している。なお、「ビリツキ」とは、パターン端部の直線乃至曲線が不均一となって寸法精度が悪化する不具合をいう。 In the case where a highly sensitive photoinitiator is used to perform patterning with a small amount of exposure, the radical moves to an unexposed portion after radical generation. Therefore, when patterning the colored layer and simultaneously forming the desired micro holes in the colored layer, the unexposed portion peripheral portion is formed without fluctuation while maintaining the shape of the unexposed portion inside the exposed portion. It was difficult. On the other hand, when an oxime ester-based photoinitiator having a fluorene skeleton is used in the combination of the coloring materials of the present invention, there is an advantage that, when the coloring layer is patterned, desired micropores are easily formed in the coloring layer at the same time. is there. Above all, when an oxime ester-based photoinitiator having a fluorene skeleton and an oxime ester-based photoinitiator having a phenyl sulfide skeleton are used in combination, the brightness and the sensitivity can be easily improved without greatly reducing the sensitivity. Is preferred. In the case where desired micropores are easily formed in the colored layer, the colored resin composition of the present invention may be used, for example, to form a colored layer on a TFT substrate in order to form a reflective color filter, It is also suitable for use in forming a through-hole for conduction in a semiconductor device. Note that “brilliance” refers to a problem that the dimensional accuracy is deteriorated due to non-uniform straight lines or curves at the pattern end.
　また、オキシムエステル系光開始剤に、前記α－アミノアセトフェノン系光開始剤を組み合わせて用いることが、水染みを抑制し、また、感度向上の点から、好ましい。α－アミノアセトフェノン系のような３級アミン構造を有する光開始剤は、分子内に酸素クエンチャーである３級アミン構造を有するため、開始剤から発生したラジカルが酸素により失活し難く、感度を向上させることができるからである。
　また、オキシムエステル系光開始剤に、チオキサントン系光開始剤を組み合わせることが感度調整、水染みを抑制し、現像耐性が向上する点から好ましく、オキシムエステル系光開始剤を２種類以上と、チオキサントン系光開始剤を組み合わせることが輝度、現像耐性が向上し、感度調整をしやすく、水染み発生抑制効果が高く、現像耐性が向上する点で好ましい。 It is preferable to use the α-aminoacetophenone-based photoinitiator in combination with the oxime ester-based photoinitiator from the viewpoints of suppressing water stain and improving sensitivity. Since a photoinitiator having a tertiary amine structure such as α-aminoacetophenone has a tertiary amine structure which is an oxygen quencher in the molecule, the radical generated from the initiator is hardly deactivated by oxygen, and the sensitivity is high. It is because it can improve.
In addition, it is preferable to combine a thioxanthone photoinitiator with an oxime ester photoinitiator from the viewpoint of sensitivity adjustment, suppressing water stain, and improving development resistance. The combination of a system photoinitiator is preferable in that the luminance and development resistance are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stain is high, and the development resistance is improved.
　本発明の着色樹脂組成物において用いられる光開始剤の合計含有量は、本発明の効果が損なわれない限り特に制限はないが、着色樹脂組成物の固形分全量に対して、好ましくは０．１質量％以上１２．０質量％以下、さらに好ましくは１．０質量％以上８．０質量％以下の範囲内である。この含有量が上記下限値以上であると十分に光硬化が進み露光部分が現像時に溶出することを抑制し、一方上記上限値以下であると、得られる着色層の黄変性が強くなって輝度が低下することを抑制できる。 The total content of the photoinitiator used in the colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 0.1 to the total solid content of the colored resin composition. It is in the range of 1% by mass to 12.0% by mass, more preferably in the range of 1.0% by mass to 8.0% by mass. When the content is equal to or more than the lower limit, the photocuring proceeds sufficiently to prevent the exposed portion from being eluted during development, while when the content is equal to or less than the upper limit, yellowing of the obtained colored layer is increased and the luminance is increased. Can be suppressed from decreasing.
＜酸化防止剤＞
　本発明に係る着色樹脂組成物は、更に酸化防止剤を含有することが、耐熱性が向上し、色材の退色が抑制され、輝度が向上する点から好ましい。本発明に係る着色樹脂組成物は、オキシムエステル系光開始剤と組み合わせて酸化防止剤を含むことにより、硬化膜に微小孔を形成する際に硬化性を損なうことなく微小孔内の過度なラジカル連鎖反応を制御できるため、所望の形状の微小孔をより容易に形成することができる。
　本発明に用いられる酸化防止剤としては、特に限定されず、従来公知のものの中から適宜選択すればよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられ、耐熱性の点及び微小孔の形状を良好にする点から、ヒンダードフェノール系酸化防止剤を用いることが好ましい。国際公開第２０１４／０２１０２３号に記載されているような潜在性酸化防止剤であっても良い。 <Antioxidant>
It is preferable that the colored resin composition according to the present invention further contains an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the coloring material, and improving luminance. The colored resin composition according to the present invention contains an antioxidant in combination with an oxime ester-based photoinitiator, whereby excessive radicals in the micropores are formed without impairing the curability when forming the micropores in the cured film. Since the chain reaction can be controlled, micropores having a desired shape can be formed more easily.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include, for example, a hindered phenol antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a hydrazine antioxidant, and the like. It is preferable to use a hindered phenolic antioxidant from the viewpoint of improving the shape of the pores and the pores. It may be a latent antioxidant as described in WO 2014/021023.
　ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］（商品名：商品名：ＩＲＧＡＮＯＸ１０１０、ＢＡＳＦ社製）、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート（商品名：イルガノックス３１１４、ＢＡＳＦ製）、２，４，６－トリス（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルベンジル）メシチレン（商品名：イルガノックス１３３０、ＢＡＳＦ製）、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）（商品名：スミライザーＭＤＰ－Ｓ、住友化学製）、６，６’－チオビス（２－ｔｅｒｔ－ブチル－４－メチルフェノール）（商品名：イルガノックス１０８１、ＢＡＳＦ製）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸ジエチル（商品名：イルガモド１９５、ＢＡＳＦ製）等が挙げられる。中でも、耐熱性及び耐光性の点から、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］（商品名：商品名：ＩＲＧＡＮＯＸ１０１０、ＢＡＳＦ社製）が好ましい。 Examples of hindered phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3 , 5-Di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6'-thiobis (2-tert-butyl-4-methylphenol (Trade name: Irganox 1081, manufactured by BASF), 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl (trade name: Irugamodo 195, manufactured by BASF), and the like. Above all, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
　酸化防止剤の含有量としては、着色樹脂組成物中の固形分全量に対して、酸化防止剤が０．１質量％以上１０．０質量％以下であることが好ましく、０．５質量％以上５．０質量％以下であることがより好ましい。上記下限値以上であれば、耐熱性及び耐光性に優れている。一方、上記上限値以下であれば、本発明の着色樹脂組成物を高感度の感光性樹脂組成物とすることができる。 The content of the antioxidant is preferably 0.1% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more, based on the total solid content in the colored resin composition. More preferably, the content is 5.0 mass% or less. If it is at least the above lower limit, it is excellent in heat resistance and light resistance. On the other hand, when the content is equal to or less than the above upper limit, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.
　酸化防止剤を前記オキシムエステル系光開始剤と組み合わせて用いる場合、酸化防止剤の含有量としては、前記オキシムエステル系光開始剤の合計量１００質量部に対して、酸化防止剤が１質量部以上２５０質量部以下であることが好ましく、３質量部以上８０質量部以下であることがより好ましく、５質量部以上６５質量部以下であることがより更に好ましい。上記範囲内であれば、上記組み合わせの効果に優れている。 When the antioxidant is used in combination with the oxime ester-based photoinitiator, the content of the antioxidant is 1 part by mass based on 100 parts by mass of the total amount of the oxime ester-based photoinitiator. The content is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and even more preferably 5 parts by mass or more and 65 parts by mass or less. Within the above range, the effect of the above combination is excellent.
＜任意添加成分＞
　本発明の着色樹脂組成物には、必要に応じて各種添加剤を含むものであってもよい。添加剤としては、例えば、メルカプト化合物、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
　界面活性剤及び可塑剤の具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のものが挙げられる。 <Optional components>
The colored resin composition of the present invention may contain various additives as necessary. Examples of the additives include a mercapto compound, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant and the plasticizer include, for example, those described in JP-A-2013-029832.
＜着色樹脂組成物における各成分の配合割合＞
　色材の合計の含有量は、着色樹脂組成物の固形分全量に対して、３質量％以上６５質量％以下、より好ましくは４質量％以上６０質量％以下の割合で配合することが好ましい。上記下限値以上であれば、着色樹脂組成物を所定の膜厚（通常は１．０μｍ以上５．０μｍ以下）に塗布した際の着色層が充分な色濃度を有する。また、上記上限値以下であれば、保存安定性に優れると共に、充分な硬度や、基板との密着性を有する着色層を得ることができる。特に色材濃度が高い着色層を形成する場合には、色材の含有量は、着色樹脂組成物の固形分全量に対して、１５質量％以上６５質量％以下、より好ましくは２５質量％以上６０質量％以下の割合で配合することが好ましい。
　分散剤の合計の含有量としては、色材を均一に分散することができるものであれば特に限定されるものではないが、例えば、着色樹脂組成物の固形分全量に対して１質量％以上４０質量％以下用いることができる。更に、着色樹脂組成物の固形分全量に対して２質量％以上３０質量％以下の割合で配合するのが好ましく、特に３質量％以上２５質量％以下の割合で配合するのが好ましい。上記下限値以上であれば、色材の分散性及び分散安定性に優れ、着色樹脂組成物の保存安定性により優れている。また、上記上限値以下であれば、現像性が良好なものとなる。特に色材濃度が高い着色層を形成する場合には、分散剤の含有量は、着色樹脂組成物の固形分全量に対して、２質量％以上２５質量％以下、より好ましくは３質量％以上２０質量％以下の割合で配合することが好ましい。
　バインダー成分の合計含有量は、着色樹脂組成物の固形分全量に対して５質量％以上９０質量％以下、好ましくは１０質量％以上８０質量％以下の割合で配合するのが好ましい。
　また、溶剤の含有量は、着色層を精度良く形成することができる範囲で適宜設定すればよい。該溶剤を含む着色樹脂組成物の全量に対して、通常、５５質量％以上９５質量％以下の範囲内であることが好ましく、中でも、６５質量％以上８８質量％以下の範囲内であることがより好ましい。上記溶剤の含有量が、上記範囲内であることにより、塗布性に優れたものとすることができる。 <Blending ratio of each component in colored resin composition>
The total content of the coloring material is preferably from 3% by mass to 65% by mass, more preferably from 4% by mass to 60% by mass, based on the total solid content of the colored resin composition. If it is at least the above lower limit, the colored layer when the colored resin composition is applied to a predetermined thickness (usually 1.0 μm or more and 5.0 μm or less) will have a sufficient color density. When the content is equal to or less than the above upper limit, a colored layer having excellent storage stability, sufficient hardness and adhesion to a substrate can be obtained. In particular, when a coloring layer having a high coloring material concentration is formed, the content of the coloring material is preferably 15% by mass or more and 65% by mass or less, more preferably 25% by mass or more, based on the total solid content of the colored resin composition. It is preferable to mix at a ratio of 60% by mass or less.
The total content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, 1% by mass or more based on the total solid content of the colored resin composition 40 mass% or less can be used. Furthermore, it is preferable to mix at a ratio of 2% by mass or more and 30% by mass or less, particularly preferably 3% by mass or more and 25% by mass or less, based on the total solid content of the colored resin composition. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material will be excellent, and the storage stability of the colored resin composition will be more excellent. Further, when the content is equal to or less than the above upper limit, the developability becomes good. In particular, when a coloring layer having a high coloring material concentration is formed, the content of the dispersant is preferably 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more, based on the total solid content of the colored resin composition. It is preferable to mix at a ratio of 20% by mass or less.
The total content of the binder component is preferably from 5% by mass to 90% by mass, and more preferably from 10% by mass to 80% by mass, based on the total solid content of the colored resin composition.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass, based on the total amount of the colored resin composition containing the solvent. More preferred. When the content of the solvent is within the above range, excellent coating properties can be obtained.
　本発明の着色樹脂組成物においては、Ｐ／Ｖ比（（組成物中の色材成分質量）／（組成物中の色材成分以外の固形分質量）比）は、青色着色樹脂組成物とする場合には、所望の発色の観点から、Ｐ／Ｖ比は０．１０以上であることが好ましく、更に０．１５以上であることが好ましく、より更に０．２以上であることが好ましい。一方、パターニング特性等に優れる点から、０．６５以下であることが好ましく、０．５０以下であることがより好ましく、０．４５以下であることがより更に好ましい。 In the colored resin composition of the present invention, the P / V ratio ((mass of coloring material component in the composition) / (mass of solid content other than the coloring material component in the composition) ratio) is different from that of the blue colored resin composition. In this case, the P / V ratio is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of desired color development. On the other hand, from the viewpoint of excellent patterning characteristics and the like, it is preferably 0.65 or less, more preferably 0.50 or less, and even more preferably 0.45 or less.
＜着色樹脂組成物の製造方法＞
　本発明の着色樹脂組成物の製造方法は特に限定されず、例えば、前記本発明の色材分散液に、バインダー成分と、必要に応じてその他の成分を添加し、公知の混合手段を用いて混合することにより得ることができる。或いは、前記分散剤を用いて、各色材の色材分散液とを各々準備し、各々の色材分散液と、バインダー成分と、必要に応じてその他の成分を、公知の混合手段を用いて混合することにより得ることができる。 <Method for producing colored resin composition>
The method for producing the colored resin composition of the present invention is not particularly limited. For example, a binder component and, if necessary, other components are added to the colorant dispersion of the present invention, and using a known mixing means. It can be obtained by mixing. Alternatively, using the dispersant, a colorant dispersion of each colorant is prepared, and each colorant dispersion, a binder component, and other components as necessary, using known mixing means. It can be obtained by mixing.
　本発明の着色樹脂組成物は、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能であることから、カラーフィルタ用途に好適に用いられる。 The colored resin composition of the present invention has excellent dispersibility and storage stability even when a predetermined lake coloring material and a phthalocyanine pigment are mixed in a desired range, and has improved substrate adhesion and coating uniformity. Since it can form a layer, it is suitably used for color filters.
ＩＩＩ．硬化物
　本発明に係る硬化物は、前記本発明に係る着色樹脂組成物の硬化物である。
　本発明に係る硬化物は、バインダー成分の硬化性に合わせて、適宜選択して製造することができる。例えば、感光性バインダー成分を用いる場合には、前記本発明に係る着色樹脂組成物の塗膜を形成し、該塗膜を乾燥させたのち、露光、及び必要に応じて現像することにより得ることができる。塗膜の形成、露光、及び現像の方法としては、例えば、後述する本発明に係るカラーフィルタが備える着色層の形成において用いられる方法と同様の方法とすることができる。また、例えば、熱硬化性バインダー成分を用いる場合には、前記本発明に係る着色樹脂組成物の塗膜を必要に応じてパターニングして塗布し、該塗膜を乾燥させたのち、加熱することにより得ることができる。
　また、本発明に係る硬化物は、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上したものであり、カラーフィルタの着色層として好適に用いられる。 III. Cured product The cured product according to the present invention is a cured product of the colored resin composition according to the present invention.
The cured product according to the present invention can be appropriately selected and produced according to the curability of the binder component. For example, when a photosensitive binder component is used, it is obtained by forming a coating film of the colored resin composition according to the present invention, drying the coating film, exposing, and developing as necessary. Can be. As a method of forming a coating film, exposing, and developing, for example, a method similar to a method used in forming a colored layer included in a color filter according to the present invention described later can be used. Further, for example, when a thermosetting binder component is used, a coating film of the colored resin composition according to the present invention is applied by patterning as necessary, and after drying the coating film, heating is performed. Can be obtained by
Further, the cured product according to the present invention has excellent dispersibility and storage stability even when a predetermined lake color material and a phthalocyanine pigment are mixed in a desired range, and has improved substrate adhesion and coating film uniformity. This is suitably used as a coloring layer of a color filter.
ＩＶ．カラーフィルタ
　本発明に係るカラーフィルタは、透明基板と、当該透明基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、前記着色層の少なくとも一つが、色材と、酸性分散剤とを含み、前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、カラーフィルタである。 IV. Color filter The color filter according to the present invention is a color filter including at least a transparent substrate and a coloring layer provided on the transparent substrate, at least one of the coloring layers, a coloring material, an acidic dispersant, Wherein the colorant comprises at least one lake colorant selected from the group consisting of a colorant represented by the general formula (1) and a colorant represented by the general formula (2), and a base A phthalocyanine pigment that has been subjected to a sexual treatment, and wherein the acidic dispersant contains a polymer having at least one selected from the structural units represented by the general formula (I).
　本発明に係るカラーフィルタは、前記着色層の少なくとも一つが、色材と、酸性分散剤とを含み、前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含むことにより、分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を備えており、高輝度で耐熱性が向上したカラーフィルタである。前記特定の色材が、前記特定の分散剤に分散されていることにより、分散性及び保存安定性が向上し、着色層の輝度及び耐熱性が向上する。また、基板密着性が向上した着色層は、パターニングプロセスで微細なパターンを形成しても、塗膜が剥離し難く、製造時の管理やコストの負担を軽減できる。また、塗膜均一性が向上すると、大型基板においても色ムラが低減されたカラーフィルタを得ることができる。
　このような本発明に係るカラーフィルタについて、図を参照しながら説明する。図１は、本発明のカラーフィルタの一例を示す概略断面図である。図１によれば、本発明のカラーフィルタ１０は、透明基板１と、遮光部２と、着色層３とを有している。 In the color filter according to the present invention, at least one of the coloring layers includes a coloring material and an acidic dispersant, and the coloring material includes a coloring material represented by the general formula (1) and a coloring material represented by the general formula (2). ), Comprising at least one lake colorant selected from the group consisting of colorants and a phthalocyanine pigment which has been subjected to a basic treatment, wherein the acidic dispersant is represented by the general formula (I). By containing a polymer having at least one selected from the structural units, it is excellent in dispersibility and storage stability, and has a colored layer with improved substrate adhesion and coating uniformity, and has high brightness. This is a color filter with improved heat resistance. By dispersing the specific color material in the specific dispersant, dispersibility and storage stability are improved, and luminance and heat resistance of the colored layer are improved. Moreover, even if a fine pattern is formed by a patterning process, the coating layer of the colored layer having improved substrate adhesion is difficult to peel off, and the burden of management and cost during manufacturing can be reduced. Further, when the uniformity of the coating film is improved, a color filter with reduced color unevenness can be obtained even on a large-sized substrate.
Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, a color filter 10 of the present invention has a transparent substrate 1, a light shielding portion 2, and a coloring layer 3.
［着色層］
　本発明のカラーフィルタに用いられる着色層は、少なくとも１つが、色材と、酸性分散剤とを含み、前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、着色層である。
　着色層は、通常、後述する透明基板上の遮光部の開口部に形成され、通常３色以上の着色パターンから構成される。
　また、当該着色層の配列としては、特に限定されず、例えば、ストライプ型、モザイク型、トライアングル型、４画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は任意に設定することができる。
　当該着色層の厚みは、塗布方法、着色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、１μｍ以上５μｍ以下の範囲であることが好ましい。 [Coloring layer]
At least one of the coloring layers used in the color filter of the present invention includes a coloring material and an acidic dispersant, and the coloring material includes the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2). ) And at least one lake coloring material selected from the group consisting of coloring materials and a phthalocyanine pigment subjected to a basic treatment, wherein the acidic dispersant is represented by the general formula (I). The colored layer contains a polymer having at least one selected from structural units.
The coloring layer is usually formed in an opening of a light-shielding portion on a transparent substrate described later, and usually includes a coloring pattern of three or more colors.
The arrangement of the coloring layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. Further, the width, the area, and the like of the coloring layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but is usually preferably in the range of 1 μm to 5 μm.
　当該着色層は、例えば、前記着色樹脂組成物が感光性樹脂組成物の場合、下記の方法により形成することができる。カラーフィルタに用いられる前記着色層は、前述した色材と、酸性分散剤と、溶剤と、バインダー成分を含有し、前記色材が、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、着色樹脂組成物を用いて形成されることが好ましく、当該着色樹脂組成物の硬化物であることが好ましい。
　まず、着色樹脂組成物を、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法などの塗布手段を用いて後述する透明基板上に塗布して、ウェット塗膜を形成させる。
　次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させたのち、これに、所定のパターンのマスクを介して露光し、アルカリ可溶性樹脂及び多官能モノマー等を光重合反応させて、感光性の塗膜とする。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。
　また、露光後に重合反応を促進させるために、加熱処理を行ってもよい。加熱条件は、使用する着色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択される。 For example, when the colored resin composition is a photosensitive resin composition, the colored layer can be formed by the following method. The coloring layer used in the color filter contains the coloring material described above, an acidic dispersant, a solvent, and a binder component, and the coloring material is represented by the general formula (1) and the coloring material described above. It comprises at least one lake colorant selected from the group consisting of the colorants represented by the formula (2) and a phthalocyanine pigment which has been subjected to a basic treatment, wherein the acidic dispersant is represented by the general formula (I) It is preferably formed using a colored resin composition containing a polymer having at least one selected from the structural units represented, and is preferably a cured product of the colored resin composition.
First, the colored resin composition is applied to a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method to form a wet coating film. .
Next, using a hot plate or an oven, etc., after drying the wet coating film, this is exposed to light through a mask of a predetermined pattern, the alkali-soluble resin and polyfunctional monomer and the like, photopolymerization reaction, A photosensitive coating film. Examples of the light source used for the exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Further, heat treatment may be performed after the exposure in order to accelerate the polymerization reaction. The heating conditions are appropriately selected depending on the mixing ratio of each component in the coloring resin composition to be used, the thickness of the coating film, and the like.
　次に、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。
　現像処理後は、通常、現像液の洗浄、着色樹脂組成物の硬化塗膜の乾燥が行われ、着色層が形成される。なお、現像処理後に、塗膜を十分に硬化させるために加熱処理を行ってもよい。加熱条件としては特に限定はなく、塗膜の用途に応じて適宜選択される。 Next, the coating film is formed in a desired pattern by performing development processing using a developing solution and dissolving and removing the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Further, a general method can be adopted as a developing method.
After the development, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
［遮光部］
　本発明のカラーフィルタにおける遮光部は、後述する基板上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
　当該遮光部のパターン形状としては、特に限定されず、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。 [Shading part]
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and may be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding portion may be a thin metal film of chromium or the like by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, and the like are described. is there.
　遮光部の膜厚としては、金属薄膜の場合は０．２μｍ以上０．４μｍ以下程度で設定され、黒色顔料をバインダー樹脂中に分散又は溶解させたものである場合は０．５μｍ以上２μｍ以下程度で設定される。 The thickness of the light-shielding portion is set at about 0.2 μm or more and 0.4 μm or less for a metal thin film, and about 0.5 μm or more and 2 μm or less for a black pigment dispersed or dissolved in a binder resin. Is set by
［透明基板］
　透明基板としては、可視光に対して透明な基材であればよく、特に限定されず、一般的なカラーフィルタに用いられる透明基板を使用することができる。具体的には、石英ガラス、無アルカリガラス、合成石英板等の可撓性のない透明なリジッド材、あるいは、透明樹脂フィルム、光学用樹脂板、フレキシブルガラス等の可撓性やフレキシブル性を有する透明なフレキシブル材が挙げられる。このようなカラーフィルタに用いられる透明基板は、通常、表面に極性基を有する。
　本発明の着色樹脂組成物の基板密着性が向上する点から、透明基板としては、石英ガラス、無アルカリガラス、合成石英板等の二酸化ケイ素を含む基板であることが好ましい。
　当該透明基板の厚みは、特に限定されるものではないが、カラーフィルタの用途に応じて、例えば５０μｍ以上１ｍｍ以下程度のものを使用することができる。
　なお、本発明のカラーフィルタは、上記透明基板、遮光部及び着色層以外にも、例えば、オーバーコート層や透明電極層、さらには液晶材料を配向させるための配向膜や、柱状スペーサ等が形成されたものであってもよい。本発明のカラーフィルタは、前記例示された構成に限定されるものではなく、一般的にカラーフィルタに用いられている公知の構成を適宜選択して用いることができる。 [Transparent substrate]
The transparent substrate is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, synthetic quartz plate or the like, or a flexible resin film, an optical resin plate, a flexible glass or the like having flexibility or flexibility. A transparent flexible material may be used. The transparent substrate used for such a color filter usually has a polar group on the surface.
From the viewpoint that the substrate adhesion of the colored resin composition of the present invention is improved, the transparent substrate is preferably a substrate containing silicon dioxide, such as quartz glass, non-alkali glass, and synthetic quartz plate.
Although the thickness of the transparent substrate is not particularly limited, a thickness of, for example, about 50 μm or more and 1 mm or less can be used depending on the use of the color filter.
In addition, the color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, a columnar spacer, and the like, in addition to the transparent substrate, the light-shielding portion, and the coloring layer. May be done. The color filter of the present invention is not limited to the above-described configuration, and a known configuration generally used for a color filter can be appropriately selected and used.
Ｖ．表示装置
　本発明に係る表示装置は、前記本発明に係るカラーフィルタを有することを特徴とする。本発明において表示装置の構成は特に限定されず、従来公知の表示装置の中から適宜選択することができ、例えば、液晶表示装置や、有機発光表示装置などが挙げられる。 V. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.
　［液晶表示装置］
　本発明の液晶表示装置は、前述した本発明に係るカラーフィルタと、対向基板と、前記カラーフィルタと前記対向基板との間に形成された液晶層とを有することを特徴とする。
　このような本発明の液晶表示装置について、図を参照しながら説明する。図２は、本発明の表示装置の一例を示す概略図であり、液晶表示装置の一例を示す概略図である。図２に例示するように本発明の液晶表示装置４０は、カラーフィルタ１０と、ＴＦＴアレイ基板等を有する対向基板２０と、上記カラーフィルタ１０と上記対向基板２０との間に形成された液晶層３０とを有している。
　なお、本発明の液晶表示装置は、この図２に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた液晶表示装置として公知の構成とすることができる。 [Liquid crystal display]
A liquid crystal display device according to the present invention includes the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of the display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
The configuration of the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may be a configuration generally known as a liquid crystal display device using a color filter.
　本発明の液晶表示装置の駆動方式としては、特に限定はなく一般的に液晶表示装置に用いられている駆動方式を採用することができる。このような駆動方式としては、例えば、ＴＮ方式、ＩＰＳ方式、ＯＣＢ方式、及びＭＶＡ方式等を挙げることができる。本発明においてはこれらのいずれの方式であっても好適に用いることができる。
　また、対向基板としては、本発明の液晶表示装置の駆動方式等に応じて適宜選択して用いることができる。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be adopted. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
The counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention and the like.
　液晶層の形成方法としては、一般に液晶セルの作製方法として用いられる方法を使用することができ、例えば、真空注入方式や液晶滴下方式等が挙げられる。 (4) As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
　［有機発光表示装置］
　本発明に係る有機発光表示装置は、前述した本発明に係るカラーフィルタと、有機発光体とを有することを特徴とする。
　このような本発明の有機発光表示装置について、図を参照しながら説明する。図３は、本発明の表示装置の他の一例を示す概略図であり、有機発光表示装置の一例を示す概略図である。図３に例示するように本発明の有機発光表示装置１００は、カラーフィルタ１０と、有機発光体８０とを有している。カラーフィルタ１０と、有機発光体８０との間に、有機保護層５０や無機酸化膜６０を有していても良い。 [Organic light emitting display]
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitting body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of the organic light emitting display device. As illustrated in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic luminous body 80.
　有機発光体８０の積層方法としては、例えば、カラーフィルタ上面へ透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６を逐次形成していく方法や、別基板上へ形成した有機発光体８０を無機酸化膜６０上に貼り合わせる方法などが挙げられる。有機発光体８０における、透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６、その他の構成は、公知のものを適宜用いることができる。このようにして作製された有機発光表示装置１００は、例えば、パッシブ駆動方式の有機ＥＬディスプレイにもアクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。
　なお、本発明の有機発光表示装置は、この図３に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた有機発光表示装置として公知の構成とすることができる。 As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. And a method of bonding the organic light emitting body 80 formed on another substrate to the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting body 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this manner is applicable to, for example, a passive drive organic EL display and an active drive organic EL display.
The organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3, but may have a structure generally known as an organic light emitting display device using a color filter.
　以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。
　酸価は、ＪＩＳ　Ｋ　００７０：１９９２に記載の方法に準ずる方法により求めた。
　質量平均分子量（Ｍｗ）は、前述の本発明の測定方法に従って、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により標準ポリスチレン換算値として求めた。 Hereinafter, the present invention will be described specifically with reference to examples. The description is not intended to limit the invention.
The acid value was determined by a method according to JIS K 0070: 1992.
The weight average molecular weight (Mw) was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
（合成例１：レーキ色材１の合成）
（１）中間体１の合成
　特開２０１８－３０１３号に記載の中間体Ａ－２、中間体Ｂ－１、及び化合物１－３の製造方法を参照して、下記化学式（ａ）で示される中間体１を得た（収率８７％）。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）　（ｍ／ｚ）：６７７（＋）、２価
・元素分析値：ＣＨＮ実測値　（８１．８１％、７．３１％、５．８５％）；理論値（８１．７７％、７．３６％、５．９０％） (Synthesis Example 1: Synthesis of Rake Coloring Material 1)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate A-2, Intermediate B-1 and Compound 1-3 described in JP-A-2018-3013, the compound is represented by the following chemical formula (a). Intermediate 1 was obtained (87% yield).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 677 (+), divalent Elemental analysis: CHN actual (81.81%, 7.31%, 5.85%); theoretical (81.77%) , 7.36%, 5.90%)
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（２）レーキ色材１の合成
　関東化学製１２タングストリン酸・ｎ水和物２．５９ｇ（０．７６ｍｍｏｌ）をメタノール４０ｍＬ、水４０ｍＬの混合液に加熱溶解させ、前記中間体１　１．６ｇ（１．１９ｍｍｏｌ）を加え、１時間攪拌した。沈殿物を濾取し、水で洗浄した。得られた沈殿物を減圧乾燥して下記化学式（ｂ）で示されるレーキ色材１を（収率９５％）得た。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・３１Ｐ　ＮＭＲ（ｄ－ｄｍｓｏ、ｐｐｍ）δ－１５．１５
・ＭＳ（ＭＡＬＤＩ）　（ｍ／ｚ）：１３５５（Ｍ＋）、２８７９（ＭＨ２ －）
・元素分析値：ＣＨＮ実測値　（３５．５５％、３．２４％、２．６１％）；理論値（３５．６１％、３．２０％、２．５７％）
・蛍光Ｘ線分析：ＭｏＷ実測比　（０％、１００％）；理論値（０％、１００％） (2) Synthesis of Lake Coloring Material 1 2.59 g (0.76 mmol) of 12-tungstophosphoric acid / n-hydrate manufactured by Kanto Chemical Co., Ltd. was dissolved by heating in a mixed solution of 40 mL of methanol and 40 mL of water, and 1.6 g of Intermediate 1 was obtained. (1.19 mmol) was added and stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain a lake color material 1 represented by the following chemical formula (b) (95% yield).
The obtained compound was confirmed to be the target compound from the following analysis results.
31P NMR (d-dmso, ppm) δ-15.15
MS (MALDI) (m / z): 1355 (M + ), 2879 (MH 2 − )
Elemental analysis value: CHN actual measurement value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)
X-ray fluorescence analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（合成例２：レーキ色材２の合成）
（１）中間体２の合成
　国際公開第２０１２／１４４５２１号に記載の中間体３及び中間体４の製造方法を参照して、下記化学式（ｃ）で示される中間体２を１５．９ｇ（収率７０％）得た。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。
・ＭＳ（ＥＳＩ）　（ｍ／ｚ）：５１１（＋）、２価
・元素分析値：ＣＨＮ実測値　（７８．１３％、７．４８％、７．７８％）；理論値（７８．０６％、７．７５％、７．６９％） (Synthesis example 2: synthesis of rake color material 2)
(1) Synthesis of Intermediate 2 Referring to the production method of Intermediate 3 and Intermediate 4 described in WO2012 / 144521, 15.9 g (yield) of Intermediate 2 represented by the following chemical formula (c) 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent Elemental analysis: CHN actual (78.13%, 7.48%, 7.78%); theoretical (78.06%) , 7.75%, 7.69%)
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（２）レーキ色材２の合成
　中間体２　５．００ｇ（４．５８ｍｍｏｌ）を水３００ｍｌに加え、９０℃で溶解させ中間体２溶液とした。次に日本無機化学工業製リンタングステン酸・ｎ水和物　Ｈ３［ＰＷ１２Ｏ４０］・ｎＨ２Ｏ（ｎ＝３０）　１０．４４ｇ（３．０５ｍｍｏｌ）を水１００ｍＬに入れ、９０℃で攪拌し、リンタングステン酸水溶液を調製した。先の中間体２溶液にリンタングステン酸水溶液を９０℃で混合し、生成した沈殿物を濾取し、水で洗浄した。得られたケーキを乾燥して下記化学式（ｄ）で表されるレーキ色材２を１３．２５ｇ（収率９８％）を得た。
　得られた化合物は、下記の分析結果より目的の化合物であることを確認した。（モル比Ｗ／Ｍｏ＝１００／０）
・ＭＳ（ＥＳＩ）　（ｍ／ｚ）：５１０（＋）、２価
・元素分析値：ＣＨＮ実測値　（４１．５５％、５．３４％、４．３２％）；理論値（４１．６６％、５．１７％、４．１１％）
　また、リンタングステン酸のポリ酸構造がレーキ色材２となった後も保たれていることを３１Ｐ－ＮＭＲにより確認した。 (2) Synthesis of Lake Coloring Material 2 5.00 g (4.58 mmol) of Intermediate 2 was added to 300 ml of water and dissolved at 90 ° C. to obtain a solution of Intermediate 2. Next, 10.44 g (3.05 mmol) of phosphotungstic acid / n-hydrate H 3 [PW 12 O 40 ] · nH 2 O (n = 30) manufactured by Nippon Inorganic Chemical Industry was added to 100 mL of water and stirred at 90 ° C. Then, an aqueous solution of phosphotungstic acid was prepared. An aqueous solution of phosphotungstic acid was mixed with the intermediate 2 solution at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of lake color material 2 represented by the following chemical formula (d).
The obtained compound was confirmed to be the target compound from the following analysis results. (Molar ratio W / Mo = 100/0)
MS (ESI) (m / z): 510 (+) Bivalent Elemental analysis: CHN actual (41.55%, 5.34%, 4.32%); theoretical (41.66%) , 5.17%, 4.11%)
It was confirmed by 31 P-NMR that the polyacid structure of phosphotungstic acid was maintained even after the lake color material 2 was formed.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（合成例３：塩基性処理フタロシアニン顔料１の合成）
　反応容器中、クロロスルホン酸３００質量部および銅フタロシアニン３０質量部を加え、完全に溶解した後、塩化チオニル２４質量部を加え、徐々に昇温して１０１℃で３時間反応させた。その反応液を氷水９０００質量部中に注入し、撹拌後、濾過、水洗した。得られたプレスケーキを水３００質量部でスラリーとした後、１，１－ジエチル－１，５－ジアザペンタン１３質量部を加え、６５℃で４時間撹拌した後、濾過、水洗、乾燥し、表面処理に用いられる塩基性部位を有する青色色材誘導体１を得た。得られた塩基性部位を有する青色色材誘導体１について、下記化学式（ｅ）の構造であることを確認した。
・ＴＯＦ-ＭＳ：７６８．３５ (Synthesis Example 3: Synthesis of basic treated phthalocyanine pigment 1)
In a reaction vessel, 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added and completely dissolved. Then, 24 parts by mass of thionyl chloride was added, and the mixture was gradually heated and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, and after stirring, filtered and washed with water. The obtained press cake was slurried with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, and the mixture was stirred at 65 ° C. for 4 hours, filtered, washed with water, dried, and dried. A blue coloring material derivative 1 having a basic site used in the treatment was obtained. It was confirmed that the obtained blue coloring material derivative 1 having a basic site had a structure represented by the following chemical formula (e).
・ TOF-MS: 768.35
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　市販のＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６（ε型銅フタロシアニン顔料、ＤＩＣ製　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　Ａ５１０）１００質量部と、前記塩基性部位を有する青色色材誘導体１の５質量部とをアトライターで６０℃にて１．５時間乾式粉砕した。この粉砕生成物に、更に前記塩基性部位を有する青色色材誘導体１の５質量部を混合することにより、目的とする塩基性処理されたフタロシアニン顔料である、塩基性処理フタロシアニン顔料１を得た。 Commercially available C.I. I. Pigment Blue 15: 6 (ε-type copper phthalocyanine pigment, DIC FASTOGEN BLUE A510) and 5 parts by weight of the blue coloring material derivative 1 having a basic site are 1.5 hours at 60 ° C. with an attritor. Dry pulverized. This pulverized product was further mixed with 5 parts by mass of the blue coloring material derivative 1 having a basic site to obtain a basic-treated phthalocyanine pigment 1, which is an objective basic-treated phthalocyanine pigment. .
（合成例４：塩基性処理フタロシアニン顔料２の合成）
　合成例３の塩基性処理フタロシアニン顔料１の合成において、前記塩基性部位を有する青色色材誘導体１で表面処理する顔料として、市販のＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６を用いる代わりに、市販のＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：３（β型銅フタロシアニン顔料、ＤＩＣ製、ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　ＳＦＪ-ＳＤ）を用いた以外は、合成例３と同様にして、塩基性処理フタロシアニン顔料２を得た。 (Synthesis Example 4: Synthesis of basic treated phthalocyanine pigment 2)
In the synthesis of the base-treated phthalocyanine pigment 1 of Synthesis Example 3, commercially available C.I. I. Pigment Blue 15: 6 instead of using commercially available C.I. I. Pigment Blue 15: 3 (β-type copper phthalocyanine pigment, manufactured by DIC, FASTOGEN BLUE SFJ-SD) was used in the same manner as in Synthesis Example 3 to obtain a basic-treated phthalocyanine pigment 2.
（合成例５：塩基性処理フタロシアニン顔料３の合成）
　合成例３において、青色色材誘導体１の合成法のうち、１，１－ジエチル－１，５－ジアザペンタン１３質量部を用いる代わりに、１，１－ジイソプロピル－１，５－ジアザペンタンを１６質量部用いた以外は、青色色材誘導体１の合成方法と同様にして、青色色材誘導体２を合成した。
　得られた塩基性部位を有する青色色材誘導体２について、下記化学式（ｆ）の構造であることを確認した。
・ＴＯＦ-ＭＳ：７９６．４ (Synthesis Example 5: Synthesis of Basic Treated Phthalocyanine Pigment 3)
In Synthesis Example 3, 16 parts by mass of 1,1-diisopropyl-1,5-diazapentane was used instead of using 13 parts by mass of 1,1-diethyl-1,5-diazapentane in the method of synthesizing the blue colorant derivative 1. A blue colorant derivative 2 was synthesized in the same manner as in the synthesis method of the blue colorant derivative 1 except that it was used.
It was confirmed that the obtained blue coloring material derivative 2 having a basic site had the structure represented by the following chemical formula (f).
・ TOF-MS: 796.4
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　合成例３の塩基性処理フタロシアニン顔料１の合成において、青色色材誘導体１の代わりに青色色材誘導体２を用いた以外は、合成例３と同様にして、塩基性処理フタロシアニン顔料３を得た。 A basic treated phthalocyanine pigment 3 was obtained in the same manner as in Synthesis Example 3 except that the blue colored material derivative 1 was used instead of the blue colored material derivative 1 in the synthesis of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. .
（合成例６：塩基性処理フタロシアニン顔料４の合成）
　合成例３において、青色色材誘導体１の合成法のうち、１，１－ジエチル－１，５－ジアザペンタン１３質量部を用いる代わりに、１，１－ジブチル－１，５－ジアザペンタンを１９質量部用いた以外は、青色色材誘導体１の合成方法と同様にして、青色色材誘導体３を合成した。
　得られた塩基性部位を有する青色色材誘導体３について、下記化学式（ｇ）の構造であることを確認した。
・ＴＯＦ-ＭＳ：８２４．１５ (Synthesis Example 6: Synthesis of Basic Treated Phthalocyanine Pigment 4)
In Synthesis Example 3, 19 parts by mass of 1,1-dibutyl-1,5-diazapentane was used instead of using 13 parts by mass of 1,1-diethyl-1,5-diazapentane in the method of synthesizing the blue colorant derivative 1. Except for using, the blue color material derivative 3 was synthesized in the same manner as the synthesis method of the blue color material derivative 1.
It was confirmed that the resulting blue coloring material derivative 3 having a basic site had the structure represented by the following chemical formula (g).
・ TOF-MS: 824.15
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　合成例３の塩基性処理フタロシアニン顔料１の合成において、青色色材誘導体１の代わりに青色色材誘導体３を用いた以外は、合成例３と同様にして、塩基性処理フタロシアニン顔料４を得た。 A basic treated phthalocyanine pigment 4 was obtained in the same manner as in Synthesis Example 3 except that the blue coloring material derivative 3 was used instead of the blue coloring material derivative 1 in the synthesis of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. .
（合成例７：酸性分散剤Ａ１（前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体）の合成）
　（１）マクロモノマーＭＭ－１の合成
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、プロピレングリコールモノメチルエーテルアセテート（略称ＰＧＭＥＡ）８０．０質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。メタクリル酸メチル５０．０質量部、メタクリル酸－ｎ－ブチル３０．０質量部、メタクリル酸ベンジル２０．０質量部、２－メルカプトエタノール４．０質量部、ＰＧＭＥＡ３０質量部、α，α’－アゾビスイソブチロニトリル（略称ＡＩＢＮ）１．０質量部の混合溶液を１．５時間かけて滴下し、さらに３時間反応した。次に、窒素気流を止めて、この反応溶液を８０℃に冷却し、カレンズＭＯＩ（昭和電工製）８．７４質量部、ジラウリン酸ジブチルすず０．１２５質量部、ｐ－メトキシフェノール０．１２５質量部、及びＰＧＭＥＡ１０質量部、を加えて３時間攪拌することで、マクロモノマーＭＭ－１の４９．５質量％溶液を得た。得られたマクロモノマーＭＭ－１は、ＧＰＣ測定の結果、質量平均分子量（Ｍｗ）４０１０、数平均分子量（Ｍｎ）１９１０、分子量分布（Ｍｗ／Ｍｎ）２．１０であった。 (Synthesis Example 7: Synthesis of acidic dispersant A1 (polymer having at least one selected from structural units represented by formula (I)))
(1) Synthesis of Macromonomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated PGMEA) was placed in a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was charged and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, α, α'-azo A mixed solution of bisisobutyronitrile (abbreviation: AIBN) (1.0 part by mass) was added dropwise over 1.5 hours, and the mixture was further reacted for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol And 10 parts by mass of PGMEA, and stirred for 3 hours to obtain a 49.5% by mass solution of the macromonomer MM-1. As a result of GPC measurement, the obtained macromonomer MM-1 had a weight average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910, and a molecular weight distribution (Mw / Mn) of 2.10.
（２）グラフト共重合体Ａ１の合成
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、ＰＧＭＥＡ８５．０質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。前記マクロモノマーＭＭ－１溶液６７．３４質量部（固形分３３．３３質量部）、メタクリル酸グリシジル（略称ＧＭＡ）１６．６７質量部、ｎ－ドデシルメルカプタン１．２４質量部、ＰＧＭＥＡ２５．０質量部、ＡＩＢＮ０．５質量部の混合溶液を１．５時間かけて滴下し、３時間加熱攪拌したのち、ＡＩＢＮ０．１０質量部　、ＰＧＭＥＡ１０．０質量部　の混合液を１０分かけて滴下し、さらに同温で１時間熟成することで、グラフト共重合体Ａ１の２５．０質量％溶液を得た。得られたグラフト共重合体Ａ１は、ＧＰＣ測定の結果、質量平均分子量（Ｍｗ）１０５７０、数平均分子量（Ｍｎ）４３７０、分子量分布（Ｍｗ／Ｍｎ）２．４２であった。 (2) Synthesis of graft copolymer A1 85.0 parts by mass of PGMEA was charged into a reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and stirred under a nitrogen stream. Heated to a temperature of 90 ° C. 67.34 parts by mass of the macromonomer MM-1 solution (33.33 parts by mass of solid content), 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecylmercaptan, 25.0 parts by mass of PGMEA , AIBN 0.5 parts by mass over 1.5 hours, and after heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes. After aging for 1 hour at a temperature, a 25.0% by mass solution of the graft copolymer A1 was obtained. As a result of GPC measurement, the obtained graft copolymer A1 had a mass average molecular weight (Mw) of 10,570, a number average molecular weight (Mn) of 4,370, and a molecular weight distribution (Mw / Mn) of 2.42.
（３）前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ１）の製造
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、ＰＧＭＥＡ２７．８０質量部、フェニルホスホン酸（製品名「ＰＰＡ」日産化学製）９．２７質量部を仕込み、窒素気流下攪拌しながら、温度９０℃に加温した。
前記グラフト共重合体Ａ１の１００．０質量部を３０分かけて滴下し、２時間加熱攪拌することで、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ１）溶液（固形分２５．０質量％）を得た。得られた酸性分散剤Ａ１のＧＭＡとＰＰＡのエステル化反応の進行は、酸価測定と１Ｈ－ＮＭＲ測定によって確認した（エポキシ由来のピークが消失していることを確認）。得られた酸性分散剤Ａ１の酸価は９８ｍｇＫＯＨ／ｇであった。 (3) Production of polymer having at least one selected from structural units represented by formula (I) (acidic dispersant A1) Cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, digital A reactor equipped with a thermometer was charged with 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name “PPA” manufactured by Nissan Chemical Industries, Ltd.) and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. .
By dripping 100.0 parts by mass of the graft copolymer A1 over 30 minutes and heating and stirring for 2 hours, a polymer having at least one selected from the structural units represented by the general formula (I) is obtained. A combined (acidic dispersant A1) solution (solid content: 25.0% by mass) was obtained. The progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and 1 H-NMR measurement (confirmed that the peak derived from epoxy had disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH / g.
（合成例８：酸性分散剤Ａ２（前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体）の合成）
（１）ブロック共重合体Ａ２の合成
　特許第５８９５９２５号に記載の合成例６を参照し、メタクリル酸メチル（ＭＭＡ）５０質量部、メタクリル酸－ｎ－ブチル（ＢＭＡ）３０質量部、メタクリル酸ベンジル（ＢｚＭＡ）２０質量部のブロックと、メタクリル酸グリシジル（ＧＭＡ）２５質量部のブロックとを有するジブロック共重合体の４０質量％ＰＧＭＥＡ溶液を得た。得られたブロック共重合体Ａ２は、質量平均分子量（Ｍｗ）９４７０、数平均分子量（Ｍｎ）７８８０、分子量分布（Ｍｗ／Ｍｎ）は１．２０であった。
（２）前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ２）の製造
　反応器に、ブロック共重合体Ａ２　１００.０質量部、ＰＧＭＥＡ８６．７０質量部、フェニルホスホン酸（ＰＰＡ）８．９０質量部を仕込み、９０℃で２時間撹拌することで、前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体（酸性分散剤Ａ２）溶液（固形分２５質量％）を得た。ブロック共重合体Ａ２のＧＭＡとＰＰＡのエステル化反応の進行は、酸価測定と１Ｈ－ＮＭＲ測定によって確認した。得られた酸性分散剤Ａ２の酸価は６５ｍｇＫＯＨ／ｇであった。 (Synthesis Example 8: Synthesis of acidic dispersant A2 (a polymer having at least one selected from structural units represented by formula (I)))
(1) Synthesis of Block Copolymer A2 Referring to Synthesis Example 6 described in Japanese Patent No. 5889525, 50 parts by mass of methyl methacrylate (MMA), 30 parts by mass of n-butyl methacrylate (BMA), benzyl methacrylate A 40% by mass PGMEA solution of a diblock copolymer having (BzMA) 20 parts by mass and glycidyl methacrylate (GMA) 25 parts by mass was obtained. The obtained block copolymer A2 had a weight average molecular weight (Mw) of 9470, a number average molecular weight (Mn) of 7880, and a molecular weight distribution (Mw / Mn) of 1.20.
(2) Production of polymer (acid dispersant A2) having at least one selected from the structural units represented by formula (I): 100.0 parts by mass of block copolymer A2, PGMEA86 .70 parts by mass and 8.90 parts by mass of phenylphosphonic acid (PPA) were charged and stirred at 90 ° C. for 2 hours to have at least one selected from the structural units represented by the general formula (I). A polymer (acid dispersant A2) solution (solid content 25% by mass) was obtained. The progress of the esterification reaction between GMA and PPA of the block copolymer A2 was confirmed by acid value measurement and 1 H-NMR measurement. The acid value of the obtained acidic dispersant A2 was 65 mgKOH / g.
（合成例９：酸性分散剤Ｂ１（カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体）の合成）
　国際公開２０１６／１３２８６３号に記載の実施例１を参照し、ＭＭＡ２０質量部、ＢＭＡ４０質量部のブロックと、アクリル酸（ＭＡＡ）２０質量部、ＢＭＡ２０質量部のブロックと、ＭＭＡ２０質量部、ＢＭＡ４０質量部のブロックとを有する、トリブロック共重合体を合成した。得られたブロック共重合体は、質量平均分子量（Ｍｗ）１１０００、分子量分布（Ｍｗ／Ｍｎ）１．５０、酸価１３０ｍｇＫＯＨ／ｇだった。 (Synthesis Example 9) Acid dispersant B1 (a block copolymer including an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth) acrylate). Synthesis)
With reference to Example 1 described in International Publication WO 2016/1328643, a block of 20 parts by mass of MMA and 40 parts by mass of BMA, a block of 20 parts by mass of acrylic acid (MAA) and 20 parts by mass of BMA, and 20 parts by mass of MMA and 40 parts by mass of BMA A triblock copolymer having the following blocks was synthesized. The obtained block copolymer had a weight average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw / Mn) of 1.50, and an acid value of 130 mgKOH / g.
（合成例１０：酸性分散剤Ｂ２（カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体）の合成）
　モノマー仕込み比を下記組成に変更したこと以外は、合成例９と同様にして、ＭＭＡ３０質量部、ＢＭＡ４０質量部のブロックと、アクリル酸（ＭＡＡ）１０質量部、ＢＭＡ２０質量部のブロックと、ＭＭＡ２０質量部、ＢＭＡ４０質量部のブロックとを有する、トリブロック共重合体を合成した。得られたブロック共重合体は、質量平均分子量（Ｍｗ）１５５００、分子量分布（Ｍｗ／Ｍｎ）１．３５，酸価８０ｍｇＫＯＨ／ｇだった。 (Synthesis Example 10) Acid dispersant B2 (a block copolymer including an A block including a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block including a structural unit derived from an alkyl (meth) acrylate). Synthesis)
Except that the monomer charging ratio was changed to the following composition, a block of MMA 30 parts by mass, 40 parts by mass of BMA, a block of 10 parts by mass of acrylic acid (MAA), a block of 20 parts by mass of BMA, and 20 parts by mass of MMA And a block of 40 parts by mass of BMA were synthesized. The obtained block copolymer had a weight average molecular weight (Mw) of 15,500, a molecular weight distribution (Mw / Mn) of 1.35, and an acid value of 80 mgKOH / g.
（合成例１１：塩基性分散剤１の合成）
　反応器に、ＰＧＭＥＡ５１．１３質量部と３級アミノ基を含むブロック共重合体（商品名：ＢＹＫ－ＬＰＮ６９１９、ビックケミー製）（アミン価１２０ｍｇＫＯＨ／ｇ、固形分６０質量％）３０．００質量部（固形分１８．００質量部）を仕込み、ＰＰＡを３．０４質量部（ブロック共重合体の３級アミノ基に対して０．５モル当量）を加え、４０℃で３０分攪拌することで塩型アミン系ブロック共重合体（塩基性分散剤１）溶液（固形分２５質量％）を調製した。 (Synthesis Example 11: Synthesis of Basic Dispersant 1)
In a reactor, 51.13 parts by mass of a block copolymer containing PGMEA (51.13 parts by mass) and a tertiary amino group (trade name: BYK-LPN6919, manufactured by BYK-Chemie) (amine value: 120 mgKOH / g, solid content: 60% by mass) ( The solid content was 18.00 parts by mass, and 3.04 parts by mass of PPA (0.5 molar equivalent based on the tertiary amino group of the block copolymer) was added. The mixture was stirred at 40 ° C. for 30 minutes to form a salt. A type amine block copolymer (basic dispersant 1) solution (solid content: 25% by mass) was prepared.
（合成例１２：アルカリ可溶性樹脂Ａの合成）
　重合槽に、ＰＧＭＥＡを１５０質量部仕込み、窒素雰囲気下で１００℃に昇温した後、メタクリル酸（ＭＡＡ）２２質量部、メタクリル酸シクロヘキシル（ＣＨＭＡ）６４質量部及びパーブチルＯ（日油株式会社製）６質量部、連鎖移動剤（ｎ－ドデシルメルカプタン）２質量部を１．５時間かけて連続的に滴下した。その後、１００℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から２時間後に重合禁止剤として、ｐ－メトキシフェノール０．１質量部を添加して重合を停止した。
　次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル（ＧＭＡ）１４質量部を添加して、１１０℃に昇温した後、トリエチルアミン０．８質量部を添加して１１０℃で１５時間付加反応させ、アルカリ可溶性樹脂Ａ溶液（質量平均分子量（Ｍｗ）９，０００、酸価９０ｍｇＫＯＨ／ｇ、固形分４０質量％）を得た。 (Synthesis Example 12: Synthesis of alkali-soluble resin A)
After 150 parts by mass of PGMEA was charged into a polymerization tank and heated to 100 ° C. in a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA) and perbutyl O (manufactured by NOF CORPORATION) 6) parts by weight and 2 parts by weight of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100 ° C., and two hours after the completion of dropping of the mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing in air, 14 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and the temperature was raised to 110 ° C. Then, 0.8 parts by mass of triethylamine was added, and the mixture was added at 110 ° C for 15 hours. The addition reaction was carried out to obtain an alkali-soluble resin A solution (mass average molecular weight (Mw) 9,000, acid value 90 mgKOH / g, solid content 40% by mass).
　（調製例１：感光性バインダー成分ＣＲ－１の調製）
　合成例１２で得られたアルカリ可溶性樹脂Ａ溶液（固形分４０質量％）３６．５質量部に対して、光重合性化合物としてジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）（アロニックスＭ４０２（東亜合成製））２１．９質量部、開始剤としてイルガキュア９０７（ＢＡＳＦ製、α－アミノアセトフェノン系光開始剤）１．１質量部、ＳＰＩ－０４（三養製、フルオレン骨格を有するオキシムエステル系光開始剤）１．３質量部、カヤキュアーＤＥＴＸ－Ｓ（日本化薬製、チオキサントン系光開始剤）０．３質量部、酸化防止剤ＩＲＧＡＮＯＸ１０１０（ＢＡＳＦ製）０．８質量部、ＰＧＭＥＡ３８．１質量部を加えて、感光性バインダー成分ＣＲ－１を得た。 (Preparation Example 1: Preparation of photosensitive binder component CR-1)
With respect to 36.5 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Synthesis Example 12, dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toagosei)) as a photopolymerizable compound. 21.9 parts by mass, 1.1 parts by mass of Irgacure 907 (manufactured by BASF, α-aminoacetophenone photoinitiator), SPI-04 (manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton) 1 0.3 parts by mass, Kayacure DETX-S (manufactured by Nippon Kayaku, thioxanthone-based photoinitiator) 0.3 part by mass, antioxidant IRGANOX1010 (manufactured by BASF) 0.8 part by mass, and PGMEA 38.1 parts by mass, Thus, a photosensitive binder component CR-1 was obtained.
（実施例１）
（１）色材分散液Ｂ１
（１－１）レーキ色材１の色材分散液Ｂ１ａ１の調製
　合成例１のレーキ色材１　１０質量部と、合成例７の酸性分散剤Ａ１溶液　２０質量部（有効固形分　５.０質量部）と、合成例１２のアルカリ可溶性樹脂Ａ　７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡ　６２．５質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで４時間分散し、色材分散液Ｂ１ａ１を得た。
（１－２）塩基性処理フタロシアニン顔料１の色材分散液Ｂ１ｂ１の調製
　合成例３の塩基性処理フタロシアニン顔料１　１０質量部と、合成例９の酸性分散剤Ｂ１溶液　１６．７質量部（有効固形分　５．０質量部）と、合成例１２のアルカリ可溶性樹脂Ａ　７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡ　６５．８質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで６時間分散し、色材分散液Ｂ１ｂ１を得た。
（１－３）色材分散液Ｂ１の調製
　前記（１－１）で得られた色材分散液Ｂ１ａ１を２質量部に対して、前記（１－２）で得られた色材分散液Ｂ１ｂ１を９８質量部混合することにより、色材分散液Ｂ１を調製した。
（２）着色樹脂組成物Ｂ１
　色材分散液Ｂ１　１６．７質量部、調製例１の感光性バインダー成分ＣＲ－１　２４．０質量部、界面活性剤メガファックＲ０８ＭＨ（ＤＩＣ製）　０．３質量部、ＰＧＭＥＡ　５９．０質量部を混合し、実施例１の着色樹脂組成物Ｂ１を得た。 (Example 1)
(1) Colorant dispersion B1
(1-1) Preparation of Coloring Material Dispersion B1a1 of Lake Coloring Material 1 10 parts by mass of Lake Coloring Material 1 of Synthesis Example 1 and 20 parts by mass of Acid Dispersant A1 Solution of Synthesis Example 7 (5.0 mass of effective solids) Parts), 7.5 parts by mass of the alkali-soluble resin A of Synthesis Example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA, and the mixture was preliminarily prepared using a paint shaker (made by Asada Iron Works). Dispersion was performed with 2 mm zirconia beads for 1 hour and further with 0.1 mm zirconia beads for 4 hours to obtain a colorant dispersion B1a1.
(1-2) Preparation of Coloring Material Dispersion B1b1 of Basic Treated Phthalocyanine Pigment 1 10 parts by mass of basic treated phthalocyanine pigment 1 of Synthesis Example 3 and 16.7 parts by mass of acidic dispersant B1 solution of Synthesis Example 9 (effective A solid content of 5.0 parts by mass), 7.5 parts by mass of the alkali-soluble resin A of Synthesis Example 12 (3.0 parts by mass of effective solids), and 65.8 parts by mass of PGMEA were mixed, and a paint shaker (Asada) was added. As a preliminary dispersion, the mixture was dispersed with 2 mm zirconia beads for 1 hour and further dispersed with 0.1 mm zirconia beads for 6 hours to obtain a colorant dispersion B1b1.
(1-3) Preparation of Color Material Dispersion B1 The color material Dispersion B1b1 obtained in (1-2) is based on 2 parts by mass of the Color Material Dispersion B1a1 obtained in (1-1). Was mixed by 98 parts by mass to prepare a coloring material dispersion B1.
(2) Colored resin composition B1
Color material dispersion B1 16.7 parts by mass, photosensitive binder component CR-1 of Preparation Example 1 24.0 parts by mass, surfactant Megafac R08MH (manufactured by DIC) 0.3 part by mass, PGMEA 59.0 parts by mass Was mixed to obtain a colored resin composition B1 of Example 1.
（実施例２～１３）
（１）色材分散液Ｂ２～Ｂ１３
　表１に示した色材比率（質量比）になるように、色材分散液Ｂ１ａ１と色材分散液Ｂ１ｂ１との混合割合を変更した以外は、実施例１と同様にして、色材分散液Ｂ２～Ｂ１３を調製した。
（２）着色樹脂組成物Ｂ２～Ｂ１３
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液Ｂ２～Ｂ１３をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物Ｂ２～Ｂ１３を得た。 (Examples 2 to 13)
(1) Colorant dispersions B2 to B13
Except that the mixing ratio of the color material dispersion B1a1 and the color material dispersion B1b1 was changed so that the color material ratio (mass ratio) shown in Table 1 was obtained, the color material dispersion was obtained in the same manner as in Example 1. B2 to B13 were prepared.
(2) Colored resin compositions B2 to B13
Colored resin compositions B2 to B13 were obtained in the same manner as in Example 1 except that the colorant dispersions B2 to B13 were used instead of the colorant dispersion B1.
（実施例１４～２１）
（１）色材分散液Ｂ１４～Ｂ２１
　実施例１の（１－１）と同様にして、色材分散液Ｂ１ａ１を得た。
　実施例１の（１－１）において、合成例１のレーキ色材１の代わりに、合成例２のレーキ色材２を用いた以外は同様にして、色材分散液Ｂ２ａ１を得た。
　また、実施例１の（１－１）において、合成例７の酸性分散剤Ａ１溶液の代わりに、合成例８の酸性分散剤Ａ２溶液を用いた以外は同様にして、色材分散液Ｂ１ａ２を得た。
　更に、実施例１の（１－２）と同様にして、色材分散液Ｂ１ｂ１を得た。
　実施例１の（１－２）において、合成例３の塩基性処理フタロシアニン顔料１の代わりに、合成例４の塩基性処理フタロシアニン顔料２を用いた以外は同様にして、色材分散液Ｂ２ｂ１を得た。
　実施例１の（１－２）において、合成例３の塩基性処理フタロシアニン顔料１の代わりに、合成例５の塩基性処理フタロシアニン顔料３を用いた以外は同様にして、色材分散液Ｂ３ｂ１を得た。
　実施例１の（１－２）において、合成例３の塩基性処理フタロシアニン顔料１の代わりに、合成例６の塩基性処理フタロシアニン顔料４を用いた以外は同様にして、色材分散液Ｂ４ｂ１を得た。
　また、実施例１の（１－２）において、合成例９の酸性分散剤Ｂ１溶液の代わりに、合成例１０の酸性分散剤Ｂ２溶液を用いた以外は同様にして、色材分散液Ｂ１ｂ２を得た。
　表２に示した色材比率（質量比）になるように、色材分散液Ｂ１ａ１、Ｂ２ａ１又はＢ１ａ２と、色材分散液Ｂ１ｂ１、Ｂ２ｂ１、Ｂ３ｂ１、Ｂ４ｂ１又はＢ１ｂ２との混合割合を変更した以外は、実施例１と同様にして、色材分散液Ｂ１４～Ｂ２１を調製した。
（２）着色樹脂組成物Ｂ１４～Ｂ２１
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液Ｂ１４～Ｂ２１をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物Ｂ１４～Ｂ２１を得た。 (Examples 14 to 21)
(1) Colorant dispersions B14 to B21
A colorant dispersion B1a1 was obtained in the same manner as in (1-1) of Example 1.
A colorant dispersion B2a1 was obtained in the same manner as in (1-1) of Example 1, except that the rake colorant 2 of Synthesis Example 2 was used instead of the rake colorant 1 of Synthesis Example 1.
Further, in the same manner as in (1-1) of Example 1, except that the acidic dispersant A2 solution of Synthesis Example 8 was used instead of the acidic dispersant A1 solution of Synthesis Example 7, the coloring material dispersion B1a2 was prepared in the same manner. Obtained.
Further, a colorant dispersion B1b1 was obtained in the same manner as in (1-2) of Example 1.
The colorant dispersion B2b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 2 of Synthesis Example 4 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained.
The colorant dispersion B3b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 3 of Synthesis Example 5 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained.
A colorant dispersion B4b1 was prepared in the same manner as in (1-2) of Example 1, except that the basic treated phthalocyanine pigment 4 of Synthesis Example 6 was used instead of the basic treated phthalocyanine pigment 1 of Synthesis Example 3. Obtained.
Further, in the same manner as in (1-2) of Example 1, except that the acidic dispersant B2 solution of Synthesis Example 10 was used instead of the acidic dispersant B1 solution of Synthesis Example 9, the coloring material dispersion B1b2 was prepared in the same manner. Obtained.
Except that the mixing ratio of the color material dispersion B1a1, B2a1 or B1a2 and the color material dispersion B1b1, B2b1, B3b1, B4b1 or B1b2 was changed so that the color material ratio (mass ratio) shown in Table 2 was obtained. In the same manner as in Example 1, colorant dispersions B14 to B21 were prepared.
(2) Colored resin compositions B14 to B21
Colored resin compositions B14 to B21 were obtained in the same manner as in Example 1 except that the colorant dispersions B14 to B21 were used instead of the colorant dispersion B1.
（実施例２２）
（１）色材分散液Ｂ２２
　合成例１のレーキ色材１　５．０質量部と、合成例３の塩基性処理フタロシアニン顔料１　５．０質量部と、合成例７の酸性分散剤Ａ１溶液　２０質量部（有効固形分　５．０質量部）と、合成例１２のアルカリ可溶性樹脂Ａ　７．５質量部（有効固形分　３．０質量部）と、ＰＧＭＥＡ　６２．５質量部とを混合し、ペイントシェーカー（浅田鉄工製）にて予備分散として２ｍｍジルコニアビーズで１時間、さらに本分散として０．１ｍｍジルコニアビーズで６時間分散し、色材分散液Ｂ２２を得た。
（２）着色樹脂組成物Ｂ２２
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液Ｂ２２をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物Ｂ２２を得た。 (Example 22)
(1) Colorant dispersion B22
5.0 parts by mass of the lake color material 1 of Synthesis Example 1, 1 part by mass of the basic treated phthalocyanine pigment of Synthesis Example 3, and 20 parts by mass of the acidic dispersant A1 solution of Synthesis Example 7 (effective solid content: 5. 0 parts by mass), 7.5 parts by mass of the alkali-soluble resin A of Synthesis Example 12 (3.0 parts by mass of the effective solid content), and 62.5 parts by mass of PGMEA, and mixed with a paint shaker (made by Asada Tekko). The resultant was dispersed for 1 hour with 2 mm zirconia beads as a preliminary dispersion and further for 6 hours with 0.1 mm zirconia beads as a main dispersion to obtain a colorant dispersion B22.
(2) Colored resin composition B22
A colored resin composition B22 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid B22 was used instead of the coloring material dispersion liquid B1.
（実施例２３～２４）
（１）色材分散液Ｂ２３～Ｂ２４
　実施例２２において、色材の含有比率と、レーキ色材の種類について、表２に示したように変更した以外は、実施例２２と同様にして、色材分散液Ｂ２３～Ｂ２４を調製した。
（２）着色樹脂組成物Ｂ２３～Ｂ２４
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液Ｂ２３～Ｂ２４をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物Ｂ２３～Ｂ２４を得た。 (Examples 23 and 24)
(1) Colorant dispersions B23 to B24
Coloring material dispersions B23 to B24 were prepared in the same manner as in Example 22, except that the content ratio of the coloring material and the type of the rake coloring material were changed as shown in Table 2.
(2) Colored resin composition B23 to B24
Colored resin compositions B23 to B24 were obtained in the same manner as in Example 1 except that the colorant dispersions B23 to B24 were used instead of the colorant dispersion B1.
（比較例１及び５）
（１）色材分散液ＣＢ１及びＣＢ５
　実施例２２において、塩基性処理フタロシアニン顔料１の代わりに、市販のピグメントブルー１５：６（ＤＩＣ　製　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　Ａ５１０）を用い、色材の含有比率を、表２に示したように変更した以外は、実施例２２と同様にして、色材分散液ＣＢ１及びＣＢ５を調製した。
（２）着色樹脂組成物ＣＢ１及びＣＢ５
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液ＣＢ１及びＣＢ５をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物ＣＢ１及びＣＢ５を得た。 (Comparative Examples 1 and 5)
(1) Colorant dispersions CB1 and CB5
In Example 22, in place of the basic-treated phthalocyanine pigment 1, a commercially available Pigment Blue 15: 6 (manufactured by DIC, FASTOGEN BLUE A510) was used, and the content ratio of the coloring material was changed as shown in Table 2. In the same manner as in Example 22, colorant dispersions CB1 and CB5 were prepared.
(2) Colored resin compositions CB1 and CB5
Colored resin compositions CB1 and CB5 were obtained in the same manner as in Example 1 except that the colorant dispersions CB1 and CB5 were used instead of the colorant dispersion B1.
（比較例２）
（１）色材分散液ＣＢ２
　比較例１において、合成例７の酸性分散剤Ａ１溶液を用いる代わりに、合成例１１の塩基性分散剤１溶液に変更した以外は、比較例１と同様にして、色材分散液ＣＢ２を調製した。
（２）着色樹脂組成物ＣＢ２
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液ＣＢ２を用いた以外は、実施例１と同様にして、着色樹脂組成物ＣＢ２を得た。 (Comparative Example 2)
(1) Colorant dispersion CB2
In Comparative Example 1, a colorant dispersion CB2 was prepared in the same manner as in Comparative Example 1 except that the acidic dispersant A1 solution of Synthesis Example 7 was changed to the basic dispersant 1 solution of Synthesis Example 11. did.
(2) Colored resin composition CB2
A colored resin composition CB2 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid CB2 was used instead of the coloring material dispersion liquid B1.
（比較例３）
（１）色材分散液ＣＢ３
　実施例２２において、塩基性処理フタロシアニン顔料１を用いず、合成例１のレーキ色材１　１０質量部用いた以外は、実施例２２と同様にして、色材分散液ＣＢ３を調製した。
（２）着色樹脂組成物ＣＢ３
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液ＣＢ３をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物ＣＢ３を得た。 (Comparative Example 3)
(1) Colorant dispersion CB3
A colorant dispersion CB3 was prepared in the same manner as in Example 22 except that the basic treated phthalocyanine pigment 1 was not used and the lake colorant 110 of Synthesis Example 1 was used in an amount of 10 parts by mass.
(2) Colored resin composition CB3
A colored resin composition CB3 was obtained in the same manner as in Example 1, except that the coloring material dispersion liquid CB3 was used instead of the coloring material dispersion liquid B1.
（比較例４）
（１）色材分散液ＣＢ４
　実施例２２において、合成例１のレーキ色材１及び塩基性処理フタロシアニン顔料１を用いず、市販のピグメントブルー１５：６（ＤＩＣ　製　ＦＡＳＴＯＧＥＮ　ＢＬＵＥ　Ａ５１０）を１０質量部用いた以外は、実施例２２と同様にして、色材分散液ＣＢ４を調製した。
（２）着色樹脂組成物ＣＢ４
　実施例１において、色材分散液Ｂ１の代わりに、色材分散液ＣＢ４をそれぞれ用いた以外は、実施例１と同様にして、着色樹脂組成物ＣＢ４を得た。 (Comparative Example 4)
(1) Colorant dispersion CB4
Example 22 Example 22 was repeated except that the lake color material 1 and the basic phthalocyanine pigment 1 of Synthesis Example 1 were not used, and 10 parts by mass of a commercially available Pigment Blue 15: 6 (FASTOGEN BLUE A510 manufactured by DIC) was used. In the same manner as in the above, a colorant dispersion CB4 was prepared.
(2) Colored resin composition CB4
A colored resin composition CB4 was obtained in the same manner as in Example 1, except that the coloring material dispersion liquid CB4 was used instead of the coloring material dispersion liquid B1.
［評価方法］
＜分散性＞
　実施例及び比較例で得られた色材分散液についてそれぞれ、調製直後の初期粘度を測定した。なお粘度は、振動式粘度計を用いて、２５．０±０．５℃における粘度を測定した。
（分散性評価基準）
ＡＡ：粘度が５ｃＰ未満
Ａ：　粘度が５ｃＰ以上１０ｃＰ未満
Ｂ：　粘度が１０ｃＰ以上１５ｃＰ未満
Ｃ：　粘度が１５ｃＰ以上２０ｃＰ未満
Ｄ：　粘度が２０ｃＰ以上
　ただし、色材分散液の溶剤を含めた合計質量に対して、色材を１０質量％としたときの値である。 [Evaluation method]
<Dispersibility>
The initial viscosities immediately after preparation were measured for the colorant dispersions obtained in Examples and Comparative Examples. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer.
(Dispersibility evaluation criteria)
AA: viscosity is less than 5 cP A: viscosity is 5 cP or more and less than 10 cP B: viscosity is 10 cP or more and less than 15 cP C: viscosity is 15 cP or more and less than 20 cP D: viscosity is 20 cP or more, provided that the total mass of the colorant dispersion including the solvent is included. On the other hand, it is a value when the color material is 10% by mass.
＜保存安定性＞
　実施例及び比較例で得られた色材分散液についてそれぞれ、調製直後の初期粘度と、２５℃で７日間保存後の粘度を測定し、粘度変化を確認した。
（保存安定性評価基準）
Ａ：保存前後の粘度の差の絶対値が測定誤差範囲内（０．５ｃＰ未満）
Ｂ：保存前後の粘度の差の絶対値が　０．５ｃＰ以上１．０ｃＰ未満
Ｃ：保存前後の粘度の差の絶対値が１．０ｃＰ以上
　ただし、色材分散液の溶剤を含めた合計質量に対して、色材を１０質量％としたときの値である。 <Storage stability>
With respect to the colorant dispersions obtained in Examples and Comparative Examples, the initial viscosity immediately after preparation and the viscosity after storage at 25 ° C. for 7 days were measured to confirm the change in viscosity.
(Storage stability evaluation criteria)
A: Absolute value of difference in viscosity before and after storage is within measurement error range (less than 0.5 cP)
B: Absolute value of the difference in viscosity before and after storage is 0.5 cP or more and less than 1.0 cP C: Absolute value of the difference in viscosity before and after storage is 1.0 cP or more, provided that the total mass of the colorant dispersion including the solvent is included. On the other hand, it is a value when the color material is 10% by mass.
＜光学性能＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、ポストベーク後の色度がｙ＝０．１００になるようにスピンコーターを用いて塗布した。その後、８０℃のホットプレート上で３分間加熱乾燥を行った。フォトマスクを介さずに超高圧水銀灯を用いて６０ｍＪ／ｃｍ２の紫外線を照射し、次いで２３０℃のクリーンオーブンで３０分間ポストベークすることによってすることによって硬化膜（青色着色膜）を得た。得られた着色基板の色度（ｘ、ｙ）、輝度（Ｙ）をオリンパス社製「顕微分光測定装置ＯＳＰ－ＳＰ２００」を用いて測定した。 <Optical performance>
Each of the colored resin compositions of Examples and Comparative Examples was placed on a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) to have a chromaticity of y = 0.100 after post-baking. As described above using a spin coater. Thereafter, heating and drying were performed on a hot plate at 80 ° C. for 3 minutes. The cured film (blue colored film) was obtained by irradiating an ultraviolet ray of 60 mJ / cm 2 using a super-high pressure mercury lamp without using a photomask and then performing post-baking in a clean oven at 230 ° C. for 30 minutes. The chromaticity (x, y) and luminance (Y) of the obtained colored substrate were measured using an Olympus “Microspectrophotometer OSP-SP200”.
＜基板密着性＞
　各実施例及び比較例で得られた硬化膜（青色着色膜）について、ＪＩＳ Ｋ ５６００－５－６に準拠したクロスカット試験を行い、テープによる剥離操作を繰り返し５回実施した後、硬化膜の剥がれの有無を観察し、下記評価基準により評価した。
（基板密着性評価基準）
ＡＡ：どの格子の目も剥がれがない
Ａ：　カットの線に沿って硬化膜が剥がれている箇所はあるが、格子全体が剥がれている箇所はない
Ｂ：　格子全体が剥がれている箇所があり、剥がれの専有面積が２５％未満
Ｃ：　格子全体が剥がれている箇所があり、剥がれの専有面積が２５％以上 <Substrate adhesion>
A cross-cut test according to JIS K 5600-5-6 was performed on the cured film (blue colored film) obtained in each of the examples and comparative examples, and a peeling operation using a tape was repeatedly performed five times. The presence or absence of peeling was observed and evaluated according to the following evaluation criteria.
(Substrate adhesion evaluation criteria)
AA: There is no peeling of any grid A: There is a place where the cured film is peeled along the cut line, but there is no place where the whole grid is peeled B: There is a place where the whole grid is peeled, Exclusive area of peeling is less than 25% C: There is a place where the entire grid is peeled off, and the exclusive area of peeling is 25% or more
＜塗膜均一性＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、クロム蒸着した１００ｍｍ角のガラス基板に、スピンコーターを用いて塗布した。塗布した基板を減圧乾燥機に入れ、３０Ｐａで減圧乾燥を行った。このように作製した硬化膜を干渉縞検査灯（ナトリウムランプ）を用いて観察し、塗膜に発生する乾燥ムラの有無を目視評価した。
（塗膜均一性評価基準）
Ａ：硬化膜にムラが無い
Ｂ：硬化膜全体の５０％未満の範囲に軽微なムラがある
Ｃ：硬化膜全体の５０％以上の範囲にムラがある <Coating uniformity>
Each of the colored resin compositions of Examples and Comparative Examples was applied to a 100 mm square glass substrate on which chromium was vapor-deposited, using a spin coater. The coated substrate was placed in a reduced-pressure drier and dried at 30 Pa under reduced pressure. The cured film thus produced was observed using an interference fringe inspection lamp (sodium lamp), and the presence or absence of drying unevenness generated in the coating film was visually evaluated.
(Coating film uniformity evaluation criteria)
A: no unevenness in the cured film B: slight unevenness in less than 50% of the entire cured film C: unevenness in 50% or more of the entire cured film
＜現像性＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、スピンコーターを用いて塗布した。その後、８０℃のホットプレート上で３分間加熱乾燥を行った。この着色層に、線幅１μｍから１００μｍまでの独立細線パターンフォトマスクを介して、超高圧水銀灯を用いて、６０ｍＪ／ｃｍ２の紫外線で露光することにより、ガラス基板上に厚さ２．０μｍの着色層を形成した。
　次いで、０．０５質量％の水酸化カリウム（ＫＯＨ）水溶液を現像液として、スピン現像し、現像液に接液させた後に純水で洗浄することで現像処理し、パターン形成を行い、現像性を評価した。上記現像処理において、未露光部が溶解し除去されるまでの時間を測定した。現像の終了は、目視により観察し、現像時間について下記基準で判定した。
（現像性評価基準）
ＡＡ：４０秒未満
Ａ：　４０秒以上６０秒未満
Ｂ：　６０秒以上８０秒未満
Ｃ：　８０秒以上 <Developability>
Each of the colored resin compositions of Examples and Comparative Examples was applied on a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. Thereafter, heating and drying were performed on a hot plate at 80 ° C. for 3 minutes. The colored layer is exposed to ultraviolet light of 60 mJ / cm 2 using an ultrahigh-pressure mercury lamp through an independent fine line pattern photomask having a line width of 1 μm to 100 μm to form a 2.0 μm thick glass substrate. A colored layer was formed.
Next, spin development is performed using a 0.05% by mass aqueous solution of potassium hydroxide (KOH) as a developing solution, and the developing process is performed by contacting the developing solution and then washing with pure water to form a pattern. Was evaluated. In the above-mentioned development processing, the time until the unexposed portion was dissolved and removed was measured. The end of the development was visually observed, and the development time was determined based on the following criteria.
(Developability evaluation criteria)
AA: less than 40 seconds A: 40 seconds or more and less than 60 seconds B: 60 seconds or more and less than 80 seconds C: 80 seconds or more
＜線幅シフト＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、スピンコーターを用いて膜厚が３μｍになるように塗布した。その後、８０℃のホットプレート上で３分間加熱乾燥を行った後、開口幅が９０μｍである細線パターン（線幅シフト評価用パターン）と開口寸法９０μｍ×３００μｍの独立細線内の中央に２０μｍ×２０μｍのクロムマスクを配置したパターン（微小孔評価用パターン）を有するフォトマスクパターンを介して、超高圧水銀灯を用いて６０ｍＪ／ｃｍ２の紫外線を照射した。その後、着色層が形成されたガラス板を、アルカリ現像液として０．０５質量％水酸化カリウム水溶液を用いてシャワー現像し、２３０℃のクリーンオーブンで３０分間ポストベークした。ガラス基板に形成された着色層細線パターンの独立細線のうち、フォトマスクの開口幅が９０μｍで、設計線幅を９５μｍとした時の実際に測定した独立細線の幅（線幅）を測定し、下記基準で評価した。
（線幅シフト評価基準）
　下記式により、設計線幅からのずれである線幅シフト値（μｍ）を算出した。
　　線幅シフト値（μｍ）＝測定した線幅（μｍ）－９５（μｍ）
Ａ：線幅シフト値が－２μｍ以上２μｍ以下
Ｂ：線幅シフト値が－４μｍ以上－２μｍ未満
Ｃ：線幅シフト値が－４μｍ未満又は２μｍ超過
　設計線幅からのずれが小さいほど所望の線幅でパターンを形成できると評価される。 <Line width shift>
Each of the colored resin compositions of Examples and Comparative Examples was applied to a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater so that the film thickness became 3 μm. did. Thereafter, after heating and drying on a hot plate at 80 ° C. for 3 minutes, a fine line pattern having an opening width of 90 μm (a pattern for evaluating line width shift) and a center of 20 μm × 20 μm in an independent fine line having an opening size of 90 μm × 300 μm. Ultraviolet light of 60 mJ / cm 2 was irradiated using an ultrahigh pressure mercury lamp through a photomask pattern having a pattern (a pattern for evaluating micropores) on which a chromium mask was arranged. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous solution of potassium hydroxide as an alkaline developer, and was post-baked in a 230 ° C. clean oven for 30 minutes. Among the independent fine lines of the colored layer fine line pattern formed on the glass substrate, the width (line width) of the actually measured independent fine line when the opening width of the photomask is 90 μm and the design line width is 95 μm, Evaluation was made according to the following criteria.
(Evaluation criteria for line width shift)
A line width shift value (μm), which is a deviation from the design line width, was calculated by the following equation.
Line width shift value (μm) = measured line width (μm) −95 (μm)
A: Line width shift value is −2 μm or more and 2 μm or less B: Line width shift value is −4 μm or more and less than −2 μm C: Line width shift value is less than −4 μm or more than 2 μm The smaller the deviation from the design line width, the more a desired line It is evaluated that a pattern can be formed with the width.
＜加熱工程後の色度変化（ΔＥａｂ）＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）製、「ＮＡ３５」）上に、ポストベーク後の色度がｙ＝０．１００になるようにスピンコーターを用いて塗布した。その後、８０℃のホットプレート上で３分間加熱乾燥を行った。フォトマスクを介さずに超高圧水銀灯を用いて６０ｍＪ／ｃｍ２の紫外線を照射することによって硬化膜（青色着色膜）を得た。得られた膜を２３０℃のクリーンオーブンで３０分間ポストベークし、オリンパス（株）社製「顕微分光測定装置ＯＳＰ－ＳＰ２００」を用いて、この着色膜の色度（Ｌ０、ａ０、ｂ０）を測定した。その後、前記着色膜を更に２３０℃のクリーンオーブンで１５０分間ポストベークし、得られた着色膜の色度（Ｌ１、ａ１、ｂ１）を再び測定した
　下記式により、２３０℃３０分後から１５０分後にかけての着色膜の色度変化を評価した。
　　　ΔＥａｂ＝｛（Ｌ１－Ｌ０）２＋（ａ１－ａ０）２＋（ｂ１－ｂ０）２｝１／２
（ΔＥａｂ評価基準）
ＡＡ：ΔＥａｂが３以下
Ａ：　ΔＥａｂが３超過５以下
Ｂ：　ΔＥａｂが５超過７以下
Ｃ：　ΔＥａｂが７超過１０以下
Ｄ：　ΔＥａｂが１０超過 <Change in chromaticity after heating step (ΔEab)>
Each of the colored resin compositions of Examples and Comparative Examples was placed on a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) to have a chromaticity of y = 0.100 after post-baking. As described above using a spin coater. Thereafter, heating and drying were performed on a hot plate at 80 ° C. for 3 minutes. The cured film (blue colored film) was obtained by irradiating an ultraviolet ray of 60 mJ / cm 2 using an ultra-high pressure mercury lamp without using a photomask. The obtained film is post-baked in a clean oven at 230 ° C. for 30 minutes, and the chromaticity (L 0 , a 0 , b) of this colored film is measured using “Microspectrophotometer OSP-SP200” manufactured by Olympus Corporation. 0 ) was measured. Thereafter, the colored film was further post-baked in a clean oven at 230 ° C. for 150 minutes, and the chromaticity (L 1 , a 1 , b 1 ) of the obtained colored film was measured again. The change in chromaticity of the colored film from 150 minutes after was evaluated.
ΔEab = {(L 1 −L 0 ) 2 + (a 1 −a 0 ) 2 + (b 1 −b 0 ) 2 } 1/2
(ΔEab evaluation criteria)
AA: ΔEab is 3 or less A: ΔEab exceeds 3 and 5 or less B: ΔEab exceeds 5 and 7 or less C: ΔEab exceeds 7 and 10 or less D: ΔEab exceeds 10
＜現像残渣評価＞
　実施例及び比較例の着色樹脂組成物をそれぞれ、厚み０．７ｍｍのガラス基板（ＮＨテクノグラス（株）社製、「ＮＡ３５」）上に、スピンコーターを用いて塗布した後、ホットプレートを用いて６０℃で３分間乾燥することにより、厚さ２．５μｍの着色層を形成した。上記着色層が形成されたガラス板を、アルカリ現像液として０．０５質量％水酸化カリウム水溶液を用いて６０秒間シャワー現像した。上記着色層の形成後のガラス基板の未露光部（５０ｍｍ×５０ｍｍ）を、目視により観察した後、エタノールを含ませたレンズクリーナー（東レ社製、商品名トレシーＭＫクリーンクロス）で十分に拭き取り、そのレンズクリーナーの着色度合いを目視で観察した。
（現像残渣評価基準）
　Ａ：目視により現像残渣が確認されず、レンズクリーナーが全く着色しなかった
　Ｂ：目視により現像残渣が確認されず、レンズクリーナーの着色がわずかに確認された
　Ｃ：目視により現像残渣がわずかに確認され、レンズクリーナーの着色が確認された
　Ｄ：目視により現像残渣が確認され、レンズクリーナーの着色が確認された <Development residue evaluation>
Each of the colored resin compositions of Examples and Comparative Examples was applied on a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater and then using a hot plate. And dried at 60 ° C. for 3 minutes to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass aqueous solution of potassium hydroxide as an alkaline developer. After visually observing an unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, it was sufficiently wiped off with a lens cleaner (trade name: Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.) containing ethanol. The degree of coloring of the lens cleaner was visually observed.
(Development residue evaluation criteria)
A: No development residue was visually observed, and the lens cleaner was not colored at all. B: No development residue was visually observed, and slight coloring of the lens cleaner was confirmed. C: Development residue was slightly visually confirmed. D: Coloring of the lens cleaner was confirmed. D: Development residue was visually confirmed, and coloring of the lens cleaner was confirmed.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
 　表１及び表２において、色材比率は、全色材量を１００とした時の比率、分散剤比率は、全分散剤量を１００とした時の比率である。
Figure JPOXMLDOC01-appb-T000031
 In Tables 1 and 2, the color material ratio is a ratio when the total color material amount is 100, and the dispersant ratio is a ratio when the total dispersant amount is 100.
［結果のまとめ］
　表の結果から、前記一般式（１）で表される色材及び前記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材に、塩基性処理されたフタロシアニン顔料を組み合わせ、且つ、分散剤として前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む酸性分散剤を組み合わせて用いた実施例１～２４は、所定のレーキ色材とフタロシアニン顔料とを所望の範囲で混合しても分散性と保存安定性に優れ、且つ、基板密着性と塗膜均一性が向上した着色層を形成可能であることが示された。
　一方、フタロシアニン顔料として、塩基性処理されていない市販のフタロシアニン顔料を用いた比較例１及び５では、当該フタロシアニン顔料の含有量を少し増加させただけで分散性及び保存安定性が悪化していくことが示された。更に、フタロシアニン顔料として、塩基性処理されていない市販のフタロシアニン顔料を用いた比較例１及び５では、実施例に比べて基板密着性と塗膜均一性が劣るものであった。
　フタロシアニン顔料として、塩基性処理されていない市販のフタロシアニン顔料を用い、更に分散剤として塩基性分散剤を用いた比較例２では、色材の分散性及び保存安定性が悪く、基板密着性と塗膜均一性が劣るものであり、更に、現像性と加熱後の色度変化及び現像残渣の点からも劣るものであった。
　フタロシアニン顔料を用いずに、レーキ色材のみを用いた比較例３では、実施例と比べて分散性に劣り、且つ、基板密着性と塗膜均一性が劣るものであった。
　塩基性処理されていない市販のフタロシアニン顔料のみを前記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体で分散させた比較例４では、初期粘度が高すぎて、評価可能な塗膜を形成するに至らなかった。 [Summary of results]
From the results in the table, a basic treatment was performed on at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2). Examples 1 to 24 using a phthalocyanine pigment in combination with an acidic dispersant containing a polymer having at least one kind selected from the structural units represented by formula (I) as a dispersant, Even if a predetermined lake colorant and a phthalocyanine pigment are mixed in a desired range, it is possible to form a colored layer having excellent dispersibility and storage stability, and improved substrate adhesion and coating film uniformity. Indicated.
On the other hand, in Comparative Examples 1 and 5 in which a commercially available phthalocyanine pigment not subjected to basic treatment was used as the phthalocyanine pigment, the dispersibility and storage stability deteriorated only by slightly increasing the content of the phthalocyanine pigment. It was shown that. Furthermore, in Comparative Examples 1 and 5 in which a commercially available phthalocyanine pigment that had not been subjected to a basic treatment was used as the phthalocyanine pigment, the substrate adhesion and the coating film uniformity were inferior to those of the examples.
In Comparative Example 2 in which a commercially available phthalocyanine pigment that had not been subjected to basic treatment was used as the phthalocyanine pigment and a basic dispersant was used as the dispersant, the dispersibility and storage stability of the coloring material were poor, and the adhesion to the substrate was poor. The film uniformity was poor, and the developability, chromaticity change after heating and development residue were also poor.
In Comparative Example 3 using only the lake coloring material without using the phthalocyanine pigment, the dispersibility was poor, and the substrate adhesion and the coating film uniformity were poor as compared with the examples.
In Comparative Example 4 in which only a commercially available phthalocyanine pigment not subjected to basic treatment was dispersed with a polymer having at least one selected from the structural units represented by the general formula (I), the initial viscosity was too high. And no evaluable coating film was formed.
　実施例の中でも、実施例１～１３を比較すると、前記レーキ色材の含有量が、前記レーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下であると、高温加熱工程後の色度変化が抑制されながら、線幅シフトが抑制されて所望の線幅でパターンを形成可能な点から好ましいものであることが示された。
　また、実施例１～１３と実施例２２～２４とを比較すると、前記酸性分散剤が、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含むと、現像残渣の抑制性が向上することが示された。 Among the examples, when comparing Examples 1 to 13, it is found that the content of the lake color material is 20% by mass or more and 85% by mass or less with respect to the total content of the lake color material and the phthalocyanine pigment. It was shown that this is preferable because the line width shift is suppressed while a chromaticity change after the high-temperature heating step is suppressed, and a pattern can be formed with a desired line width.
Also, comparing Examples 1 to 13 and Examples 22 to 24, the acidic dispersant was found to be composed of an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and an alkyl (meth) acrylate-derived ester. It was shown that when a block copolymer containing a B block containing a structural unit was further contained, the suppression of development residue was improved.
　１　基板
　２　遮光部
　３　着色層
　１０　カラーフィルタ
　２０　対向基板
　３０　液晶層
　４０　液晶表示装置
　５０　有機保護層
　６０　無機酸化膜
　７１　透明陽極
　７２　正孔注入層
　７３　正孔輸送層
　７４　発光層
　７５　電子注入層
　７６　陰極
　８０　有機発光体
１００　有機発光表示装置 DESCRIPTION OF SYMBOLS 1 Substrate 2 Light shielding part 3 Color layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic luminous body 100 Organic luminous display

Claims (12)

  1. 　色材と、酸性分散剤と、溶剤とを含有する色材分散液であって、
    　前記色材が、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
    　前記酸性分散剤が、下記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、色材分散液。
    Figure JPOXMLDOC01-appb-C000001
     （一般式（１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
    　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000002
     （一般式（２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
    　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000003
     （一般式（Ｉ）中、Ｌ１は、直接結合又は２価の連結基、Ｒ１は、水素原子又はメチル基、Ｒ２は、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であり、Ｒ６は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、－Ｃ（Ｒ７）（Ｒ８）－Ｃ（Ｒ９）（Ｒ１０）－ＯＨ、又は、－ＣＨ２－Ｃ（Ｒ１１）（Ｒ１２）－ＣＨ２－ＯＨで示される１価の基である。
    　Ｒ３及びＲ４は、それぞれ独立に水素原子又はメチル基であり、Ｒ５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ、－ＣＯ－ＣＨ＝ＣＨ２、－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２又は－ＣＨ２ＣＯＯＲ１３で示される１価の基であり、Ｒ１３は水素原子又は炭素原子数が１個以上５個以下のアルキル基である。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２は、それぞれ独立に、水素原子、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基であり、Ｒ７及びＲ９は、互いに結合して環構造を形成してもよい。上記環状構造を形成した場合、当該環状構造が更に置換基Ｒ１４を有していてもよく、Ｒ１４は、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基である。前記炭化水素基は、置換基を有していてもよい。Ｘは、水素原子又は有機カチオンを表す。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。）     A coloring material, an acidic dispersant, and a coloring material dispersion containing a solvent,
    The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2). Phthalocyanine pigments,
    A colorant dispersion, wherein the acidic dispersant contains a polymer having at least one selected from structural units represented by the following general formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group has a saturated aliphatic carbon at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may have a hetero atom in the carbon chain, and B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may combine to form a ring structure, and R vi and R vii each independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. .Ar 1 2 may have a substituent divalent aromatic group represents a group I represent. R i ~ R vii and Ar 1 there are a plurality of may each be the same or different.
    a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f, and g may be the same or different. )
    Figure JPOXMLDOC01-appb-C000002
     (In the general formula (2) represents R I ~ R VI are each independently a hydrogen atom, which may have an alkyl group or a substituted group which may have a substituent aryl group, R I and R II , R III and R IV , or R V and R VI may combine to form a ring structure, wherein R VII and R VIII each independently represent an alkyl group or a substituent which may have a substituent; alkoxy group which may have, .Ar 2 represents a halogen atom or a cyano group represents an aromatic heterocyclic group which may have a substituent, plural R I ~ R VIII and Ar 2 E m- represents an m-valent polyacid anion.
    m represents an integer of 2 or more. j is 0 or 1, and when j is 0, no bond exists. k and l represent an integer of 0 or more and 4 or less, and k + j and 1 + j are 0 or more and 4 or less. A plurality of j, k and l may be the same or different. )
    Figure JPOXMLDOC01-appb-C000003
     (In the general formula (I), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydroxyl group, a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , — [(CH 2 ) y1 —O] z1 —R 5 , or —O—R 6 is a monovalent group, and R 6 is a hydrocarbon group ,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , -C (R 7 ) (R 8 ) -C ( R 9 ) (R 10 ) —OH or a monovalent group represented by —CH 2 —C (R 11 ) (R 12 ) —CH 2 —OH.
    R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is a hydrogen atom, a hydrocarbon group, —CHO, —CH 2 CHO, —CO—CH ＝ CH 2 , —CO—C ( CH 3 ) = CH 2 or —CH 2 COOR 13 is a monovalent group, and R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having at least one selected from an ether bond and an ester bond. Yes, R 7 and R 9 may combine with each other to form a ring structure. When the above-mentioned cyclic structure is formed, the cyclic structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon having one or more types selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 to 18; y1 is an integer of 1 to 5; z1 is an integer of 1 to 18; )
  2. 　前記レーキ色材の含有量が、前記レーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下である、請求項１に記載の色材分散液。 The colorant dispersion according to claim 1, wherein the content of the lake colorant is 20% by mass or more and 85% by mass or less based on the total content of the lake colorant and the phthalocyanine pigment.
  3. 　前記酸性分散剤が、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含む、請求項１又は２に記載の色材分散液。 The acidic dispersant further includes a block copolymer including an A block including a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block including a structural unit derived from an alkyl (meth) acrylate. The colorant dispersion according to claim 1.
  4. 　色材と、酸性分散剤と、バインダー成分と、溶剤とを含有する着色樹脂組成物であって、
    　前記色材が、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、
    　前記酸性分散剤が、下記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、着色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     （一般式（１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
    　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000005
     （一般式（２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
    　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000006
     （一般式（Ｉ）中、Ｌ１は、直接結合又は２価の連結基、Ｒ１は、水素原子又はメチル基、Ｒ２は、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であり、Ｒ６は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、－Ｃ（Ｒ７）（Ｒ８）－Ｃ（Ｒ９）（Ｒ１０）－ＯＨ、又は、－ＣＨ２－Ｃ（Ｒ１１）（Ｒ１２）－ＣＨ２－ＯＨで示される１価の基である。
    　Ｒ３及びＲ４は、それぞれ独立に水素原子又はメチル基であり、Ｒ５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ、－ＣＯ－ＣＨ＝ＣＨ２、－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２又は－ＣＨ２ＣＯＯＲ１３で示される１価の基であり、Ｒ１３は水素原子又は炭素原子数が１個以上５個以下のアルキル基である。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２は、それぞれ独立に、水素原子、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基であり、Ｒ７及びＲ９は、互いに結合して環構造を形成してもよい。上記環状構造を形成した場合、当該環状構造が更に置換基Ｒ１４を有していてもよく、Ｒ１４は、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基である。前記炭化水素基は、置換基を有していてもよい。Ｘは、水素原子又は有機カチオンを表す。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。）     Coloring material, an acidic dispersant, a binder component, a colored resin composition containing a solvent,
    The color material is subjected to a basic treatment with at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2). Phthalocyanine pigments,
    A colored resin composition, wherein the acidic dispersant contains a polymer having at least one selected from structural units represented by the following general formula (I).
    Figure JPOXMLDOC01-appb-C000004
     (In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group has a saturated aliphatic carbon at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may have a hetero atom in the carbon chain, and B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may combine to form a ring structure, and R vi and R vii each independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. .Ar 1 2 may have a substituent divalent aromatic group represents a group I represent. R i ~ R vii and Ar 1 there are a plurality of may each be the same or different.
    a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f, and g may be the same or different. )
    Figure JPOXMLDOC01-appb-C000005
     (In the general formula (2) represents R I ~ R VI are each independently a hydrogen atom, which may have an alkyl group or a substituted group which may have a substituent aryl group, R I and R II , R III and R IV , or R V and R VI may combine to form a ring structure, wherein R VII and R VIII each independently represent an alkyl group or a substituent which may have a substituent; alkoxy group which may have, .Ar 2 represents a halogen atom or a cyano group represents an aromatic heterocyclic group which may have a substituent, plural R I ~ R VIII and Ar 2 E m- represents an m-valent polyacid anion.
    m represents an integer of 2 or more. j is 0 or 1, and when j is 0, no bond exists. k and l represent an integer of 0 or more and 4 or less, and k + j and 1 + j are 0 or more and 4 or less. A plurality of j, k and l may be the same or different. )
    Figure JPOXMLDOC01-appb-C000006
     (In the general formula (I), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydroxyl group, a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , — [(CH 2 ) y1 —O] z1 —R 5 , or —O—R 6 is a monovalent group, and R 6 is a hydrocarbon group ,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , -C (R 7 ) (R 8 ) -C ( R 9 ) (R 10 ) —OH or a monovalent group represented by —CH 2 —C (R 11 ) (R 12 ) —CH 2 —OH.
    R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is a hydrogen atom, a hydrocarbon group, —CHO, —CH 2 CHO, —CO—CH ＝ CH 2 , —CO—C ( CH 3 ) = CH 2 or —CH 2 COOR 13 is a monovalent group, and R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having at least one selected from an ether bond and an ester bond. Yes, R 7 and R 9 may combine with each other to form a ring structure. When the above-mentioned cyclic structure is formed, the cyclic structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon having one or more types selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 to 18; y1 is an integer of 1 to 5; z1 is an integer of 1 to 18; )
  5. 　前記レーキ色材の含有量が、前記レーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下である、請求項４に記載の着色樹脂組成物。 The colored resin composition according to claim 4, wherein the content of the lake color material is 20% by mass or more and 85% by mass or less based on the total content of the lake color material and the phthalocyanine pigment.
  6. 　前記バインダー成分が、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤とを含み、感光性である、請求項４又は５に記載の着色樹脂組成物。 6. The colored resin composition according to claim 4, wherein the binder component contains an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, and is photosensitive.
  7. 　前記酸性分散剤が、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含む、請求項４～６のいずれか１項に記載の着色樹脂組成物。 The acidic dispersant further includes a block copolymer including an A block including a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block including a structural unit derived from an alkyl (meth) acrylate. The colored resin composition according to any one of claims 4 to 6.
  8. 　請求項４～７のいずれか１項に記載の着色樹脂組成物の硬化物。 (8) A cured product of the colored resin composition according to any one of (4) to (7).
  9. 　透明基板と、当該透明基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、前記着色層の少なくとも一つが、色材と、酸性分散剤とを含み、前記色材が、下記一般式（１）で表される色材及び下記一般式（２）で表される色材からなる群から選択される少なくとも１種のレーキ色材と、塩基性処理されたフタロシアニン顔料とを含み、前記酸性分散剤が、下記一般式（Ｉ）で表される構成単位から選択される少なくとも１種を有する重合体を含む、カラーフィルタ。
    Figure JPOXMLDOC01-appb-C000007
     （一般式（１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にヘテロ原子が含まれていてもよい。Ｂｃ－はｃ価のポリ酸アニオンを表す。Ｒｉ～Ｒｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲｉｉとＲｉｉｉ、ＲｉｖとＲｖが結合して環構造を形成してもよい。Ｒｖｉ及びＲｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲｉ～Ｒｖｉｉ及びＡｒ１はそれぞれ同一であっても異なっていてもよい。
    　ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000008
     （一般式（２）中、ＲＩ～ＲＶＩは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、ＲＩとＲＩＩ、ＲＩＩＩとＲＩＶ、ＲＶとＲＶＩが結合して環構造を形成してもよい。ＲＶＩＩ及びＲＶＩＩＩは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ２は置換基を有していてもよい２価の芳香族複素環基を表し、複数あるＲＩ～ＲＶＩＩＩ及びＡｒ２はそれぞれ同一であっても異なっていてもよい。Ｅｍ－はｍ価のポリ酸アニオンを表す。
    　ｍは２以上の整数を表す。ｊは０又は１であり、ｊが０のとき結合は存在しない。ｋ及びｌは０以上４以下の整数を表し、ｋ＋ｊ及びｌ＋ｊは０以上４以下である。複数あるｊ、ｋ及びｌはそれぞれ同一であっても異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000009
     （一般式（Ｉ）中、Ｌ１は、直接結合又は２価の連結基、Ｒ１は、水素原子又はメチル基、Ｒ２は、水酸基、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、又は－Ｏ－Ｒ６で示される１価の基であり、Ｒ６は、炭化水素基、－［ＣＨ（Ｒ３）－ＣＨ（Ｒ４）－Ｏ］ｘ１－Ｒ５、－［（ＣＨ２）ｙ１－Ｏ］ｚ１－Ｒ５、－Ｃ（Ｒ７）（Ｒ８）－Ｃ（Ｒ９）（Ｒ１０）－ＯＨ、又は、－ＣＨ２－Ｃ（Ｒ１１）（Ｒ１２）－ＣＨ２－ＯＨで示される１価の基である。
    　Ｒ３及びＲ４は、それぞれ独立に水素原子又はメチル基であり、Ｒ５は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ２ＣＨＯ、－ＣＯ－ＣＨ＝ＣＨ２、－ＣＯ－Ｃ（ＣＨ３）＝ＣＨ２又は－ＣＨ２ＣＯＯＲ１３で示される１価の基であり、Ｒ１３は水素原子又は炭素原子数が１個以上５個以下のアルキル基である。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１及びＲ１２は、それぞれ独立に、水素原子、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基であり、Ｒ７及びＲ９は、互いに結合して環構造を形成してもよい。上記環状構造を形成した場合、当該環状構造が更に置換基Ｒ１４を有していてもよく、Ｒ１４は、炭化水素基、又は、エーテル結合及びエステル結合から選択される１種以上を有する炭化水素基である。前記炭化水素基は、置換基を有していてもよい。Ｘは、水素原子又は有機カチオンを表す。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。）     A transparent substrate, a color filter comprising at least a coloring layer provided on the transparent substrate, wherein at least one of the coloring layers contains a coloring material and an acidic dispersant, the coloring material has the following general A color material represented by the formula (1) and at least one lake color material selected from the group consisting of a color material represented by the following general formula (2), and a basic-treated phthalocyanine pigment; A color filter, wherein the acidic dispersant contains a polymer having at least one selected from structural units represented by the following general formula (I).
    Figure JPOXMLDOC01-appb-C000007
     (In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group has a saturated aliphatic carbon at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may have a hetero atom in the carbon chain, and B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii and R iii , R iv and R v may combine to form a ring structure, and R vi and R vii each independently represent an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a halogen atom or a cyano group. .Ar 1 2 may have a substituent divalent aromatic group represents a group I represent. R i ~ R vii and Ar 1 there are a plurality of may each be the same or different.
    a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, no bond exists. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f, and g may be the same or different. )
    Figure JPOXMLDOC01-appb-C000008
     (In the general formula (2) represents R I ~ R VI are each independently a hydrogen atom, which may have an alkyl group or a substituted group which may have a substituent aryl group, R I and R II , R III and R IV , or R V and R VI may combine to form a ring structure, wherein R VII and R VIII each independently represent an alkyl group or a substituent which may have a substituent; alkoxy group which may have, .Ar 2 represents a halogen atom or a cyano group represents an aromatic heterocyclic group which may have a substituent, plural R I ~ R VIII and Ar 2 E m- represents an m-valent polyacid anion.
    m represents an integer of 2 or more. j is 0 or 1, and when j is 0, no bond exists. k and l represent an integer of 0 or more and 4 or less, and k + j and 1 + j are 0 or more and 4 or less. A plurality of j, k and l may be the same or different. )
    Figure JPOXMLDOC01-appb-C000009
     (In the general formula (I), L 1 is a direct bond or a divalent linking group, R 1 is a hydrogen atom or a methyl group, R 2 is a hydroxyl group, a hydrocarbon group, — [CH (R 3 ) —CH (R 4 ) —O] x1 —R 5 , — [(CH 2 ) y1 —O] z1 —R 5 , or —O—R 6 is a monovalent group, and R 6 is a hydrocarbon group ,-[CH (R 3 ) -CH (R 4 ) -O] x1 -R 5 ,-[(CH 2 ) y1 -O] z1 -R 5 , -C (R 7 ) (R 8 ) -C ( R 9 ) (R 10 ) —OH or a monovalent group represented by —CH 2 —C (R 11 ) (R 12 ) —CH 2 —OH.
    R 3 and R 4 are each independently a hydrogen atom or a methyl group, and R 5 is a hydrogen atom, a hydrocarbon group, —CHO, —CH 2 CHO, —CO—CH ＝ CH 2 , —CO—C ( CH 3 ) = CH 2 or —CH 2 COOR 13 is a monovalent group, and R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having at least one selected from an ether bond and an ester bond. Yes, R 7 and R 9 may combine with each other to form a ring structure. When the above-mentioned cyclic structure is formed, the cyclic structure may further have a substituent R 14 , and R 14 is a hydrocarbon group or a hydrocarbon having one or more types selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 to 18; y1 is an integer of 1 to 5; z1 is an integer of 1 to 18; )
  10. 　前記レーキ色材の含有量が、前記レーキ色材及び前記フタロシアニン顔料の合計含有量に対して２０質量％以上８５質量％以下である、請求項９に記載のカラーフィルタ。 The color filter according to claim 9, wherein the content of the lake color material is 20% by mass or more and 85% by mass or less based on the total content of the lake color material and the phthalocyanine pigment.
  11. 　前記酸性分散剤が、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位を含むＡブロックと（メタ）アクリル酸アルキルエステル由来の構成単位を含むＢブロックとを含むブロック共重合体を、更に含む、請求項９又は１０に記載のカラーフィルタ。 The acidic dispersant further includes a block copolymer including an A block including a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block including a structural unit derived from an alkyl (meth) acrylate. The color filter according to claim 9.
  12. 　前記請求項９～１１のいずれか１項に記載のカラーフィルタを有することを特徴とする表示装置。 A display device comprising the color filter according to any one of claims 9 to 11.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022202208A1 (en) * 2021-03-24 2022-09-29 株式会社Ｄｎｐファインケミカル Color material liquid dispersion, modified color material, curable coloring composition, color filter, and display device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012144521A1 (en) * 2011-04-21 2012-10-26 大日本印刷株式会社 Colorant dispersion liquid, colored resin composition for use in color filters, color filter, liquid crystal display device, and organic light-emitting display device
JP2013225091A (en) * 2012-03-21 2013-10-31 Dic Corp Blue pigment composition for color filter, blue photocurable composition for color filter, and color filter
WO2016171193A1 (en) * 2015-04-22 2016-10-27 大日本印刷株式会社 Color material dispersion, colored resin composition, color material, color filter and method for producing same, liquid crystal display device, and light-emitting display device
JP2017002191A (en) * 2015-06-10 2017-01-05 大日本印刷株式会社 Color material dispersion liquid, coloring resin composition for color filter, manufacturing method of color filter, manufacturing method of liquid crystal display device and manufacturing method of light-emitting display device
WO2017145627A1 (en) * 2016-02-25 2017-08-31 Dic株式会社 Compound and color filter

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001164142A (en) 1999-12-07 2001-06-19 Mitsubishi Chemicals Corp Pigment dispersion composition
JPWO2012053201A1 (en) * 2010-10-21 2014-02-24 日本化薬株式会社 Colored resin composition for color filter, color filter, display device, and solid-state imaging device
JP5646663B2 (en) * 2013-02-08 2014-12-24 株式会社Ｄｎｐファインケミカル Colored resin composition for color filter, color material dispersion, color filter, liquid crystal display device, and organic light emitting display device
JP6056844B2 (en) * 2014-12-26 2017-01-11 大日本印刷株式会社 Color material dispersion for color filter, colored resin composition for color filter, color material, color filter, liquid crystal display device and light emitting display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012144521A1 (en) * 2011-04-21 2012-10-26 大日本印刷株式会社 Colorant dispersion liquid, colored resin composition for use in color filters, color filter, liquid crystal display device, and organic light-emitting display device
JP2013225091A (en) * 2012-03-21 2013-10-31 Dic Corp Blue pigment composition for color filter, blue photocurable composition for color filter, and color filter
WO2016171193A1 (en) * 2015-04-22 2016-10-27 大日本印刷株式会社 Color material dispersion, colored resin composition, color material, color filter and method for producing same, liquid crystal display device, and light-emitting display device
JP2017002191A (en) * 2015-06-10 2017-01-05 大日本印刷株式会社 Color material dispersion liquid, coloring resin composition for color filter, manufacturing method of color filter, manufacturing method of liquid crystal display device and manufacturing method of light-emitting display device
WO2017145627A1 (en) * 2016-02-25 2017-08-31 Dic株式会社 Compound and color filter

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022202208A1 (en) * 2021-03-24 2022-09-29 株式会社Ｄｎｐファインケミカル Color material liquid dispersion, modified color material, curable coloring composition, color filter, and display device

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