WO2016067865A1 - Azo pigment alkali metal salt, alkaline earth metal salt and tautomer thereof, coloring composition and dyeing method and dyed product - Google Patents

Azo pigment alkali metal salt, alkaline earth metal salt and tautomer thereof, coloring composition and dyeing method and dyed product Download PDF

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WO2016067865A1
WO2016067865A1 PCT/JP2015/078536 JP2015078536W WO2016067865A1 WO 2016067865 A1 WO2016067865 A1 WO 2016067865A1 JP 2015078536 W JP2015078536 W JP 2015078536W WO 2016067865 A1 WO2016067865 A1 WO 2016067865A1
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group
heterocyclic
alkyl
aryl
groups
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神保　良弘
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富士フイルム株式会社
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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
    • C09B45/00—Complex metal compounds of azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/10—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes containing metal
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form

Definitions

  • the present invention relates to a novel azo dye alkali metal salt, alkaline earth metal salt and tautomer thereof having a good hue and fastness and a high molecular extinction coefficient, and further, a coloring composition using them Article, dyeing method, and dyed article.
  • azo dyes often have various visible light absorption, they have been used as dyes in various fields. For example, it has come to be used in various fields such as coloring of synthetic resins, printing inks, dyes for sublimation thermal transfer materials, inks for inkjets, and dyes for color filters.
  • color images have become mainstream as image recording materials, and the uses of dyes have also diversified. Specifically, it is actively used for inkjet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, and the like.
  • a color filter that records and reproduces a color image is used in an imaging device such as a CCD or a CMOS in a photographing apparatus and in an LCD or a PDP in a display.
  • three primary colorants (dyes or pigments) of the so-called additive color mixture method or subtractive color mixture method are used to reproduce or record a full color image.
  • the present situation is that there is no colorant that has an absorption characteristic capable of realizing a preferable color gamut, can withstand various use conditions and environmental conditions, and has a good hue and is robust, and improvement is strongly desired.
  • Examples of conventional azo dyes having dissociable protons include azo dyes disclosed in Japanese Patent No. 4080947.
  • An object of one embodiment of the present invention is to provide alkali metal salts, alkaline earth metal salts and tautomers of azo dyes having a novel dissociative proton having a good hue and fastness and a high molecular extinction coefficient. Is to provide.
  • the present inventor has found that the alkali metal salts, alkaline earth metal salts and tautomers of the azo dyes having a novel dissociative proton have a good hue and good fastness. As a result, the present invention has been completed.
  • the present invention includes the following aspects.
  • a ⁇ N NB
  • A is a heterocyclic group represented by any of the following formulas (A-1) to (A-25) which may have a substituent, and is a carboxy group or a sulfo group. A group which does not contain and is bonded to an azo group via a carbon atom is shown.
  • R 21 to R 50 are independently hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group Alternatively, it represents a carbamoyl group, and adjacent groups among R 21 to R 50 may be bonded to each other to form a saturated or unsaturated 5-membere
  • B represents a group containing a dissociable proton represented by any of the following formulas (B-1) to (B-12) and not containing a carboxy group or a sulfo group.
  • R 101 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, Represents a sulfamoyl group, an alkylsulfonyl group or a carbamoyl group
  • R 102 and R 104 are each independently a cyano group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group or carb
  • Z 1 represents an oxygen atom, a sulfur atom or —N (R 103 ) —
  • R 103 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • v represents an integer of 0 to 4
  • R 101s may be the same or different.
  • R 105 and R 106 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • R107 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group.
  • Z 2 and Z 3 independently represent —C (R 108 ) ⁇ or —N ⁇
  • R 108 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group
  • Z 2 and Z 3 are both —C (R 108 ) ⁇
  • the two R 108 groups may be the same or different and are bonded together to form a carbocyclic or heterocyclic ring. Also good.
  • R 109 represents an alkyl group, an aryl group or a heterocyclic group
  • R 110 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group
  • R 111 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group or a carbamoyl group
  • R 112 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • R 113 Represents a hydroxyl group or an amino group.
  • R 114 and R 115 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, nitro groups, alkoxy groups, aryloxy groups, amino groups (including anilino groups), acylamino groups, alkoxycarbonylamino groups, aminocarbonylamino groups.
  • w represents an integer of 0 to 4, and w R 114 groups may be the same or different.
  • R x represents an integer of 0 to 6, and the x R 115 groups may be the same or different.
  • R 116 , R 117 , R 118 and R 119 independently represent an alkyl group or an aryl group.
  • R 120 and R 121 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group
  • R 122 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group or an arylsulfonylamino group.
  • R 123 and R 124 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group
  • Z 4 represents a nonmetallic atomic group that forms a 5- or 6-membered ring with two nitrogen atoms and one carbon atom
  • y represents an integer of 0-2
  • Z 4 forms a 6-membered ring y represents an integer of 0-3
  • R 125 represents an alkyl group, aryl group, alkoxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group or carbamoyl group
  • R 126 represents an alkyl group, an aryl group
  • R 201 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group
  • R 202 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • R 203 , R 205 and R 207 are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group , an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group,
  • R 206 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group.
  • R 208 is a halogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group Represents an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group, aa represents an integer of 0 to 4, and aa R 208 may be the same or different.
  • R 210 and R 211 are independently a hydrogen atom, halogen atom, alkyl group, aryl group, acylamino group, alkoxycarbonyl group, aminocarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group or carbamoyl. And at least one of R 210 and R 211 is a hydrogen atom, and R 212 and R 213 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an acylamino group.
  • R 214 and R 215 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • R216 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group , A sulfamoyl group, an alkylsulfonyl group or a carbamoyl group, Z 5 represents an oxygen atom, a sulfur atom or —N (R 217 ) —, and R 217 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • R 216s may be the same or different.
  • R 218 is synonymous with R 210 or represents a sulfamoyl group
  • R 220 and R 223 are a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group.
  • R 219 , R 221 and R 222 represent a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group.
  • R 224 represents an alkylcarbonyl group or an arylcarbonyl group.
  • M represents alkali metal or alkaline earth metal 1/2
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present invention are excellent in hue and are effective against light, heat, humidity and the active gas in the environment.
  • novel compounds and dyes having sufficient fastness and a high molecular absorption coefficient can be provided.
  • This relates to the reflection spectrum of the dyed product obtained in Example 15. This relates to the reflection spectrum of the dyed product obtained in Example 16. This relates to the reflection spectrum of the dyed product obtained in Example 17.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of an azo dye according to one embodiment of the present invention are an alkali metal salt and an alkaline earth metal salt of an azo dye represented by the following general formula (1). And tautomers thereof.
  • a and B in the general formula (1) have the same meaning as described above. That is, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present invention are represented by the above formula in which A may have a substituent in the general formula (1) described in detail below.
  • the general formula (1) will be described in detail.
  • the heterocyclic group represented by A is a 5-membered or 6-membered heterocyclic group containing one or more heteroatoms selected from an oxygen atom, a sulfur atom or a nitrogen atom in the ring.
  • the aromatic heterocyclic group is more preferable.
  • the heterocyclic group represented by A may be a ring condensed with another ring. Of such fused ring groups, those fused with a 5-membered or 6-membered ring are preferred.
  • the number of carbon atoms in the heterocyclic group represented by A is preferably 2 to 20, and more preferably 2 to 10.
  • the heterocyclic group represented by A in the general formula (1) those derived from a diazo component are preferable.
  • the diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent into a diazo compound and reacting with a coupler by a diazo coupling reaction.
  • the heterocyclic group represented by A is a substituent which is a monovalent group by removing the amino group in an amino-substituted heterocyclic compound capable of diazotization reaction.
  • the heterocyclic group represented by A can include one or more substituents, and the two or more substituents may be the same or different.
  • substituents include a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and an alkoxy group.
  • aryloxy group silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, arylazo group, heterocyclic
  • examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (a straight chain having 1 to 10, preferably 1 to 6 carbon atoms, Branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl-2-chloroethyl-2-cyanoethyl-2-ethylhexyl, cyclopropyl, cyclopentyl), alkenyl groups (2-10 Linear, branched or cyclic alkenyl groups having 2 to 6 carbon atoms, such as vinyl, allyl, prenyl, cyclopenten-1-yl, alkynyl groups (2 to 10, preferably 2 to 6) Alkynyl groups having 1 carbon atom, eg ethynyl, propargyl),
  • these groups are groups that can be further substituted, these groups can further contain a substituent, and this substituent is preferably described as a preferred substituent of the heterocyclic group represented by A. And groups having the same meaning. When these groups are substituted with two or more substituents, these substituents may be the same or different.
  • the substituent of the heterocyclic group represented by A in the general formula (1) is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy Group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl Group, arylsulfonyl group, acyl group, alkoxycarbonyl group and carbamoyl group, and more preferably, this substituent is a halogen atom, alkyl group, cyano group, hydroxyl group, nitro group, alkoxy group, amino group (anilino group),
  • heterocyclic group represented by A examples include heterocyclic groups represented by any one of the above formulas (A-1) to (A-25) which may have a substituent.
  • R 21 to R 50 independently represent a hydrogen atom or a substituent, preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, cyano Group, hydroxyl group, nitro group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio Group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group and carbam
  • a, p, q, r and s represent an integer of 0 to 4
  • b and c represent an integer of 0 to 6
  • d, e, f, g, t and u represent an integer of 0 to 3
  • h, i, j, k, l, and o represent an integer of 0 to 2
  • m represents an integer of 0 to 1.
  • groups adjacent to each other represented by R 21 to R 50 may be bonded to form a ring structure.
  • the ring structure thus formed may be a heterocyclic ring or a carbocyclic ring, and may be a saturated ring or an unsaturated ring.
  • the total number of carbon atoms and heteroatoms is 3-6, preferably 5 or 6.
  • R 21 to R 50 can further include a substituent.
  • the substituent is represented by A in the general formula (1). The same as those listed as the substituent of the heterocyclic group.
  • the heterocyclic group represented by A is preferably a group represented by the formula (A-1), (A-5), (A-8), (A -9), (A-10), (A-11), (A-12), (A-13), (A-14), (A-15), (A-17), (A-19) ), (A-22), (A-23), (A-24) and (A-25), more preferably (A-8), (A-9), (A-10), (A A-11), (A-14), (A-15), (A-22) and (A-23).
  • B in the general formula (1) represents an atomic group essential for forming the azo dye represented by the general formula (1), and is preferably derived from a coupler component.
  • the coupler component means a partial structure derived from a coupler compound that can react with a diazonium salt to obtain an azo dye.
  • the carbon number of B in the azo dye represented by the general formula (1) is preferably 3 to 30, more preferably 3 to 20, and further preferably 3 to 12.
  • B in the general formula (1) is a 5-membered or 6-membered heterocyclic ring or condensed condensed ring containing one or more heteroatoms selected from a sulfur atom, a nitrogen atom or an oxygen atom; An optionally fused aromatic ring; or a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group, optionally containing an ⁇ -CO group, of these rings and groups Each can contain one or more substituents.
  • the coupler component is preferably a residue of what is known as a coupler in the field of silver halide color photographic materials.
  • Research Disclosure 37038 (February 1995), pages 80 to 85, and pages 87 to 89.
  • the skeleton portion of a silver halide color photographic coupler described in detail on the page (the portion which becomes a chromophore of a dye upon coupling with an oxidized aromatic amine developing agent such as p-phenylenediamine) can be used.
  • couplers known as yellow color image-forming couplers in the field of silver halide color photographic materials include pivaloyl acetamide type, benzoylacetamide type, malon diester type, malon diamide type, dibenzoyl methane type, benzo type.
  • couplers known as magenta color image forming couplers in the field of silver halide color photographic light-sensitive materials include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5, 1-c] [1,2,4] triazole type, 1H-pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type ,
  • couplers known as cyan image forming couplers in the field of silver halide color photographic light-sensitive materials include phenol type, naphthol type, and 2,5-diphenylimidazole described in European Patent Application No. 0249453.
  • Examples of the group represented by B include groups represented by any of the above formulas (B-1) to (B-12).
  • R 101 is preferably a halogen atom, an acylamino group, an alkylsulfonylamino group, a sulfamoyl group and a carbamoyl group
  • R 102 is preferably a cyano group and a carbamoyl group
  • 1 is preferably an oxygen atom, a sulfur atom or —N (R 103 ) — in which R 103 is an alkyl group.
  • v represents an integer of 0 to 4. When v is 1 to 4, the R 101 groups may be the same or different.
  • R 104 is preferably a cyano group, an acyl group, or a carbamoyl group, and one of R 105 and R 106 is preferably a hydrogen atom.
  • R 107 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • R 108 is preferably an alkyl group, an aryl group or a heterocyclic ring, and more preferably an alkyl group.
  • R 109 is preferably an alkyl group or an aryl group
  • R 110 is preferably a hydrogen atom or an alkyl group.
  • R 111 is preferably an alkoxycarbonyl group, a cyano group, or a carbamoyl group
  • R 112 is preferably an alkyl group or an aryl group.
  • R 114 is preferably a halogen atom, an alkyl group, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group or a carbamoyl group. More preferably, they are an atom, an alkyl group, an acylamino group, or an alkylsulfonylamino group.
  • w represents an integer of 0 to 4, and when w is 2 to 4, the R 114 groups may be the same or different.
  • R 115 is preferably a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group or a carbamoyl group.
  • a sulfonylamino group or a carbamoyl group is more preferable.
  • x represents an integer of 0 to 6, and when x is 2 to 6, the R 115 groups may be the same or different.
  • R 116 and R 117 , and R 118 and R 119 are preferably the same as each other.
  • R 120 and R 121 are preferably an alkyl group, an aryl group, a heterocyclic group, or a cyano group
  • R 122 is a hydrogen atom, an alkyl group, an aryl group, an acylamino group, or an alkylsulfonyl group.
  • An amino group is preferred.
  • R 123 is preferably an alkyl group, an aryl group, a heterocyclic group, or a cyano group
  • R 124 is an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group
  • R 125 is preferably an alkyl group, an aryl group, an alkylthio group, an amino group, or an acylamino group.
  • R 126 is preferably an alkyl group or an aryl group.
  • R 101 to R 126 in formulas (B-1) to (B-12) are groups that can be further substituted, R 101 to R 126 can further have a substituent, and in this case, the substituent Are the same as those enumerated as substituents of the heterocyclic group represented by A in the general formula (1).
  • azo dyes represented by the general formula (1) are particularly preferable.
  • a in the formulas DS-1 to DS-9 has the same meaning as A in the general formula (1).
  • R 201 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group
  • R 202 represents a hydrogen atom
  • R 201 is preferably an alkoxycarbonyl group, a cyano group, or a carbamoyl group
  • R 202 is preferably an alkyl group or an aryl group.
  • R 203 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group. It represents group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or carbamoyl group, R 204 represents an alkyl group, an aryl group or a heterocyclic group.
  • R 203 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group.
  • R 204 is preferably an alkyl group.
  • R 205 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group.
  • R 206 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group.
  • R 205 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group, or a t-butyl group.
  • R 206 is preferably an alkyl group, an aryl group or an alkylthio group, and more preferably an alkyl group.
  • R 207 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group.
  • R 208 represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (an anilino group).
  • acylamino group an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group, aa represents an integer of 0 to 4, aa number of R 08 may be the same or different.
  • R 207 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group.
  • R 208 is preferably a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or an alkylsulfonylamino group.
  • R 210 and R 211 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino.
  • R 212 and R 213 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group.
  • R 210 and R 211 are preferably a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group, and more preferably at least one of R 210 and R 211 is a hydrogen atom.
  • R 214 and R 215 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and one of R 214 and R 215 is preferably a hydrogen atom.
  • R 216 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group , an alkylthio group, an arylthio group, a sulfamoyl group, an alkylsulfonyl group or a carbamoyl group, Z 5 represents an oxygen atom, a sulfur atom, or -N (R217) - represents, R 217 is a hydrogen atom, an alkyl group, an aryl group Or represents a heterocyclic group.
  • R 216 is preferably a halogen atom, an acylamino group, an alkylsulfonylamino group, a sulfamoyl group or a carbamoyl group.
  • Z 5 is preferably an oxygen atom, a sulfur atom, or —N (R 217 ) — in which R 217 is an alkyl group, and more preferably Z 5 is an oxygen atom or a sulfur atom.
  • R 218 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, a carbamoyl group, or a sulfamoyl group.
  • R 220 and R 223 represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group
  • R 219 , R 221 and R 222 are A hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group is represented.
  • R 218 is preferably a hydrogen atom, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, a carbamoyl group, and a sulfamoyl group, and R 220 and R 223 are a hydrogen atom.
  • An acylamino group, an alkoxycarbonylamino group or an alkylsulfonylamino group, and R 219 , R 221 and R 222 are preferably hydrogen atoms.
  • R 224 represents an alkyl group or an aryl group.
  • M represents an alkali metal or an alkaline earth metal 1/2.
  • alkali metal lithium, sodium, potassium, and cesium are preferable, and sodium and potassium are more preferable.
  • Alkaline earth metal 1/2 is an alkaline earth metal in the state where one alkaline earth metal ion is bonded to two molecules of the dissociated azo dye of the general formula (1) having a dissociating proton.
  • alkaline earth metal calcium, strontium and barium are preferable, and calcium and barium are more preferable.
  • R 201 to R 224 in the formulas DS-1 to DS-9 are groups with the possibility of further substitution, these can have further substituents.
  • the substituent is the same as that described in the description of the substituent for the heterocyclic group represented by A in the general formula (1).
  • alkali metal salt and alkaline earth metal salt of the azo dye represented by the general formula (1) are described below, but are not limited by these examples.
  • the azo dye represented by the general formula (1) can be synthesized, for example, by the method described in Japanese Patent No. 4080947.
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are prepared by replacing the azo dye represented by the general formula (1) with the corresponding alkali metal salt, alkaline earth salt. It can be obtained by reacting with a metal salt.
  • Examples of the alkali metal salt that can be used in the reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium t-butoxide. And sodium hydride.
  • Examples of the alkaline earth metal salt that can be used for the reaction include magnesium hydroxide, magnesium chloride, magnesium acetate, calcium hydroxide, calcium chloride, calcium acetate, barium hydroxide, barium chloride, and barium acetate.
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are prepared by replacing the azo dye represented by the general formula (1) with the corresponding alkali metal salt, alkaline earth salt.
  • a solvent As the solvent that can be used, water, methanol, ethanol, n-propanol, isopropanol, t-butanol and the like are preferable.
  • the reaction temperature is preferably ⁇ 20 ° C. to the boiling point of the reaction solvent, more preferably room temperature to 100 ° C.
  • the alkali metal salt, alkaline earth metal salt or tautomer of the azo dye according to one embodiment of the present invention is preferably used as a coloring composition, and the alkali metal salt of the azo dye, the alkali A colored composition containing an earth metal salt or a tautomer is more preferable.
  • the dyeing method using the alkali metal salt, alkaline earth metal salt or tautomer of the azo dye according to one embodiment of the present invention includes the alkali metal salt, alkaline earth metal salt or tautomer of the azo dye of the present invention.
  • Mutant bodies can be used in methods such as dipping, kneading, coating, printing, or inkjet printing.
  • the dyeing materials include cashmere, wool, silk, cotton, hemp and other natural fibers, nylon, polyester, acrylic, polyurethane and other inorganic materials, glass, metal, ceramics and other inorganic materials, plain paper, resin-coated paper, and inkjet. Paper such as dedicated recording paper can be used.
  • alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are used for solid-state imaging devices such as CCD and CMOS, and displays such as LCD and PDP.
  • solid-state imaging devices such as CCD and CMOS
  • displays such as LCD and PDP.
  • Examples thereof include a color filter for reproducing a color image, a curable composition for producing these color filters, and a color image recording material for forming a color image.
  • color filters and curable compositions for producing these color filters ink jet recording materials, sublimation thermal recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials, printing It is used for ink, recording pen, fiber dyeing, hair dyeing and the like, and preferably used for ink jet recording material, transfer type silver halide photosensitive material, printing ink, fiber dyeing and the like.
  • the alkali metal salt, alkaline earth metal salt, and tautomer thereof of the azo dye according to one embodiment of the present invention can be obtained by adjusting the physical properties such as solubility and dispersibility suitable for the application by adjusting substituents. Can be optimized and used.
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present embodiment can be used in a dissolved state, an emulsified dispersion state, and a solid dispersion state depending on the system used.
  • the colored composition of the present embodiment means a composition containing at least one of an alkali metal salt, an alkaline earth metal salt and a tautomer thereof of the azo dye represented by the general formula (1).
  • the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) may be used alone or other direct dyes or You may use it in combination with a disperse dye.
  • the coloring composition of the present embodiment can contain a medium.
  • the coloring composition of the present embodiment uses a lipophilic medium or an aqueous medium as a medium, and includes an alkali metal salt or alkaline earth metal salt of an azo dye that is a compound according to an embodiment of the present invention. And its tautomers can be made by dissolving and / or dispersing.
  • an aqueous medium is used.
  • the total content of the alkali metal salt, alkaline earth metal salt and tautomer of the azo dye represented by the general formula (1) contained in the coloring composition is the general formula (1) used in the coloring composition.
  • the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) in the coloring composition is 0.001 with respect to the total mass of the coloring composition. It is preferably contained in an amount of ⁇ 20% by mass, more preferably 0.1 ⁇ 10% by mass.
  • the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) By coloring the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) to 0.001% by mass or more, coloring of the dye on the coloring medium The concentration can be secured. Moreover, the low-viscosity coloring composition is obtained by setting the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) to 20% by mass or less. It can be adjusted and is easy to handle.
  • the coloring composition containing at least one selected from the alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) has any pH within the range of pH 5-11.
  • the colored composition is preferably used in the range of pH 6 or higher, from the viewpoint of the stability and dyeability of alkali metal salts, alkaline earth metal salts and tautomers thereof of azo dyes. It is more preferable to use in the range of pH 7-11.
  • pH adjuster used in the coloring composition of the present embodiment examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, monoethanolamine, diethanolamine, guanidine, and the like. Is mentioned.
  • the coloring composition of the present embodiment can contain a surfactant.
  • a surfactant that can be used, an anionic, nonionic, cationic, amphoteric or zwitterionic surfactant can be added.
  • surfactant may be used individually by 1 type and may be used in combination of 2 or more types.
  • anionic surfactant examples include monoalkyl sulfuric acid or a salt thereof, alkylbenzene sulfonic acid or a salt thereof, and ⁇ -olefin sulfonate or a salt thereof.
  • Particularly preferred are sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and alkali salts of sulfosuccinic acid half ester, such as monooctylsulfosuccinic acid disodium salt and long-chain monoalkylethoxysulfosuccinic acid alkali salt.
  • nonionic surfactant examples include alkyl polyglycosides; sorbitan esters such as polyethylene glycol sorbitan stearate.
  • Examples of the cationic surfactant that can be used in the coloring composition of the present embodiment include a long-chain quaternary ammonium compound.
  • Examples of long-chain quaternary ammonium compounds include cetyltrimethylammonium chloride, dimethylstearylammonium chloride, trimethylacetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldi-hydrogenated-tallow Examples include ammonium chloride, lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, tris (oligooxy-ethyl) alkylammonium phosphate, cetylpyridinium chloride and the like.
  • amphoteric or zwitterionic surfactants that can be used in the coloring composition of the present embodiment include fatty acids-amide alkylbetaines, sulfobetaines and the like (eg, lauryl hydroxysulfobetaine), cocoaminoacetate, cocoaminopro Long chain alkyl amino acids such as pionate, sodium cocoamphopropionate, sodium cocoamphoacetate and the like can be mentioned.
  • aqueous solvent When the coloring composition of the present embodiment is used as an aqueous coloring composition, the following aqueous solvent can be used in combination.
  • Usable aqueous solvents include ethanol, isopropanol, n-propanol, butanol, n-pentanol, propylene glycol, ethylene glycol monoethyl ether, 1,2-hexanediol, butoxyethanol, phenoxyethanol, benzyl alcohol, propylene carbonate, and And mixtures thereof, among which 1,2- or 1,3-propanediol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,3- or 1,4-butane Diol, diethylene glycol and its monomethyl or monoethyl ether, and dipropylene glycol and its monomethyl or monoethyl ether are preferred.
  • the blending amount of these aqueous solvents is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, and further preferably 5 to 10% by mass with respect to the total mass of the colored composition.
  • a component selected from polyhydric alcohols such as glycerin and hexanetriol; ethyl carbitol; benzyl alcohol; benzyloxyethanol; n-alkylpyrrolidone; and urea may be used in combination.
  • the coloring composition of the present embodiment can contain a thickener.
  • the blending amount of the thickener is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% with respect to the total mass of the coloring composition. More preferably, it is mass%.
  • the thickener that can be used for the colored composition of the present embodiment include oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, and stearyl alcohol.
  • the colored composition of the present embodiment contains other colored compounds together with at least one selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1).
  • magenta dye that can be used can be used.
  • magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; azomethine dyes having pyrazolones, pyrazolotriazoles, etc.
  • coupler components arylidene dyes, styryl dyes, merocyanine dyes Methine dyes such as cyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensations such as dioxazine dyes Examples include polycyclic dyes.
  • cyan dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; azomethine dyes having heterocycles such as phenols, naphthols, and pyrrolotriazole as coupler components; cyanine Polymethine dyes such as dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.
  • each of the above-mentioned dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated.
  • the counter cation is an alkali metal or an inorganic cation such as ammonium.
  • it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
  • the coloring composition of this embodiment can also contain a black dye.
  • black dyes that can be used include disazo, trisazo, and tetraazo dyes.
  • examples of the black coloring compound include a dispersion of carbon black.
  • silicone oil polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane are suitable examples of silicone oil
  • cationic silicone and silicone.
  • silicone resin silicone resin
  • hydrocarbon oil polyolefin, fatty acid ester and the like.
  • the coloring composition of the present embodiment can be blended with other additives as necessary within a range that does not impair the effects of the present invention. Examples of additives in each application will be described later.
  • the coloring composition according to one embodiment of the present invention can be a coloring composition (coloring composition for color filter) used for color filter applications.
  • the coloring composition for color filters contains a polymeric compound.
  • the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.
  • Specific examples of the polymerizable compound include a compound group having at least one terminal ethylenically unsaturated bond, preferably two or more.
  • Such a group of compounds may be any of chemical forms such as, for example, monomers, polymers, that is, dimers, trimers and oligomers, or mixtures thereof, and (co) polymers thereof.
  • unsaturated carboxylic acid for example, acrylic acid, methacrylic acid
  • its ester body, amide body, these (co) polymer, etc. are mentioned.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy A dehydration condensation reaction product with a polyfunctional carboxylic acid can also be used.
  • a compound in which an unsaturated phosphonic acid, styrene, vinyl ether, or the like is substituted for the above unsaturated carboxylic acid may be used.
  • the content of the polymerizable compound in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass from the viewpoint of more effectively obtaining the effects of the present invention. More preferably, it is more preferably 20 to 60% by mass.
  • the coloring composition for color filters contains at least 1 type of photoinitiator.
  • the photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
  • Examples of the photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds.
  • an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.
  • the content of the photopolymerization initiator in the total solid content of the color filter coloring composition is preferably 3 to 20% by mass, more preferably 4 to 19% by mass, and 5 to 18% by mass. More preferably it is.
  • the color filter coloring composition preferably contains at least one organic solvent.
  • the organic solvent is basically not limited as long as it can satisfy the solubility of the coexisting core components and the coating property of the coloring composition, and may be selected in consideration of solubility, coating property, and safety. preferable.
  • esters, ethers, ketones, and aromatic hydrocarbons can be used as the organic solvent. These organic solvents may contain only 1 type, and can also mix and use 2 or more types.
  • a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferable.
  • the content of the organic solvent in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, and more preferably 15 to 60% by mass.
  • the color filter coloring composition preferably contains at least one alkali-soluble binder.
  • the alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
  • the alkali-soluble bath binder is preferably a linear organic high molecular weight polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No.
  • the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain.
  • Polymers and the like are also useful. Examples of the polymer containing a polymerizable group described above include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Corporation), and the like.
  • alcohol-soluble nylon polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
  • alkali-soluble binders from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
  • acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
  • acrylic resins include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (manufactured by Daicel Corporation) are preferred.
  • the alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferred is a polymer of 5,000 to 50,000.
  • the content of the alkali-soluble binder in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass.
  • the acid value of the alkali-soluble binder is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 105 to 200 mg / KOH.
  • the coloring composition for color filters may contain only one type of alkali-soluble binder, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the color filter coloring composition preferably contains at least one crosslinking agent.
  • the crosslinking agent is not particularly limited as long as it can cure the film by a crosslinking reaction.
  • the crosslinking agent is substituted with at least one substituent selected from an epoxy resin, a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, a methylol group, an alkoxymethyl group, and an acyloxymethyl group .
  • polyfunctional epoxy resins are preferred.
  • the coloring composition for a color filter contains at least one kind of antioxidant.
  • the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
  • radical scavengers include phenolic antioxidants and hindered amine antioxidants.
  • phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
  • ultraviolet absorbers examples include salicylate-based antioxidants and benzophenone-based antioxidants.
  • the singlet oxygen quencher examples include ethylenic compounds such as tetramethylethylene and cyclopentene, amines such as diethylamine, triethylamine, 1,4-diazabicyclooctane (DABCO), and N-ethylimidazole.
  • ethylenic compounds such as tetramethylethylene and cyclopentene
  • amines such as diethylamine, triethylamine, 1,4-diazabicyclooctane (DABCO), and N-ethylimidazole.
  • Good condensed polycyclic aromatic compounds such as naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenyl
  • aromatic compounds such
  • the antioxidants can be used alone or in admixture of two or more.
  • the content of the antioxidant in the total solid content of the color filter coloring composition is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant. .
  • the colored composition according to one embodiment of the present invention can be a colored composition (colored composition for color toner) used for color toner applications.
  • the content of at least one selected from the alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) in the color toner coloring composition is
  • the coloring composition for toner is 100 parts by mass, it is preferably contained in an amount of 0.1 part by mass or more, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass.
  • the color toner coloring composition preferably contains a binder resin.
  • a binder resin all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
  • inorganic fine powder and organic fine powder can be externally added for the purpose of fluidity of the composition, charge control and the like.
  • silica fine particles or titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferable.
  • the number average primary particle diameter of these is preferably 10 to 500 nm, and 0.1 to 20% by mass is preferably added to the toner.
  • the color toner coloring composition preferably contains a release agent.
  • a release agent all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax.
  • the addition amount of the release agent is preferably 1 to 5% by mass based on the total mass of the color toner composition.
  • the color toner coloring composition preferably contains a charge control agent.
  • the charge control agent include those having a quaternary ammonium salt structure and those having a calixarene structure.
  • the coloring composition for color toner can contain a carrier.
  • a carrier either an uncoated carrier constituted only by magnetic material particles such as iron or ferrite, or a resin-coated carrier obtained by coating the surface of the magnetic material particles with a resin or the like may be used.
  • the average particle diameter of the carrier is preferably 30 to 150 ⁇ m in volume average particle diameter.
  • the colored composition according to an embodiment of the present invention can be a colored composition (inkjet recording ink) used for inkjet recording ink applications.
  • the ink for inkjet recording is preferably an ink obtained by dissolving and / or dispersing a coloring composition in an oleophilic medium or an aqueous medium, and more preferably an ink using an aqueous medium. .
  • drying inhibitor for ink jet recording ink, drying inhibitor (wetting agent), anti-fading agent, emulsification stabilizer, penetration enhancer, ultraviolet absorber, preservative, antifungal agent, pH adjuster, surface hearing adjuster as necessary
  • Known additives such as an agent, an antifoaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used.
  • these various additives are directly added to the ink liquid in the case of water-soluble ink.
  • an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
  • the anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for ink jet recording at the ink ejection port of the nozzle used in the ink jet recording method.
  • a drying inhibitor a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
  • Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin.
  • Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives.
  • lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether
  • drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink for inkjet recording in an amount of 10 to 50% by mass.
  • UV absorbers are used for the purpose of improving image storage stability.
  • examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like.
  • the anti-fading agent is used for the purpose of improving image storage stability.
  • various organic and metal complex antifading agents can be used.
  • Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by mass in the ink.
  • a neutralizer organic base, inorganic alkali
  • the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, more preferably 7 to 10.
  • the surface tension adjusting agent examples include nonionic, cationic or anionic surfactants.
  • the surface tension of the ink for ink jet recording of the present invention is preferably 25 to 70 mN / m. Further, 25 to 60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa ⁇ s or less. Furthermore, it is more preferable to adjust to 20 mPa ⁇ s or less.
  • surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates.
  • Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester
  • Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred.
  • SURFYNOLS Air Products & Chemicals
  • An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.
  • fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
  • an alkali metal salt, alkaline earth metal salt of an azo dye or a tautomer thereof, which is a compound according to an embodiment of the present invention is dispersed in an aqueous medium
  • JP-A-11-286637 and JP-A-2001-2001 As described in each publication such as No. 240763, JP-A No. 2001-262039, JP-A No. 2001-247788, etc., colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium
  • the specific method for dispersing the compound of the present embodiment in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount used thereof are preferably those described in the above-mentioned patent publications, etc. can do. Or you may disperse
  • Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer)
  • mill method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
  • ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
  • ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
  • ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
  • ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator
  • JP-A-5-148436 JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7- Details are described in Japanese Patent Nos. 118584, 11-286637, and 2001-271003, and can be used for the preparation of an ink for ink jet recording containing a colored composition according to an embodiment of the present invention.
  • a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used.
  • the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene
  • the ink for inkjet recording 0.2 parts of at least one selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) with respect to 100 parts by mass of the ink for inkjet recording.
  • the content is preferably 10 to 10 parts by mass, and more preferably 1 to 6 parts by mass.
  • the ink for ink jet recording may be used in combination with other pigments. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably in the above range.
  • a dyed product can be obtained by applying various dyeing methods to an object to be dyed using the colored composition according to an embodiment of the present invention. Although it does not limit as a dyeing
  • the material to be dyed (the material to be dyed) is not limited as long as it can be dyed such as fiber, cloth, leather, paper, film and the like.
  • Example 1 Synthesis of Exemplified Compound D-115
  • Compound D-200 represented by the following formula, 321 mg, was dissolved in 3.2 mL of isopropyl alcohol. To this solution, 36 mg of lithium hydroxide monohydrate was added and stirred at room temperature for 2 days. The precipitated crystals were collected by filtration and dried to obtain 152 mg (yield 47%) of Exemplary Compound D-115.
  • Example 2 Synthesis of Exemplary Compound D-114
  • Example 3 Synthesis of Exemplary Compound D-113
  • Example 4 Synthesis of Exemplary Compound D-54 A mixture of compound D-201, 255 mg represented by the following formula, potassium tert-butoxide 138 mg, and isopropyl alcohol 2.0 mL was stirred at room temperature for 2 days. The precipitated crystals were collected by filtration and dried to obtain 204 mg (yield 70%) of Exemplary Compound D-54.
  • Example 5 Synthesis of Exemplary Compound D-126 A mixture of Compound D-202 represented by the following formula, 221 mg, potassium acetate 96 mg, and isopropyl alcohol 3.2 mL was stirred at room temperature for 1 day. The precipitated crystals were collected by filtration and dried to obtain 86 mg (yield 34%) of Exemplary Compound D-126.
  • Example 6 Synthesis of Exemplary Compound D-131 After heating a mixture of Compound D-203 represented by the following formula, 304 mg, 124 mg of potassium tert-butoxide, and 3.0 mL of t-amyl alcohol to 50 ° C. And stirred for 18 hours at room temperature. The precipitated crystals were collected by filtration and dried to obtain 196 mg (yield 57%) of Exemplary Compound D-131.
  • Example 7 Preparation of Colored Composition Containing Example Compound D-114 and Measurement of Absorption Spectrum 2.03 mg of the above D-200 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-114 at a concentration of 8.56 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
  • Example 8 Preparation of colored composition containing exemplary compound D-55 and measurement of absorption spectrum 2.00 mg of the above D-201 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-55 at a concentration of 9.19 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
  • Example 9 Preparation of Colored Composition Containing Example Compound D-127 and Measurement of Absorption Spectrum 2.02 mg of the above D-202 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-127 at a concentration of 9.21 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
  • Example 10 Preparation of colored composition containing exemplary compound D-132 and measurement of absorption spectrum 2.00 mg of the above D-203 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. Thus, a composition containing Exemplary Compound D-132 at a concentration of 9.00 ppm was prepared. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
  • comparative compounds D-200 to D-203 are the above-mentioned compounds D-200 to D-203, respectively.
  • the compounds of Examples 11 to 14 and Comparative Examples 1 to 4 exhibit a high thermal decomposition temperature of 270 ° C. or higher.
  • the thermal decomposition temperature is increased with respect to comparative compounds that are not potassium salts, and the stability to heat is increased.
  • Example 15 Dyeing of inkjet paper by D-114 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.100 g of Compound D-200 and 0.5 mL of 1M aqueous sodium hydroxide solution. This obtained the coloring composition containing exemplary compound D-114. This was applied to inkjet paper painting (manufactured by FUJIFILM Corporation) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright purple dyeing was obtained.
  • Example 16 Dyeing of inkjet paper with D-55 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.111 g of Compound D-201 and 0.5 mL of 1M aqueous sodium hydroxide solution. As a result, a colored composition containing Exemplified Compound D-55 was obtained, and this was applied to an inkjet paper image (Fuji Film Co., Ltd.) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright red dyeing was obtained.
  • Emulgen 109P manufactured by Kao Corporation
  • Example 17 Dyeing of inkjet paper with D-132 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.093 g of Compound D-203 and 0.5 mL of 1M aqueous sodium hydroxide solution. This obtained the coloring composition containing exemplary compound D-132. This was applied to inkjet paper painting (manufactured by FUJIFILM Corporation) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright yellow dyeing was obtained.
  • the reflection spectra of the dyed products obtained in Examples 15 to 17 are shown in FIGS.
  • the L *, a *, and b * values are shown in Table 3.

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Abstract

Provided are: an azo pigment alkali metal salt, in which the azo pigment is represented by general formula (1); an alkaline earth metal salt and a tautomer thereof; and a coloring composition, a dyeing method, and a dyed product that use the foregoing. A-N=N-B (1)

Description

アゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体、着色組成物、染色方法及び染色物Alkali metal salts, alkaline earth metal salts and tautomers thereof, coloring compositions, dyeing methods and dyed articles of azo dyes
　本発明は、良好な色相及び堅牢性を有し、高い分子吸光係数を有する新規なアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体に関し、更にこれらを用いた、着色組成物、染色方法、及び染色物に関する。 The present invention relates to a novel azo dye alkali metal salt, alkaline earth metal salt and tautomer thereof having a good hue and fastness and a high molecular extinction coefficient, and further, a coloring composition using them Article, dyeing method, and dyed article.
　従来、アゾ色素は種々の可視光吸収を有することが多いため、色素として種々の分野で利用されてきた。例えば、合成樹脂の着色、印刷インク、昇華型感熱転写材料用色素、インクジェット用インク、カラーフィルタ用色素等、種々の分野で用いられるようになってきている。 Conventionally, since azo dyes often have various visible light absorption, they have been used as dyes in various fields. For example, it has come to be used in various fields such as coloring of synthetic resins, printing inks, dyes for sublimation thermal transfer materials, inks for inkjets, and dyes for color filters.
　近年、画像記録材料として、カラー画像が主流となり、色素の使用用途も多様化してきた。具体的には、インクジェット方式の記録材料、感熱転写方式の記録材料、電子写真方式の記録材料、転写式ハロゲン化銀感光材料、印刷インク等に盛んに利用されている。また、撮影機器ではＣＣＤやＣＭＯＳなどの撮像素子において、ディスプレイではＬＣＤやＰＤＰにおいて、カラー画像を記録、再現するカラーフィルタが使用されている。これらのカラー画像記録材料やカラーフィルタでは、フルカラー画像を再現あるいは記録するために、いわゆる加法混色法又は減法混色法の３原色の着色剤（染料又は顔料）が使用されている。
　しかし、好ましい色再現域を実現できる吸収特性を有し、かつ様々な使用条件、環境条件に耐えうる、色相が良く堅牢な着色剤が無いのが現状であり、改善が強く望まれている。 In recent years, color images have become mainstream as image recording materials, and the uses of dyes have also diversified. Specifically, it is actively used for inkjet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, and the like. In addition, a color filter that records and reproduces a color image is used in an imaging device such as a CCD or a CMOS in a photographing apparatus and in an LCD or a PDP in a display. In these color image recording materials and color filters, three primary colorants (dyes or pigments) of the so-called additive color mixture method or subtractive color mixture method are used to reproduce or record a full color image.
However, the present situation is that there is no colorant that has an absorption characteristic capable of realizing a preferable color gamut, can withstand various use conditions and environmental conditions, and has a good hue and is robust, and improvement is strongly desired.
　従来の解離性プロトンを有するアゾ色素としては、例えば、特許第４０８０９４７号公報に開示されているアゾ色素が挙げられる。 Examples of conventional azo dyes having dissociable protons include azo dyes disclosed in Japanese Patent No. 4080947.
　本発明一実施形態の目的は、良好な色相及び堅牢性を有し、高い分子吸光係数を有する新規の解離性プロトンを有するアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体を提供することである。 An object of one embodiment of the present invention is to provide alkali metal salts, alkaline earth metal salts and tautomers of azo dyes having a novel dissociative proton having a good hue and fastness and a high molecular extinction coefficient. Is to provide.
　本発明者は、鋭意研究を重ねた結果、新規な解離性プロトンを有するアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体が、良好な色相を有し、かつ良好な堅牢性を発揮することを見出し、本発明を完成させた。 As a result of extensive research, the present inventor has found that the alkali metal salts, alkaline earth metal salts and tautomers of the azo dyes having a novel dissociative proton have a good hue and good fastness. As a result, the present invention has been completed.
　本発明は、以下の態様を含む。 The present invention includes the following aspects.
［１］　下記一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体。
Ａ－Ｎ＝Ｎ－Ｂ　　　（１）
　一般式（１）中、Ａは置換基を有してもよい下記式（Ａ－１）～（Ａ－２５）のいずれかで表される複素環基であって、カルボキシ基、スルホ基を含まず、アゾ基に炭素原子を介して結合する基を示す。 [1] Alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dyes represented by the following general formula (1).
A−N = NB (1)
In the general formula (1), A is a heterocyclic group represented by any of the following formulas (A-1) to (A-25) which may have a substituent, and is a carboxy group or a sulfo group. A group which does not contain and is bonded to an azo group via a carbon atom is shown.
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000006
 
Figure JPOXMLDOC01-appb-C000006
 
　式（Ａ－１）～（Ａ－２５）中、＊は、一般式（１）中のアゾ基に結合する位置を表す。
　Ｒ２１～Ｒ５０は、独立に水素原子、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、水酸基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、スルファモイル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基又はカルバモイル基を表し、Ｒ２１～Ｒ５０のうち隣接する基は互いに結合して飽和又は不飽和の５員又は６員環構造を形成してもよい。
　ａ、ｐ、ｑ、ｒ及びｓは０～４の整数を表し、ｂ及びｃは０～６の整数を表し、ｄ、ｅ、ｆ、ｇ、ｔ及びｕは０～３の整数を表し、ｈ、ｉ、ｊ、ｋ、ｌ及びｏは０～２の整数を表し、ｍは０～１の整数を表し、同一分子中のＲ２１～Ｒ５０で表される２以上の基は、同一であっても互いに異なっていてもよい。
　一般式（１）中、Ｂは下記式（Ｂ－１）～（Ｂ－１２）のいずれかで表される解離性プロトンを含み、かつカルボキシ基、スルホ基を含まない基を表す。 In formulas (A-1) to (A-25), * represents a position bonded to the azo group in general formula (1).
R 21 to R 50 are independently hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group Alternatively, it represents a carbamoyl group, and adjacent groups among R 21 to R 50 may be bonded to each other to form a saturated or unsaturated 5-membered or 6-membered ring structure.
a, p, q, r and s represent an integer of 0 to 4, b and c represent an integer of 0 to 6, d, e, f, g, t and u represent an integer of 0 to 3, h, i, j, k, l and o represent an integer of 0 to 2, m represents an integer of 0 to 1, and two or more groups represented by R 21 to R 50 in the same molecule are the same. Or they may be different from each other.
In the general formula (1), B represents a group containing a dissociable proton represented by any of the following formulas (B-1) to (B-12) and not containing a carboxy group or a sulfo group.
Figure JPOXMLDOC01-appb-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
　式（Ｂ－１）～（Ｂ－１２）中、＊＊は一般式（１）中のアゾ基に結合する位置を表す。
　Ｒ１０１はハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、スルファモイル基、アルキルスルホニル基又はカルバモイル基を表し、
　Ｒ１０２及びＲ１０４は、それぞれ独立にシアノ基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基又はカルバモイル基を表し、
　Ｚ１は酸素原子、硫黄原子又は－Ｎ（Ｒ１０３）－を表し、
　Ｒ１０３は水素原子、アルキル基、アリール基又は複素環基を表し、
　ｖは０～４の整数を表し、ｖ個のＲ１０１は同一であっても異なっていてもよい。
　Ｒ１０５及びＲ１０６は、独立して、水素原子、アルキル基、アリール基又は複素環基を表す。
　Ｒ１０７は水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、
　Ｚ２及びＺ３は、独立に－Ｃ（Ｒ１０８）＝又は－Ｎ＝を表し、
　Ｒ１０８はアルキル基、アリール基、複素環基、アルキルチオ基、アリールチオ基、アルコキシカルボニル基又はカルバモイル基を表し、
　Ｚ２及びＺ３が両方とも－Ｃ（Ｒ１０８）＝である場合、２個のＲ１０８基は同一であっても異なっていてもよく、互いに結合して炭素環又は複素環を形成してもよい。
　Ｒ１０９はアルキル基、アリール基又は複素環基を表し、Ｒ１１０は水素原子、アルキル基、アリール基、複素環基、アシル基、アルキルスルホニル基又はアリールスルホニル基を表し、Ｒ１１１はアルキル基、アリール基、アルコキシ基、アミノ基（アニリノ基を含む）、アルコキシカルボニル基、シアノ基、アシルアミノ基又はカルバモイル基を表し、Ｒ１１２は水素原子、アルキル基、アリール基又は複素環基を表し、Ｒ１１３はヒドロキシル基又はアミノ基を表す。
　Ｒ１１４及びＲ１１５はハロゲン原子、アルキル基、アリール基、複素環基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルコキシカルボニル基又はカルバモイル基を表す。
　ｗは０～４の整数を表し、ｗ個のＲ１１４基は同一であっても異なっていてもよい。
　ｘは０～６の整数を表し、ｘ個のＲ１１５基は同一であっても異なっていてもよい。
　Ｒ１１６、Ｒ１１７、Ｒ１１８及びＲ１１９は、独立にアルキル基又はアリール基を表す。
　Ｒ１２０及びＲ１２１は、独立にアルキル基、アリール基、複素環基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、
　Ｒ１２２は、水素原子、アルキル基、アリール基、複素環基、アシルアミノ基、アルキルスルホニルアミノ基又はアリールスルホニルアミノ基を表す。
　Ｒ１２３及びＲ１２４は、独立に、アルキル基、アリール基、複素環基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、
　Ｚ４は２個の窒素原子と１個の炭素原子と共に５員又は６員環を形成する非金属原子団を表し、
　Ｚ４が５員環を形成する場合、ｙは０～２の整数を表し、Ｚ４が６員環を形成する場合、ｙは０～３の整数を表し、
　Ｒ１２５はアルキル基、アリール基、アルコキシ基、アミノ基、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アシル基、アルコキシカルボニル基又はカルバモイル基を表し、
　Ｒ１２６はアルキルカルボニル基又はアリールカルボニル基を表す。 In the formulas (B-1) to (B-12), ** represents a position bonded to the azo group in the general formula (1).
R 101 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, Represents a sulfamoyl group, an alkylsulfonyl group or a carbamoyl group,
R 102 and R 104 are each independently a cyano group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group or carbamoyl. Represents a group,
Z 1 represents an oxygen atom, a sulfur atom or —N (R 103 ) —,
R 103 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
v represents an integer of 0 to 4, and v R 101s may be the same or different.
R 105 and R 106 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R107 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group. Represents an alkylsulfonyl group, an arylsulfonyl group or a carbamoyl group,
Z 2 and Z 3 independently represent —C (R 108 ) ═ or —N═,
R 108 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group,
When Z 2 and Z 3 are both —C (R 108 ) ═, the two R 108 groups may be the same or different and are bonded together to form a carbocyclic or heterocyclic ring. Also good.
R 109 represents an alkyl group, an aryl group or a heterocyclic group, R 110 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, R 111 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group or a carbamoyl group, R 112 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R 113 Represents a hydroxyl group or an amino group.
R 114 and R 115 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, nitro groups, alkoxy groups, aryloxy groups, amino groups (including anilino groups), acylamino groups, alkoxycarbonylamino groups, aminocarbonylamino groups. Represents an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonyl group or a carbamoyl group.
w represents an integer of 0 to 4, and w R 114 groups may be the same or different.
x represents an integer of 0 to 6, and the x R 115 groups may be the same or different.
R 116 , R 117 , R 118 and R 119 independently represent an alkyl group or an aryl group.
R 120 and R 121 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group,
R 122 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group or an arylsulfonylamino group.
R 123 and R 124 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group,
Z 4 represents a nonmetallic atomic group that forms a 5- or 6-membered ring with two nitrogen atoms and one carbon atom,
When Z 4 forms a 5-membered ring, y represents an integer of 0-2, and when Z 4 forms a 6-membered ring, y represents an integer of 0-3,
R 125 represents an alkyl group, aryl group, alkoxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group or carbamoyl group,
R 126 represents an alkylcarbonyl group or an arylcarbonyl group.
［２］　アゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の構造が、下記式ＤＳ－１～ＤＳ－９のいずれかで表されるものである［１］記載のアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体。 [2] The azo according to [1], wherein the structure of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye is represented by any of the following formulas DS-1 to DS-9 Alkali metal salts, alkaline earth metal salts and tautomers thereof.
Figure JPOXMLDOC01-appb-C000008
 
Figure JPOXMLDOC01-appb-C000008
 
　式（ＤＳ－１～ＤＳ－９）中、Ａは上記[１]で定義されたＡと同様の意味を有し、
　Ｒ２０１はアルキル基、アリール基、アルコキシ基、アミノ基（アニリノ基を含む）、アルコキシカルボニル基、シアノ基、アシルアミノ基又はカルバモイル基を表し、
　Ｒ２０２は水素原子、アルキル基、アリール基又は複素環基を表し、
　Ｒ２０３、Ｒ２０５及びＲ２０７は、それぞれ独立に、水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、Ｒ２０４はアルキル基、アリール基又は複素環基を表す。
　Ｒ２０６はアルキル基、アリール基、複素環基、アルキルチオ基、アリールチオ基、アルコキシカルボニル基又はカルバモイル基を表す。
　Ｒ２０８はハロゲン原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、ａａは、０～４の整数を表し、ａａ個のＲ２０８は同一であっても異なっていてもよい。
　Ｒ２１０及びＲ２１１は、独立に、水素原子、ハロゲン原子、アルキル基、アリール基、アシルアミノ基、アルコキシカルボニル基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルコキシカルボニルアミノ基又はカルバモイル基を示し、Ｒ２１０及びＲ２１１の少なくとも一方が水素原子であり、Ｒ２１２及びＲ２１３は、独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基又はアシルアミノ基を表す。
　Ｒ２１４及びＲ２１５は、独立に、水素原子、アルキル基、アリール基又は複素環基を表す。
　Ｒ２１６は、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、スルファモイル基、アルキルスルホニル基又はカルバモイル基を示し、Ｚ５は酸素原子、硫黄原子又は－Ｎ（Ｒ２１７）－を示し、Ｒ２１７は水素原子、アルキル基、アリール基又は複素環基を示す。ｂｂは、０～４の整数を示し、ｂｂ個のＲ２１６は同一であっても異なっていてもよい。
　Ｒ２１８はＲ２１０と同義か、又はスルファモイル基を示し、Ｒ２２０及びＲ２２３は、水素原子、ハロゲン原子、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基又はアリールスルホニルアミノ基を示し、Ｒ２１９、Ｒ２２１及びＲ２２２は、水素原子、塩素原子、臭素原子、アルキル基又はアシルアミノ基を示す。
　Ｒ２２４は、アルキルカルボニル基又はアリールカルボニル基を示す。
　Ｍはアルカリ金属またはアルカリ土類金属１／２を示す In the formulas (DS-1 to DS-9), A has the same meaning as A defined in [1] above,
R 201 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group,
R 202 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R 203 , R 205 and R 207 are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group , an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or carbamoyl group, R 204 represents an alkyl group, an aryl group or a heterocyclic group.
R 206 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group.
R 208 is a halogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group Represents an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group, aa represents an integer of 0 to 4, and aa R 208 may be the same or different.
R 210 and R 211 are independently a hydrogen atom, halogen atom, alkyl group, aryl group, acylamino group, alkoxycarbonyl group, aminocarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group or carbamoyl. And at least one of R 210 and R 211 is a hydrogen atom, and R 212 and R 213 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an acylamino group.
R 214 and R 215 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
R216 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group , A sulfamoyl group, an alkylsulfonyl group or a carbamoyl group, Z 5 represents an oxygen atom, a sulfur atom or —N (R 217 ) —, and R 217 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. bb represents an integer of 0 to 4, and bb R 216s may be the same or different.
R 218 is synonymous with R 210 or represents a sulfamoyl group, and R 220 and R 223 are a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group. R 219 , R 221 and R 222 represent a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group.
R 224 represents an alkylcarbonyl group or an arylcarbonyl group.
M represents alkali metal or alkaline earth metal 1/2
［３］　［１］又は［２］に記載の一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種の化合物を含む着色組成物。
［４］　［１］又は［２］に記載の一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種の化合物を水性溶媒中に含む着色組成物。
［５］　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の総含有量が、着色組成物の総質量に対して０．０００１～２０質量％である［３］又は［４］に記載の着色組成物。
［６］　［３］～［５］のいずれか１項に記載の着色組成物を用いた染色方法。
［７］　［６］に記載の染色方法により得られる染色物。 [3] At least one compound selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dyes represented by the general formula (1) according to [1] or [2] A coloring composition comprising.
[4] At least one compound selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dyes represented by the general formula (1) according to [1] or [2] A coloring composition contained in an aqueous solvent.
[5] The total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) is 0.0001 to 20 with respect to the total mass of the colored composition. The coloring composition according to [3] or [4], which is mass%.
[6] A dyeing method using the coloring composition according to any one of [3] to [5].
[7] A dyed product obtained by the dyeing method according to [6].
　本発明の一実施形態によれば、本発明のアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、色相に優れ、光、熱、湿度および環境中の活性ガスに対して充分な堅牢性を有し、高い分子吸収係数を有する新規の化合物および色素を提供することができる。 According to one embodiment of the present invention, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present invention are excellent in hue and are effective against light, heat, humidity and the active gas in the environment. In addition, novel compounds and dyes having sufficient fastness and a high molecular absorption coefficient can be provided.
実施例１５にて得られた染色物の反射スペクトルに関する。This relates to the reflection spectrum of the dyed product obtained in Example 15. 実施例１６にて得られた染色物の反射スペクトルに関する。This relates to the reflection spectrum of the dyed product obtained in Example 16. 実施例１７にて得られた染色物の反射スペクトルに関する。This relates to the reflection spectrum of the dyed product obtained in Example 17.
　以下、本発明の実施形態に係るアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体について詳細に説明する。
　本明細書中において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書において、組成物中の各成分の量は、各成分に該当する物質が組成物中に複数存在する場合には、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。 Hereinafter, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye according to the embodiment of the present invention will be described in detail.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
　本発明の一実施形態に係るアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、下記一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体である。 The alkali metal salt, alkaline earth metal salt and tautomer thereof of an azo dye according to one embodiment of the present invention are an alkali metal salt and an alkaline earth metal salt of an azo dye represented by the following general formula (1). And tautomers thereof.
　Ａ－Ｎ＝Ｎ－Ｂ　　　（１）
　一般式（１）中のＡ及びＢは上記と同様の意味を有する。
　即ち、本発明のアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、以下に詳述する一般式（１）において、Ａが、置換基を有してもよい上記式（Ａ－１）～（Ａ－２５）のいずれかで表される複素環基であって、カルボキシ基、スルホ基を含まず、アゾ基に炭素原子を介して結合する基を示し、Ｂが、上記式（Ｂ－１）～（Ｂ－１２）のいずれかで表される解離性プロトンを含み、かつカルボキシ基、スルホ基を含まない基を表すアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体である。
　以下、一般式（１）について詳細に説明する。 A−N = NB (1)
A and B in the general formula (1) have the same meaning as described above.
That is, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present invention are represented by the above formula in which A may have a substituent in the general formula (1) described in detail below. A heterocyclic group represented by any one of (A-1) to (A-25), which does not include a carboxy group or a sulfo group, and represents a group bonded to an azo group via a carbon atom; An alkali metal salt of an azo dye containing a dissociable proton represented by any of the above formulas (B-1) to (B-12) and not containing a carboxy group or a sulfo group, an alkaline earth metal Salts and tautomers thereof.
Hereinafter, the general formula (1) will be described in detail.
　一般式（１）中、Ａで表される複素環基は、環内に酸素原子、硫黄原子又は窒素原子から選択されるヘテロ原子の一種以上を含む５員又は６員の複素環基であることが好ましく、芳香族複素環基であることがより好ましい。
　Ａで表される複素環基は、別の環と縮合した環であってもよい。このような縮合環基のうち、５員又は６員環と縮合環したものが好ましい。
　Ａで表される複素環基における炭素原子の数は、２～２０が好ましく、２～１０がより好ましい。 In general formula (1), the heterocyclic group represented by A is a 5-membered or 6-membered heterocyclic group containing one or more heteroatoms selected from an oxygen atom, a sulfur atom or a nitrogen atom in the ring. The aromatic heterocyclic group is more preferable.
The heterocyclic group represented by A may be a ring condensed with another ring. Of such fused ring groups, those fused with a 5-membered or 6-membered ring are preferred.
The number of carbon atoms in the heterocyclic group represented by A is preferably 2 to 20, and more preferably 2 to 10.
　一般式（１）中のＡで表される複素環基としては、ジアゾ成分から誘導されるものが好ましい。ここで、ジアゾ成分とは、アミノ基を置換基として有する複素環化合物をジアゾ化号物に変換して、カプラーとジアゾカップリング反応させて導入できる部分構造のことである。
　言い換えれば、Ａで表される複素環基は、ジアゾ化反応が可能であるアミノ置換されたヘテロ環化合物において、アミノ基を取り去り、一価の基とした置換基である。 As the heterocyclic group represented by A in the general formula (1), those derived from a diazo component are preferable. Here, the diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent into a diazo compound and reacting with a coupler by a diazo coupling reaction.
In other words, the heterocyclic group represented by A is a substituent which is a monovalent group by removing the amino group in an amino-substituted heterocyclic compound capable of diazotization reaction.
　一般式（１）において、Ａで表される複素環基は一以上の置換基を含むことができ、二以上の置換基は同一であっても異なっていてもよい。
　この置換基としては、例えば、ハロゲン原子、アルキル基（シクロアルキル基を含む）、アルケニル基（シクロアルケニル基を含む）、アルキニル基、アリール基、複素環基、シアノ基、水酸基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、複素環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ、アミノ基（アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基、スルファモイル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アリールアゾ基、複素環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基及びシリル基が挙げられる。より詳細には、この置換基としては、例えば、ハロゲン原子（例えば、塩素原子、臭素原子、ヨウ素原子）、アルキル基（１～１０個、好ましくは１～６個の炭素原子を有する直鎖、分岐又は環状アルキル基、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｔ－ブチル、ｎ－オクチル－２－クロロエチル－２－シアノエチル－２－エチルヘキシル、シクロプロピル、シクロペンチル）、アルケニル基（２～１０個、好ましくは２～６個の炭素原子を有する直鎖、分岐又は環状アルケニル基、例えば、ビニル、アリル、プレニル、シクロペンテン－１－イル）、アルキニル基（２～１０個、好ましくは２～６個の炭素原子を有するアルキニル基、例えば、エチニル、プロパルギル）、アリール基（６～１２個、好ましくは６～８個の炭素原子を有するアリール基、例えば、フェニル、ｐ－トリル、ナフチル、３－クロロフェニル－２－アミノフェニル）、複素環基（５員環又は６員環の芳香族又は非芳香族の複素環化合物から１個の水素原子を取り除くことによって得られる、１～１２個、好ましくは２～６個の炭素原子を有する一価の基、例えば１－ピラゾリル－１－イミダゾリル－２－フリル－２－チエニル、４－ピリミジニル－２－ベンゾチアゾリル）、シアノ基、水酸基、ニトロ基、アルコキシ基（１～１０個、好ましくは１～６個の炭素原子を有する直鎖、分岐又は環状アルコキシ基、例えば、メトキシ、エトキシ、イソプロポキシ、ｔ－ブトキシ、シクロペンチルオキシ－２－ブテン－１－イルオキシ－２－メトキシエトキシ）、アリールオキシ基（６～１２個、好ましくは６～８個の炭素原子を有するアリールオキシ基、例えば、フェノキシ－２－メチルフェノキシ、４－ｔ－ブチルフェノキシ、３－ニトロフェノキシ）、シリルオキシ基（３～１０個、好ましくは３～６個の炭素原子を有するシリルオキシ基、例えば、トリメチルシリルオキシ、ｔ－ブチルジメチルシリルオキシ）、複素環オキシ基（１～１２個、好ましくは２～６個の炭素原子を有する複素環オキシ基、例えば１－フェニルテトラゾール－５－オキシ－２－テトラヒドロピラニルオキシ）、アシルオキシ基（１～１２個、好ましくは１～８個の炭素原子を有するアシルオキシ基、例えば、ホルミルオキシ基、アセチルオキシ、ピバロイルオキシ、ベンゾイルオキシ、ｐ－メトキシフェニルカルボニルオキシ）、カルバモイルオキシ基（１～１０個、好ましくは１～６個の炭素原子を有するカルバモイルオキシ基、例えば、Ｎ，Ｎ－ジメチルカルバモイルオキシ、Ｎ，Ｎ－ジエチルカルバモイルオキシ、モルホリノカルボニルオキシ、Ｎ，Ｎ－オクチルカルバモイルオキシ）、アルコキシカルボニルオキシ基（２～１０個、好ましくは２～６個の炭素原子を有するアルコキシカルボニルオキシ基、例えば、メトキシカルボニルオキシ、エトキシカルボニルオキシ、ｔ－ブトキシカルボニルオキシ、ｎ－オクチルオキシカルボニルオキシ）、アリールオキシカルボニルオキシ基（７～１２個、好ましくは７～１０個の炭素原子を有するアリールオキシカルボニルオキシ基、例えば、フェノキシカルボニルオキシ、ｐ－メトキシフェノキシカルボニルオキシ）、アミノ基（アミノ基、１～１０個、好ましくは１～６個の炭素原子を有するアルキルアミノ基、６～１２個、好ましくは６～８個の炭素原子を有するアニリノ基、或いは１～１２個、好ましくは２～６個の炭素原子を有する複素環アミノ基、例えば、アミノ、メチルアミノ、ジメチルアミノ、アニリノ、Ｎ－メチル－アニリノ、ジフェニルアミノ、イミダゾール－２－イルアミノ、ピラゾール－３－イルアミノを含む）、アシルアミノ基（１～１０個、好ましくは１～６個の炭素原子を有するアルキルカルボニルアミノ基、６～１２個、好ましくは６～８個の炭素原子を有するアリールカルボニルアミノ基、或いは２～１２個、好ましくは２～６個の炭素原子を有する複素環カルボニルアミノ基、例えば、ホルミルアミノ、アセチルアミノ、ピバロイルアミノ、ベンゾイルアミノ、ピリジン－４－カルボニルアミノ、チオフェン－２－カルボニルアミノを含む）、アミノカルボニルアミノ基（１～１２個、好ましくは１～６個の炭素原子を有するアミノカルボニルアミノ、例えば、カルバモイルアミノ、Ｎ，Ｎ－ジメチルアミノカルボニルアミノ、Ｎ，Ｎ－ジエチルアミノカルボニルアミノ、モルホリン－４－イルカルボニルアミノ）、アルコキシカルボニルアミノ基（２～１０個、好ましくは２～６個の炭素原子を有するアルコキシカルボニルアミノ基、例えば、メトキシカルボニルアミノ、エトキシカルボニルアミノ、ｔ－ブトキシカルボニルアミノ）、アリールオキシカルボニルアミノ基（７～１２個、好ましくは７～９個の炭素原子を有するアリールオキシカルボニルアミノ基、例えば、フェノキシカルボニルアミノ、ｐ－クロロフェノキシカルボニルアミノ、４－メトキシフェノキシカルボニルアミノ）、スルファモイルアミノ基（０～１０個、好ましくは０～６個の炭素原子を有するスルファモイルアミノ基、例えば、スルファモイルアミノ、Ｎ，Ｎ－ジメチルアミノスルホニルアミノ、Ｎ－（２－ヒドロキシエチル）スルファモイルアミノ）、アルキルスルホニルアミノ基（１～１０個、好ましくは１～６個の炭素原子を有するアルキルスルホニルアミノ基、例えば、メチルスルホニルアミノ、ブチルスルホニルアミノ）、アリールスルホニルアミノ基（６～１２個、好ましくは６～８個の炭素原子を有するアリールスルホニルアミノ基、例えば、フェニルスルホニルアミノ、２，３，５－トリクロロフェニルスルホニルアミノ基、ｐ－メチルフェニルスルホニルアミノ）、メルカプト基、アルキルチオ基（１～１０個、好ましくは１～６個の炭素原子を有するアルキルチオ基、例えば、メチルチオ、エチルチオ、ブチルチオ）、アリールチオ基（６～１２個、好ましくは６～８個の炭素原子を有するアリールチオ、例えば、フェニルチオ、ｐ－クロロフェニルチオ、ｍ－メトキシチオ）、複素環チオ基（２～１０個、好ましくは１～６個の炭素原子を有する複素環チオ基、例えば－２－ベンゾチアゾリルチオ－１－フェニルテトラゾール－５－イルチオ）、スルファモイル基（０～１０個、好ましくは０～６個の炭素原子を有するスルファモイル基、例えば、スルファモイル、Ｎ－エチルスルファモイル、Ｎ，Ｎ－ジメチルスルファモイル、Ｎ－アセチルスルファモイル、Ｎ－ベンゾイルスルファモイル）、アルキルスルフィニル基（１～１０個、好ましくは１～６個の炭素原子を有するアルキルスルフィニル基、例えば、メチルスルフィニル、エチルスルフィニル）、アリールスルフィニル基（６～１２個、好ましくは６～８個の炭素原子を有するアリールスルフィニル基、例えば、フェニルスルフィニル、ｐ－メチルフェニルスルフィニル）、アルキルスルホニル基（１～１０個、好ましくは１～６個の炭素原子を有するアルキルスルホニル基、例えば、メチルスルホニル、エチルスルホニル）、アリールスルホニル基（６～１２個、好ましくは６～８個の炭素原子を有するアリールスルホニル基、例えば、フェニルスルホニル、ｐ－クロロフェニルスルホニル）、アシル基（ホルミル基、２～１０個、好ましくは２～６個の炭素原子を有するアルキルカルボニル基、或いは７～１２個、好ましくは７～９個の炭素原子を有するアリールカルボニル基、例えば、アセチル、ピバロイル－２－クロロアセチル、ベンゾイル、２，４－ジクロロベンゾイルを含む）、アルコキシカルボニル基（２～１０個、好ましくは２～６個の炭素原子を有するアルコキシカルボニル基、例えば、メトキシカルボニル、エトキシカルボニル、ｔ－ブトキシカルボニル、イソブチルオキシカルボニル）、アリールオキシカルボニル基（７～１２個、好ましくは７～９個の炭素原子を有するアリールオキシカルボニル基、例えば、フェノキシカルボニル－２－クロロフェノキシカルボニル、３－ニトロフェノキシカルボニル、４－ｔ－ブチルフェノキシカルボニル）、カルバモイル基（１～１０個、好ましくは１～６個の炭素原子を有するカルバモイル基、例えば、カルバモイル、Ｎ－メチルカルバモイル、Ｎ，Ｎ－ジメチルカルバモイル、Ｎ－（２－ヒドロキシエチル）カルバモイル、Ｎ－（メチルスルホニル）カルバモイル）、アリールアゾ基（６～１２個、好ましくは６～８個の炭素原子を有するアリールアゾ基、例えば、フェニルアゾ、ｐ－クロロフェニルアゾ）、複素環アゾ基（１～１０個、好ましくは１～６個の炭素原子を有する複素環アゾ基、例えば、ピラゾール－３－イルアゾ、チアゾール－２－イルアゾ－５－エチルチオ－１，３，４－チアジアゾール－２－イルアゾ）、イミド基（２～１０個、好ましくは４～８個の炭素原子を有するイミド基、例えば、Ｎ－スクシンイミド、Ｎ－フタルイミド）、ホスフィノ基（２～１２個、好ましくは２～６個の炭素原子を有するホスフィノ基、例えば、ジメチルホスフィノ、ジフェニルホスフィノ、メチルフェノキシホスフィノ）、ホスフィニル基（２～１２個炭素原子、好ましくは２～６個の炭素原子を有するホスフィニル基、例えば、ホスフィニル、ジエトキシホスフィニル）、ホスフィニルオキシ基（２～１２個、好ましくは２～６個の炭素原子を有するホスフィニルオキシ基、例えば、ジフェノキシホスフィニルオキシ、ジブトキシホスフィニルオキシ）、ホスフィニルアミノ基（２～１２個、好ましくは２～６個の炭素原子を有するホスフィニルアミノ基、例えば、ジメトキシホスフィニルアミノ、ジメチルアミノホスフィニルアミノ）、及びシリル基（３～１２個、好ましくは３～８個の炭素原子を有するシリル基、例えば、トリメチルシリル、ｔ－ブチルジメチルシリル、フェニルジメチルシリル）が挙げられる。これらの基が更に置換され得る基である場合、これらの基は更に置換基を含むことができ、この置換基として、好ましくは、Ａで表される複素環基の好ましい置換基として記載したものと同じ意味を有する基が挙げられる。これらの基が二以上の置換基で置換される場合、これらの置換基は同一であっても異なっていてもよい。 In the general formula (1), the heterocyclic group represented by A can include one or more substituents, and the two or more substituents may be the same or different.
Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and an alkoxy group. Group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, A phosphinylamino group and a silyl group are mentioned. More specifically, examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (a straight chain having 1 to 10, preferably 1 to 6 carbon atoms, Branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl-2-chloroethyl-2-cyanoethyl-2-ethylhexyl, cyclopropyl, cyclopentyl), alkenyl groups (2-10 Linear, branched or cyclic alkenyl groups having 2 to 6 carbon atoms, such as vinyl, allyl, prenyl, cyclopenten-1-yl, alkynyl groups (2 to 10, preferably 2 to 6) Alkynyl groups having 1 carbon atom, eg ethynyl, propargyl), aryl groups (6-12, preferably 6-8 An aryl group having an elementary atom, for example, phenyl, p-tolyl, naphthyl, 3-chlorophenyl-2-aminophenyl), a heterocyclic group (5-membered or 6-membered aromatic or non-aromatic heterocyclic compound) Monovalent groups having 1 to 12, preferably 2 to 6 carbon atoms obtained by removing one hydrogen atom, such as 1-pyrazolyl-1-imidazolyl-2-furyl-2-thienyl, 4-pyrimidinyl-2-benzothiazolyl), cyano group, hydroxyl group, nitro group, alkoxy group (straight chain, branched or cyclic alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms, for example, methoxy, ethoxy , Isopropoxy, t-butoxy, cyclopentyloxy-2-buten-1-yloxy-2-methoxyethoxy), aryloxy group (6-12) An aryloxy group having preferably 6 to 8 carbon atoms, for example, phenoxy-2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy), silyloxy group (3 to 10, preferably 3 to Silyloxy groups having 6 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, heterocyclic oxy groups (1-12, preferably 2-6 carbon atoms having heterocyclic atoms such as 1-phenyltetrazol-5-oxy-2-tetrahydropyranyloxy), acyloxy groups (1-12, preferably 1-8 acyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, Benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy Ci groups (carbamoyloxy groups having 1 to 10, preferably 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-octyl Carbamoyloxy), alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having 2 to 10, preferably 2 to 6 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octyloxy Carbonyloxy), aryloxycarbonyloxy group (aryloxycarbonyloxy group having 7 to 12, preferably 7 to 10 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy), amino group (a Group, an alkylamino group having 1 to 10, preferably 1 to 6 carbon atoms, an anilino group having 6 to 12, preferably 6 to 8 carbon atoms, or 1 to 12, preferably Heterocyclic amino groups having 2 to 6 carbon atoms, including amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, imidazol-2-ylamino, pyrazol-3-ylamino), An acylamino group (an alkylcarbonylamino group having 1-10, preferably 1-6 carbon atoms, an arylcarbonylamino group having 6-12, preferably 6-8 carbon atoms, or 2-12 Preferably a heterocyclic carbonylamino group having 2 to 6 carbon atoms, such as formylamino, acetylamino, pivaloyl Amino, benzoylamino, pyridine-4-carbonylamino, thiophene-2-carbonylamino), aminocarbonylamino groups (aminocarbonylamino having 1 to 12, preferably 1 to 6 carbon atoms, eg carbamoyl) Amino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholin-4-ylcarbonylamino), alkoxycarbonylamino group (alkoxy having 2 to 10, preferably 2 to 6 carbon atoms) A carbonylamino group such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino), an aryloxycarbonylamino group (an aryloxycarbonylamino group having 7 to 12, preferably 7 to 9 carbon atoms such as , Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, 4-methoxyphenoxycarbonylamino), sulfamoylamino groups (sulfamoylamino groups having 0 to 10, preferably 0 to 6 carbon atoms, such as Famoylamino, N, N-dimethylaminosulfonylamino, N- (2-hydroxyethyl) sulfamoylamino), alkylsulfonylamino groups (alkylsulfonyl having 1 to 10, preferably 1 to 6 carbon atoms) Amino groups such as methylsulfonylamino, butylsulfonylamino), arylsulfonylamino groups (arylsulfonylamino groups having 6 to 12, preferably 6 to 8 carbon atoms such as phenylsulfonylamino, 2,3, 5-trichlorophenylsulfonyl Mino group, p-methylphenylsulfonylamino), mercapto group, alkylthio group (1-10, preferably 1-6 alkylthio groups such as methylthio, ethylthio, butylthio), arylthio group (6- Arylthio having 12 and preferably 6 to 8 carbon atoms, for example phenylthio, p-chlorophenylthio, m-methoxythio), heterocyclic thio groups (2 to 10, preferably 1 to 6 carbon atoms) A heterocyclic thio group having, for example, 2-benzothiazolylthio-1-phenyltetrazol-5-ylthio), a sulfamoyl group (0-10, preferably 0-6, sulfamoyl groups having, for example, sulfamoyl N-ethylsulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl Amoyl, N-benzoylsulfamoyl), alkylsulfinyl groups (1-10, preferably alkylsulfinyl groups having 1-6 carbon atoms, such as methylsulfinyl, ethylsulfinyl), arylsulfinyl groups (6-12) Arylsulfinyl groups having 6 to 8 carbon atoms, for example phenylsulfinyl, p-methylphenylsulfinyl), alkylsulfonyl groups (1 to 10, preferably 1 to 6 carbon atoms alkyl Sulfonyl groups such as methylsulfonyl, ethylsulfonyl), arylsulfonyl groups (arylsulfonyl groups having 6 to 12, preferably 6 to 8 carbon atoms, such as phenylsulfonyl, p-chlorophenylsulfonyl), acyl groups ( Formyl group, 2 to 1 An alkylcarbonyl group having 0, preferably 2-6 carbon atoms, or an arylcarbonyl group having 7-12, preferably 7-9 carbon atoms, such as acetyl, pivaloyl-2-chloroacetyl, Benzoyl, including 2,4-dichlorobenzoyl), alkoxycarbonyl groups (alkoxycarbonyl groups having 2 to 10, preferably 2 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, isobutyl Oxycarbonyl), aryloxycarbonyl groups (aryloxycarbonyl groups having 7 to 12, preferably 7 to 9, carbon atoms such as phenoxycarbonyl-2-chlorophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-t -Butylphenoxycarboni ), A carbamoyl group (carbamoyl group having 1 to 10, preferably 1 to 6 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N- (2-hydroxyethyl) carbamoyl, N- (methylsulfonyl) carbamoyl), arylazo groups (6-12, preferably arylazo groups having 6-8 carbon atoms, such as phenylazo, p-chlorophenylazo), heterocyclic azo groups (1-10) A heterocyclic azo group having preferably 1 to 6 carbon atoms, such as pyrazol-3-ylazo, thiazol-2-ylazo-5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (Imido groups having 2 to 10, preferably 4 to 8, carbon atoms, eg N-succinimide, N Phthalimide), phosphino groups (phosphino groups having 2 to 12, preferably 2 to 6 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (2 to 12 carbon atoms) A phosphinyl group having preferably 2 to 6 carbon atoms, eg phosphinyl, diethoxyphosphinyl), a phosphinyloxy group (2 to 12, preferably 2 to 6 carbon atoms, Ruoxy groups such as diphenoxyphosphinyloxy, dibutoxyphosphinyloxy), phosphinylamino groups (phosphinylamino groups having 2 to 12, preferably 2 to 6 carbon atoms such as , Dimethoxyphosphinylamino, dimethylaminophosphinylamino), and silyl groups (3-12, preferably Preferable examples include silyl groups having 3 to 8 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl. In the case where these groups are groups that can be further substituted, these groups can further contain a substituent, and this substituent is preferably described as a preferred substituent of the heterocyclic group represented by A. And groups having the same meaning. When these groups are substituted with two or more substituents, these substituents may be the same or different.
　特に好ましくは、一般式（１）中のＡで表される複素環基の置換基は、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、水酸基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、スルファモイル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基及びカルバモイル基であり、より好ましくは、この置換基は、ハロゲン原子、アルキル基、シアノ基、水酸基、ニトロ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基及びカルバモイル基である。 Particularly preferably, the substituent of the heterocyclic group represented by A in the general formula (1) is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy Group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl Group, arylsulfonyl group, acyl group, alkoxycarbonyl group and carbamoyl group, and more preferably, this substituent is a halogen atom, alkyl group, cyano group, hydroxyl group, nitro group, alkoxy group, amino group (anilino group). Including), acylamino group, alkylsulfonylamino And a carbamoyl group.
　Ａで表される複素環基としては、置換基を有してもよい上記の式（Ａ－１）～（Ａ－２５）のいずれかで表される複素環基が挙げられる。
　式（Ａ－１）～（Ａ－２５）において、Ｒ２１～Ｒ５０は、独立して、水素原子又は置換基を表し、好ましくは、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、水酸基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、スルファモイル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基及びカルバモイル基が挙げられ、より好ましくは、この置換基は、ハロゲン原子、アルキル基、シアノ基、水酸基、ニトロ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基及びカルバモイル基である。
　ａ、ｐ、ｑ、ｒ及びｓは０～４の整数を表し、ｂ、ｃは０～６の整数を表し、ｄ、ｅ、ｆ、ｇ、ｔ及びｕは０～３の整数を表し、ｈ、ｉ、ｊ、ｋ、ｌ及びｏは０～２の整数を表し、ｍは０～１の整数を表す。ａ～ｕが２以上の整数を示す場合、Ｒ２１～Ｒ５０で表される基（各々２個以上存在する）は、同一であっても互いに異なっていてもよい。 Examples of the heterocyclic group represented by A include heterocyclic groups represented by any one of the above formulas (A-1) to (A-25) which may have a substituent.
In formulas (A-1) to (A-25), R 21 to R 50 independently represent a hydrogen atom or a substituent, preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, cyano Group, hydroxyl group, nitro group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio Group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group and carbamoyl group, more preferably, this substituent is a halogen atom, alkyl group, cyano group, hydroxyl group , Nitro group, alkoxy group, amino group (including anilino group) An acylamino group, an alkylsulfonylamino group and carbamoyl group.
a, p, q, r and s represent an integer of 0 to 4, b and c represent an integer of 0 to 6, d, e, f, g, t and u represent an integer of 0 to 3, h, i, j, k, l, and o represent an integer of 0 to 2, and m represents an integer of 0 to 1. When a to u each represent an integer of 2 or more, the groups represented by R 21 to R 50 (each having two or more) may be the same or different from each other.
　更に、Ｒ２１～Ｒ５０で表される互いに隣接する基が結合して環構造を形成してもよい。こうして形成された環構造は複素環でも炭素環でもよく、また、飽和環でも不飽和環でもよい。炭素原子及びヘテロ原子の総数は３～６であり、好ましくは５又は６である。
　Ｒ２１～Ｒ５０が更に置換され得る基である場合、Ｒ２１～Ｒ５０は更に置換基を含むことができ、この場合、この置換基は、一般式（１）中のＡで表される複素環基の置換基として列挙したものと同じである。 Further, groups adjacent to each other represented by R 21 to R 50 may be bonded to form a ring structure. The ring structure thus formed may be a heterocyclic ring or a carbocyclic ring, and may be a saturated ring or an unsaturated ring. The total number of carbon atoms and heteroatoms is 3-6, preferably 5 or 6.
When R 21 to R 50 are groups that can be further substituted, R 21 to R 50 can further include a substituent. In this case, the substituent is represented by A in the general formula (1). The same as those listed as the substituent of the heterocyclic group.
　一般式（１）で表されるアゾ色素である化合物において、Ａで表される複素環基は、好ましくは、式（Ａ－１）、（Ａ－５）、（Ａ－８）、（Ａ－９）、（Ａ－１０）、（Ａ－１１）、（Ａ－１２）、（Ａ－１３）、（Ａ－１４）、（Ａ－１５）、（Ａ－１７）、（Ａ－１９）、（Ａ－２２）、（Ａ－２３）、（Ａ－２４）及び（Ａ－２５）であり、より好ましくは（Ａ－８）、（Ａ－９）、（Ａ－１０）、（Ａ－１１）、（Ａ－１４）、（Ａ－１５）、（Ａ－２２）及び（Ａ－２３）である。 In the compound which is an azo dye represented by the general formula (1), the heterocyclic group represented by A is preferably a group represented by the formula (A-1), (A-5), (A-8), (A -9), (A-10), (A-11), (A-12), (A-13), (A-14), (A-15), (A-17), (A-19) ), (A-22), (A-23), (A-24) and (A-25), more preferably (A-8), (A-9), (A-10), (A A-11), (A-14), (A-15), (A-22) and (A-23).
　一般式（１）におけるＢは、一般式（１）で表されるアゾ色素を形成するために必須な原子団を示し、カプラー成分由来のものが好ましい。ここでカプラー成分とは、ジアゾニウム塩と反応しアゾ染料を得ることの可能なカプラー化合物由来の部分構造を意味する。
　一般式（１）で表されるアゾ色素におけるＢの炭素数は、３～３０が好ましく、３～２０がより好ましく、３～１２がさらに好ましい。 B in the general formula (1) represents an atomic group essential for forming the azo dye represented by the general formula (1), and is preferably derived from a coupler component. Here, the coupler component means a partial structure derived from a coupler compound that can react with a diazonium salt to obtain an azo dye.
The carbon number of B in the azo dye represented by the general formula (1) is preferably 3 to 30, more preferably 3 to 20, and further preferably 3 to 12.
　好ましくは、一般式（１）中のＢは、硫黄原子、窒素原子又は酸素原子から選択されるヘテロ原子を一種以上含む、５員又は６員の複素環又は複素縮合環；５員又は６員の任意に縮合された芳香環；又はα－ＣＯ基を任意に含む、Ｃ１～Ｃ６アルキル基、Ｃ２～Ｃ６アルケニル基又はＣ２～Ｃ６アルキニル基であり、これら環及び基の各々は一以上の置換基を含むことができる。 Preferably, B in the general formula (1) is a 5-membered or 6-membered heterocyclic ring or condensed condensed ring containing one or more heteroatoms selected from a sulfur atom, a nitrogen atom or an oxygen atom; An optionally fused aromatic ring; or a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group, optionally containing an α-CO group, of these rings and groups Each can contain one or more substituents.
　上記カプラー成分としては、ハロゲン化銀カラー写真感光材料の分野において、カプラーとして知られているものの残基が好ましく、リサーチディスクロージャー３７０３８（１９９５年２月）の８０頁から８５頁、及び８７頁から８９頁に詳しく記載されているハロゲン化銀カラー写真用カプラーの骨格部分（ｐ－フェニレンジアミン等の芳香族アミン現像主薬酸化体とカップリングして色素のクロモフォアになる部分）を使用することができる。 The coupler component is preferably a residue of what is known as a coupler in the field of silver halide color photographic materials. Research Disclosure 37038 (February 1995), pages 80 to 85, and pages 87 to 89. The skeleton portion of a silver halide color photographic coupler described in detail on the page (the portion which becomes a chromophore of a dye upon coupling with an oxidized aromatic amine developing agent such as p-phenylenediamine) can be used.
　ハロゲン化銀カラー写真感光材料の分野でイエロー色画像形成カプラーとして知られているカプラーとしては、例えば、ピバロイルアセトアミド型、ベンゾイルアセトアミド型、マロンジエステル型、マロンジアミド型、ジベンゾイルメタン型、ベンゾチアゾリルアセトアミド型、マロンエステルモノアミド型、ベンゾオキサゾリルアセトアミド型、ベンゾイミダゾリルアセトアミド型、シアノアセトアミド型、シクロアルキルカルボニルアセトアミド型、インドリン－２－イルアセトアミド型、米国特許第５，０２１，３３２号明細書に記載されたキナゾリン－４－オン－２－イルアセトアミド型、米国特許第５，０２１，３３０号明細書に記載されたベンゾ－１，２，４－チアジアジン－１，１－ジオキシド－３－イルアセトアミド型、欧州特許出願公開第０４２１２２１号明細書に記載されたカプラー、米国特許第５，４５５，１４９号明細書に記載されたカプラー、欧州特許出願公開第０６２２６７３号明細書に記載されたカプラー、欧州特許出願公開第０９５３８７１号明細書、同第０９５３８７２号明細書、同第０９５３８７３号明細書に記載された３－インドロイルアセトアミド型カプラーが、好ましいカプラー骨格として挙げられる。 Examples of couplers known as yellow color image-forming couplers in the field of silver halide color photographic materials include pivaloyl acetamide type, benzoylacetamide type, malon diester type, malon diamide type, dibenzoyl methane type, benzo type. Thiazolylacetamide type, malon ester monoamide type, benzoxazolylacetamide type, benzimidazolylacetamide type, cyanoacetamide type, cycloalkylcarbonylacetamide type, indoline-2-ylacetamide type, US Pat. No. 5,021,332 Quinazolin-4-one-2-ylacetamide type described in US Pat. No. 5,021,330, benzo-1,2,4-thiadiazine-1,1-dioxide-3- Ilacetamide type Couplers described in European Patent Application No. 0422221, couplers described in US Pat. No. 5,455,149, couplers described in European Patent Application No. 0622673, European patent applications The 3-indoloylacetamide-type couplers described in JP-A-0953871, JP-A-0953872 and JP-A-0953873 are mentioned as preferred coupler skeletons.
　ハロゲン化銀カラー写真感光材料の分野でマゼンタ色画像形成カプラーとして知られているカプラーとしては、例えば５－ピラゾロン型、１Ｈ－ピラゾロ［１，５－ａ］ベンズイミダゾール型、１Ｈ－ピラゾロ［５，１－ｃ］［１，２，４］トリアゾール型、１Ｈ－ピラゾロ［１，５－ｂ］［１，２，４］トリアゾール型、１Ｈ－イミダゾ［１，２－ｂ］ピラゾール型、シアノアセトフェノン型、ＷＯ９３／０１５２３に記載された活性プロペン型、ＷＯ９３／０７５３４に記載されたエナミン型、１Ｈ－イミダゾ［１，２－ｂ］［１，２，４］トリアゾール型カプラー、及び米国特許第４，８７１，６５２号明細書に記載されたカプラーが好ましいカプラー骨格として挙げられる。 Examples of couplers known as magenta color image forming couplers in the field of silver halide color photographic light-sensitive materials include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5, 1-c] [1,2,4] triazole type, 1H-pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type , The active propene type described in WO 93/01523, the enamine type, 1H-imidazo [1,2-b] [1,2,4] triazole type coupler described in WO 93/07534, and US Pat. No. 4,871. , 652 is mentioned as a preferred coupler skeleton.
　ハロゲン化銀カラー写真感光材料の分野でシアン色画像形成カプラーとして知られているカプラーとしては、例えばフェノール型、ナフトール型、欧州特許出願公開第０２４９４５３号明細書に記載された２，５－ジフェニルイミダゾール型、１Ｈ－ピロロ［１，２－ｂ］［１，２，４］トリアゾール型、１Ｈ－ピロロ［２，１－ｃ］［１，２，４］トリアゾール型、特開平４－１８８１３７号公報、同４－１９０３４７号公報に記載されたピロール型、特開平１－３１５７３６号公報に記載された３－ヒドロキシピリジン型、米国特許第５，１６４，２８９号明細書に記載されたピロロピラゾール型、特開平４－１７４４２９号公報に記載されたピロロイミダゾール型、米国特許第４，９５０，５８５号明細書に記載されたピラゾロピリミジン型、特開平４－２０４７３０号公報に記載されたピロロトリアジン型カプラー、米国特許第４，７４６，６０２号明細書に記載されたカプラー、米国特許第５，１０４，７８３号明細書に記載されたカプラー、米国特許第５，１６２，１９６号明細書に記載されたカプラー、及び欧州特許第０５５６７００号明細書に記載されたカプラーが好ましいカプラー骨格として挙げられる。 Examples of couplers known as cyan image forming couplers in the field of silver halide color photographic light-sensitive materials include phenol type, naphthol type, and 2,5-diphenylimidazole described in European Patent Application No. 0249453. Type, 1H-pyrrolo [1,2-b] [1,2,4] triazole type, 1H-pyrrolo [2,1-c] [1,2,4] triazole type, JP-A-4-188137, The pyrrole type described in JP-A-4-190347, the 3-hydroxypyridine type described in JP-A-1-315736, the pyrrolopyrazole type described in US Pat. No. 5,164,289, The pyrroloimidazole type described in Kaihei 4-174429 and the pyrazolopyr described in US Pat. No. 4,950,585 Gin type, pyrrolotriazine type coupler described in JP-A-4-204730, coupler described in US Pat. No. 4,746,602, described in US Pat. No. 5,104,783 Preferred coupler skeletons include couplers described in US Pat. No. 5,162,196, and those described in EP 0556700.
　Ｂで表される基としては、上記の式（Ｂ－１）～（Ｂ－１２）のいずれかで表される基が挙げられる。
　式（Ｂ－１）において、Ｒ１０１が、ハロゲン原子、アシルアミノ基、アルキルスルホニルアミノ基、スルファモイル基及びカルバモイル基であることが好ましく、Ｒ１０２が、シアノ基及びカルバモイル基であることが好ましく、Ｚ１が、酸素原子、硫黄原子又はＲ１０３がアルキル基である－Ｎ（Ｒ１０３）－であることが好ましい。ｖは０～４の整数を表し、ｖが１～４の場合、Ｒ１０１基は同一であっても異なっていてもよい。 Examples of the group represented by B include groups represented by any of the above formulas (B-1) to (B-12).
In formula (B-1), R 101 is preferably a halogen atom, an acylamino group, an alkylsulfonylamino group, a sulfamoyl group and a carbamoyl group, and R 102 is preferably a cyano group and a carbamoyl group, 1 is preferably an oxygen atom, a sulfur atom or —N (R 103 ) — in which R 103 is an alkyl group. v represents an integer of 0 to 4. When v is 1 to 4, the R 101 groups may be the same or different.
　式（Ｂ－２）において、Ｒ１０４が、シアノ基、アシル基又はカルバモイル基であることが好ましく、Ｒ１０５及びＲ１０６の一方が水素原子であることが好ましい。 In the formula (B-2), R 104 is preferably a cyano group, an acyl group, or a carbamoyl group, and one of R 105 and R 106 is preferably a hydrogen atom.
　式（Ｂ－３）において、Ｒ１０７が、水素原子、アルキル基又はアリール基であることが好ましく、水素原子又はアルキル基であることが好ましい。Ｒ１０８が、アルキル基、アリール基又は複素環であることが好ましく、アルキル基であることがより好ましい。 In formula (B-3), R 107 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. R 108 is preferably an alkyl group, an aryl group or a heterocyclic ring, and more preferably an alkyl group.
　式（Ｂ－４）において、Ｒ１０９が、アルキル基又はアリール基であることが好ましく、Ｒ１１０が、水素原子及びアルキル基であることが好ましい。 In formula (B-4), R 109 is preferably an alkyl group or an aryl group, and R 110 is preferably a hydrogen atom or an alkyl group.
　式（Ｂ－５）において、Ｒ１１１が、アルコキシカルボニル基、シアノ基又はカルバモイル基であることが好ましく、Ｒ１１２が、アルキル基又はアリール基であることが好ましい。 In formula (B-5), R 111 is preferably an alkoxycarbonyl group, a cyano group, or a carbamoyl group, and R 112 is preferably an alkyl group or an aryl group.
　式（Ｂ－６）において、Ｒ１１４が、ハロゲン原子、アルキル基、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基又はカルバモイル基であることが好ましく、ハロゲン原子、アルキル基、アシルアミノ基又はアルキルスルホニルアミノ基であることがより好ましい。ｗは０～４の整数を表し、ｗが２～４の場合、Ｒ１１４基は同一であっても異なっていてもよい。 In the formula (B-6), R 114 is preferably a halogen atom, an alkyl group, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group or a carbamoyl group. More preferably, they are an atom, an alkyl group, an acylamino group, or an alkylsulfonylamino group. w represents an integer of 0 to 4, and when w is 2 to 4, the R 114 groups may be the same or different.
　式（Ｂ－７）において、Ｒ１１５が、ハロゲン原子、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基又はカルバモイル基であることが好ましく、アシルアミノ基、アルキルスルホニルアミノ基又はカルバモイル基であることがより好ましい。ｘは０～６の整数を表し、ｘが２～６の場合、Ｒ１１５基は同一であっても異なっていてもよい。 In the formula (B-7), R 115 is preferably a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group or a carbamoyl group. A sulfonylamino group or a carbamoyl group is more preferable. x represents an integer of 0 to 6, and when x is 2 to 6, the R 115 groups may be the same or different.
　式（Ｂ－８）及び（Ｂ－９）において、Ｒ１１６とＲ１１７、Ｒ１１８とＲ１１９は、互いに同一であることが好ましい。 In formulas (B-8) and (B-9), R 116 and R 117 , and R 118 and R 119 are preferably the same as each other.
　式（Ｂ－１０）において、Ｒ１２０及びＲ１２１が、アルキルキ、アリール基、複素環基又はシアノ基であることが好ましく、Ｒ１２２が、水素原子、アルキル基、アリール基、アシルアミノ基又はアルキルスルホニルアミノ基であることが好ましい。 In the formula (B-10), R 120 and R 121 are preferably an alkyl group, an aryl group, a heterocyclic group, or a cyano group, and R 122 is a hydrogen atom, an alkyl group, an aryl group, an acylamino group, or an alkylsulfonyl group. An amino group is preferred.
　式（Ｂ－１１）において、Ｒ１２３が、アルキル基、アリール基、複素環基又はシアノ基であることが好ましく、Ｒ１２４が、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基であることが好ましく、Ｒ１２５が、アルキル基、アリール基、アルキルチオ基、アミノ基又はアシルアミノ基であることが好ましい。Ｚ４が５員環を形成する場合、ｙは０～２の整数を表し、Ｚ４が６員環を形成する場合、ｙは０～３の整数を表す。 In Formula (B-11), R 123 is preferably an alkyl group, an aryl group, a heterocyclic group, or a cyano group, and R 124 is an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group. R 125 is preferably an alkyl group, an aryl group, an alkylthio group, an amino group, or an acylamino group. When Z 4 forms a 5-membered ring, y represents an integer of 0 to 2, and when Z 4 forms a 6-membered ring, y represents an integer of 0 to 3.
　式（Ｂ－１２）において、Ｒ１２６が、アルキル基又はアリール基であることが好ましい。 In the formula (B-12), R 126 is preferably an alkyl group or an aryl group.
　式（Ｂ－１）～（Ｂ－１２）において、好ましい炭素数、また、Ｒ１０１～Ｒ１２６で表される基の記載で列挙した個々の基の具体例は、一般式（１）のＡで表される複素環基の置換基の記載で列挙したものと同じである。 In formulas (B-1) to (B-12), preferred examples of the number of carbon atoms and the individual groups listed in the description of the groups represented by R 101 to R 126 include A in formula (1). The same as those enumerated in the description of the substituent of the heterocyclic group represented by
　式（Ｂ－１）～（Ｂ－１２）中のＲ１０１～Ｒ１２６が更に置換され得る基である場合、Ｒ１０１～Ｒ１２６は更に置換基を有することができ、この場合、この置換基は、一般式（１）のＡで表される複素環基の置換基として列挙したものと同じである。 When R 101 to R 126 in formulas (B-1) to (B-12) are groups that can be further substituted, R 101 to R 126 can further have a substituent, and in this case, the substituent Are the same as those enumerated as substituents of the heterocyclic group represented by A in the general formula (1).
　一般式（１）で表されるアゾ色素である化合物のうち、下記式ＤＳ－１～ＤＳ－９で表されるアゾ色素が特に好ましい。式ＤＳ－１～ＤＳ－９中のＡは、一般式（１）中のＡと同じ意味を有する。 Of the compounds that are azo dyes represented by the general formula (1), azo dyes represented by the following formulas DS-1 to DS-9 are particularly preferable. A in the formulas DS-1 to DS-9 has the same meaning as A in the general formula (1).
Figure JPOXMLDOC01-appb-C000009
 
Figure JPOXMLDOC01-appb-C000009
 
　式ＤＳ－１において、Ｒ２０１は、アルキル基、アリール基、アルコキシ基、アミノ基（アニリノ基を含む）、アルコキシカルボニル基、シアノ基、アシルアミノ基又はカルバモイル基を表し、Ｒ２０２は、水素原子、アルキル基、アリール基又は複素環基を表す。Ｒ２０１は、アルコキシカルボニル基、シアノ基又はカルバモイル基であることが好ましく、Ｒ２０２は、アルキル基又はアリール基であることが好ましい。 In the formula DS-1, R 201 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group, and R 202 represents a hydrogen atom, Represents an alkyl group, an aryl group or a heterocyclic group; R 201 is preferably an alkoxycarbonyl group, a cyano group, or a carbamoyl group, and R 202 is preferably an alkyl group or an aryl group.
　式ＤＳ－２において、Ｒ２０３は、水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、Ｒ２０４はアルキル基、アリール基又は複素環基を表す。Ｒ２０３は水素原子又はアルキル基であることが好ましく、アルキル基が、メチル基、エチル基、イソプロピル基又はｔ－ブチル基であることがより好ましい。Ｒ２０４はアルキル基であることが好ましい。 In formula DS-2, R 203 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group. It represents group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or carbamoyl group, R 204 represents an alkyl group, an aryl group or a heterocyclic group. R 203 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group. R 204 is preferably an alkyl group.
　式ＤＳ－３において、Ｒ２０５は、水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、Ｒ２０６はアルキル基、アリール基、複素環基、アルキルチオ基、アリールチオ基、アルコキシカルボニル基又はカルバモイル基を表す。Ｒ２０５は、水素原子又はアルキル基であることが好ましく、アルキル基が、メチル基、エチル基、イソプロピル基又はｔ－ブチル基であることがより好ましい。Ｒ２０６は、アルキル基、アリール基又はアルキルチオ基であることが好ましく、アルキル基であることがより好ましい。 In the formula DS-3, R 205 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group. A group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a carbamoyl group, and R 206 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group. R 205 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group, or a t-butyl group. R 206 is preferably an alkyl group, an aryl group or an alkylthio group, and more preferably an alkyl group.
　式ＤＳ－４において、Ｒ２０７は、水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を示し、Ｒ２０８はハロゲン原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、ａａは、０～４の整数を表し、ａａ個のＲ２０８は同一であっても異なっていてもよい。Ｒ２０７は水素原子又はアルキル基であることが好ましく、アルキル基が、メチル基、エチル基、イソプロピル基又はｔ－ブチル基であることがより好ましい。Ｒ２０８は、ハロゲン原子、アルキル基、アルコキシ基、アシルアミノ基又はアルキルスルホニルアミノ基であることが好ましい。 In the formula DS-4, R 207 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group. Group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a carbamoyl group, and R 208 represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group (an anilino group). An acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group, aa represents an integer of 0 to 4, aa number of R 08 may be the same or different. R 207 is preferably a hydrogen atom or an alkyl group, and the alkyl group is more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group. R 208 is preferably a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or an alkylsulfonylamino group.
　式ＤＳ－５において、Ｒ２１０及びＲ２１１は、水素原子、ハロゲン原子、アルキル基、アリール基、アシルアミノ基、アルコキシカルボニル基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルコキシカルボニルアミノ基又はカルバモイル基を表し、Ｒ２１２及びＲ２１３は水素原子、ハロゲン原子、アルキル基、アルコキシ基又はアシルアミノ基を表す。Ｒ２１０及びＲ２１１は、水素原子、塩素原子、臭素原子、アルキル基又はアシルアミノ基であることが好ましく、Ｒ２１０及びＲ２１１の少なくとも一方が水素原子であることがより好ましい。 In the formula DS-5, R 210 and R 211 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino. Represents a group or a carbamoyl group, and R 212 and R 213 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group. R 210 and R 211 are preferably a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group, and more preferably at least one of R 210 and R 211 is a hydrogen atom.
　式ＤＳ－６において、Ｒ２１４とＲ２１５は、独立に、水素原子、アルキル基、アリール基又は複素環基を示し、Ｒ２１４とＲ２１５の一方は水素原子であることが好ましい。 In the formula DS-6, R 214 and R 215 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and one of R 214 and R 215 is preferably a hydrogen atom.
　式ＤＳ－７において、Ｒ２１６は、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、スルファモイル基、アルキルスルホニル基又はカルバモイル基を表し、Ｚ５は、酸素原子、硫黄原子、又は－Ｎ（Ｒ２１７）－を表し、Ｒ２１７は水素原子、アルキル基、アリール基又は複素環基を表す。ｂｂは、１～４の整数を表す。ｂｂが２～４である場合には、複数のＲ２１６は同一であっても異なっていてもよい。Ｒ２１６は、ハロゲン原子、アシルアミノ基、アルキルスルホニルアミノ基、スルファモイル基又はカルバモイル基であることが好ましい。Ｚ５は、酸素原子、硫黄原子、又はＲ２１７がアルキル基である－Ｎ（Ｒ２１７）－であることが好ましく、Ｚ５が、酸素原子又は硫黄原子であることがより好ましい。 In the formula DS-7, R 216 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group , an alkylthio group, an arylthio group, a sulfamoyl group, an alkylsulfonyl group or a carbamoyl group, Z 5 represents an oxygen atom, a sulfur atom, or -N (R217) - represents, R 217 is a hydrogen atom, an alkyl group, an aryl group Or represents a heterocyclic group. bb represents an integer of 1 to 4. When bb is 2 to 4, the plurality of R 216 may be the same or different. R 216 is preferably a halogen atom, an acylamino group, an alkylsulfonylamino group, a sulfamoyl group or a carbamoyl group. Z 5 is preferably an oxygen atom, a sulfur atom, or —N (R 217 ) — in which R 217 is an alkyl group, and more preferably Z 5 is an oxygen atom or a sulfur atom.
　式ＤＳ－８において、Ｒ２１８は、水素原子、ハロゲン原子、アルキル基、アリール基、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルコキシカルボニル基、アミノカルボニルアミノ基、カルバモイル基又はスルファモイル基を示し、Ｒ２２０及びＲ２２３は、水素原子、ハロゲン原子、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基又はアリールスルホニルアミノ基を表し、Ｒ２１９、Ｒ２２１及びＲ２２２は、水素原子、塩素原子、臭素原子、アルキル基又はアシルアミノ基を表す。Ｒ２１８は、水素原子、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルコキシカルボニル基、アミノカルボニルアミノ基、カルバモイル基又は及びスルファモイル基であることが好ましく、Ｒ２２０及びＲ２２３は、水素原子、アシルアミノ基、アルコキシカルボニルアミノ基又はアルキルスルホニルアミノ基であることが好ましく、Ｒ２１９、Ｒ２２１及びＲ２２２は、水素原子であることが好ましい。 In the formula DS-8, R 218 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, a carbamoyl group, or a sulfamoyl group. R 220 and R 223 represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group, and R 219 , R 221 and R 222 are A hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group is represented. R 218 is preferably a hydrogen atom, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, a carbamoyl group, and a sulfamoyl group, and R 220 and R 223 are a hydrogen atom. , An acylamino group, an alkoxycarbonylamino group or an alkylsulfonylamino group, and R 219 , R 221 and R 222 are preferably hydrogen atoms.
　式ＤＳ－９において、Ｒ２２４はアルキル基又はアリール基を表す。 In the formula DS-9, R 224 represents an alkyl group or an aryl group.
　式ＤＳ－１～ＤＳ－９において、Ｍはアルカリ金属又はアルカリ土類金属１／２を表す。アルカリ金属としては、リチウム、ナトリウム、カリウム、セシウムが好ましく、ナトリウム、カリウムがより好ましい。アルカリ土類金属１／２は、解離性プロトンを有する一般式（１）のアゾ色素の解離体２分子に対してアルカリ土類金属イオンが１つ結合している状態でのアルカリ土類金属を表す。アルカリ土類金属としては、カルシウム、ストロンチウム、バリウムが好ましく、カルシウム、バリウムがより好ましい。 In the formulas DS-1 to DS-9, M represents an alkali metal or an alkaline earth metal 1/2. As the alkali metal, lithium, sodium, potassium, and cesium are preferable, and sodium and potassium are more preferable. Alkaline earth metal 1/2 is an alkaline earth metal in the state where one alkaline earth metal ion is bonded to two molecules of the dissociated azo dye of the general formula (1) having a dissociating proton. To express. As the alkaline earth metal, calcium, strontium and barium are preferable, and calcium and barium are more preferable.
　式ＤＳ－１～ＤＳ－９において、Ｒ２０１～Ｒ２２４で表される基の記述で挙げた個々の基の具体例及び好ましい炭素数は、一般式（１）のＡで表す複素環基に対する置換基の記述で挙げたものと同一である。 In the formulas DS-1 to DS-9, specific examples and preferred carbon numbers of the individual groups mentioned in the description of the groups represented by R 201 to R 224 are the same as those for the heterocyclic group represented by A in the general formula (1). The same as those described in the description of the substituent.
　式ＤＳ－１～ＤＳ－９におけるＲ２０１～Ｒ２２４が更なる置換の可能性を有する基である場合には、これらは更なる置換基を有することができる。その場合の置換基は、一般式（１）のＡで表される複素環基に対する置換基の記述で挙げたものと同一である。 If R 201 to R 224 in the formulas DS-1 to DS-9 are groups with the possibility of further substitution, these can have further substituents. In this case, the substituent is the same as that described in the description of the substituent for the heterocyclic group represented by A in the general formula (1).
　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩の具体的化合物例を次に記載するが、これらの例によって限定されるものではない。 Specific examples of the alkali metal salt and alkaline earth metal salt of the azo dye represented by the general formula (1) are described below, but are not limited by these examples.
Figure JPOXMLDOC01-appb-C000010
 
Figure JPOXMLDOC01-appb-C000010
 
Figure JPOXMLDOC01-appb-C000011
 
Figure JPOXMLDOC01-appb-C000011
 
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000018
 
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
 
Figure JPOXMLDOC01-appb-C000024
 
Figure JPOXMLDOC01-appb-C000025
 
Figure JPOXMLDOC01-appb-C000025
 
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　一般式（１）で表されるアゾ色素は、例えば、特許第４０８０９４７号公報に記載の方法により合成することができる。一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、一般式（１）で表されるアゾ色素を、対応するアルカリ金属塩、アルカリ土類金属塩と反応させることにより得ることができる。
　反応に用いることのできるアルカリ金属塩としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、酢酸ナトリウム、酢酸カリウム、ナトリウムメトキシド、ナトリウムエトキシド、カリウム－ｔ－ブトキシド、水素化ナトリウム等が挙げられる。
　反応に用いることのできるアルカリ土類金属塩としては、水酸化マグネシウム、塩化マグネシウム、酢酸マグネシウム、水酸化カルシウム、塩化カルシウム、酢酸カルシウム、水酸化バリウム、塩化化バリウム、酢酸化バリウム等が挙げられる。
　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、一般式（１）で表されるアゾ色素を、対応するアルカリ金属塩、アルカリ土類金属塩と反応させる際に、溶媒中で反応させることが好ましい。用いることのできる溶媒としては、水、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｔ－ブタノール等が好ましい。
　反応温度としては、－２０℃～反応溶媒の沸点であることが好ましく、室温～１００℃であることがより好ましい。 The azo dye represented by the general formula (1) can be synthesized, for example, by the method described in Japanese Patent No. 4080947. The alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are prepared by replacing the azo dye represented by the general formula (1) with the corresponding alkali metal salt, alkaline earth salt. It can be obtained by reacting with a metal salt.
Examples of the alkali metal salt that can be used in the reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium t-butoxide. And sodium hydride.
Examples of the alkaline earth metal salt that can be used for the reaction include magnesium hydroxide, magnesium chloride, magnesium acetate, calcium hydroxide, calcium chloride, calcium acetate, barium hydroxide, barium chloride, and barium acetate.
The alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are prepared by replacing the azo dye represented by the general formula (1) with the corresponding alkali metal salt, alkaline earth salt. When reacting with a metal salt, it is preferable to react in a solvent. As the solvent that can be used, water, methanol, ethanol, n-propanol, isopropanol, t-butanol and the like are preferable.
The reaction temperature is preferably −20 ° C. to the boiling point of the reaction solvent, more preferably room temperature to 100 ° C.
　本発明の一実施形態に係るアゾ色素のアルカリ金属塩、アルカリ土類金属塩又は互変異性体は、着色組成物として使用されることが好ましく、水溶液中に、アゾ色素のアルカリ金属塩、アルカリ土類金属塩又は互変異性体を含む着色組成物であることがより好ましい。 The alkali metal salt, alkaline earth metal salt or tautomer of the azo dye according to one embodiment of the present invention is preferably used as a coloring composition, and the alkali metal salt of the azo dye, the alkali A colored composition containing an earth metal salt or a tautomer is more preferable.
　本発明の一実施形態に係るアゾ色素のアルカリ金属塩、アルカリ土類金属塩又は互変異性体を用いた染色方法としては、本発明のアゾ色素のアルカリ金属塩、アルカリ土類金属塩又は互変異性体を浸漬、混練、塗布、印刷、又はインクジェット印画等の方法に用いることができる。
　また、染色物としては、カシミヤ、ウール、絹、木綿、麻等の天然繊維、ナイロン、ポリエステル、アクリル、ポリウレタン等の合成繊維、ガラス、金属、陶器等の無機物、普通紙、樹脂コート紙、インクジェット専用記録紙等の紙を用いることができる。 The dyeing method using the alkali metal salt, alkaline earth metal salt or tautomer of the azo dye according to one embodiment of the present invention includes the alkali metal salt, alkaline earth metal salt or tautomer of the azo dye of the present invention. Mutant bodies can be used in methods such as dipping, kneading, coating, printing, or inkjet printing.
The dyeing materials include cashmere, wool, silk, cotton, hemp and other natural fibers, nylon, polyester, acrylic, polyurethane and other inorganic materials, glass, metal, ceramics and other inorganic materials, plain paper, resin-coated paper, and inkjet. Paper such as dedicated recording paper can be used.
　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の用途としては、ＣＣＤ、ＣＭＯＳなどの固体撮像素子、ＬＣＤ、ＰＤＰ等のディスプレイに用いられるカラー画像を再現するためのカラーフィルタ、これらのカラーフィルタを作製するための硬化性組成物、カラー画像を形成するためのカラー画像記録材料等が挙げられる。具体的には、カラーフィルタ及びこれらのカラーフィルタを作製するための硬化性組成物、インクジェット方式記録材料、昇華型感熱記録材料、電子写真方式を用いる記録材料、転写式ハロゲン化銀感光材料、印刷インク、記録ペン、繊維の染色、毛髪の染色等への使用があり、好ましくはインクジェット方式記録材料、転写式ハロゲン化銀感光材料、印刷インク、繊維の染色等への使用が挙げられる。 Applications of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) are used for solid-state imaging devices such as CCD and CMOS, and displays such as LCD and PDP. Examples thereof include a color filter for reproducing a color image, a curable composition for producing these color filters, and a color image recording material for forming a color image. Specifically, color filters and curable compositions for producing these color filters, ink jet recording materials, sublimation thermal recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials, printing It is used for ink, recording pen, fiber dyeing, hair dyeing and the like, and preferably used for ink jet recording material, transfer type silver halide photosensitive material, printing ink, fiber dyeing and the like.
　本発明の一実施形態に係るアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、その用途に適した溶解性、分散性などの物性を、置換基を調整することによって最適化し、使用することができる。また、本実施形態のアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、用いられる系に応じて溶解状態、乳化分散状態、固体分散状態でも使用することができる。
　本実施形態の着色組成物は、一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体のうち少なくとも一種を含む組成物を意味する。　本実施形態の着色組成物において、一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体は、単独で用いてもよく、他の直接染料又は分散染料と組み合わせて用いてもよい。 The alkali metal salt, alkaline earth metal salt, and tautomer thereof of the azo dye according to one embodiment of the present invention can be obtained by adjusting the physical properties such as solubility and dispersibility suitable for the application by adjusting substituents. Can be optimized and used. In addition, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye of the present embodiment can be used in a dissolved state, an emulsified dispersion state, and a solid dispersion state depending on the system used.
The colored composition of the present embodiment means a composition containing at least one of an alkali metal salt, an alkaline earth metal salt and a tautomer thereof of the azo dye represented by the general formula (1). In the coloring composition of the present embodiment, the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) may be used alone or other direct dyes or You may use it in combination with a disperse dye.
　本実施形態の着色組成物には、媒体を含有させることができる。本実施形態の着色組成物は、媒体として、親油性媒体や水性媒体を用いて、それらの中に、本発明の一実施形態に係る化合物であるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体を、溶解及び／又は分散させることによって作製することができる。好ましくは、水性媒体を用いる場合である。
　着色組成物中に含まれる一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の総含有量は、着色組成物に用いられる一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体における置換基の種類、及び着色組成物を製造するために用いる溶媒成分の種類等により決められる。着色組成物中の一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩およびその互変異性体の総含有量が、着色組成物の総質量に対して０．００１～２０質量％含まれることが好ましく、０．１～１０質量％含まれることが更に好ましい。 The coloring composition of the present embodiment can contain a medium. The coloring composition of the present embodiment uses a lipophilic medium or an aqueous medium as a medium, and includes an alkali metal salt or alkaline earth metal salt of an azo dye that is a compound according to an embodiment of the present invention. And its tautomers can be made by dissolving and / or dispersing. Preferably, an aqueous medium is used.
The total content of the alkali metal salt, alkaline earth metal salt and tautomer of the azo dye represented by the general formula (1) contained in the coloring composition is the general formula (1) used in the coloring composition. The alkali metal salt, alkaline earth metal salt of the azo dye and the tautomer thereof, the type of substituents, the type of solvent component used to produce the colored composition, and the like. The total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) in the coloring composition is 0.001 with respect to the total mass of the coloring composition. It is preferably contained in an amount of ˜20% by mass, more preferably 0.1˜10% by mass.
　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩およびその互変異性体の総含有量を０．００１質量％以上にすることで、着色媒体上における色素の着色濃度を確保できる。また、一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の総含有量を２０質量％以下にすることで、低粘度の着色組成物を調整することができ、取り扱いが容易となる。一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種を含む着色組成物は、ｐＨ５～１１の範囲の任意のｐＨで使用することができる。染色性の観点から、着色組成物は、ｐＨ６以上の範囲で使用することが好ましく、アゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の安定性及び染色性の観点から、ｐＨ７～１１の範囲で使用することがより好ましい。 By coloring the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) to 0.001% by mass or more, coloring of the dye on the coloring medium The concentration can be secured. Moreover, the low-viscosity coloring composition is obtained by setting the total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) to 20% by mass or less. It can be adjusted and is easy to handle. The coloring composition containing at least one selected from the alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) has any pH within the range of pH 5-11. Can be used in From the viewpoint of dyeability, the colored composition is preferably used in the range of pH 6 or higher, from the viewpoint of the stability and dyeability of alkali metal salts, alkaline earth metal salts and tautomers thereof of azo dyes. It is more preferable to use in the range of pH 7-11.
　本実施形態の着色組成物に用いられるｐＨ調整剤としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、アンモニア、モノエタノールアミン、ジエタノールアミン、グアニジン等が挙げられる。 Examples of the pH adjuster used in the coloring composition of the present embodiment include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, monoethanolamine, diethanolamine, guanidine, and the like. Is mentioned.
　本実施形態の着色組成物には、界面活性剤を含むことができる。用いることのできる界面活性剤としては、アニオン性、ノニオン性、カチオン性、両性又は双イオン性界面活性剤を添加することができる。また、界面活性剤は一種単独で使用してもよく、二種以上を併せて使用してもよい。 The coloring composition of the present embodiment can contain a surfactant. As the surfactant that can be used, an anionic, nonionic, cationic, amphoteric or zwitterionic surfactant can be added. Moreover, surfactant may be used individually by 1 type and may be used in combination of 2 or more types.
　本実施形態の着色組成物に使用できるアニオン性界面活性剤としては、モノアルキル硫酸又はその塩、アルキルベンゼンスルホン酸又はその塩、α－オレフィンスルホネート又はその塩が挙げられる。特に、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウム、スルホコハク酸ハーフエステルのアルカリ塩、例えばモノオクチルスルホコハク酸二ナトリウム塩や長鎖モノアルキルエトキシスルホコハク酸アルカリ塩等が好ましく挙げられる。 Examples of the anionic surfactant that can be used in the coloring composition of the present embodiment include monoalkyl sulfuric acid or a salt thereof, alkylbenzene sulfonic acid or a salt thereof, and α-olefin sulfonate or a salt thereof. Particularly preferred are sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and alkali salts of sulfosuccinic acid half ester, such as monooctylsulfosuccinic acid disodium salt and long-chain monoalkylethoxysulfosuccinic acid alkali salt.
　本実施形態の着色組成物に使用できるノニオン性界面活性剤としては、アルキルポリグリコシド；ポリエチレングリコールソルビタンステアレート等のソルビタンエステル等が挙げられる。 Examples of the nonionic surfactant that can be used in the coloring composition of the present embodiment include alkyl polyglycosides; sorbitan esters such as polyethylene glycol sorbitan stearate.
　本実施形態の着色組成物に使用できるカチオン性界面活性剤としては、長鎖四級アンモニウム化合物が挙げられる。長鎖四級アンモニウム化合物の例としては、セチルトリメチルアンモニウムクロリド、ジメチルステアリルアンモニウムクロリド、トリメチルアセチルアンモニウムブロミド、ステアリルトリメチルアンモニウムクロリド、ジメチルステアリルベンジルアンモニウムクロリド、ベンジルテトラデシルジメチルアンモニウムクロリド、ジメチルジ－水素化－牛脂アンモニウムクロリド、ラウリルジメチルベンジルアンモニウムクロリド、ベヘニルトリメチルアンモニウムクロリド、ラウリルトリメチルアンモニウムクロリド、トリス（オリゴオキシ－エチル）アルキルアンモニウムホスフェート、セチルピリジニウムクロリド等が挙げられる。 Examples of the cationic surfactant that can be used in the coloring composition of the present embodiment include a long-chain quaternary ammonium compound. Examples of long-chain quaternary ammonium compounds include cetyltrimethylammonium chloride, dimethylstearylammonium chloride, trimethylacetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldi-hydrogenated-tallow Examples include ammonium chloride, lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, tris (oligooxy-ethyl) alkylammonium phosphate, cetylpyridinium chloride and the like.
　本実施形態の着色組成物に使用可能な両性又は双イオン性界面活性剤としては、脂肪酸－アミドアルキルベタインやスルホベタイン等（例えばラウリルヒドロキシスルホベタイン）のベタイン類や、ココアミノアセテート、ココアミノプロピオネート、ナトリウムココアンホプロピオネート、ナトリウムココアンホアセテート等の長鎖アルキルアミノ酸が挙げられる。 Examples of amphoteric or zwitterionic surfactants that can be used in the coloring composition of the present embodiment include fatty acids-amide alkylbetaines, sulfobetaines and the like (eg, lauryl hydroxysulfobetaine), cocoaminoacetate, cocoaminopro Long chain alkyl amino acids such as pionate, sodium cocoamphopropionate, sodium cocoamphoacetate and the like can be mentioned.
　本実施形態の着色組成物を水性着色組成物として使用する場合、以下に示す水性溶媒を併用することができる。使用できる水性溶媒としては、エタノール、イソプロパノール、ｎ－プロパノール、ブタノール、ｎ－ペンタノール、プロピレングリコール、エチレングリコールモノエチルエーテル、１，２－ヘキサンジオール、ブトキシエタノール、フェノキシエタノール、ベンジルアルコール、プロピレンカーボネート、及びそれらの混合物等が挙げることができ、中でも、１，２－又は１，３－プロパンジオール、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、１，３－又は１，４－ブタンジオール、ジエチレングリコールとそのモノメチル又はモノエチルエーテル、及びジプロピレングリコールとそのモノメチル又はモノエチルエーテルが好ましい。 When the coloring composition of the present embodiment is used as an aqueous coloring composition, the following aqueous solvent can be used in combination. Usable aqueous solvents include ethanol, isopropanol, n-propanol, butanol, n-pentanol, propylene glycol, ethylene glycol monoethyl ether, 1,2-hexanediol, butoxyethanol, phenoxyethanol, benzyl alcohol, propylene carbonate, and And mixtures thereof, among which 1,2- or 1,3-propanediol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,3- or 1,4-butane Diol, diethylene glycol and its monomethyl or monoethyl ether, and dipropylene glycol and its monomethyl or monoethyl ether are preferred.
　これらの水性溶媒の配合量としては、着色組成物の全質量に対して０．５～３０質量％が好ましく、１～１５質量％がより好ましく、５～１０質量％がさらに好ましい。
　また、グリセリン、ヘキサントリオール等の多価アルコール；エチルカルビトール；ベンジルアルコール；ベンジルオキシエタノール；ｎ－アルキルピロリドン；及び尿素から選択される成分を併用してもよい。 The blending amount of these aqueous solvents is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, and further preferably 5 to 10% by mass with respect to the total mass of the colored composition.
Further, a component selected from polyhydric alcohols such as glycerin and hexanetriol; ethyl carbitol; benzyl alcohol; benzyloxyethanol; n-alkylpyrrolidone; and urea may be used in combination.
　本実施形態の着色組成物は、増粘剤を含むことができる。増粘剤の配合量としては、着色組成物の全質量に対して０．０５～２０質量％であることが好ましく、０．１～１０質量％であることがより好ましく、０．５～５質量％であることがより好ましい。本実施形態の着色組成物へ使用することのできる増粘剤としては、オレイン酸、セチルアルコール、オレイルアルコール、塩化ナトリウム、セテアリルアルコール及びステアリルアルコール等が挙げられる。 The coloring composition of the present embodiment can contain a thickener. The blending amount of the thickener is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% with respect to the total mass of the coloring composition. More preferably, it is mass%. Examples of the thickener that can be used for the colored composition of the present embodiment include oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, and stearyl alcohol.
　本実施形態の着色組成物は、一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種と共に、他の着色化合物を含有することができる。
　使用できるイエロー染料としては、任意のものを使用することができる。イエロー染料としては、例えば、カプラー成分として、フェノール類、ナフトール類、アニリン類、ピラゾロンやピリドン等のようなヘテロ環類、開鎖型活性メチレン化合物類、などを有するアリールもしくはヘテリルアゾ染料；カプラー成分として開鎖型活性メチレン化合物類などを有するアゾメチン染料；ベンジリデン染料やモノメチンオキソノール染料等のようなメチン染料；ナフトキノン染料、アントラキノン染料等のようなキノン系染料などがあり、これ以外の染料種としては、キノフタロン染料、ニトロ・ニトロソ染料、アクリジン染料、アクリジノン染料等を挙げることができる。 The colored composition of the present embodiment contains other colored compounds together with at least one selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1). Can be contained.
Any yellow dye can be used. Examples of yellow dyes include aryl or heteryl azo dyes having, for example, phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as coupler components; Azomethine dyes having a type active methylene compound; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; Examples thereof include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.
　使用できるマゼンタ染料としては、任意のものを使用することができる。マゼンタ染料としては、例えば、カプラー成分としてフェノール類、ナフトール類、アニリン類などを有するアリールもしくはヘテリルアゾ染料；カプラー成分としてピラゾロン類、ピラゾロトリアゾール類などを有するアゾメチン染料；アリーリデン染料、スチリル染料、メロシアニン染料、シアニン染料、オキソノール染料などのようなメチン染料；ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料などのようなカルボニウム染料；ナフトキノン、アントラキノン、アントラピリドンなどのようなキノン染料；ジオキサジン染料等のような縮合多環染料等を挙げることができる。 Any magenta dye that can be used can be used. Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; arylidene dyes, styryl dyes, merocyanine dyes Methine dyes such as cyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensations such as dioxazine dyes Examples include polycyclic dyes.
　使用できるシアン染料としては、任意のものを使用することができる。シアン染料としては、例えば、カプラー成分としてフェノール類、ナフトール類、アニリン類などを有するアリールもしくはヘテリルアゾ染料；カプラー成分としてフェノール類、ナフトール類、ピロロトリアゾールのようなヘテロ環類などを有するアゾメチン染料；シアニン染料、オキソノール染料、メロシアニン染料などのようなポリメチン染料；ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料などのようなカルボニウム染料；フタロシアニン染料；アントラキノン染料；インジゴ・チオインジゴ染料などを挙げることができる。 Any cyan dye can be used. Examples of cyan dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; azomethine dyes having heterocycles such as phenols, naphthols, and pyrrolotriazole as coupler components; cyanine Polymethine dyes such as dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.
　上述の各染料は、クロモフォアの一部が解離して初めてイエロー、マゼンタ、シアンの各色を呈するものであってもよく、その場合のカウンターカチオンはアルカリ金属や、アンモニウムのような無機のカチオンであってもよいし、ピリジニウム、４級アンモニウム塩のような有機のカチオンであってもよく、さらにはそれらを部分構造に有するポリマーカチオンであってもよい。 Each of the above-mentioned dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
　また、本実施形態の着色組成物は、黒染料を含有することもできる。使用できる黒染料としては、ジスアゾ、トリスアゾ、テトラアゾ染料等が挙げられる。そのほか、黒色の着色化合物としては、カーボンブラックの分散体等を挙げることができる。 Moreover, the coloring composition of this embodiment can also contain a black dye. Examples of black dyes that can be used include disazo, trisazo, and tetraazo dyes. In addition, examples of the black coloring compound include a dispersion of carbon black.
　本実施形態の着色組成物に用いることのできるその他の添加剤としては、シリコーンオイル（シリコーンオイルの好適な例としては、ポリアルキルシロキサン、ポリアリールシロキサン、ポリアルキルアリールシロキサン）、カチオン性シリコーン、シリコーンガム、シリコーン樹脂）、炭化水素オイル、ポリオレフィン、脂肪酸エステル等が挙げられる。 Examples of other additives that can be used in the coloring composition of the present embodiment include silicone oil (polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane are suitable examples of silicone oil), cationic silicone, and silicone. Gum, silicone resin), hydrocarbon oil, polyolefin, fatty acid ester and the like.
　本実施形態の着色組成物は、必要に応じてさらにその他の添加剤を、本発明の効果を害しない範囲内において配合することができる。各用途における添加剤の例を後述する。 The coloring composition of the present embodiment can be blended with other additives as necessary within a range that does not impair the effects of the present invention. Examples of additives in each application will be described later.
＜カラーフィルタ＞
　本発明の一実施形態に係る着色用組成物は、カラーフィルタ用途に用いる着色組成物（カラーフィルター用着色組成物）とすることができる。この場合、カラーフィルタ用着色組成物は、重合性化合物を含有することが好ましい。重合性化合物としては、例えば、少なくとも１個のエチレン性不飽和二重結合を有する付加重合性化合物を挙げることができる。
　重合性化合物として具体的には、末端エチレン性不飽和結合を少なくとも１個、好ましくは２個以上有する化合物群が挙げられる。このような化合物群は、例えば、モノマー、ポリマー、すなわち二量体、三量体及びオリゴマー、またはそれらの混合物並びにそれらの（共）重合体などの化学的形態のいずれであってもよい。
　モノマー及びその（共）重合体の例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸）及びそのエステル体、アミド体、並びにこれらの（共）重合体等が挙げられる。また、ヒドロキシル基、アミノ基、又はメルカプと基等の求核性置換基を有する不飽和カルボン酸エステルあるいはアミド体と、単官能若しくは多官能イソシアネート体あるいはエポキシ体との付加反応物、単官能若しくは多官能カルボン酸との脱水縮合反応物等も使用することができる。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物を使用することもできる。 <Color filter>
The coloring composition according to one embodiment of the present invention can be a coloring composition (coloring composition for color filter) used for color filter applications. In this case, it is preferable that the coloring composition for color filters contains a polymeric compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.
Specific examples of the polymerizable compound include a compound group having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a group of compounds may be any of chemical forms such as, for example, monomers, polymers, that is, dimers, trimers and oligomers, or mixtures thereof, and (co) polymers thereof.
As an example of a monomer and its (co) polymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid), its ester body, amide body, these (co) polymer, etc. are mentioned. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, A dehydration condensation reaction product with a polyfunctional carboxylic acid can also be used. As another example, a compound in which an unsaturated phosphonic acid, styrene, vinyl ether, or the like is substituted for the above unsaturated carboxylic acid may be used.
　カラーフィルタ用着色組成物の全固形分中における重合性化合物の含有量は、本発明の効果をより効果的に得る観点から、１０～８０質量％であることが好ましく、１５～７５質量％であることがより好ましく、２０～６０質量％であることがさらに好ましい。 The content of the polymerizable compound in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass from the viewpoint of more effectively obtaining the effects of the present invention. More preferably, it is more preferably 20 to 60% by mass.
　カラーフィルタ用着色組成物は、少なくとも一種の光重合開始剤を含有することが好ましい。光重合開始剤は、重合性化合物を重合させ得るものであれば特に制限なく、特性、開始効率、吸収波長、入手性、コスト等の観点で選ばれることが好ましい。
　光重合開始剤としては、例えば、ハロメチルオキサジアゾール化合物及びハロメチル－ｓ－トリアジン化合物から選択される少なくとも１つの活性ハロゲン化合物、３－アリール置換クマリン化合物、ロフィン２量体、ベンゾフェノン化合物、アセトフェノン化合物及びその誘導体、シクロペンタジエン－ベンゼン－鉄錯体及びその塩、オキシム化合物等が挙げられる。中でも、重合反応が迅速である点等から、オキシム化合物又はビイミダゾール系化合物が好ましい。 It is preferable that the coloring composition for color filters contains at least 1 type of photoinitiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
Examples of the photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.
　カラーフィルタ用着色組成物の全固形分中における光重合開始剤の含有量は、３～２０質量％であることが好ましく、４～１９質量％であることがより好ましく、５～１８質量％であることがさらに好ましい。 The content of the photopolymerization initiator in the total solid content of the color filter coloring composition is preferably 3 to 20% by mass, more preferably 4 to 19% by mass, and 5 to 18% by mass. More preferably it is.
　カラーフィルタ用着色組成物は、少なくとも一種の有機溶剤を含有することが好ましい。有機溶剤は、並存する核成分の溶解性、及び着色組成物の塗布性を満足できるものであれば、基本的に制限はなく、溶解性、塗布性、安全性を考慮して選ばれることが好ましい。
　有機溶剤としては、エステル、エーテル、ケトン、芳香族炭化水素を用いることができる。これらの有機溶剤は１種類のみを含んでもよく、２種以上を混合して用いることもできる。２種類の有機溶剤を用いる場合、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液であることが特に好ましい。 The color filter coloring composition preferably contains at least one organic solvent. The organic solvent is basically not limited as long as it can satisfy the solubility of the coexisting core components and the coating property of the coloring composition, and may be selected in consideration of solubility, coating property, and safety. preferable.
As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons can be used. These organic solvents may contain only 1 type, and can also mix and use 2 or more types. When two kinds of organic solvents are used, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl A mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferable.
　カラーフィルタ用着色組成物の全固形分中における有機溶剤の含有量は、１０～８０質量％であることが好ましく、１５～６０質量％であることがより好ましい。 The content of the organic solvent in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, and more preferably 15 to 60% by mass.
　カラーフィルタ用着色組成物は、少なくとも一種のアルカリ可溶性バインダーを含有することが好ましい。
　アルカリ可溶性バインダーは、アルカリ可溶性を有すること以外は特に限定されることはなく、好ましくは耐熱性、現像性、入手性等の観点から選択することができる。
　アルカリ可溶性浴バインダーとしては、線状有機高分子重合体であり、かつ、有機溶剤に可溶で、弱アルカリ水溶液で現像できるものが好ましい。このような線状有機高分子重合体としては、側鎖にカルボン酸を有するポリマー、例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等が挙げられ、同様に側鎖にカルボン酸を有する酸性セルロース誘導体が有用である。 The color filter coloring composition preferably contains at least one alkali-soluble binder.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble bath binder is preferably a linear organic high molecular weight polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.
　また、アルカリ可溶性バインダーは、架橋効率を向上させるために、重合性基を側鎖に有してもよく、例えば、アリル基、（メタ）アクリル基、アリルオキシアルキル基等を側鎖に含有するポリマー等も有用である。上述の重合性基を含有するポリマーの例としては、市販品のＫＳレジスト－１０６（大阪有機化学工業（株）製）、サイクロマーＰシリーズ（（株)ダイセル製）等が挙げられる。また、硬化皮膜の強度を上げるためにアルコール可溶性ナイロンや２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンとのポリエーテル等も有用である。
　これら各種アルカリ可溶性バインダーの中でも、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。
　アクリル系樹脂としては、ベンジル（メタ）アクリレート、（メタ）アクリル酸、ヒドロキシエチル（メタ）アクリレート、（メタ）アクリルアミド等から選ばれるモノマーからなる共重合体や、市販品のＫＳレジスト－１０６（大阪有機化学工業（株）製）、サイクロマーＰシリーズ（（株)ダイセル製）等が好ましい。 The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing a polymerizable group described above include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Corporation), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
Examples of acrylic resins include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (manufactured by Daicel Corporation) are preferred.
　アルカリ可溶性バインダーは、現像性、液粘度等の観点から、重量平均分子量（ＧＰＣ法で測定されたポリスチレン換算値）が１，０００～２００，０００の重合体が好ましく、２，０００～１００，０００の重合体がより好ましく、５，０００～５０，０００の重合体が特に好ましい。
　カラーフィルタ用着色組成物の全固形分中におけるアルカリ可溶性バインダーの含有量は、１０～８０質量％であることが好ましく、２０～６０質量％であることがより好ましい。
　また、アルカリ可溶性バインダーの酸価は、１０～１０００ｍｇ／ＫＯＨが好ましく、５０～３００ｍｇ／ＫＯＨがより好ましく、５０～２００ｍｇ／ＫＯＨがさらに好ましく、１０５～２００ｍｇ／ＫＯＨが特に好ましい。
　カラーフィルタ用着色組成物は、アルカリ可溶性バインダーを、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferred is a polymer of 5,000 to 50,000.
The content of the alkali-soluble binder in the total solid content of the color filter coloring composition is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass.
The acid value of the alkali-soluble binder is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 105 to 200 mg / KOH.
The coloring composition for color filters may contain only one type of alkali-soluble binder, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
　カラーフィルタ用着色組成物は少なくとも一種の架橋剤を含有することが好ましい。架橋剤としては、架橋反応により膜硬化を行なえるものであれば、特に限定はなく、例えば、エポキシ樹脂、メチロール基、アルコキシメチル基、およびアシロキシメチル基から選ばれる少なくとも１つの置換基で置換された、メラミン化合物、グアナミン化合物、グリコールウリル化合物またはウレア化合物、メチロール基、アルコキシメチル基、およびアシロキシメチル基から選ばれる少なくとも１つの置換基で置換された、フェノール化合物、ナフトール化合物またはヒドロキシアントラセン化合物、が挙げられる。中でも、多官能エポキシ樹脂が好ましい。 The color filter coloring composition preferably contains at least one crosslinking agent. The crosslinking agent is not particularly limited as long as it can cure the film by a crosslinking reaction. For example, the crosslinking agent is substituted with at least one substituent selected from an epoxy resin, a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, a methylol group, an alkoxymethyl group, and an acyloxymethyl group . Of these, polyfunctional epoxy resins are preferred.
　カラーフィルタ用着色組成物は、少なくとも一種の酸化防止剤を含有することが好ましい。酸化防止剤としては、例えば、ラジカル捕捉剤、過酸化物分解剤、紫外線吸収剤、一重項酸素クエンチャー等を挙げることができる。 It is preferable that the coloring composition for a color filter contains at least one kind of antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
　ラジカル捕捉剤としては、例えば、フェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等を挙げることができる。フェノール系酸化防止剤としては、例えば、ヒドロキシフェニルプロピオネート系化合物、ヒドロキシベンジル系化合物、チオビスフェノール系化合物、チオメチルフェノール系化合物、アルカンジイルフェノール系化合物等を挙げることができる。中でも、色特性の安定性の観点から、ヒドロキシフェニルプロピオネート系化合物が好ましい。 Examples of radical scavengers include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
　紫外線吸収剤としては、例えば、サルチル酸エステル系酸化防止剤、ベンゾフェノン系酸化防止剤を挙げることができる。 Examples of ultraviolet absorbers include salicylate-based antioxidants and benzophenone-based antioxidants.
　一重項酸素クエンチャーとしては、例えば、テトラメチルエチレン、シクロペンテン等のエチレン性化合物、ジエチルアミン、トリエチルアミン、１，４－ジアザビシクロオクタン（ＤＡＢＣＯ）、Ｎ－エチルイミダゾール等のアミン類、置換されても良いナフタレン、ジメチルナフタレン、ジメトキシアントラセン、アントラセン、ジフェニルアントラセン等の縮合多環芳香族化合物；１，３－ジフェニルイソベンゾフラン、１，２，３，４－テトラフェニル－１，３－シクロペンタジエン、ペンタフェニルシクロペンタジエン等の芳香族化合物の他、Ｈａｒｒｙ　Ｈ．ｗａｓｓｅｒｍａｎ，“Ｓｉｎｇｌｅｔ　Ｏｘｙｇｅｎ”，５章，Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ（１９７９）、Ｎｉｃｈｏｌａｓ　Ｊ．Ｔｕｒｒｏ，“”Ｍｏｄｅｒｎ　Ｍｏｌｅｃｕｌａｒ　Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ“”，１４章，Ｔｈｅ　Ｂｅｎｊａｍｉｎ　Ｃｕｍｍｉｎｇｓ　Ｐｕｂｌｉｓｈｉｎｇ　Ｃｏ．，Ｉｎｃ．（１９７８）、およびＣＭＣ社発行　カラー写真感光材料用高機能ケミカルス，７章（２００２）に、一重項酸素クエンチャーとして例示されている化合物を挙げることができる。 Examples of the singlet oxygen quencher include ethylenic compounds such as tetramethylethylene and cyclopentene, amines such as diethylamine, triethylamine, 1,4-diazabicyclooctane (DABCO), and N-ethylimidazole. Good condensed polycyclic aromatic compounds such as naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenyl In addition to aromatic compounds such as cyclopentadiene, Harry H. wasserman, “Single Oxygen”, Chapter 5, Academic Press (1979), Nicholas J. et al. Turro, “” Modern Molecular Photochemistry ””, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978), and CMC Corporation, High Performance Chemicals for Color Photosensitive Materials, Chapter 7 (2002) can include compounds exemplified as singlet oxygen quenchers.
　カラーフィルタ用着色組成物において、酸化防止剤は、単独でまたは２種以上を混合して使用することができる。カラーフィルタ用着色組成物の全固形分中における酸化防止剤の含有量は、着色剤１００質量に対して、好ましくは０．０１～２０質量部、特に好ましくは０．１～１０質量部である。 In the coloring composition for color filters, the antioxidants can be used alone or in admixture of two or more. The content of the antioxidant in the total solid content of the color filter coloring composition is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant. .
＜カラートナー＞
　本発明の一実施形態に係る着色組成物は、カラートナー用途に用いる着色組成物（カラートナー用着色組成物）とすることができる。この場合、カラートナー用着色組成物における一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種の含有量は、カラートナー用着色組成物を１００質量部とした場合に０．１質量部以上含有することが好ましく、１～２０質量部含有することがより好ましく、２～１０質量部含有することがさらに好ましい。 <Color toner>
The colored composition according to one embodiment of the present invention can be a colored composition (colored composition for color toner) used for color toner applications. In this case, the content of at least one selected from the alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) in the color toner coloring composition is When the coloring composition for toner is 100 parts by mass, it is preferably contained in an amount of 0.1 part by mass or more, more preferably 1 to 20 parts by mass, and further preferably 2 to 10 parts by mass.
　カラートナー用着色組成物は、バインダー樹脂を含有することが好ましい。バインダー樹脂としては、一般に使用される全てのバインダーを使用することができる。例えば、スチレン系樹脂・アクリル系樹脂・スチレン／アクリル系樹脂・ポリエステル樹脂等が挙げられる。 The color toner coloring composition preferably contains a binder resin. As the binder resin, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
　カラートナー用着色組成物には、組成物の流動性、帯電制御等を目的として、無機微粉末、有機微粉末を外部添加することができる。例えば、表面をアルキル基含有のカップリング剤等で処理したシリカ微粒子又はチタニア微粒子等が好ましい。なお、これらの数平均一次粒子径が１０～５００ｎｍのものが好ましく、トナー中に０．１～２０質量％添加されていることが好ましい。 In the coloring composition for color toner, inorganic fine powder and organic fine powder can be externally added for the purpose of fluidity of the composition, charge control and the like. For example, silica fine particles or titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferable. The number average primary particle diameter of these is preferably 10 to 500 nm, and 0.1 to 20% by mass is preferably added to the toner.
　カラートナー用着色組成物は、離型剤を含むことが好ましい。離型剤としては、従来使用されている離型剤は全て使用することができる。具体的には、低分子量ポリプロピレン・低分子量ポリエチレン・エチレン－プロピレン共重合体等のオレフィン、マイクロクリスタリンワックス、カルナウバロウワックス、サゾールワックス、パラフィンワックス等が挙げられる。離型剤の添加量としては、カラートナー用組成物の全質量に対して１～５質量％添加することが好ましい。 The color toner coloring composition preferably contains a release agent. As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene / low molecular weight polyethylene / ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. The addition amount of the release agent is preferably 1 to 5% by mass based on the total mass of the color toner composition.
　カラートナー用着色組成物は、荷電制御剤を含むことが好ましい。荷電制御剤としては、例えば、４級アンモニウム塩構造のもの、カリックスアレン構造を有するものなどが挙げられる。 The color toner coloring composition preferably contains a charge control agent. Examples of the charge control agent include those having a quaternary ammonium salt structure and those having a calixarene structure.
　カラートナー用着色組成物は、キャリアを含むことができる。キャリアとしては、鉄、フェライト等の磁性材料粒子のみで構成される非被覆キャリア、磁性材料粒子表面を樹脂等によって被覆した樹脂被覆キャリアのいずれを使用してもよい。キャリアの平均粒径としては、体積平均粒子径で３０～１５０μｍであることが好ましい。 The coloring composition for color toner can contain a carrier. As the carrier, either an uncoated carrier constituted only by magnetic material particles such as iron or ferrite, or a resin-coated carrier obtained by coating the surface of the magnetic material particles with a resin or the like may be used. The average particle diameter of the carrier is preferably 30 to 150 μm in volume average particle diameter.
＜インクジェット記録用インク＞
　本発明の一実施形態に係る着色組成物は、インクジェット記録用インク用途に用いる着色組成物（インクジェット記録用インク）とすることができる。この場合、インクジェット記録用インクは、親油性媒体又は水性媒体中に着色組成物を溶解及び／又は分散させることによって得られるインクであることが好ましく、水性媒体を用いたインクであることがより好ましい。 <Ink for inkjet recording>
The colored composition according to an embodiment of the present invention can be a colored composition (inkjet recording ink) used for inkjet recording ink applications. In this case, the ink for inkjet recording is preferably an ink obtained by dissolving and / or dispersing a coloring composition in an oleophilic medium or an aqueous medium, and more preferably an ink using an aqueous medium. .
　インクジェット記録用インクには、必要に応じて、乾燥防止剤（湿潤剤）、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、ｐＨ調整剤、表面聴力調整剤、消泡剤、粘度調整剤、分散剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤が挙げられる。
　これらの各種添加剤は、水溶性インクの場合にはインク液に直接添加する。油溶性染料を分散物の形で用いる場合には、染料分散物の調製後分散物に添加するのが一般的であるが、調製時に油相又は水相に添加してもよい。 For ink jet recording ink, drying inhibitor (wetting agent), anti-fading agent, emulsification stabilizer, penetration enhancer, ultraviolet absorber, preservative, antifungal agent, pH adjuster, surface hearing adjuster as necessary Known additives such as an agent, an antifoaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used.
These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
　乾燥防止剤はインクジェット記録方式に用いるノズルのインク噴射口において、インクジェット記録用インクが乾燥することによる目詰まりを防止する目的で好適に使用される。
　乾燥防止剤としては、水より蒸気圧の低い水溶性有機溶剤が好ましい。具体的な例としてはエチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール、チオジグリコール、ジチオジグリコール、２－メチル－１，３－プロパンジオール、１，２，６－ヘキサントリオール、アセチレングリコール誘導体、グリセリン、トリメチロールプロパン等に代表される多価アルコール類、エチレングリコールモノメチル（又はエチル）エーテル、ジエチレングリコールモノメチル（又はエチル）エーテル、トリエチレングリコールモノエチル（又はブチル）エーテル等の多価アルコールの低級アルキルエーテル類、２－ピロリドン、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン、Ｎ－エチルモルホリン等の複素環類、スルホラン、ジメチルスルホキシド、３－スルホレン等の含硫黄化合物、ジアセトンアルコール、ジエタノールアミン等の多官能化合物、尿素誘導体が挙げられる。これらのうちグリセリン、ジエチレングリコール等の多価アルコールがより好ましい。
　また、乾燥防止剤は単独で用いてもよいし２種以上併用してもよい。
　これらの乾燥防止剤は、インクジェット記録用インク中に１０～５０質量％含有することが好ましい。 The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for ink jet recording at the ink ejection port of the nozzle used in the ink jet recording method.
As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used independently and may be used together 2 or more types.
These drying inhibitors are preferably contained in the ink for inkjet recording in an amount of 10 to 50% by mass.
　紫外線吸収剤は、画像の保存性を向上させる目的で使用される。紫外線吸収剤としては特開昭５８－１８５６７７号公報、同６１－１９０５３７号公報、特開平２－７８２号公報、同５－１９７０７５号公報、同９－３４０５７号公報等に記載されたベンゾトリアゾール系化合物、特開昭４６－２７８４号公報、特開平５－１９４４８３号公報、米国特許第３２１４４６３号明細書等に記載されたベンゾフェノン系化合物、特公昭４８－３０４９２号公報、同５６－２１１４１号公報、特開平１０－８８１０６号公報等に記載された桂皮酸系化合物、特開平４－２９８５０３号公報、同８－５３４２７号公報、同８－２３９３６８号公報、同１０－１８２６２１号公報、特表平８－５０１２９１号公報等に記載されたトリアジン系化合物、リサーチディスクロージャーＮｏ．２４２３９号に記載された化合物やスチルベン系、ベンズオキサゾール系化合物に代表される紫外線を吸収して蛍光を発する化合物、いわゆる蛍光増白剤も用いることができる。 UV absorbers are used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21141, Cinnamic acid compounds described in JP-A-10-88106 and the like, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-T-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.
　褪色防止剤は、画像の保存性を向上させる目的で使用される。褪色防止剤としては、各種の有機系及び金属錯体系の褪色防止剤を使用することができる。有機の褪色防止剤としてはハイドロキノン類、アルコキシフェノール類、ジアルコキシフェノール類、フェノール類、アニリン類、アミン類、インダン類、クロマン類、アルコキシアニリン類、ヘテロ環類などがあり、金属錯体としてはニッケル錯体、亜鉛錯体などがある。より具体的にはリサーチディスクロージャーＮｏ．１７６４３の第ＶＩＩのＩないしＪ項、同Ｎｏ．１５１６２、同Ｎｏ．１８７１６の６５０頁左欄、同Ｎｏ．３６５４４の５２７頁、同Ｎｏ．３０７１０５の８７２頁、同Ｎｏ．１５１６２に引用された特許に記載された化合物や特開昭６２－２１５２７２号公報の１２７頁～１３７頁に記載された代表的化合物の一般式及び化合物例に含まれる化合物を使用することができる。 The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.
　防黴剤としては、デヒドロ酢酸ナトリウム、安息香酸ナトリウム、ナトリウムピリジンチオン－１－オキシド、ｐ－ヒドロキシ安息香酸エチルエステル、１，２－ベンズイソチアゾリン－３－オン及びその塩等が挙げられる。これらはインク中に０．０２～１．００質量％使用するのが好ましい。 Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by mass in the ink.
　ｐＨ調整剤としては中和剤（有機塩基、無機アルカリ）を用いることができる。ｐＨ調整剤はインクジェット記録用インクの保存安定性を向上させる目的で、インクジェット記録用インクがｐＨ６～１０となる用に添加するのが好ましく、ｐＨ７～１０となるように添加するのがより好ましい。 As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, more preferably 7 to 10.
　表面張力調整剤としてはノニオン性、カチオン性あるいはアニオン性界面活性剤が挙げられる。なお、本発明のインクジェット記録用インクの表面張力は２５～７０ｍＮ／ｍが好ましい。さらに２５～６０ｍＮ／ｍが好ましい。また本発明のインクジェット記録用インクの粘度は３０ｍＰａ・ｓ以下が好ましい。更に２０ｍＰａ・ｓ以下に調整することがより好ましい。 Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. The surface tension of the ink for ink jet recording of the present invention is preferably 25 to 70 mN / m. Further, 25 to 60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.
　界面活性剤の例としては、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキル硫酸エステル塩等のアニオン系界面活性剤や、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレンオキシプロピレンブロックコポリマー等のノニオン系界面活性剤が好ましい。また、アセチレン系ポリオキシエチレンオキシド界面活性剤であるＳＵＲＦＹＮＯＬＳ（ＡｉｒＰｒｏｄｕｃｔｓ＆Ｃｈｅｍｉｃａｌｓ社）も好ましく用いられる。また、Ｎ，Ｎ－ジメチル－Ｎ－アルキルアミンオキシドのようなアミンオキシド型の両性界面活性剤等も好ましい。更に、特開昭５９－１５７，６３６号の第（３７）～（３８）頁、リサーチ・ディスクロージャーＮｏ．３０８１１９（１９８９年）記載の界面活性剤として挙げたものも使うことができる。 Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.
　消泡剤としては、フッ素系、シリコーン系化合物やＥＤＴＡに代表されるキレート剤等も必要に応じて使用することができる。 As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
　本発明の一実施形態に係る化合物であるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体を、水性媒体に分散させる場合は、特開平１１－２８６６３７号、特開２００１－２４０７６３号、特開２００１－２６２０３９号、特開２００１－２４７７８８号等の各公報に記載されるように、化合物と油溶性ポリマーとを含有する着色微粒子を水性媒体に分散したり、特開２００１－２６２０１８号、特開２００１－２４０７６３、特開２００１－３３５７３４号、特開２００２－８０７７２号の各公報のように高沸点有機溶媒に溶解した本発明の化合物を水性媒体中に分散することが好ましい。本実施形態の化合物を水性媒体に分散させる場合の具体的な方法，使用する油溶性ポリマー、高沸点有機溶剤、添加剤及びそれらの使用量は、上記特許公報等に記載されたものを好ましく使用することができる。あるいは、本実施形態の化合物を固体のまま微粒子状態に分散してもよい。分散時には、分散剤や界面活性剤を使用することができる。分散装置としては、簡単なスターラーやインペラー攪拌方式、インライン攪拌方式、ミル方式（例えば、コロイドミル、ボールミル、サンドミル、アトライター、ロールミル、アジテーターミル等）、超音波方式、高圧乳化分散方式（高圧ホモジナイザー；具体的な市販装置としてはゴーリンホモジナイザー、マイクロフルイダイザー、ＤｅＢＥＥ２０００等）を使用することができる。上記のインクジェット記録用インクの調製方法については、先述の特許以外にも特開平５－１４８４３６号、特開平５－２９５３１２号、特開平７－９７５４１号、特開平７－８２５１５号、特開平７－１１８５８４号、特開平１１－２８６６３７号、特開２００１－２７１００３号の各公報に詳細が記載されており、本発明の一実施形態に係る着色組成物を含むインクジェット記録用インクの調製に利用できる。 In the case where an alkali metal salt, alkaline earth metal salt of an azo dye or a tautomer thereof, which is a compound according to an embodiment of the present invention, is dispersed in an aqueous medium, JP-A-11-286637 and JP-A-2001-2001 As described in each publication such as No. 240763, JP-A No. 2001-262039, JP-A No. 2001-247788, etc., colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, It is preferable to disperse the compound of the present invention dissolved in a high-boiling organic solvent in an aqueous medium as described in JP-A No. 262018, JP-A No. 2001-240763, JP-A No. 2001-335734 and JP-A No. 2002-80772. The specific method for dispersing the compound of the present embodiment in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount used thereof are preferably those described in the above-mentioned patent publications, etc. can do. Or you may disperse | distribute the compound of this embodiment to a fine particle state with a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the method for preparing the ink jet recording ink described above is disclosed in JP-A-5-148436, JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7- Details are described in Japanese Patent Nos. 118584, 11-286637, and 2001-271003, and can be used for the preparation of an ink for ink jet recording containing a colored composition according to an embodiment of the present invention.
　水性媒体は、水を主成分とし、所望により、水混和性有機溶剤を添加した混合物を用いることができる。前記水混和性有機溶剤の例には、アルコール（例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔ－ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ベンジ
ルアルコール）、多価アルコール類（例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ヘキサンジオール、ペンタンジオール、グリセリン、ヘキサントリオール、チオジグリコール）、グリコール誘導体（例えば、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モノブチルエーテル、ジエチレングルコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリ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ジアセテート、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリ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モノフェニルエーテル）、アミン（例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、モルホリン、Ｎ－エチルモルホリン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ポリエチレンイミン、テトラメチルプロピレンジアミン）及びその他の極性溶媒（例えば、ホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、スルホラン、２－ピロリドン、Ｎ－メチル－２－ピロリドン、Ｎ－ビニル－２－ピロリドン、２－オキサゾリドン、１，３－ジメチル－２－イミダゾリジノン、アセトニトリル、アセトン）が含まれる。尚、前記水混和性有機溶剤は、単独で用いてもよいし、二種類以上を併用してもよい。 As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may be used independently and may use 2 or more types together.
　インクジェット記録用インクの１００質量部に対して、一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種を０．２～１０質量部含有することが好ましく、１～６質量部含有することがより好ましい。また、インクジェット記録用インクは、他の色素を併用してもよい。２種類以上の色素を併用する場合は、色素の含有量の合計が上述の範囲となっているのが好ましい。 0.2 parts of at least one selected from alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dye represented by the general formula (1) with respect to 100 parts by mass of the ink for inkjet recording. The content is preferably 10 to 10 parts by mass, and more preferably 1 to 6 parts by mass. The ink for ink jet recording may be used in combination with other pigments. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably in the above range.
　本発明の一実施形態に係る着色組成物を用いて、染色される物に対して各種の染色方法を施すことにより、染色物を得ることができる。染色方法としては、限定されないが、着色組成物の溶液等への浸漬による染色方法、インクジェット法等を用いた染色方法が挙げられる。染色される物（被染色物）としては、繊維、布、皮革、紙、フィルム等の染色しうるものであれば限定されることはない。 A dyed product can be obtained by applying various dyeing methods to an object to be dyed using the colored composition according to an embodiment of the present invention. Although it does not limit as a dyeing | staining method, the dyeing | staining method by the immersion to the solution etc. of a coloring composition, the dyeing | staining method using the inkjet method etc. are mentioned. The material to be dyed (the material to be dyed) is not limited as long as it can be dyed such as fiber, cloth, leather, paper, film and the like.
　以下に本発明を実施例に基づき詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.
＜実施例１＞　例示化合物Ｄ－１１５の合成
　下記式で表される化合物Ｄ－２００、３２１ｍｇをイソプロピルアルコール３．２ｍＬに溶解した。この溶液に水酸化リチウム一水和物３６ｍｇを加え、２日間、室温にて撹拌した。析出した結晶を濾集、乾燥し、例示化合物Ｄ－１１５を１５２ｍｇ（収率４７％）得た。 Example 1 Synthesis of Exemplified Compound D-115 Compound D-200 represented by the following formula, 321 mg, was dissolved in 3.2 mL of isopropyl alcohol. To this solution, 36 mg of lithium hydroxide monohydrate was added and stirred at room temperature for 2 days. The precipitated crystals were collected by filtration and dried to obtain 152 mg (yield 47%) of Exemplary Compound D-115.
Figure JPOXMLDOC01-appb-C000027
 
Figure JPOXMLDOC01-appb-C000027
 
＜実施例２＞　例示化合物Ｄ－１１４の合成
　上記の化合物Ｄ－２００、３２０ｍｇをイソプロピルアルコール３．２ｍＬに溶解した。この溶液に酢酸ナトリウム７２ｍｇを加え、２日間、室温にて撹拌した。析出した結晶を濾集、乾燥し、例示化合物Ｄ－１１４を３２３ｍｇ（収率９５％）得た。 Example 2 Synthesis of Exemplary Compound D-114 The above compound D-200, 320 mg, was dissolved in 3.2 mL of isopropyl alcohol. To this solution, 72 mg of sodium acetate was added and stirred at room temperature for 2 days. The precipitated crystals were collected by filtration and dried to obtain 323 mg (yield 95%) of Exemplary Compound D-114.
＜実施例３＞　例示化合物Ｄ－１１３の合成
　上記の化合物Ｄ－２００、３２２ｍｇをイソプロピルアルコール３．２ｍＬに溶解した。この溶液にカリウム－ｔ－ブトキシド９９ｍｇを加え、２日間、室温にて撹拌した。析出した結晶を濾集、乾燥し、例示化合物Ｄ－１１３を３３６ｍｇ（収率９５％）得た。 Example 3 Synthesis of Exemplary Compound D-113 The above compound D-200, 322 mg, was dissolved in 3.2 mL of isopropyl alcohol. To this solution, 99 mg of potassium tert-butoxide was added and stirred for 2 days at room temperature. The precipitated crystals were collected by filtration and dried to obtain 336 mg (yield 95%) of Exemplary Compound D-113.
＜実施例４＞　例示化合物Ｄ－５４の合成
　下記式で表される化合物Ｄ－２０１、２５５ｍｇ、カリウム－ｔ－ブトキシド１３８ｍｇ、イソプロピルアルコール２．０ｍＬの混合物を、２日間、室温にて撹拌した。析出した結晶を濾集、乾燥し、例示化合物Ｄ－５４を２０４ｍｇ（収率７０％）得た。 Example 4 Synthesis of Exemplary Compound D-54 A mixture of compound D-201, 255 mg represented by the following formula, potassium tert-butoxide 138 mg, and isopropyl alcohol 2.0 mL was stirred at room temperature for 2 days. The precipitated crystals were collected by filtration and dried to obtain 204 mg (yield 70%) of Exemplary Compound D-54.
Figure JPOXMLDOC01-appb-C000028
 
Figure JPOXMLDOC01-appb-C000028
 
＜実施例５＞　例示化合物Ｄ－１２６の合成
　下記式で表される化合物Ｄ－２０２、２２１ｍｇ、酢酸カリウム９６ｍｇ、イソプロピルアルコール３．２ｍＬの混合物を、１日間、室温にて撹拌した。析出した結晶を濾集、乾燥、例示化合物Ｄ－１２６を８６ｍｇ（収率３４％）得た。 Example 5 Synthesis of Exemplary Compound D-126 A mixture of Compound D-202 represented by the following formula, 221 mg, potassium acetate 96 mg, and isopropyl alcohol 3.2 mL was stirred at room temperature for 1 day. The precipitated crystals were collected by filtration and dried to obtain 86 mg (yield 34%) of Exemplary Compound D-126.
Figure JPOXMLDOC01-appb-C000029
 
Figure JPOXMLDOC01-appb-C000029
 
＜実施例６＞　例示化合物Ｄ－１３１の合成
　下記式で表される化合物Ｄ－２０３、３０４ｍｇ、カリウム－ｔ－ブトキシド１２４ｍｇ、ｔ－アミルアルコール３．０ｍＬの混合物を、５０℃まで昇温した後、１８時間、室温にて撹拌した。析出した結晶を濾集、乾燥し、例示化合物Ｄ－１３１を１９６ｍｇ（収率５７％）得た。 Example 6 Synthesis of Exemplary Compound D-131 After heating a mixture of Compound D-203 represented by the following formula, 304 mg, 124 mg of potassium tert-butoxide, and 3.0 mL of t-amyl alcohol to 50 ° C. And stirred for 18 hours at room temperature. The precipitated crystals were collected by filtration and dried to obtain 196 mg (yield 57%) of Exemplary Compound D-131.
Figure JPOXMLDOC01-appb-C000030
 
Figure JPOXMLDOC01-appb-C000030
 
＜実施例７＞　例示化合物Ｄ－１１４を含む着色組成物の調製と吸収スペクトルの測定
　上記のＤ－２００を２．０３ｍｇ秤量し、０．２ｍＭの水酸化ナトリウム水溶液１００ｍＬに溶解した。これを４．０ｍＬとり、純水を加え１０ｍＬにした。これにより、８．５６ｐｐｍの濃度のＤ－１１４を含む組成物を調製した。この組成物を用い、吸収極大とモル吸光係数を測定した。結果を表１に示す。 Example 7 Preparation of Colored Composition Containing Example Compound D-114 and Measurement of Absorption Spectrum 2.03 mg of the above D-200 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-114 at a concentration of 8.56 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
＜実施例８＞　例示化合物Ｄ－５５を含む着色組成物の調製と吸収スペクトルの測定
　上記のＤ－２０１を２．００ｍｇ秤量し、０．２ｍＭの水酸化ナトリウム水溶液１００ｍＬに溶解した。これを４．０ｍＬとり、純水を加え１０ｍＬにした。これにより、９．１９ｐｐｍの濃度のＤ－５５を含む組成物を調製した。この組成物を用い、吸収極大とモル吸光係数を測定した。結果を表１に示す。 <Example 8> Preparation of colored composition containing exemplary compound D-55 and measurement of absorption spectrum 2.00 mg of the above D-201 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-55 at a concentration of 9.19 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
＜実施例９＞　例示化合物Ｄ－１２７を含む着色組成物の調製と吸収スペクトルの測定
　上記のＤ－２０２を２．０２ｍｇ秤量し、０．２ｍＭの水酸化ナトリウム水溶液１００ｍＬに溶解した。これを４．０ｍＬとり、純水を加え１０ｍＬにした。これにより、９．２１ｐｐｍの濃度のＤ－１２７を含む組成物を調製した。この組成物を用い、吸収極大とモル吸光係数を測定した。結果を表１に示す。 Example 9 Preparation of Colored Composition Containing Example Compound D-127 and Measurement of Absorption Spectrum 2.02 mg of the above D-202 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. This prepared a composition containing D-127 at a concentration of 9.21 ppm. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
＜実施例１０＞例示化合物Ｄ－１３２を含む着色組成物の調製と吸収スペクトルの測定
　上記のＤ－２０３を２．００ｍｇ秤量し、０．２ｍＭの水酸化ナトリウム水溶液１００ｍＬに溶解した。これを４．０ｍＬとり、純水を加え１０ｍＬにした。これにより、９．００ｐｐｍの濃度の例示化合物Ｄ－１３２を含む組成物を調製した。この組成物を用い、吸収極大とモル吸光係数を測定した。結果を表１に示す。 <Example 10> Preparation of colored composition containing exemplary compound D-132 and measurement of absorption spectrum 2.00 mg of the above D-203 was weighed and dissolved in 100 mL of 0.2 mM aqueous sodium hydroxide solution. 4.0 mL of this was taken, and pure water was added to make 10 mL. Thus, a composition containing Exemplary Compound D-132 at a concentration of 9.00 ppm was prepared. Using this composition, the absorption maximum and molar extinction coefficient were measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000031
 
Figure JPOXMLDOC01-appb-T000031
 
＜実施例１１～１４、比較例１～４＞
　表２に示す例示化合物及び比較化合物について、熱分解温度を測定した。結果を表２に示す。表２中、比較化合物Ｄ－２００～Ｄ－２０３は、それぞれ、上記した化合物Ｄ－２００～Ｄ－２０３である。 <Examples 11 to 14, Comparative Examples 1 to 4>
The thermal decomposition temperature was measured for the exemplary compounds and comparative compounds shown in Table 2. The results are shown in Table 2. In Table 2, comparative compounds D-200 to D-203 are the above-mentioned compounds D-200 to D-203, respectively.
Figure JPOXMLDOC01-appb-T000032
 
Figure JPOXMLDOC01-appb-T000032
 
　上記の表２に示したように、実施例１１～１４、比較例１～４の化合物は、２７０℃以上の高い熱分解温度を示す。特に、実施例１２～１４に示した例示化合物は、カリウム塩とすることで、カリウム塩でない比較化合物に対して熱分解温度が上昇し、熱に対し安定性が高くなることがわかる。 As shown in Table 2 above, the compounds of Examples 11 to 14 and Comparative Examples 1 to 4 exhibit a high thermal decomposition temperature of 270 ° C. or higher. In particular, it can be seen that, when the exemplified compounds shown in Examples 12 to 14 are potassium salts, the thermal decomposition temperature is increased with respect to comparative compounds that are not potassium salts, and the stability to heat is increased.
＜実施例１５＞　Ｄ－１１４によるインクジェット用紙の染色
　純水１００ｍＬにエマルゲン１０９Ｐ（花王（株)製）の１０％水溶液を０．６ｇ加え、界面活性剤溶液を調製した。化合物Ｄ－２００　０．１００ｇ、１Ｍ水酸化ナトリウム水溶液０．５ｍＬの混合物に上記界面活性剤溶液を１０．０ｇ加え均一に溶解した。これにより、例示化合物Ｄ－１１４を含む着色組成物を得た。
　これをバーコーターにてインクジェット用紙　画彩（富士フイルム（株）製）に塗布した。得られた染色物の反射スペクトルを測定した。鮮やかな紫色の染色物が得られた。 <Example 15> Dyeing of inkjet paper by D-114 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.100 g of Compound D-200 and 0.5 mL of 1M aqueous sodium hydroxide solution. This obtained the coloring composition containing exemplary compound D-114.
This was applied to inkjet paper painting (manufactured by FUJIFILM Corporation) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright purple dyeing was obtained.
＜実施例１６＞　Ｄ－５５によるインクジェット用紙の染色
　純水１００ｍＬにエマルゲン１０９Ｐ（花王（株）製）の１０％水溶液を０．６ｇ加え、界面活性剤溶液を調製した。化合物Ｄ－２０１　０．１１１ｇ、１Ｍ水酸化ナトリウム水溶液０．５ｍＬの混合物に上記界面活性剤溶液を１０．０ｇ加え均一に溶解した。これにより、例示化合物Ｄ－５５を含む着色組成物を得た
　これをバーコーターにてインクジェット用紙　画彩（富士フイルム（株）製）に塗布した。得られた染色物の反射スペクトルを測定した。鮮やかな赤色の染色物が得られた。 <Example 16> Dyeing of inkjet paper with D-55 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.111 g of Compound D-201 and 0.5 mL of 1M aqueous sodium hydroxide solution. As a result, a colored composition containing Exemplified Compound D-55 was obtained, and this was applied to an inkjet paper image (Fuji Film Co., Ltd.) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright red dyeing was obtained.
＜実施例１７＞Ｄ－１３２によるインクジェット用紙の染色
　純水１００ｍＬにエマルゲン１０９Ｐ（花王（株）製）の１０％水溶液を０．６ｇ加え、界面活性剤溶液を調製した。化合物Ｄ－２０３　０．０９３ｇ、１Ｍ水酸化ナトリウム水溶液０．５ｍＬの混合物に上記界面活性剤溶液を１０．０ｇ加え均一に溶解した。これにより、例示化合物Ｄ－１３２を含む着色組成物を得た。
　これをバーコーターにてインクジェット用紙　画彩（富士フイルム（株）製）に塗布した。得られた染色物の反射スペクトルを測定した。鮮やかな黄色の染色物が得られた。 <Example 17> Dyeing of inkjet paper with D-132 0.6 g of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation) was added to 100 mL of pure water to prepare a surfactant solution. 10.0 g of the above surfactant solution was added and uniformly dissolved in a mixture of 0.093 g of Compound D-203 and 0.5 mL of 1M aqueous sodium hydroxide solution. This obtained the coloring composition containing exemplary compound D-132.
This was applied to inkjet paper painting (manufactured by FUJIFILM Corporation) with a bar coater. The reflection spectrum of the dyed product obtained was measured. A bright yellow dyeing was obtained.
　実施例１５～１７で得られた染色物の反射スペクトルを図１～３に示す。Ｌ＊、ａ＊、ｂ＊値を表３に示す。 The reflection spectra of the dyed products obtained in Examples 15 to 17 are shown in FIGS. The L *, a *, and b * values are shown in Table 3.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　２０１４年１０月２７日に出願された日本国特許出願２０１４－２１８２４４の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。  The disclosure of Japanese Patent Application No. 2014-218244 filed on October 27, 2014 is hereby incorporated by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims (7)

  1. 　下記一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体。
    Ａ－Ｎ＝Ｎ－Ｂ　　　（１）
    　一般式（１）中、Ａは置換基を有してもよい下記式（Ａ－１）～（Ａ－２５）のいずれかで表される複素環基であって、カルボキシ基、スルホ基を含まず、アゾ基に炭素原子を介して結合する基を示す。
    Figure JPOXMLDOC01-appb-C000001
     
    Figure JPOXMLDOC01-appb-C000002
     
    　式（Ａ－１）～（Ａ－２５）中、＊は、一般式（１）中のアゾ基に結合する位置を表す。
    　Ｒ２１～Ｒ５０は、独立に、水素原子、ハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、水酸基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、スルファモイル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基又はカルバモイル基を表し、Ｒ２１～Ｒ５０のうち隣接する基は互いに結合して飽和又は不飽和の５員又は６員環構造を形成してもよい。
    　ａ、ｐ、ｑ、ｒ及びｓは０～４の整数を表し、ｂ及びｃは０～６の整数を表し、ｄ、ｅ、ｆ、ｇ、ｔ及びｕは０～３の整数を表し、ｈ、ｉ、ｊ、ｋ、ｌ及びｏは０～２の整数を表し、ｍは０～１の整数を表し、同一分子中のＲ２１～Ｒ５０で表される２以上の基は、同一であっても互いに異なっていてもよい。
    　一般式（１）中、Ｂは下記式（Ｂ－１）～（Ｂ－１２）のいずれかで表される解離性プロトンを含み、かつカルボキシ基、スルホ基を含まない基を表す。
    Figure JPOXMLDOC01-appb-C000003
     
    　式（Ｂ－１）～（Ｂ－１２）中、＊＊は一般式（１）中のアゾ基に結合する位置を表す。
    　Ｒ１０１はハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、スルファモイル基、アルキルスルホニル基又はカルバモイル基を表し、
    　Ｒ１０２及びＲ１０４は、それぞれ独立に、シアノ基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基又はカルバモイル基を表し、
    　Ｚ１は、酸素原子、硫黄原子又は－Ｎ（Ｒ１０３）－を表し、
    　Ｒ１０３は水素原子、アルキル基、アリール基又は複素環基を表し、
    　ｖは０～４の整数を表し、ｖ個のＲ１０１は同一であっても異なっていてもよい。
    　Ｒ１０５及びＲ１０６は、独立して、水素原子、アルキル基、アリール基又は複素環基を表す。
    　Ｒ１０７は、水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、
    　Ｚ２及びＺ３は、独立に、－Ｃ（Ｒ１０８）＝又は－Ｎ＝を表し、
    　Ｒ１０８は、アルキル基、アリール基、複素環基、アルキルチオ基、アリールチオ基、アルコキシカルボニル基又はカルバモイル基を表し、
    　Ｚ２及びＺ３が両方とも－Ｃ（Ｒ１０８）＝である場合、２個のＲ１０８基は同一であっても異なっていてもよく、互いに結合して炭素環又は複素環を形成してもよい。
    　Ｒ１０９は、アルキル基、アリール基又は複素環基を表し、Ｒ１１０は、水素原子、アルキル基、アリール基、複素環基、アシル基、アルキルスルホニル基又はアリールスルホニル基を表し、Ｒ１１１は、アルキル基、アリール基、アルコキシ基、アミノ基（アニリノ基を含む）、アルコキシカルボニル基、シアノ基、アシルアミノ基又はカルバモイル基を表し、Ｒ１１２は、水素原子、アルキル基、アリール基又は複素環基を表し、Ｒ１１３は、ヒドロキシル基又はアミノ基を表す。
    　Ｒ１１４及びＲ１１５はハロゲン原子、アルキル基、アリール基、複素環基、ニトロ基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、複素環チオ基、アルコキシカルボニル基又はカルバモイル基を表す。
    　ｗは０～４の整数を表し、ｗ個のＲ１１４基は同一であっても異なっていてもよい。
    　ｘは０～６の整数を表し、ｘ個のＲ１１５基は同一であっても異なっていてもよい。
    　Ｒ１１６、Ｒ１１７、Ｒ１１８及びＲ１１９は、独立に、アルキル基又はアリール基を表す。
    　Ｒ１２０及びＲ１２１は、独立に、アルキル基、アリール基、複素環基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、
    　Ｒ１２２は水素原子、アルキル基、アリール基、複素環基、アシルアミノ基、アルキルスルホニルアミノ基又はアリールスルホニルアミノ基を表す。
    　Ｒ１２３及びＲ１２４は、独立に、アルキル基、アリール基、複素環基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、
    　Ｚ４は２個の窒素原子と１個の炭素原子と共に５員又は６員環を形成する非金属原子団を表し、
    　Ｚ４が５員環を形成する場合、ｙは０～２の整数を表し、Ｚ４が６員環を形成する場合、ｙは０～３の整数を表し、
    　Ｒ１２５はアルキル基、アリール基、アルコキシ基、アミノ基、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アシル基、アルコキシカルボニル基又はカルバモイル基を表し、
    　Ｒ１２６はアルキルカルボニル基又はアリールカルボニル基を表す。     Alkali metal salts, alkaline earth metal salts and tautomers thereof of the azo dyes represented by the following general formula (1).
    A−N = NB (1)
    In the general formula (1), A is a heterocyclic group represented by any of the following formulas (A-1) to (A-25) which may have a substituent, and is a carboxy group or a sulfo group. A group which does not contain and is bonded to an azo group via a carbon atom is shown.
    Figure JPOXMLDOC01-appb-C000001

    Figure JPOXMLDOC01-appb-C000002

    In formulas (A-1) to (A-25), * represents a position bonded to the azo group in general formula (1).
    R 21 to R 50 are independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl Represents a group or a carbamoyl group, and adjacent groups among R 21 to R 50 may be bonded to each other to form a saturated or unsaturated 5-membered or 6-membered ring structure.
    a, p, q, r and s represent an integer of 0 to 4, b and c represent an integer of 0 to 6, d, e, f, g, t and u represent an integer of 0 to 3, h, i, j, k, l and o represent an integer of 0 to 2, m represents an integer of 0 to 1, and two or more groups represented by R 21 to R 50 in the same molecule are the same. Or they may be different from each other.
    In the general formula (1), B represents a group containing a dissociable proton represented by any of the following formulas (B-1) to (B-12) and not containing a carboxy group or a sulfo group.
    Figure JPOXMLDOC01-appb-C000003

    In the formulas (B-1) to (B-12), ** represents a position bonded to the azo group in the general formula (1).
    R 101 is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, Represents a sulfamoyl group, an alkylsulfonyl group or a carbamoyl group,
    R 102 and R 104 are each independently a cyano group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group or Represents a carbamoyl group,
    Z 1 represents an oxygen atom, a sulfur atom or —N (R 103 ) —,
    R 103 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
    v represents an integer of 0 to 4, and v R 101s may be the same or different.
    R 105 and R 106 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
    R 107 is a hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio Represents a group, an alkylsulfonyl group, an arylsulfonyl group or a carbamoyl group,
    Z 2 and Z 3 independently represent -C (R 108 ) = or -N =
    R 108 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group,
    When Z 2 and Z 3 are both —C (R 108 ) ═, the two R 108 groups may be the same or different and are bonded together to form a carbocyclic or heterocyclic ring. Also good.
    R 109 represents an alkyl group, an aryl group, or a heterocyclic group, R 110 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and R 111 represents Represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group, and R 112 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 113 represents a hydroxyl group or an amino group.
    R 114 and R 115 are halogen atoms, alkyl groups, aryl groups, heterocyclic groups, nitro groups, alkoxy groups, aryloxy groups, amino groups (including anilino groups), acylamino groups, alkoxycarbonylamino groups, aminocarbonylamino groups. Represents an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonyl group or a carbamoyl group.
    w represents an integer of 0 to 4, and w R 114 groups may be the same or different.
    x represents an integer of 0 to 6, and the x R 115 groups may be the same or different.
    R 116 , R 117 , R 118 and R 119 independently represent an alkyl group or an aryl group.
    R 120 and R 121 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group,
    R 122 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group or an arylsulfonylamino group.
    R 123 and R 124 independently represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, or a carbamoyl group,
    Z 4 represents a nonmetallic atomic group that forms a 5- or 6-membered ring with two nitrogen atoms and one carbon atom,
    When Z 4 forms a 5-membered ring, y represents an integer of 0-2, and when Z 4 forms a 6-membered ring, y represents an integer of 0-3,
    R 125 represents an alkyl group, aryl group, alkoxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group or carbamoyl group,
    R 126 represents an alkylcarbonyl group or an arylcarbonyl group.
  2. 　アゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の構造が、下記式ＤＳ－１～ＤＳ－９のいずれかで表されるものである請求項１記載のアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体。
    Figure JPOXMLDOC01-appb-C000004
     
    　式（ＤＳ－１～ＤＳ－９）中、Ａは請求項１で定義されたＡと同様の意味を有し、
    　Ｒ２０１はアルキル基、アリール基、アルコキシ基、アミノ基（アニリノ基を含む）、アルコキシカルボニル基、シアノ基、アシルアミノ基又はカルバモイル基を表し、
    　Ｒ２０２は水素原子、アルキル基、アリール基又は複素環基を表し、
    　Ｒ２０３、Ｒ２０５及びＲ２０７は、それぞれ独立に水素原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基又はカルバモイル基を表し、Ｒ２０４はアルキル基、アリール基又は複素環基を表す。
    　Ｒ２０６はアルキル基、アリール基、複素環基、アルキルチオ基、アリールチオ基、アルコキシカルボニル基又はカルバモイル基を表す。
    　Ｒ２０８はハロゲン原子、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基又はカルバモイル基を表し、ａａは、０～４の整数を表し、ａａ個のＲ２０８は同一であっても異なっていてもよい。
    　Ｒ２１０及びＲ２１１は、独立に水素原子、ハロゲン原子、アルキル基、アリール基、アシルアミノ基、アルコキシカルボニル基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルコキシカルボニルアミノ基又はカルバモイル基を示し、Ｒ２１０及びＲ２１１の少なくとも一方が水素原子であり、Ｒ２１２及びＲ２１３は、独立に水素原子、ハロゲン原子、アルキル基、アルコキシ基又はアシルアミノ基を表す。
    　Ｒ２１４及びＲ２１５は、独立に水素原子、アルキル基、アリール基又は複素環基を表す。
    　Ｒ２１６はハロゲン原子、アルキル基、アリール基、複素環基、シアノ基、アルコキシ基、アミノ基（アニリノ基を含む）、アシルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、スルファモイル基、アルキルスルホニル基又はカルバモイル基を示し、Ｚ５は酸素原子、硫黄原子又は－Ｎ（Ｒ２１７）－を示し、Ｒ２１７は水素原子、アルキル基、アリール基又は複素環基を示す。ｂｂは、０～４の整数を示し、ｂｂ個のＲ２１６は同一であっても異なっていてもよい。
    　Ｒ２１８はＲ２１０と同義か、又はスルファモイル基を示し、Ｒ２２０及びＲ２２３は水素原子、ハロゲン原子、アシルアミノ基、アルコキシカルボニルアミノ基、アミノカルボニルアミノ基、アルキルスルホニルアミノ基又はアリールスルホニルアミノ基を示し、Ｒ２１９、Ｒ２２１及びＲ２２２は水素原子、塩素原子、臭素原子、アルキル基又はアシルアミノ基を示す。
    　Ｒ２２４はアルキルカルボニル基又はアリールカルボニル基を示す。
    　Ｍはアルカリ金属またはアルカリ土類金属１／２を示す。     2. The alkali of an azo dye according to claim 1, wherein the structure of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye is represented by any one of the following formulas DS-1 to DS-9: Metal salts, alkaline earth metal salts and tautomers thereof.
    Figure JPOXMLDOC01-appb-C000004

    In the formulas (DS-1 to DS-9), A has the same meaning as A defined in claim 1,
    R 201 represents an alkyl group, an aryl group, an alkoxy group, an amino group (including an anilino group), an alkoxycarbonyl group, a cyano group, an acylamino group, or a carbamoyl group,
    R 202 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
    R 203 , R 205 and R 207 are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or carbamoyl group, R 204 represents an alkyl group, an aryl group or a heterocyclic group.
    R 206 represents an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or a carbamoyl group.
    R 208 is a halogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group (including anilino group), acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group Represents an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group, aa represents an integer of 0 to 4, and aa R 208 may be the same or different.
    R 210 and R 211 are independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, an alkoxycarbonyl group, an aminocarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, or a carbamoyl group. Wherein at least one of R 210 and R 211 is a hydrogen atom, and R 212 and R 213 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an acylamino group.
    R 214 and R 215 independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
    R216 is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, A sulfamoyl group, an alkylsulfonyl group or a carbamoyl group, Z 5 represents an oxygen atom, a sulfur atom or —N (R 217 ) —, and R 217 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; bb represents an integer of 0 to 4, and bb R 216s may be the same or different.
    R 218 is synonymous with R 210 or represents a sulfamoyl group, and R 220 and R 223 represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aminocarbonylamino group, an alkylsulfonylamino group or an arylsulfonylamino group. R 219 , R 221 and R 222 represent a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group or an acylamino group.
    R 224 represents an alkylcarbonyl group or an arylcarbonyl group.
    M represents an alkali metal or an alkaline earth metal 1/2.
  3. 　請求項１又は２に記載の一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種の化合物を含む着色組成物。 A colored composition comprising at least one compound selected from an alkali metal salt, an alkaline earth metal salt of an azo dye represented by the general formula (1) according to claim 1 or 2, and a tautomer thereof.
  4. 　請求項１又は２に記載の一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体から選択される少なくとも１種の化合物を水性溶媒中に含む着色組成物。 The aqueous solvent contains at least one compound selected from an alkali metal salt, an alkaline earth metal salt of an azo dye represented by the general formula (1) according to claim 1 or 2, and a tautomer thereof. Coloring composition.
  5. 　一般式（１）で表されるアゾ色素のアルカリ金属塩、アルカリ土類金属塩及びその互変異性体の総含有量が、着色組成物の総質量に対して０．０００１～２０質量％である請求項３又は４に記載の着色組成物。 The total content of the alkali metal salt, alkaline earth metal salt and tautomer thereof of the azo dye represented by the general formula (1) is 0.0001 to 20% by mass with respect to the total mass of the coloring composition. The coloring composition according to claim 3 or 4.
  6. 　請求項３～５のいずれか１項に記載の着色組成物を用いた染色方法。 A dyeing method using the coloring composition according to any one of claims 3 to 5.
  7. 　請求項６に記載の染色方法により得られる染色物。 A dyed product obtained by the dyeing method according to claim 6.
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