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WO2011086974A1 - Composition d'encre, procédé d'impression par jet d'encre et corps coloré - Google Patents

Composition d'encre, procédé d'impression par jet d'encre et corps coloré Download PDF

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Publication number
WO2011086974A1
WO2011086974A1 PCT/JP2011/050146 JP2011050146W WO2011086974A1 WO 2011086974 A1 WO2011086974 A1 WO 2011086974A1 JP 2011050146 W JP2011050146 W JP 2011050146W WO 2011086974 A1 WO2011086974 A1 WO 2011086974A1
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Prior art keywords
group
substituted
sulfo
carboxy
formula
Prior art date
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Ceased
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PCT/JP2011/050146
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English (en)
Japanese (ja)
Inventor
彬 川口
貴彦 松井
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2011549962A priority Critical patent/JP5690747B2/ja
Publication of WO2011086974A1 publication Critical patent/WO2011086974A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0801—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
    • C09B29/0803—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing SO3H, OSO3H
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • C09B31/047—Amino-benzenes containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/068—Naphthols
    • C09B31/072—Naphthols containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/26—Trisazo dyes from other coupling components "D"
    • C09B31/28—Heterocyclic compounds
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
    • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
    • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

  • the present invention includes a dye (I) and a dye (II) each represented by a specific formula, and further containing at least three types of dyes, a dye (III) represented by a specific formula
  • the present invention relates to a composition, an ink jet recording method using the ink composition, and a colored body colored with the ink composition.
  • a recording method using an inkjet printer which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do.
  • This method is quiet because it does not generate sound because the recording head and the recording material are not in direct contact.
  • water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks for fountain pens, felt pens, and the like and inks for ink-jet recording.
  • a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
  • These inks provide a recorded image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on recording materials, have little bleeding, and have storage stability. It is required to be excellent.
  • the water-soluble dye used is required to have particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink.
  • the formed image is required to have image fastness such as water resistance, light resistance, gas resistance and moisture resistance.
  • the gas resistance is resistance to a phenomenon in which ozone gas having an oxidizing action existing in the air acts on the dye in the recording paper and discolors the printed image.
  • examples of the oxidizing gas having this kind of action include NOx, SOx, etc.
  • ozone gas is a main causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recording images. It is said that. For this reason, ozone gas resistance tends to be regarded as the most important among gas resistances.
  • a material such as a porous white inorganic material is often used for the ink receiving layer provided on the surface of the photographic image-dedicated inkjet paper for the purpose of accelerating ink drying and reducing bleeding at high image quality.
  • the discoloration due to ozone gas is noticeable. Since the discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, the improvement of ozone gas resistance is one of the most important issues in the ink jet recording method.
  • the ink composition used for inkjet recording and the colored bodies colored thereby will be light-resistant, ozone-gas resistant, moisture-resistant, water-resistant. There is a strong demand for further improvement.
  • Ink of various hues is prepared from various pigments, and among them, black ink is an important ink used for both monocolor and full-color images.
  • black ink is an important ink used for both monocolor and full-color images.
  • a black ink is prepared by blending a plurality of various pigments.
  • the hue differs depending on the medium (recording material) as compared to the case where the ink is prepared with a single dye.
  • Decomposition of the dye by light or ozone gas In particular, there is a problem that discoloration becomes large.
  • Patent Documents 1 to 4 As black ink compositions for inkjet having various durability of printed materials, for example, those disclosed in Patent Documents 1 to 4 have been proposed.
  • This ink composition has a very good hue as black, and is an ink composition in which the image fastness of the printed matter has been greatly improved.
  • Patent Document 5 discloses an ink composition containing at least two kinds of a short wave dye S and a long wave dye L, both of which are water-soluble, but an ink composition containing three kinds of dyes. Is not disclosed.
  • JP 2009-84346 A International Publication No. 2009/069279 International Publication No. 2005/097912 International Publication No. 2007/077931 Special table 2009-512737
  • the present invention provides a water-based black ink composition that gives a neutral black color with low saturation and no tint, a high density of the printed image, and a black recorded image excellent in ozone gas resistance of the recorded image. For the purpose.
  • the present inventors each contain a dye (I) and a dye (II) each represented by a specific formula, and further represented by a specific formula.
  • the present inventors have found that an ink composition containing at least three kinds of dyes (III) to solve the above-mentioned problems has been completed.
  • the present invention 1) As the dye (I), at least one compound represented by the following formula (2) or a tautomer thereof, or a salt thereof, and as the dye (II), at least 1 having ⁇ max in the range of 380 to 460 nm.
  • R 101 and R 102 each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group; an N, N-dialkylaminosulfonyl group; Phospho group; nitro group; acyl group; ureido group; C1-C4 alkyl group; C1-C4 alkyl group substituted by hydroxy group or C1-C4 alkoxy group; C1-C4 alkoxy group;
  • R 105 represents a cyano group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxycarbonyl group; or a phenyl group;
  • R 106 , R 107 , and R 108 are each independently a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a C4 alkoxy group and a sulfo group; or an acylamino group.
  • R 201 to R 204 each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; a C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; a mono C1-C4 alkylamino group; a di-C1-C4 An alkylamino group; a mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; from the group consisting of a hydroxy group, a sulfo group, and a
  • n is 0 or 1;
  • R 1 represents a carboxy group; a C1-C4 alkyl group; a C1-C4 alkyl group substituted with a carboxy group; a phenyl group; or a phenyl group substituted with a sulfo group;
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group,
  • R 3 and R 4 each independently represent a hydrogen atom; a chlorine atom; a sulfo group; a C1-C4 alkyl group; or a C1-C4 alkoxy group;
  • R 5 to R 7 are each independently hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; C1-C6 alkyl group; C1-C4 alkoxy group; hydroxy group, C1-C4 A C1-C4 alkoxy group substituted
  • the substitution position of the nitro group is the 4-position, with the substitution position of the azo group on the benzene ring substituted by the nitro group being the 1-position
  • the substitution position of the group A is the 4-position with the substitution position of the azo group on the benzene ring substituted by the group A as the 1-position
  • x is 1
  • R 101 and R 103 are sulfo groups
  • n is 1, R 1 is a C1-C4 alkyl group or a phenyl group; R 2 is a cyano group or a carbamoyl group, R 3 is a sulfo group, R 5 is a C1-C4 alkoxy group substituted with a sulfo group, R 6 is a hydrogen atom, R 7 is a C1-C4 alkyl group, R 9 is a hydrogen atom or a sulfo group, R 10 is a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a C1-C4 alkoxy group, or a C1-C4 alkylsulfonyl group,
  • R 11 is a hydrogen atom or a sulfo group
  • R 2010 and R 2030 are each independently a C1-C4 alkoxy group substituted with a hydrogen atom or a sulfo group
  • R 2020 and R 2040 are C1-C4 alkyl groups
  • R 2050 is a C1-C4 alkylamino group substituted with a sulfo group
  • a phenylmethylamino group The ink composition according to 4) above, which is a phenylmethylamino group; or a phenylmethylamino group substituted with a carboxy group;
  • the substitution position of the nitro group is the 4-position, with the substitution position of the azo group on the benzene ring substituted by the nitro group being the 1-position
  • the substitution position of the group A is the 4-position with the substitution position of the azo group on the benzene ring substituted by the group A as the 1-position
  • x is 1
  • R 101 , R 103 , and R 107 are sulfo groups
  • R 102 is a hydrogen atom
  • R 104 is a hydrogen atom, a chlorine atom, or a sulfo group
  • the ink composition according to any one of 1) to 6) above, wherein R 105 is a carboxy group;
  • m is 1, R 401 is a carboxy group or a phenyl group, R 405 is a C1-C4 alkoxy group substituted with a sulfo group, R 406 is a hydrogen atom, R 407 is a C1-C4 alkyl group, R 409 is a hydrogen atom or a sulfo group, R 410 is a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a C1-C4 alkoxy group, or a C1-C4 alkylsulfonyl group, R 411 is a hydrogen atom or a sulfo group, Any of 1) to 7) above, wherein the group D is a phenyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, a C1-C4 alkyl group, and a C1-C4 al
  • the dye (I) is a compound represented by the formula (2) or a tautomer thereof, or a salt thereof, and in the formula (2),
  • the substitution position of the nitro group is the 4-position, with the substitution position of the azo group on the benzene ring substituted by the nitro group being the 1-position
  • the substitution position of the group A is the 4-position with the substitution position of the azo group on the benzene ring substituted by the group A as the 1-position
  • x is 1, R 101 , R 103 , and R 107 are sulfo groups, R 102 , R 106 , and R 108 are hydrogen atoms, R 104 is a chlorine atom, R 105 is a carboxy group
  • the dye (II) is a compound represented by the formula (4) or a salt thereof, and in the formula (4), R 201 and R 203 are a C1-C4 alkoxy group substituted with a hydrogen atom or a sulfo group, R
  • the ratio of the dye (I) is 10 to 75% by mass
  • the ratio of the dye (II) is 10 to 40% by mass
  • the dye (III) The ink composition according to any one of 1) to 9) above, wherein the ratio is from 10 to 60% by mass
  • the total mass of the dye (I), the dye (II), and the dye (III) contained in the ink composition is 0.1 to 20% by mass with respect to the total mass of the ink composition.
  • the ink composition according to any one of 1) to 10) above,
  • a water-based black ink composition that exhibits a neutral black color with low saturation and no color, a high density of the printed image, and a black recorded image with excellent ozone gas resistance of the recorded image. It was.
  • acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids.
  • the ink composition of the present invention contains pigment (I) and pigment (II) each represented by a specific formula, and further contains at least three types of pigments, pigment (III) represented by a specific formula. These are aqueous black ink compositions each containing at least one kind.
  • the pigment (I) contained in the ink composition of the present invention will be described.
  • the dye (I) contained in the ink composition of the present invention is a compound represented by the above formula (2), a tautomer thereof, or a salt thereof. Similar to the compounds represented by formula (1) and formula (6) described later, the compound represented by formula (2) also has a tautomer, and these isomers are also included in dye (I). . Unless otherwise specified, in the following specification, in order to avoid complication, “a compound represented by the formula (2) or a tautomer thereof, or a salt thereof” includes the “formula (2)”. It will be described simply as “represented compound”.
  • the dye (I) is composed of at least one compound represented by the formula (2), and may be a dye composed of a single compound represented by the formula (2), or a mixture of dyes composed of a plurality of compounds. It may be.
  • the compound represented by Formula (2) is a water-soluble dye.
  • x is 0 or 1, and 1 is preferable.
  • examples of the halogen atom in R 101 and R 102 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a chlorine atom is more preferable.
  • examples of the N-alkylaminosulfonyl group in R 101 and R 102 include linear or branched ones, and linear ones are preferred. Specific examples include N-C1-C4 alkylaminosulfonyl groups such as N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-butyl) aminosulfonyl group and the like.
  • the N, N-dialkylaminosulfonyl group in R 101 and R 102 is N, N-diC1- such as N, N-dimethylaminosulfonyl group and N, N-di (n-propyl) aminosulfonyl group. C4 alkylaminosulfonyl group; etc. are mentioned.
  • examples of the acyl group for R 101 and R 102 include an alkylcarbonyl group and an arylcarbonyl group.
  • alkylcarbonyl group include a linear or branched alkyl group, usually a C1-C6 alkylcarbonyl group, preferably a C1-C4 alkylcarbonyl group, and a linear one is preferable.
  • Specific examples include straight chain such as acetyl (methylcarbonyl), propionyl (ethylcarbonyl), butyryl (propylcarbonyl); branched chain such as isobutyryl (isopropylcarbonyl); and the like.
  • the arylcarbonyl group include those having an aryl moiety having C6-C10, and specific examples include benzoyl, naphthoyl and the like.
  • examples of the C1-C4 alkyl group for R 101 and R 102 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and t-butyl; Of these, methyl is particularly preferred.
  • any carbon atoms of the C1-C4 alkyl group in the R 101 and R 102 And those substituted with a hydroxy group or a C1-C4 alkoxy group.
  • alkyl moiety include linear or branched ones, and linear ones are preferred.
  • hydroxy C1-C4 alkyl groups such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl; methoxyethyl, 2-ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, And C1-C4 alkoxy C1-C4 alkyl groups such as methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, n-propoxybutyl, and the like.
  • examples of the C1-C4 alkoxy group for R 101 and R 102 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, sec-butoxy and t-butoxy; Of these, methoxy is particularly preferred.
  • a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 101 and R 102 Includes those obtained by substituting these groups for any carbon atom of the C1-C4 alkoxy group in R 101 and R 102 .
  • the position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with two or more oxygen atoms.
  • hydroxy C1-C4 alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy C1-C4 alkoxy C1-C4 alkoxy groups such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; sulfo C1-C4 alkoxy such as 2-sulfoethoxy, 3-sulfopropoxy and 4-sulfobutoxy Groups; carboxy C1-C4 alkoxy groups such as carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy; and the like. Of these, a sulfo C1-C4 alkoxy group is preferred.
  • examples of the acylamino group in R 101 and R 102 include an alkylcarbonylamino group and an arylcarbonylamino group.
  • the alkylcarbonylamino group includes a linear or branched alkyl group, usually a C1-C6 alkylcarbonylamino group, preferably a C1-C4 alkylcarbonylamino group, and a linear one is preferable.
  • alkyl moieties such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), butyrylamino (propylcarbonylamino), etc .; alkyl moieties such as isobutyrylamino (isopropylcarbonylamino) Is branched chain; and the like.
  • alkyl moieties such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), butyrylamino (propylcarbonylamino), etc .
  • alkyl moieties such as isobutyrylamino (isopropylcarbonylamino) Is branched chain; and the like.
  • arylcarbonylamino group include those having a C6-C10 carbon atom in the aryl moiety, and specific examples include benzoylamino, naphthoylamino, and
  • R 101 and R 102 in formula (2) are preferably a hydrogen atom, a carboxy group, a sulfo group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group substituted with a sulfo group. More preferably, either one is a hydrogen atom and the other is a group other than a hydrogen atom; or one is a sulfo group and the other is a C1-C4 alkoxy group substituted with a sulfo group; the former is more preferable. Particularly preferably, either one is a hydrogen atom and the other is a sulfo group.
  • the substitution positions of the nitro group, R 101 and R 102 substituted on the same benzene ring are not particularly limited.
  • Preferable examples include the following combinations (a) to (d) with the substitution position of the azo group substituted on the benzene ring as the 1-position, and the combination (a) is particularly preferable.
  • C) The nitro group is in position 2, R 101 is in position 4, and R 102 is in position 6.
  • D The nitro group is in position 3, R 101 is in position 2, and R 102 is in position 5.
  • examples of the halogen atom in R 103 and R 104 include the same ones as described in the above “halogen atom in R 101 and R 102 ”, including preferable ones.
  • examples of the C1-C4 alkyl group for R 103 and R 104 include the same ones as described above for “C1-C4 alkyl group for R 101 and R 102 ”, including preferable ones. It is done.
  • examples of the C1-C4 alkoxy group in R 103 and R 104 include the same ones as described in the above “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group Is described in the above-mentioned “C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 101 and R 102 ”. And the same including preferred ones.
  • R 103 and R 104 in the formula (2) are preferably a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, or a C1-C4 alkoxy group. More preferably, one of which is a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, or a C1-C4 alkoxy group and the other is a carboxy group or a sulfo group.
  • any one is a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, or a C1-C4 alkoxy group, the other is a sulfo group; or one of them is a hydrogen atom,
  • the other is a carboxy group.
  • Particularly preferred are those in which either one is a halogen atom and the other is a sulfo group.
  • substitution positions of R 103 , R 104 and group A substituted on the same benzene ring are not particularly limited. Preferred examples include the following combinations (e) to (h) with the substitution position of the azo group substituted on the benzene ring as the 1-position, and the combination (e) is particularly preferable.
  • E) One of R 103 and R 104 is the 3rd position, the other is the 5th position, and the group A is the 4th position.
  • One of R 103 and R 104 is in the 2nd position, the other is in the 5th position, and the group A is in the 4th position.
  • R 103 and R 104 are in the 2nd position, the other is in the 4th position, and the group A is in the 5th position.
  • R 103 and R 104 is the 3rd position, the other is the 4th position, and the group A is the 5th position.
  • the group A is a group represented by the above formula (3).
  • examples of the C1-C4 alkyl group for R 105 include the same ones as described above for “C1-C4 alkyl group for R 101 and R 102 ”, including preferable ones.
  • examples of the C1-C4 alkoxycarbonyl group for R 105 include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include linear chains such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, and n-butoxycarbonyl; branched chains such as isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and t-butoxycarbonyl. And the like.
  • R 105 in Formula (3) is preferably a cyano group, a carboxy group, a C1-C4 alkyl group, or a phenyl group, more preferably a cyano group or a carboxy group, and even more preferably a carboxy group.
  • examples of the halogen atom in R 106 , R 107 , and R 108 include the same ones as described in the above-mentioned “halogen atom in R 101 and R 102 ”, including preferable ones.
  • the C1-C4 alkyl group in R 106 , R 107 , and R 108 includes those described in the above-mentioned “C1-C4 alkyl group in R 101 and R 102 ”, preferable ones, and the like. The same can be mentioned.
  • the C1-C4 alkoxy group in R 106 , R 107 , and R 108 includes those described in the above-mentioned “C1-C4 alkoxy group in R 101 and R 102 ”, preferable ones, and the like. The same can be mentioned.
  • examples thereof include those in which any group of the C1-C4 alkoxy group in R 106 , R 107 , and R 108 is substituted with these groups.
  • the position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with two or more oxygen atoms.
  • hydroxy C1-C4 alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy C1-C4 alkoxy C1-C4 alkoxy groups such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy and n-propoxybutoxy; sulfo C1-C4 alkoxy groups such as 3-sulfopropoxy and 4-sulfobutoxy; It is done.
  • examples of the acylamino group for R 106 , R 107 , and R 108 include the same ones as described above for “acylamino group for R 101 and R 102 ”, including preferable ones.
  • R 106 , R 107 and R 108 in the formula (3) are preferably a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a C1-C4 alkyl group, or a C1-C4 alkoxy group. More preferably, any one of which is a hydrogen atom and the remainder is selected from a halogen atom, a carboxy group, and a sulfo group; or any two of which are a hydrogen atom and the remaining one is a sulfo group; The latter is particularly preferred.
  • the substitution positions of R 106 , R 107 and R 108 substituted on the same benzene ring are not particularly limited.
  • the following combinations (i) to (k) are exemplified with the substitution position of the nitrogen atom (of the pyrazolone ring) substituted on the benzene ring as the 1-position.
  • (I) When all three are other than hydrogen atoms, the 2nd, 4th and 5th positions; or the 2nd, 4th and 6th positions.
  • groups other than a hydrogen atom are the 2nd and 4th positions; the 2nd and 5th positions; the 3rd and 5th positions.
  • K When one is a group other than a hydrogen atom and two are hydrogen atoms, the group other than a hydrogen atom is in the 4-position.
  • the pigment (II) contained in the ink composition of the present invention will be described.
  • the dye (II) contained in the ink composition of the present invention is a compound represented by the above formula (4) or a salt thereof.
  • “compound represented by formula (4)” including “a compound represented by formula (4) or a salt thereof” is simplified. To describe.
  • the dye (II) is composed of at least one compound represented by the formula (4), and may be a dye composed of a single compound represented by the formula (4), or a mixture of dyes composed of a plurality of compounds. It may be.
  • the compound represented by Formula (4) is a water-soluble dye.
  • “Having ⁇ max in the range of 380 to 460 nm” means that the pH of the aqueous solution containing the dye is in the range of 5.5 to 8.0, and the absorbance at ⁇ max (maximum absorption wavelength) in water is 0.5. Means that the dye has a ⁇ max in the range of 380 to 720 nm in the range of 380 to 460 nm when the concentration of the aqueous dye solution is measured so that the absorbance is in the range of 1.5 to 1.5. .
  • the water-soluble compound (pigment) having such physical properties is usually a yellow-orange-brown-red dye, and the compound represented by the formula (4) is also a dye having the same hue.
  • examples of the C1-C4 alkyl group in R 201 to R 204 include the same ones as those described above in “C1-C4 alkyl group in R 101 and R 102 ”, including preferable ones. It is done.
  • examples of the C1-C4 alkoxy group in R 201 to R 204 include the same ones as described in the above “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • R 201 to R 204 are substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group.
  • the C1-C4 alkoxy group include those in which any carbon atom in the “C1-C4 alkoxy group in R 201 to R 204 ” is substituted with these groups.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with two or more oxygen atoms.
  • hydroxy C1-C4 alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy C1-C4 alkoxy C1-C4 alkoxy groups such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 2-sulfo Sulfo C1-C4 alkoxy groups such as ethoxy, 3-sulfopropoxy, 4-sulfobutoxy; carboxy C1-C such as carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, etc. Alkoxy group; and the like.
  • examples of the mono C1-C4 alkylamino group in R 201 to R 204 include linear or branched ones. Specific examples include straight chain such as methylamino, ethylamino, n-propylamino, n-butylamino; branched chain such as isopropylamino, isobutylamino, sec-butylamino, t-butylamino; etc. Is mentioned.
  • examples of the di-C1-C4 alkylamino group in R 201 to R 204 include linear or branched ones.
  • the two “C1-C4 alkyl” moieties may be the same or different, but are preferably the same.
  • Specific examples include linear ones such as dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; diisopropylamino, diisobutylamino, di-sec-butylamino, di-t-butylamino, etc.
  • the mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 is the above “ Examples thereof include those in which any carbon atom in the “mono C1-C4 alkylamino group in R 201 to R 204 ” is substituted with these groups.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but those in which the amino group and the hydroxy group are not substituted on the same carbon atom are preferable.
  • Specific examples include hydroxy-substituted mono C1-C4 alkylamino groups such as 2-hydroxyethylamino and 2-hydroxypropylamino; sulfo-substituted mono such as 2-sulfoethylamino, 3-sulfopropylamino and 4-sulfobutylamino.
  • C1-C4 alkylamino group carboxy-substituted mono C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino; and the like.
  • the di C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 is the above “ Examples thereof include those in which any carbon atom in “di-C1-C4 alkylamino group in R 201 to R 204 ” is substituted with these groups.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but those in which the amino group and the hydroxy group are not substituted on the same carbon atom are preferable. Moreover, although the kind of substituent may be the same or different, the same thing is preferable.
  • hydroxy-substituted diC1-C4 alkylamino groups such as 2,2′-dihydroxydiethylamino
  • sulfo-substituted diC1-C4 alkylamino groups such as 3,3′-disulfodipropylamino
  • 2,2 ′ A carboxy-substituted diC1-C4 alkylamino group such as dicarboxydiethylamino
  • examples of the C1-C4 alkylcarbonylamino group in R 201 to R 204 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight-chain alkyl moieties such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), butyrylamino (propylcarbonylamino), pentylylamino (butylcarbonylamino); isobutyrylamino (Alkyl moieties such as (isopropylcarbonylamino) and pivaloylamino (t-butylcarbonylamino) are branched;
  • examples of C1-C4 alkyl carbonyl amino group substituted by a carboxy group any alkyl moiety in the "C1-C4 alkyl carbonyl amino group from R 201 in R 204" In which the carbon atom is substituted with a carboxy group.
  • the number of substitution of the carboxy group is usually 1 or 2, and preferably 1.
  • Specific examples include carboxy C1-C4 alkylcarbonylamino groups such as 2-carboxyethylcarbonylamino and 3-carboxypropylcarbonylamino.
  • examples of the mono C1-C4 alkylureido group in R 201 to R 204 include those in which the alkyl moiety is linear or branched.
  • the substitution position of the C1-C4 alkyl is not particularly limited, but is preferably substituted with “N ′”.
  • the “mono C1-C4 alkylureido group” means a “C1-C4 alkyl NH—CO—NH—” group or an “H 2 N—CO—N (C1-C4 alkyl) —” group.
  • the nitrogen atom directly bonded to the benzene ring is defined as “N”, and the nitrogen atom bonded to the nitrogen atom via a carbonyl (CO) group is defined as “N ′”.
  • N ′ the substitution position of the C1-C4 alkyl is “N ′” for the former and “N” for the latter.
  • Specific examples include N′-ethylureido, N′-propylureido, N′-butylureido and the like; N′-isopropylureido, N′-isobutylureido, N′-t-butylureido, etc. Branched chain; and the like.
  • examples of the di-C1-C4 alkylureido group in R 201 to R 204 include those in which the alkyl moiety is linear or branched.
  • the substitution position of the C1-C4 alkyl is not particularly limited, but according to the substitution position in the “mono C1-C4 alkylureido group”, one each for “N” and “N ′”, or two for “N ′”. And the latter is preferred.
  • the two C1-C4 alkyls may be the same or different, but the same is preferable.
  • N ′ N′-dimethylureido, N ′, N′-diethylureido, N ′, N′-dipropylureido, N ′, N′-dibutylureido and the like; N ′ , N′-diisopropylureido, N ′, N′-diisobutylureido and the like;
  • the mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 is the above “ from R 201 to any carbon atom of the alkyl moiety in mono-C1-C4 alkyl ureido group "for R 204, these groups include those substituted.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with a nitrogen atom and a hydroxy group.
  • N′-mono (hydroxyC1-C4) alkylureido groups such as N′-2-hydroxyethylureido and N′-3-hydroxypropylureido; N′-2-sulfoethylureido, N′- N′-mono (sulfo C1-C4 alkyl) ureido groups such as 3-sulfopropylureido; N′-carboxymethylureido, N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-4 -N'-mono (carboxy C1-C4 alkyl) ureido groups such as carboxybutylureido; and the like.
  • the di C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 is the above “ Examples thereof include those in which any carbon atom of the alkyl moiety in the “di-C1-C4 alkylureido group in R 201 to R 204 ” is substituted with these groups.
  • the number of substituents is usually one or two, preferably one.
  • the position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with a nitrogen atom and a hydroxy group.
  • substituents when it has two or more substituents, the kind may be same or different, but the same thing is preferable.
  • Specific examples include those substituted with a hydroxy group such as N ′, N′-di (2-hydroxyethyl) ureido, N ′, N′-di (2-hydroxypropyl) ureido; N ′, N′— And those substituted with a sulfo group such as di (3-sulfopropyl) ureido; those substituted with a carboxy group such as N ′, N′-di (carboxymethyl) ureido; and the like.
  • the benzene ring in R 201 to R 204 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylamino group include those having 1 to 3, preferably 1 or 2 of these substituents.
  • the types thereof may be the same or different.
  • Specific examples include those substituted with a chlorine atom such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, 4-t-butylphenylamino Substituted with a C1-C4 alkyl group such as 2-nitrophenylamino, substituted with a nitro group such as 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4- Substituted with a sulfo group such as disulfophenylamino, 3,5-disulfophenylamino; 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, 3,5-dicarboxy And the like substituted with a carboxy group such as phenylamino;
  • the benzene ring in R 201 to R 204 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the benzoylamino group include those having 1 to 3, preferably 1 or 2 of these substituents.
  • the types may be the same or different, but the same are preferable.
  • Specific examples include those substituted with a chlorine atom such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorobenzoylamino; 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoyl Substituted with a C1-C4 group such as amino; substituted with a nitro group such as 2-nitrobenzoylamino, 4-nitrobenzoylamino, 3,5-dinitrobenzoylamino; 2-sulfobenzoylamino, 4- Those substituted with a sulfo group such as sulfobenzoylamino; those substituted with a carboxy group such as 2-carboxybenzoylamino, 4-carboxybenzoylamino, 3,5-dicarboxybenzoylamino; and the like.
  • the benzene ring in R 201 to R 204 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylsulfonylamino group include those having 1 to 3, preferably 1 or 2, and more preferably 1 of these substituents.
  • the types of substituents may be the same or different, but the same is preferable.
  • Specific examples include those substituted with a chlorine atom such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-t-butylphenylsulfonylamino, etc.
  • Substituted with a C1-C4 alkyl group substituted with a nitro group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino; 3-sulfophenylsulfonylamino, 4- Those substituted with a sulfo group such as sulfophenylsulfonylamino; those substituted with a carboxy group such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino; and the like.
  • a nitro group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino; 3-sulfophenylsulfonylamino, 4- Those substituted with a sulfo group such as sulf
  • R 201 and R 203 are preferably a C1-C4 alkoxy group substituted with a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a sulfo group, and more preferably a hydrogen atom or a sulfo group.
  • a C1-C4 alkoxy group is particularly preferred.
  • R 202 and R 204 are A hydrogen atom; a ureido group; a C1-C4 alkyl group; a C1-C4 alkoxy group; a C1-C4 alkylcarbonylamino group; a C1-C4 alkylcarbonylamino group substituted with a carboxy group; a hydroxy group, a sulfo group, and a carboxy group
  • a particularly preferred combination of R 201 to R 204 is a combination in which when R 201 and R 203 are a hydrogen atom, R 202 and R 204 are a C1-C4 alkyl group; or R 201 and R 203 And when R is a C1-C4 alkoxy group substituted with a sulfo group, R 202 and R 204 are C1-C4 alkyl groups.
  • the substitution positions of R 201 to R 204 are not particularly limited, but in each benzene ring substituted by these, the substitution position of the nitrogen atom bonded to the triazine ring is the 1st position, and the substitution position of the azo group is As the 4-position, one is preferably substituted at the 2-position and the other at the 5-position, more preferably R 201 and R 203 are substituted at the 2-position, and R 202 and R 204 are respectively substituted at the 5-position.
  • examples of the mono C1-C4 alkylamino group for R 205 include the same groups as those described above for the “mono C1-C4 alkylamino group for R 201 to R 204 ”.
  • the mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 205 is the above “from R 201.
  • the di C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 205 is the above-mentioned “from R 201 The same as those described in the “di-C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 204 ”, including preferable examples. Things.
  • the phenylamino group substituted with 1 include those having 1 to 3, preferably 1 or 2 of these substituents. When having a plurality of substituents, the types thereof may be the same or different.
  • Specific examples include those substituted with a chlorine atom such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, 4-t-butylphenylamino Substituted with a C1-C4 alkyl group such as 2-methoxyphenylamino, 4-methoxyphenylamino, 2,5-dimethoxyphenylamino, 4-ethoxyphenylamino, etc.
  • Substituted with a nitro group such as 2-nitrophenylamino, 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 3,5-disulfophenyl; Substituted with a sulfo group such as amino; 2-carboxyphenylamino, 4 Carboxyphenyl amino, 2,5-di-carboxyphenylamino, those substituted with 3,5-carboxyphenyl carboxy group of the amino or the like; and the like.
  • a nitro group such as 2-nitrophenylamino, 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 3,5-disulfophenyl; Substituted with a sulfo group such as amino; 2-carboxyphenylamino,
  • the benzene ring in R 205 is a sulfo group, a carboxy group, a nitro group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, and a trifluoromethyl group.
  • the types of substituents may be the same or different.
  • a sulfo-substituted phenylmethylamino group such as 4-sulfophenylmethylamino, 2,4-disulfophenylmethylamino, etc., with the substitution position of “methylamino” on the benzene ring being the 1-position;
  • Substituted with a carboxy group such as phenylmethylamino, 4-carboxyphenylmethylamino, 2,5-dicarboxyphenylmethylamino, 3,5-dicarboxyphenylmethylamino; 2-nitrophenylmethylamino, 4-nitro
  • a nitro group such as phenylmethylamino
  • substituted with a C1-C4 alkyl group such as 2-methylphenylmethylamino, 4-methylphenylmethylamino, 4-t-butylphenylmethylamino
  • R 205 when R 205 is a naphthylmethylamino group, the substitution position of “methylamino” on the naphthalene ring is not particularly limited. 1-naphthylmethylamino group or 2-naphthylmethylamino group is preferable.
  • the naphthalene ring in R 205 is substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, a C1-C4 alkyl group, a C1-C4 alkoxy group, and a chlorine atom.
  • the naphthylmethylamino group includes one to three, preferably one or more of these substituents at any position on the naphthalene ring of the naphthylamino group described in the above-mentioned “ R205 is naphthylmethylamino group”. What has two is mentioned.
  • the types of substituents may be the same or different, but the same type is preferred.
  • sulfo group such as 4-sulfo-1-naphthylmethylamino, 1-sulfo-2-naphthylmethylamino, 4,8-disulfo-1-naphthylmethylamino; 4-carboxy- Substituted with a carboxy group such as 1-naphthylmethylamino, 1-carboxy-2-naphthylmethylamino; 4-methyl-1-naphthylmethylamino, 1-methyl-2-naphthylmethylamino, 4-ethyl-1 Substituted with a C1-C4 alkyl group such as naphthylmethylamino, 1-ethyl-2-naphthylmethylamino; 4-methoxy-1-naphthylmethylamino, 1-methoxy-2-naphthylmethylamino, 4-ethoxy Substit
  • R 205 is a mono C1-C4 alkylamino group substituted with a sulfo group; a diC1-C4 alkylamino group substituted with a carboxy group; a phenylamino group; a phenylamino group substituted with a sulfo group; Phenylmethylamino group; at least one selected from the group consisting of a sulfo group, a carboxy group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, and a trifluoromethyl group; A phenylmethylamino group substituted with various groups; a naphthylmethylamino group; or a naphthylmethylamino group in which a naphthalene ring is substituted with a sulfo group; More preferably, it is a mono C
  • substitution positions of the four sulfo groups whose substitution positions are not specified are not particularly limited.
  • the sulfo group substituted on the benzene ring having one azo bond is preferably substituted at the 2-position, 3-position or 4-position with the substitution position of the azo bond as the 1-position, and substituted at the 4-position.
  • a sulfo group substituted with a benzene ring having two azo bonds has a substitution position of an azo bond that bonds the benzene ring and a benzene ring substituted with R 201 and R 202 or R 203 and R 204.
  • the 1-position is preferably substituted at the 2- or 3-position, and preferably substituted at the 2-position.
  • One of the preferable compounds represented by the above formula (4) is a compound represented by the above formula (8).
  • examples of the C1-C4 alkyl group for R 2010 and R 2030 include the same ones as described above for “C1-C4 alkyl group for R 101 and R 102 ”, including preferable ones. It is done.
  • examples of the C1-C4 alkoxy group for R 2010 and R 2030 include the same ones as described above for “C1-C4 alkoxy group for R 101 and R 102 ”, including preferable ones. It is done.
  • R 2010 and R 2030 are substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group.
  • the C1-C4 alkoxy group is at least one selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 201 to R 204 above. And the same as those described in “C1-C4 alkoxy group substituted with a group of the above”.
  • R 2010 and R 2030 are each a hydrogen atom; or at least one selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group C1-C4 alkoxy groups substituted with different groups are preferred. More preferably, it is a C1-C4 alkoxy group substituted with a hydrogen atom or a sulfo group.
  • examples of the C1-C4 alkyl group for R 2020 and R 2040 include the same ones as described above for “C1-C4 alkyl group for R 101 and R 102 ”, including preferable ones. It is done.
  • R 2050 represents the same meaning as R 205 in formula (4), including preferred ones.
  • the combination of the R 2010 to R 2050, compounds in combination with each other preferred and more preferably, a combination of each other more preferred are more preferred. The same applies to preferable combinations, preferable combinations and more preferable combinations.
  • R 2010 and R 2030 are each independently a C1-C4 alkoxy group substituted with a hydrogen atom or a sulfo group
  • R 2020 and R 2040 are a C1-C4 alkyl group
  • R 2050 is a mono C1-C4 amino group substituted with a sulfo group, a di C1-C4 alkylamino group substituted with a carboxy group, a phenylamino group, a phenylamino group substituted with a sulfo group, a phenylmethylamino group, or , A combination of phenylmethylamino groups in which the benzene ring is substituted with a sulfo group or a carboxy group.
  • R 2050 is replaced by a mono C1-C4 amino group substituted with a sulfo group, a phenylamino group, a phenylmethylamino group, or a phenylmethylamino group in which the benzene ring is substituted with a sulfo group. More preferred.
  • the pigment (III) contained in the ink composition of the present invention will be described.
  • the dye (III) contained in the ink composition of the present invention is represented by the compound represented by the above formula (1) or a tautomer thereof, or a salt thereof, and / or the above formula (6). It is a compound or a tautomer thereof, or a salt thereof. Unless otherwise specified, in the following specification, in order to avoid complication, “a compound represented by the formula (1) or a tautomer thereof, or a salt thereof” includes the “formula (1)”. It will be described simply as “represented compound”. In addition, “compound represented by formula (6)” including “a compound represented by formula (6) or a tautomer thereof, or a salt thereof” is simply described.
  • the dye (III) is composed of at least one compound represented by the formula (1) or the formula (6), and may be a dye composed of a single compound represented by the formula (1) or the formula (6). It may be a mixture of pigments composed of a plurality of compounds. Furthermore, it may be a mixture of dyes of the compounds represented by the formulas (1) and (6), and one or both of the dyes represented by a plurality of formulas (1) and (6) It may be a mixture. Preferably, any one of the compounds represented by formula (1) or formula (6) is used as the dye (III).
  • the compounds represented by formula (1) and formula (6) are both water-soluble dyes.
  • the compound represented by the formula (1) has a tautomer, and in addition to the formula (1), isomers represented by the following formulas (9) to (13) and the like can be considered. These tautomers are also included in the compound represented by the formula (1).
  • n, R 1 to R 11 , and a to c all have the same meaning as in the above formula (1).
  • n is 0 or 1, and 1 is preferable.
  • examples of the C1-C4 alkyl group for R 1 include the same groups as those described above for the “C1-C4 alkyl group for R 101 and R 102 ”.
  • Preferred specific examples include methyl , Ethyl, n-propyl and tert-butyl; more preferably methyl and n-propyl; and still more preferably methyl.
  • a carboxy group is substituted on any carbon atom of the alkyl moiety in the “C1-C4 alkyl group in R 1 ” above. Things.
  • the number of substitution of the carboxy group is usually 1 or 2, and preferably 1.
  • the substitution position of the carboxy group is not particularly limited. Specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and the like.
  • the phenyl group substituted with a sulfo group in R 1 is a sulfo group such as 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, etc. Examples include one or two substituted groups.
  • R 1 in Formula (1) is preferably a C1-C4 alkyl group or a phenyl group, and more preferably a C1-C4 alkyl group.
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group, preferably a cyano group or a carbamoyl group, and more preferably a cyano group.
  • examples of the C1-C4 alkyl group in R 3 and R 4 include the same ones as described above in “C1-C4 alkyl group in R 101 and R 102 ”, including preferable ones. .
  • examples of the C1-C4 alkoxy group for R 3 and R 4 include the same groups as those described above for “C1-C4 alkoxy group for R 101 and R 102 ”, including preferable ones. It is done.
  • R 3 and R 4 in formula (1) are preferably a hydrogen atom; a sulfo group; a C1-C4 alkyl group; or a C1-C4 alkoxy group. More preferably, either one is a sulfo group, and the other is a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. More preferably, either one is a sulfo group and the other is a hydrogen atom.
  • examples of the C1-C6 alkyl group for R 5 to R 7 include linear or branched ones.
  • the range of carbon number is usually C1-C6, preferably C1-C5, more preferably C1-C4.
  • Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl; isopropyl, isobutyl, sec-butyl, t-butyl, isoamyl, t-pentyl, 2 , 2-dimethylpropyl, isohexyl, t-hexyl and the like; Among these, methyl, t-butyl, t-pentyl, and 2,2-dimethylpropyl are preferable, methyl and t-butyl are more preferable, and t-butyl is more preferable.
  • examples of the C1-C4 alkoxy group in R 5 to R 7 include the same ones as described in the above “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • R 5 to R 7 are substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group.
  • the C1-C4 alkoxy group is at least one selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 201 to R 204 above. And the same as those described in “C1-C4 alkoxy group substituted with a group of the above”.
  • examples of the mono C1-C4 alkylamino group in R 5 to R 7 include the same as those described above in the “mono C1-C4 alkylamino group in R 201 to R 204 ”.
  • examples of the di-C1-C4 alkylamino group in R 5 to R 7 include the same ones as those described in the above-mentioned “di-C1-C4 alkylamino group in R 201 to R 204 ”.
  • the mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 5 to R 7 is the above “ And the same as those described in the “mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 ”. It is done.
  • the di C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 5 to R 7 is the above “ And the same groups as those described in the “di-C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 ”. It is done.
  • examples of the C1-C4 alkylcarbonylamino group for R 5 to R 7 include the same groups as those described above for the “C1-C4 alkylcarbonylamino group for R 201 to R 204 ”.
  • the C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group in R 5 to R 7 is the alkyl in the above-mentioned “C1-C4 alkylcarbonylamino group in R 201 to R 204 ”. Those in which these groups are substituted on any carbon atom of the moiety can be mentioned. The number of substitutions of these groups is usually 1 or 2, preferably 1.
  • hydroxy C1-C4 alkylcarbonylamino groups such as hydroxyacetylamino (hydroxymethylcarbonylamino), 2-hydroxyethylcarbonylamino, 3-hydroxypropylcarbonylamino; 2-carboxyethylcarbonylamino, 3-carboxypropyl A carboxy C1-C4 alkylcarbonylamino group such as carbonylamino; and the like.
  • the mono C1-C4 alkylureido group in R 5 to R 7 includes those described in the above-mentioned “mono C1-C4 alkylureido group in R 201 to R 204 ”, preferable ones, and the like. The same can be mentioned.
  • the mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 5 to R 7 is the above “ Those described in “Mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 ”, preferred ones, etc. Including the same thing.
  • the benzene ring in R 5 to R 7 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylamino group at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the above “R 201 to R 204 ”. The same thing as what is described in the "phenylamino group substituted by" and a preferable thing etc. is mentioned.
  • the benzene ring in R 5 to R 7 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the benzoylamino group includes at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the above “R 201 to R 204 ”. The same thing as what is described in the "benzoylamino group substituted by" and a preferable thing etc. is mentioned.
  • the benzene ring in R 5 to R 7 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylsulfonylamino group at least one kind selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the above-mentioned “R 201 to R 204 ”.
  • the same thing as what is described in "the phenylsulfonylamino group substituted by group” and a preferable thing etc. is mentioned.
  • R 5 is a sulfo group; a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group And more preferred is a C1-C4 alkoxy group substituted with a sulfo group.
  • R 6 is particularly preferably a hydrogen atom.
  • R 7 preferable as R 7 are C1-C6 alkyl group; C1-C4 alkoxy group; C1-C4 alkoxy group substituted with hydroxy group; C1-C4 alkylcarbonylamino group; substituted with sulfo group or carboxy group N′-C1-C4 alkylureido group; benzoylamino group; more preferred is C1-C6 alkyl group.
  • the substitution position of the azo group of the naphthalene ring in which the benzimidazolopyridone ring substituted with R 1 to R 4 is bonded via an azo group is preferably b,
  • the substitution position of the substituted sulfo group is preferably c.
  • examples of the C1-C4 alkyl group in R 9 to R 11 include the same ones as described in the above “C1-C4 alkyl group in R 101 and R 102 ”, including preferable ones. It is done.
  • examples of the C1-C4 alkoxy group in R 9 to R 11 include the same ones as described in the above “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 9 to R 11 Is described in the above-mentioned “C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 101 and R 102 ”. And the same ones including preferred ones.
  • examples of the C1-C4 alkylsulfonyl group for R 9 to R 11 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl; branched chains such as isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, and t-butylsulfonyl; Is mentioned.
  • straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl
  • branched chains such as isopropylsulfonyl, isobutylsulfonyl, sec-butyls
  • the C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 9 to R 11 is the above “R Examples thereof include those in which any carbon atom of the alkyl moiety in “C1-C4 alkylsulfonyl group in 9 to R 11 ” is substituted with these groups.
  • the number of substitutions of these groups is usually 1 or 2, preferably 1.
  • Specific examples include those substituted with a hydroxy group such as 2-hydroxyethylsulfonyl and 3-hydroxypropylsulfonyl; substituted with a sulfo group such as 2-sulfoethylsulfonyl, 3-sulfopropylsulfonyl and 4-sulfobutylsulfonyl. And those substituted with a carboxy group such as carboxymethylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl and the like.
  • the benzene ring in R 9 to R 11 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylsulfonyl group include those having 1 to 3, preferably 1 or 2, and more preferably 1 of these substituents.
  • the types of substituents may be the same or different.
  • Specific examples include those substituted with a chlorine atom such as 2-chlorophenylsulfonyl, 4-chlorophenylsulfonyl, etc., with the substitution position of “sulfonyl” on the benzene ring being the 1-position; 2-methylphenylsulfonyl, 4-methylphenyl Substituted with a C1-C4 alkyl group such as sulfonyl, 2,4-dimethylphenylsulfonyl, 4-t-butylphenylsulfonyl; substituted with a nitro group such as 2-nitrophenylsulfonyl, 4-nitrophenylsulfonyl Substituted by a sulfo group such as 3-sulfophenylsulfonyl, 4-sulfophenylsulfonyl, 3,5-disulfophenylsulfonyl; 2-carboxyphenylsulfon
  • At least one of R 9 to R 11 is preferably a group other than a hydrogen atom, and at least one of them is more preferably a sulfo group or a carboxy group.
  • R 9 is preferably a hydrogen atom, a chlorine atom, or sulfo.
  • Preferred as R 10 is a chlorine atom, carboxy, sulfo, nitro, C1-C4 alkyl group, C1-C4 alkoxy, or C1-C4 alkylsulfonyl group.
  • R 11 is preferably a hydrogen atom or sulfo.
  • R 9 to R 11 substitution positions on the benzothiazole ring are as follows: R 9 is the 4th or 5th position, R 10 is the 6th position, and R 11 is the 7th position.
  • the compound which combined the preferable thing described about the substituent of the said Formula (1) is more preferable, and the compound which combined more preferable things is further more preferable.
  • a preferred combination of R 9 to R 11 in formula (1) is a combination of R 9 as a hydrogen atom, R 10 as a sulfo or C1-C4 alkoxy group, and R 11 as a C1-C4 alkoxy group or sulfo.
  • R 9 is in the 4-position
  • R 10 is in the 5-position or 6-position
  • R 11 is in the 6-position or 7-position in the substitution position of the benzothiazole ring.
  • R 9 is a hydrogen atom and the substitution position is 4-position
  • R 10 is sulfo and the substitution position is 5-position
  • R 11 is a C1-C4 alkoxy group and the substitution position is 6-position
  • R 9 is a hydrogen atom and the substitution position is 4-position
  • R 10 is a C1-C4 alkoxy group
  • the substitution position is 6-position
  • R 11 is sulfo
  • the substitution position is 7-position.
  • One of the preferable compounds represented by the above formula (1) is a compound represented by the above formula (7).
  • n and R 1 to R 11 represent the same meaning as in the above formula (1), and include the same ones as described in the above formula (1), including preferable ones. .
  • the compound represented by the formula (6) has a tautomer, and in addition to the formula (6), isomers represented by the following formula (41), formula (42), formula (43) and the like are considered. . These tautomers are also included in the present invention.
  • R 401 to R 411 all have the same meaning as in formula (6).
  • m is 0 or 1, and 1 is preferable.
  • examples of the C1-C4 alkyl group for R 401 include the same ones as described above for “C1-C4 alkyl group for R 101 and R 102 ”, including preferable ones.
  • the C1-C4 alkyl group substituted with a carboxy group in R 401 is preferably the one described in the above-mentioned “C1-C4 alkyl group substituted with a carboxy group in R 1 ”. The same thing is mentioned including etc.
  • examples of the C1-C4 alkoxycarbonyl group for R 401 include the same ones as described above for “C1-C4 alkoxycarbonyl group for R 105 ”, including preferable ones.
  • examples of the phenyl group substituted with a sulfo group in R 401 include those having 1 to 3, preferably 1 or 2, and more preferably 1 sulfo group. Specific examples include 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like.
  • R 401 in Formula (6) is preferably a carboxy group or a phenyl group, and more preferably a carboxy group.
  • the C1-C4 alkyl group in R 405 to R 407 includes those described in the above-mentioned “C1-C4 alkyl group substituted with a carboxy group in R 1 ”, preferred ones, and the like. The same can be mentioned.
  • examples of the C1-C4 alkoxy group in R 405 to R 407 include the same groups as those described above in “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • the C1-C4 alkoxy group is at least one selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 201 to R 204 .
  • examples of the mono C1-C4 alkylamino group in R 405 to R 407 include the same as those described above in the “mono C1-C4 alkylamino group in R 201 to R 204 ”.
  • the mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 405 to R 407 is as described above.
  • examples of the di-C1-C4 alkylamino group in R 405 to R 407 include the same ones as those described in the above-mentioned “di-C1-C4 alkylamino group in R 201 to R 204 ”.
  • the mono C1-C4 alkylamino group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 405 to R 407 is as described above.
  • examples of the C1-C4 alkylcarbonylamino group in R 405 to R 407 include the same groups as those described above for the “C1-C4 alkylcarbonylamino group in R 201 to R 204 ”.
  • the C1-C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group in R 405 to R 407 is the above-mentioned “substituted with a hydroxy group or a carboxy group in R 5 to R 7 ” Examples thereof include those described in the “C1-C4 alkylcarbonylamino group”, including the preferable ones.
  • the mono C1-C4 alkylureido group in R 405 to R 407 includes those described in the above-mentioned “mono C1-C4 alkylureido group in R 201 to R 204 ”, preferable ones, and the like. The same can be mentioned.
  • examples of the mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 405 to R 407 include the above “ Those described in “Mono C1-C4 alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 201 to R 204 ”, preferred ones, etc. Including the same thing.
  • the benzene ring in R 405 to R 407 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylamino group at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the above “R 201 to R 204 ”. The same thing as what is described in the "phenylamino group substituted by" and a preferable thing etc. is mentioned.
  • the benzene ring in R 405 to R 407 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the benzoylamino group includes at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the above “R 201 to R 204 ”. The same thing as what is described in the "benzoylamino group substituted by" and a preferable thing etc. is mentioned.
  • the benzene ring in R 405 to R 407 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the “phenylsulfonylamino group” is selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • R 405 is a sulfo group; a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group More preferably a C1-C4 alkoxy group substituted with a sulfo group.
  • R 406 is particularly preferably a hydrogen atom.
  • R 407 is a mono-substituted group substituted with at least one group selected from the group consisting of a C1-C4 alkyl group; a C1-C4 alkylcarbonylamino group; a hydroxy group, a sulfo group, and a carboxy group.
  • a C1-C4 alkylureido group More preferred are a C1-C4 alkyl group; a C1-C4 alkylcarbonylamino group; and a mono C1-C4 alkylureido group substituted with a sulfo group. More preferred is a C1-C4 alkyl group.
  • the C1-C4 alkyl group in R 409 to R 411 includes those described in the above-mentioned “C1-C4 alkyl group substituted with a carboxy group in R 1 ”, preferred ones, and the like. The same can be mentioned.
  • examples of the C1-C4 alkoxy group in R 409 to R 411 include the same ones as those described above in “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones. It is done.
  • a C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 409 to R 411 Is described in the above-mentioned “C1-C4 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group in R 101 and R 102 ”. And the same ones including preferred ones.
  • the C1-C4 alkylsulfonyl group for R 409 to R 411 is the same as described above for “C1-C4 alkylsulfonyl group for R 9 to R 11 ”, including preferred ones. Is mentioned.
  • the C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 409 to R 411 is the above “R Including those described in “C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in 9 to R 11 ”, preferable ones, and the like. The same can be mentioned.
  • the benzene ring in R 409 to R 411 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group.
  • the phenylsulfonyl group the above “at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in R 9 to R 11 ”
  • the same thing as what is described in the "phenylsulfonyl group substituted by" and a preferable thing etc. is mentioned.
  • R 409 is preferably a hydrogen atom, a sulfo group, or a C1-C4 alkyl group, and more preferably a hydrogen atom or a sulfo group.
  • R 410 is preferably a chlorine atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkylsulfonyl group, more preferably a C1-C4 alkoxy group. is there.
  • R 411 is preferably a hydrogen atom or a sulfo group.
  • Preferable substitution positions of R 409 to R 411 on the benzothiazole ring are R 409 at the 4th or 5th position, R 410 at the 6th position, and R 411 at the 7th position.
  • R 409 to R 411 in formula (6) is as follows: R 409 is a sulfo group and its substitution position is at position 5, R 410 is a C1-C4 alkoxy group and its substitution position is at position 6, and R 411 is hydrogen Or a combination of R 409 is a hydrogen atom, R 410 is a C1-C4 alkoxy group and the substitution position is at position 6, and R 411 is a sulfo group and the substitution position is at position 7.
  • the group D is a phenyl group or a naphthyl group.
  • the phenyl group and naphthyl group may each be substituted with at least one group selected from the group of specific groups described above.
  • the group D is a phenyl group
  • the phenyl group substituted with the specific group is described.
  • the number of substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.
  • the type of the substituent is not particularly limited, but the same one is preferable.
  • the position of the substituent is not particularly limited, but when the position of bonding with the nitrogen atom of the pyrazolone ring is 1-position, the 2-position, 3-position, and 5-position when the number of substituents is 3, the number of substituents is 2 It is preferably substituted at the 2-position and the 4-position, or the 3-position and the 5-position; when the number of substituents is 1, the 4-position.
  • the position of the substituent on the phenyl group in each of the following structures is described with the bonding position with the nitrogen atom of the pyrazolone ring as the first position.
  • Examples of the phenyl group substituted with a hydroxy group in the group D include 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl and the like.
  • Examples of the phenyl group substituted with the sulfo group in the group D include 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like.
  • Examples of the phenyl group substituted with the carboxy group in the group D include 4-carboxyphenyl, 3,5-dicarboxyphenyl, and the like.
  • Examples of the phenyl group substituted with the C1-C4 alkyl group in the group D include 4-methylphenyl, 3-methylphenyl and the like.
  • examples of the C1-C4 alkyl group as a substituent include the same groups as those described above in “C1-C4 alkyl group in R 101 and R 102 ”, including preferable ones.
  • Examples of the phenyl group substituted with the C1-C4 alkoxy group in the group D include 4-methoxyphenyl and the like.
  • examples of the C1-C4 alkoxy group as a substituent include the same groups as those described above in “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones.
  • Examples of the phenyl group substituted with the mono C1-C4 alkylamino group in the group D include 4-methylaminophenyl and the like.
  • examples of the mono-C1-C4 alkylamino group as a substituent include the same groups as those described above in “Mono-C1-C4 alkylamino group in R 201 to R 204 ”, including preferable ones.
  • Examples of the phenyl group substituted with the diC1-C4 alkylamino group in the group D include 4-dimethylaminophenyl and the like.
  • Examples of the di-C1-C4 alkyl amino group as a substituent and those described in "di C1-C4 alkyl amino group in R 204 from R 201" above, include those the same, including the preferred ones, and the like.
  • Examples of the phenyl group substituted with the C1-C4 alkylcarbonylamino group in the group D include 4-acetylaminophenyl and the like.
  • examples of the di-C1-C4 alkylcarbonylamino group as a substituent include the same as those described above in “C1-C4 alkylcarbonylamino group in R 201 to R 204 ”, including preferable ones. .
  • a phenyl group substituted with a “benzoylamino group substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the group D” are 4- (4-chlorophenylbenzoylamino) phenyl, 4- (4-methylphenylbenzoylamino) phenyl, 4- (4-nitrophenylbenzoylamino) phenyl, 4- (4-sulfophenylbenzoylamino) phenyl, 4 -(4-Carboxyphenylbenzoylamino) phenyl and the like.
  • the substituent “the benzoylamino group in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group” A benzoylamino group in which the benzene ring in R 201 to R 204 is substituted with at least one group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group; The same thing as what is described and a preferable thing etc. are mentioned.
  • Examples of the phenyl group substituted with plural kinds of groups in the group D include those substituted with a hydroxy group and a carboxy group, such as 3-hydroxy-4-carboxyphenyl; 3-carboxy-2-hydroxy-5- And those substituted with a hydroxy group, a sulfo group, and a carboxy group, such as sulfophenyl;
  • the group D is a naphthyl group
  • the naphthyl group substituted with the specific group is described.
  • the number of substituents is 1 to 3.
  • the type of the substituent is not particularly limited, but the same one is preferable.
  • the bonding position between the nitrogen atom of the pyrazolone ring and the group D is preferably the 1- or 2-position, that is, 1-naphthyl or 2-naphthyl.
  • the position of the substituent on the naphthyl group is not particularly limited, but the following are preferable.
  • Examples of the naphthyl group substituted with a hydroxy group in the group D include 4-hydroxynaphth-1-yl, 6-hydroxynaphth-1-yl, 5-hydroxynaphth-2-yl and the like.
  • Examples of the naphthyl group substituted with the sulfo group in the group D include 7-sulfonaphth-1-yl, 5,7-disulfonaphth-2-yl, 6,8-disulfonaphth-2-yl, 4,8-disulfonaphth-2- Yl, 4,6,8-trisulfonaphth-2-yl, 4,7,8-trisulfonaphth-2-yl and the like.
  • Examples of the naphthyl group substituted with the C1-C4 alkoxy group in the group D include 4-methoxynaphth-1-yl, 6-methoxynaphth-2-yl and the like.
  • examples of the C1-C4 alkoxy group as a substituent include the same groups as those described above in “C1-C4 alkoxy group in R 101 and R 102 ”, including preferable ones.
  • Examples of the naphthyl group substituted with the phenylsulfonyloxy group in the group D include 4-phenylsulfonyloxynaphth-1-yl, 5-phenylsulfonyloxynaphth-2-yl and the like.
  • the naphthyl group substituted with “a phenylsulfonyloxy group in which the naphthalene ring is substituted with at least one group selected from the group consisting of a chlorine atom, a nitro group, and a C1-C4 alkyl group” is usually one to three, preferably And those substituted with one or two of these groups.
  • the type of the substituent is not particularly limited, but the same one is preferable.
  • the position of the substituent is not particularly limited. Specific examples include those substituted with a chlorine atom such as 4-chlorophenylsulfonyloxy, 2,4-dichlorophenylsulfonyloxy, 3,5-dichlorophenylsulfonyloxy; 2-nitrophenylsulfonyloxy, 4-nitrophenylsulfonyloxy, etc. And those substituted with a C1-C4 alkyl group such as 4-methylphenylsulfonyloxy and 2,4-dimethylphenylsulfonyloxy; and the like.
  • examples of the C1-C4 alkyl group include the same ones as described above in the “C1-C4 alkyl group in R 101 and R 102 ”, including preferable ones.
  • the naphthyl group substituted by the above substituted phenylsulfonyloxy group includes 4- (4-methylphenyl) sulfonyloxynaphth-1-yl, 5- (4-methylphenyl) sulfonyloxynaphth-2- Ir etc. are mentioned.
  • group D is a phenyl group; substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, a carboxy group, a C1-C4 alkyl group, and a C1-C4 alkoxy group. And a naphthyl group substituted with a sulfo group. More preferred are a phenyl group, a phenyl group substituted with a sulfo group, and a phenyl group substituted with a carboxy group, and still more preferred is a phenyl group substituted with a sulfo group.
  • the salt of the compound represented by the above formula (1), formula (2), formula (4), formula (6) to (8) or a tautomer thereof is a salt with an inorganic or organic cation.
  • inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts.
  • Preferred inorganic salts include lithium, sodium, and potassium salts and ammonium salts.
  • organic cation salt include salts with quaternary ammonium represented by the following formula (5), but are not limited thereto.
  • the free acid, its tautomer, and various salts thereof may be a mixture.
  • any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used.
  • the physical properties such as solubility in each compound may differ, and if necessary, select the type of salt as appropriate, or change the ratio when multiple salts are included.
  • a mixture having physical properties suitable for the purpose can also be obtained.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group.
  • One represents a group other than a hydrogen atom.
  • Specific examples of the alkyl group of Z 1 , Z 2 , Z 3 and Z 4 in the formula (5) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. Can be mentioned.
  • hydroxyalkyl group examples include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
  • hydroxyalkoxyalkyl group examples include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc.
  • hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl,
  • hydroxyethoxy C1-C4 alkyl groups such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. It is done.
  • the compounds represented by the above formulas (1) and (7) can be obtained by appropriately selecting synthetic raw materials according to the method described in International Publication No. 2009/069279 or the method described in International Publication Those skilled in the art can easily synthesize them.
  • the compound represented by the above formula (2) can be obtained by a person skilled in the art by appropriately selecting a synthesis raw material according to the method described in International Publication No. 2005/097912 or the method described in International Publication. Can be easily synthesized.
  • the compound represented by the above formula (6) can be obtained by a person skilled in the art by appropriately selecting a synthesis raw material according to the method described in JP-A-2009-84346 or the method described in the publication. It can be easily synthesized.
  • the compounds represented by the above formulas (4) and (8) can be synthesized, for example, by the following method.
  • the structural formula of the compound in each step shall be expressed in the form of a free acid, and R 201 to R 205 used as appropriate in the following formulas (A) to (K) are those in formula (4), respectively.
  • a compound represented by the following formula (A) is diazotized by a conventional method, and a compound represented by the following formula (B) is subjected to a coupling reaction by a conventional method to obtain a compound represented by the following formula (C). obtain.
  • the following method is mentioned as another synthesis method of the compound represented by Formula (C).
  • a compound represented by the following formula (A) is diazotized by a conventional method, and this is coupled with a methyl- ⁇ -sulfonic acid derivative of aniline by a conventional method, followed by hydrolysis under alkaline conditions.
  • a compound represented by the following formula (D) is obtained.
  • the compound represented by the formula (C) can also be obtained by treating the resulting compound represented by the formula (D) with fuming sulfuric acid or the like for sulfonation. Further, some of the compounds represented by the formula (C) can be purchased as commercial products (for example, CI Acid Yellow 9).
  • the obtained compound represented by the formula (J) and the compound represented by “HR 205 ” corresponding to R 205 are subjected to a condensation reaction by a conventional method to obtain a compound represented by the above formula (4).
  • an appropriate synthesis raw material is selected (for example, CI Acid Yellow 9 is used as the compound represented by the above formula (C)). If it is a trader, it is compoundable similarly to Formula (4).
  • the diazotization of the compound represented by the above formula (A) is carried out by a method known per se.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • an inorganic acid medium for example at a temperature of ⁇ 5 to 30 ° C., preferably 0 to 20 ° C.
  • the coupling reaction of the diazotized compound of the compound represented by the formula (A) and the compound represented by the formula (B) is also carried out under reaction conditions known per se.
  • the reaction liquid is preferably adjusted to the above pH value by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; acetates such as sodium acetate; ammonia or organic amines; Can be used.
  • the compound represented by the formula (A) and the compound represented by the formula (B) are used in a substantially stoichiometric amount.
  • the diazotization of the compound represented by the above formula (C) is carried out by a method known per se.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • an inorganic acid medium for example at a temperature of ⁇ 5 to 30 ° C., preferably 0 to 25 ° C.
  • the coupling reaction between the diazotized product of the compound represented by the formula (C) and the compound represented by the formula (E) or the formula (G) is also carried out under reaction conditions known per se.
  • the reaction liquid is preferably adjusted to the above pH value by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; acetates such as sodium acetate; ammonia or organic amines; Can be used.
  • the compound represented by the formula (C) and the compound represented by the formula (E) or the formula (G) are used in a substantially stoichiometric amount.
  • the condensation reaction between the compound represented by the above formula (F) and cyanuric halide such as cyanuric chloride is carried out by a method known per se.
  • cyanuric halide such as cyanuric chloride
  • Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; acetates such as sodium acetate; ammonia or organic amines; Can be used.
  • the compound represented by the formula (F) and the cyanuric halide are used in a substantially stoichiometric amount.
  • the condensation reaction between the compound represented by the above formula (H) and the compound represented by the above formula (L) is carried out by a method known per se.
  • a method known per se it is advantageous to carry out the reaction in water or an aqueous organic medium at a temperature of 10 to 80 ° C., preferably 25 to 70 ° C., and at a weakly acidic to weakly alkaline pH value, for example pH 5-9.
  • the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; acetates such as sodium acetate; ammonia or organic amines; Can be used.
  • the compound represented by the formula (H) and the compound represented by the formula (L) are used in approximately stoichiometric amounts.
  • the condensation reaction between the compound represented by the above formula (J) and the compound represented by the above “HR 205 ” is carried out by a method known per se.
  • a method known per se it is advantageous to carry out the reaction in water or an aqueous organic medium at a temperature of 50 to 100 ° C., preferably 60 to 95 ° C., and at a weakly acidic to weakly alkaline pH value, for example, pH 3 to 10.
  • the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; acetates such as sodium acetate; ammonia or organic amines; Can be used.
  • the compound represented by “HR 205 ” is used in an amount of 1 to 10 equivalents, preferably 2 to 5 equivalents, relative to 1 equivalent of the compound represented by Formula (J).
  • acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water.
  • aqueous organic medium include an organic substance miscible with water, or a so-called organic solvent miscible with water (specific examples include a water-soluble organic solvent described later) and water.
  • the inorganic salt include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide.
  • organic cation salts include quaternary ammonium halogen salts represented by the above formula (5).
  • inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (ammonia water); alkali metal such as lithium carbonate, sodium carbonate, and potassium carbonate.
  • organic base include organic amines such as diethanolamine and triethanolamine; quaternary ammonium hydroxides and halides represented by the above formula (5); and the like. However, it is not limited to these.
  • each reaction solution after completion of the final step is the It can be used directly in the manufacture of ink compositions.
  • a method of individually drying for example, spray-drying the reaction solution containing each pigment; a method of salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; hydrochloric acid, sulfuric acid, nitric acid
  • Each compound is isolated by a method of acid precipitation by adding a mineral acid such as the above; or a method of acid precipitation by combining the salting-out and acid precipitation described above; You can also
  • Preferred dyes as the dyes (I) to (III) contained in the ink composition of the present invention are represented by the above formulas (1), (2), (4), and (6) to (8). In each compound, it is the compound mentioned as a preferable thing, and it is the same also about a more preferable pigment
  • One of the preferable combinations of the dyes (I) to (III) is a compound represented by the formula (2) described in the above 7) as the dye (I), and a formula described in the above 6) as the dye (II).
  • the ink composition of the present invention containing this combination of dyes is one of the preferred ink compositions of the present invention.
  • Particularly preferred combinations of the dyes (I) to (III) include those described in 9) above, and the ink composition of the present invention containing the combination of dyes is particularly preferred.
  • the proportion of the coloring matter (I) is 10 to 75 mass%, preferably 30 to 65 mass%; the proportion of the coloring matter (II) is 10 to 40 mass%. %, Preferably 10 to 30% by weight; the proportion of dye (III) is 10 to 60% by weight, preferably 20 to 45% by weight.
  • the total mass of the dye (I), the dye (II), and the dye (III) contained in the ink composition of the present invention is usually 0.1 to 20 mass with respect to the total mass of the ink composition. %, Preferably 1 to 10% by mass, more preferably 2 to 8% by mass.
  • the ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent as necessary within a range that does not impair the effects of the present invention.
  • the water-soluble organic solvent is used for the purpose of dissolving the dye in the ink composition of the present invention, preventing drying (maintaining a wet state), adjusting the viscosity, promoting penetration, adjusting the surface tension, and defoaming.
  • the ink composition of the present invention is preferably contained.
  • the ink preparation agent include antifungal preservatives, pH adjusters, chelating reagents, rust inhibitors, ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, surfactants, antioxidants (fading inhibitors).
  • the content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass with respect to the total mass of the ink composition of the present invention, and the ink preparation agent is similarly 0 to 20% by mass, preferably Is preferably used in an amount of 0 to 15% by mass.
  • the remainder other than the above is water.
  • the pH of the ink composition of the present invention is preferably pH 5 to 11 and more preferably pH 7 to 10 for the purpose of improving storage stability.
  • the surface tension of the ink composition is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m.
  • the viscosity of the ink composition is preferably 30 mPa ⁇ s or less, and more preferably 20 mPa ⁇ s or less.
  • the pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.
  • each dye contained in the ink composition of the present invention [ie, the above formula (1), formula (2), formula (4), formula (6) ) To (8)], it is preferable to use a metal cation chloride (for example, sodium chloride) or an inorganic impurity such as sulfate (for example, sodium sulfate) with a small content.
  • a metal cation chloride for example, sodium chloride
  • an inorganic impurity for example, sodium sulfate
  • the standard of the inorganic impurity content is about 1% by mass or less with respect to the total mass of the dye, and the lower limit may be the detection limit of the analytical instrument or less, that is, 0%.
  • a conventional method using a reverse osmosis membrane a dried pigment product or a wet cake is stirred in a mixed solvent of C1-C4 alcohol such as methanol and water, and the precipitate is separated by filtration. Then, it may be desalted by a method such as drying; a method using an ion exchange resin;
  • water-soluble organic solvent examples include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol; N, N-dimethylformamide, N, N A carboxylic acid amide such as dimethylacetamide; a lactam such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidin-2-one, 1,3-dimethyl Cyclic ureas such as hexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1 , 2-Propylene glycol, 1,3
  • the water-soluble organic solvent includes substances that are solid at room temperature, such as trimethylolpropane.
  • the substance is a solid, it shows water solubility, and an aqueous solution containing the substance shows the same properties as a water-soluble organic solvent and can be used for the same purpose. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used for the same purpose as described above.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof.
  • preservative examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole, Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl brom Acetate-based and inorganic salt-based compounds are exemplified.
  • organic halogen compound examples include, for example, sodium pentachlorophenol.
  • pyridine oxide compound include sodium 2-pyridinethiol-1-oxide.
  • isothiazoline-based compound examples include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium Examples include chloride.
  • antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, trade name, Proxel RTM GXL (S), Proxel RTM XL-2 (S), and the like.
  • RTM means a registered trademark.
  • any substance can be used as long as it can control the pH of the ink in the range of, for example, 5 to 11 without adversely affecting the prepared ink.
  • alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate
  • alkali metal salts of organic acids such as sodium silicate and potassium acetate
  • inorganic bases such as disodium phosphate
  • aminosulfones such as taurine; Acids; and the like.
  • chelating reagent examples include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
  • rust preventive examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
  • ultraviolet absorber examples include water-soluble sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, triazine compounds, and the like.
  • water-soluble polymer compounds examples include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.
  • dye solubilizer examples include ⁇ -caprolactam, ethylene carbonate, urea and the like.
  • antioxidant for example, various organic and metal complex anti-fading agents can be used.
  • anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like.
  • surfactant examples include known surfactants such as anionic, cationic, and nonionic surfactants.
  • anionic surfactants include alkyl sulfonates, alkyl carboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurates, alkyls Sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonic acid Examples thereof include salts, diethylsulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.
  • cationic surfactants examples include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, or Examples include imidazoline derivatives.
  • nonionic surfactants include ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether.
  • Polyesters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate System; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5- Methyl-1-hexyne-3-acetylene alcohol such as ol; for example, as other specific examples, Nissin Chemical Industry Co., Ltd., trade name Surfynol RTM 104,105,82,465, Olfine RTM STG and the like. These ink preparation agents are used alone or in combination.
  • the ink composition of the present invention there is no particular limitation on the order of dissolving each agent such as an additive.
  • the water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition.
  • fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition.
  • the pore size of the filter used for microfiltration is usually 1 to 0.1 ⁇ m, preferably 0.8 to 0.1 ⁇ m.
  • the ink composition of the present invention can be used in addition to the dyes (I) to (III) for the purpose of finely adjusting a neutral and high-quality black hue with low saturation and no color to a desired hue. Further, other pigments having various hues may be contained within a range that does not impair the effects obtained by the present invention.
  • a black pigment having another hue yellow (e.g., CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 142, CI Direct Yellow 161, etc.) Orange (eg CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49 etc.) Brown; Scarlet (eg CI Direct Red 89 etc.); Red (eg CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, C CI Direct Red 225, CI Direct Red 226, etc.), Magenta (eg CI Direct Red 227, CI Acid Red 249, CI Acid Red 254, etc.); Blue (eg C.I.
  • the ink composition of the present invention (I. Acid Blue 9, CI Acid Blue 83, CI Acid Blue 90, etc.); Violet; Navy; Cyan; Green; it can.
  • the total amount of these dyes and the dye (II) is 10 to It is 40% by mass, preferably 10 to 30% by mass. It is difficult to determine the content ratio of these dyes to the dye (II) in general, but as a guide, the ratio of the dye (II) is 50 masses in the total mass of these dyes and the dye (II). %, And the ratio of the dye (II) is 100% by mass, that is, these dyes may not be contained.
  • the ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drafting, stamping, or recording (printing), particularly inkjet recording.
  • the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.
  • the ink jet recording method of the present invention performs recording by using the ink composition of the present invention as an ink, ejecting ink droplets of the ink in accordance with a recording signal, and attaching the ink droplets to a recording material.
  • the ink nozzles used for recording are not particularly limited and can be appropriately selected according to the purpose.
  • the recording method is a known method, for example, a charge control method in which ink is ejected using electrostatic attraction force; a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element; Acoustic ink jet system that irradiates ink by changing to beam and ejects ink using its radiation pressure; thermal ink jet that heats ink to form bubbles and uses generated pressure, that is, bubble jet (registered trademark) system Etc. can be adopted.
  • a method called a photo ink in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentrations in the ink differ with substantially the same hue.
  • the colored product of the present invention is a) the ink composition of the present invention described in 1) to 11) above, and b) A substance colored by any one of the inkjet recording methods of the present invention described in 12) above, and preferably a substance colored by the ink composition of the present invention by the inkjet recording method of the present invention.
  • the following recording material is preferable.
  • the recording material that can be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters.
  • An information transmission sheet is preferable.
  • the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer.
  • the ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are made hydrophilic with polyvinyl alcohol and polyvinylpyrrolidone.
  • a sheet coated with a porous white inorganic material on the surface is particularly suitable for recording photographic image quality because of its high surface gloss and excellent water resistance.
  • the images recorded in these images are greatly discolored by ozone gas.
  • the ink composition of the present invention is excellent in ozone gas resistance, it exhibits a great effect even when ink jet recording is performed on such a recording material.
  • An example of a typical commercially available sheet coated with the above porous white inorganic material is Canon Inc., trade name: Photo Paper / Gloss Pro “Platinum Grade”, Photo Paper / Gloss Gold: manufactured by Seiko Epson Corporation, trade name: photographic paper Krispia (high gloss), photo paper (gloss), photo matte paper; manufactured by Hewlett-Packard Japan, trade name: advanced photo paper (gloss); Fuji Manufactured by Film Co., Ltd., trade name: painting photo finish Pro; and the like, but the use of the ink composition of the present invention is not limited to these dedicated papers.
  • Plain paper is a paper that is not provided with the above ink-receiving layer.
  • Examples of commercially available products include Canon Inc., trade name: GF-500, Canon plain paper / white; Seiko Epson Corporation.
  • Examples include plain paper dedicated to inkjet such as manufactured and trade name: double-sided fine plain paper;
  • PPC plain paper copy
  • a container containing the above ink composition is loaded in a predetermined position of an ink jet printer, and the above normal recording method is used. What is necessary is just to record on a recording material.
  • the ink jet recording method of the present invention comprises the ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, ink compositions of each color such as green, blue (or violet) and red (or orange). A thing can also be used together.
  • the ink composition of each color is injected into each container, and each container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the ink composition of the present invention and used for ink jet recording.
  • each compound contained as the pigments (I) to (III) in the ink composition of the present invention is easily synthesized and inexpensive.
  • each compound has high solubility in an aqueous medium and is excellent in water solubility, so that the filterability by a membrane filter in the process of producing an ink composition is good.
  • the ink composition of the present invention or an ink prepared from the ink composition is also excellent in storage stability and ejection stability. That is, the ink composition of the present invention has good storage stability without solid precipitation, changes in physical properties, changes in hue, etc. after long-term storage.
  • the ink composition of the present invention is suitably used for inkjet recording, writing instruments, etc., and particularly when recorded on inkjet dedicated paper, there is no neutral in both dark and light color printing. Even when recorded on different media, the hue changes little.
  • the printed image has a very high print density, and even when a high concentration solution is printed, the image does not cause bronzing, and also has various fastnesses such as moisture resistance and water resistance, particularly light resistance and ozone gas resistance. Both are excellent.
  • full-color ink jet recording with excellent fastness and storage stability is possible, and of course can be used on plain paper. .
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • This wet cake was suspended in 350 parts of water, and dissolved at pH 7.0 to 8.0 by adding 25% sodium hydroxide. 700 parts of ethanol was added to this solution and stirred for 30 minutes. The precipitated solid was collected by filtration to obtain a wet cake. The wet cake was added to 300 parts of water, dissolved by stirring, and 300 parts of ethanol and 600 parts of 2-propanol were added. The precipitated solid was collected by filtration and dried to obtain 35.0 parts of a compound ( ⁇ max: 419 nm) corresponding to the dye (II) represented by the following formula (20) as a sodium salt.
  • the compound represented by the above formula (19) was synthesized as follows. 70.0 parts of 30% fuming sulfuric acid was added to 63.3 parts of 98% sulfuric acid. The solution was cooled in an ice bath and 17.8 parts of benzylamine was added dropwise. During this time, the drop acceleration was adjusted so that the reaction temperature was 40 ° C. or lower. After completion of dropping, the mixture was stirred at room temperature for 1 hour, and then the reaction solution was slowly added dropwise to 400 g of ice water. After completion of the dropwise addition, the suspension is filtered, washed with 20 parts of hydrochloric acid, and the resulting wet cake is dried at 80 ° C. to give 4- (aminomethylbenzene) sulfonic acid 22 represented by the above formula (19). .8 parts were obtained.
  • Step 6 To 200 parts of water, 30.5 parts of a wet cake of a mixture of the compound represented by the formula (30) obtained in the above (Step 5) and the compound represented by the formula (31) was added and stirred for 1 hour. An aqueous solution was obtained. After adding 100 parts of crushed ice to this solution and cooling to 0 to 5 ° C., 2.0 parts of 35% hydrochloric acid and 1.0 part of 40% sodium nitrite aqueous solution were added and reacted at the same temperature for 1 hour, thereby causing a diazo reaction. A liquid was obtained.
  • the obtained wet cake was dissolved in 280 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 27.4 parts of lithium chloride was added, and the mixture was stirred for 1 hour to obtain an aqueous solution.
  • 350 parts of 2-propanol was added, and the precipitated solid was collected by filtration to obtain a wet cake.
  • the obtained wet cake was dissolved in 80 parts of water, 350 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • the obtained wet cake was again dissolved in 50 parts of water, 250 parts of 2-propanol was added, and the precipitated solid was separated by filtration and dried, and expressed by the following formula (33) corresponding to the dye (III).
  • 4.4 parts of a mixture of the compound represented by the following formula (34) and a mixed salt of a sodium salt and a lithium salt were obtained. ⁇ max: 590 nm.
  • Examples 1 to 6 and Comparative Examples 1 to 3 [(A) Preparation of ink]
  • the ink composition for comparison with the present invention was obtained, and then the contaminants were filtered off with a 0.45 ⁇ m membrane filter to obtain the test ink. Obtained.
  • the inks were prepared as Examples 1 to 6 and Comparative Examples 1 to 3, respectively.
  • the obtained ink of the present invention did not cause precipitation separation during storage, and no change in physical properties even after long-term storage.
  • ion-exchanged water was used for ink preparation.
  • the pH of each ink was adjusted to 8 to 10 using lithium hydroxide, and ion exchange water was added to make a total amount of 100 parts. Since the ink of Comparative Example 1 was prepared by following the ink disclosed in Example 3-2 of Patent Document 4, the composition of the inks of the other Examples and Comparative Examples was The pH was adjusted slightly with sodium hydroxide as described in Patent Document 4. The ink of Comparative Example 1 contains three types of pigments.
  • pigments (I) to (III) correspond to pigments (I) to (III), respectively, contained in the ink composition of the present invention.
  • the “other dye” means a dye not corresponding to the dyes (I) to (III).
  • Each dye column is vertically divided into two by a broken line, and the numbers in parentheses described in the upper column correspond to the formula numbers of the compounds described in the examples, and the number of parts used in the lower column Was described.
  • the numbers described in the columns of the water-soluble organic solvent, each additive and the like other than the pigment column all indicate the number of parts in the composition. Further, the symbol “-” means that the corresponding item is not contained.
  • “Surfactant” in Table 30 is trade name Surfinol RTM 104 manufactured by Nissin Chemical. In addition, the symbol in Table 30 represents the following meaning. DY86: C.I. I. Direct Yellow86. NMP: N-methyl-2-pyrrolidone. IPA: isopropanol. BCTL: Butyl carbitol. EDTA ⁇ 2Na: disodium ethylenediaminetetraacetate.
  • (38) is a sodium salt of a compound represented by the following formula (38) disclosed in JP-A-2002-332426.
  • (44) used in Comparative Example 1 is a sodium salt of a compound represented by the following formula (44) disclosed in Synthesis Example 4 of International Publication No. 2007/077931.
  • Ozone gas resistance test-1 A test piece was placed on a product name “ozone weatherometer” manufactured by Suga Test Instruments Co., Ltd., and allowed to stand for 16 hours under conditions of an ozone concentration of 15 ppm, a humidity of 60% RH, and a temperature of 24 ° C.
  • CIE L * , a * , and b * were measured for the recorded images of each test piece before and after exposure to ozone, and a color difference ⁇ E was calculated by the following equation.
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the difference between L * , a * , and b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. The evaluation results are shown in Table 31. A smaller ⁇ E represents an excellent result with less color change before and after the test. A: ⁇ E is less than 15 B: ⁇ E is 15 or more and less than 20 C: ⁇ E is 20 or more
  • Ozone gas resistance test-2 A test piece was placed on a trade name “Ozone Weather Omometer” manufactured by Suga Test Instruments Co., Ltd., and allowed to stand for 16 hours under conditions of an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C. CIE L * , a * , and b * were measured for the recorded images of each specimen before and after exposure to ozone, and the color difference ⁇ E was calculated in the same manner as in “1) Ozone gas resistance test-1” above. . The test results were evaluated according to the following criteria. The evaluation results are shown in Table 31. A smaller ⁇ E represents an excellent result with less color change before and after the test. A: ⁇ E is less than 30 B: ⁇ E is 30 or more and less than 40 C: ⁇ E is 40 or more
  • Example 7 to 9 and Comparative Example 4 The ink compositions of Examples 7 to 9 and Comparative Example 4 were prepared by mixing the components described in Table 32 below in the same manner as in “(A) Preparation of ink”.
  • the inks of the respective examples showed very excellent results in all the test items. Specifically, the ink of each example showed excellent results in any ozone gas resistance test as compared with the ink of Comparative Example 1. In contrast, the ink of Comparative Example 1 has a decrease in print density due to the bronze phenomenon in the darkest printed portion, whereas the ink of the present invention does not cause the bronze phenomenon and provides a high print density. It became clear. Furthermore, it is clear that the ink compositions of Comparative Examples 2 to 4 that do not contain the dye (II) have the worst saturation and are inappropriate as a black quality.
  • the ink composition of the present invention containing any of the three kinds of specific dyes (I) to (III) is required for inkjet recording images as compared with the conventional black ink composition. It has been found that it is excellent in various fastness properties, in particular, ozone gas resistance, has a sufficiently high printing density, and gives a neutral, high-quality, black recorded image with low saturation and no color.
  • the ink composition of the present invention is suitable as a black ink liquid for various recordings such as inkjet recording and writing instruments, particularly inkjet recording.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)

Abstract

L'invention porte sur une composition d'encre qui contient (I) une matière colorante représentée par la formule générale (2), (II) une matière colorante représentée par la formule générale (4) et (III) une matière colorante choisie parmi les matières colorantes représentées par les formules générales (1) et (6). Dans la formule générale (2), R101 et R102 représentent chacun un groupe sulfo ou similaire ; R103 et R104 représentent chacun un atome d'halogène ou similaire ; x vaut 0 ou 1 ; et A représente un groupe représenté par la formule générale (3). Dans la formule générale (4), R201 à R204 représentent chacun un groupe alkyle en C1-4 ou similaire ; et R205 représente un groupe mono(alkyl en C1-4)amino substitué par sulfo ou similaire. Dans la formule générale (1), n vaut 0 ou 1 ; R1 représente un groupe alkyle en C1-4 ou similaire ; R2 représente un groupe cyano ou similaire ; R3 et R4 représentent chacun un groupe sulfo ou similaire ; R5 à R7 représentent chacun un groupe alkyle en C1-6 ou similaire ; et R9 à R11 représentent chacun un groupe sulfo ou similaire. Dans la formule générale (6), m vaut 0 ou 1 ; R401 représente un groupe carboxy ou similaire ; R405 à R407 représentent chacun un groupe alkyle en C1-4 ou similaire ; R409 à R411 représentent chacun un groupe sulfo ou similaire ; et D représente un groupe phényle substitué par sulfo ou similaire.
PCT/JP2011/050146 2010-01-12 2011-01-07 Composition d'encre, procédé d'impression par jet d'encre et corps coloré Ceased WO2011086974A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree
JP2009030023A (ja) * 2007-07-05 2009-02-12 Canon Inc インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
JP2009040861A (ja) * 2007-08-08 2009-02-26 Fujifilm Corp 黒色インク組成物、インクセット、インクカートリッジ、インクジェットプリンター、及びインクジェット記録方法
JP2009512737A (ja) * 2005-10-20 2009-03-26 富士フイルム株式会社 インク組成物、インクの製造方法、インクセット、並びに記録方法
JP2009084346A (ja) * 2007-09-28 2009-04-23 Nippon Kayaku Co Ltd トリスアゾ化合物、インク組成物、記録方法及び着色体
WO2009069279A1 (fr) * 2007-11-27 2009-06-04 Nippon Kayaku Kabushiki Kaisha Composé triazoïque, composition d'encre, procédé d'impression et corps coloré
JP2009185133A (ja) * 2008-02-05 2009-08-20 Nippon Kayaku Co Ltd インク組成物、インクジェット記録方法及び着色体
WO2009136577A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composition d'encre, procédé d'impression par jet d'encre et corps coloré

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009512737A (ja) * 2005-10-20 2009-03-26 富士フイルム株式会社 インク組成物、インクの製造方法、インクセット、並びに記録方法
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree
JP2009030023A (ja) * 2007-07-05 2009-02-12 Canon Inc インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
JP2009040861A (ja) * 2007-08-08 2009-02-26 Fujifilm Corp 黒色インク組成物、インクセット、インクカートリッジ、インクジェットプリンター、及びインクジェット記録方法
JP2009084346A (ja) * 2007-09-28 2009-04-23 Nippon Kayaku Co Ltd トリスアゾ化合物、インク組成物、記録方法及び着色体
WO2009069279A1 (fr) * 2007-11-27 2009-06-04 Nippon Kayaku Kabushiki Kaisha Composé triazoïque, composition d'encre, procédé d'impression et corps coloré
JP2009185133A (ja) * 2008-02-05 2009-08-20 Nippon Kayaku Co Ltd インク組成物、インクジェット記録方法及び着色体
WO2009136577A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composition d'encre, procédé d'impression par jet d'encre et corps coloré

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