Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/14—Monoazo compounds
  • C09B45/18—Monoazo compounds containing copper
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/14—Monoazo compounds
  • C09B45/22—Monoazo compounds containing other metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/24—Disazo or polyazo 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
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/34—Preparation from o-monohydroxy azo compounds having in the o'-position an atom or functional group other than hydroxyl, alkoxy, carboxyl, amino or keto groups
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0083—Solutions of dyes
• • 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
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

• the present invention relates to a water-soluble complex dye, a recording liquid, particularly a recording liquid for inkjet, and an inkjet recording method. More specifically, the present invention provides a water-soluble complex dye capable of satisfying three characteristics of high chroma, high light fastness and high gas fastness when forming a color image, a recording solution containing the dye, To an ink jet recording liquid, an ink set using the recording liquid, and an ink jet recording method.
• the ink jet recording method is a recording method in which droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye are ejected from a minute ejection orifice to perform recording, and a recording method capable of high-speed recording and multicolor color image recording. It is.
• the fixation speed is fast to general-purpose recording paper such as electrophotographic paper such as PPC (plain paper copier) paper and fan-hold paper (continuous paper such as a computer). It is necessary that the printing quality be good, that is, the printing be free of bleeding and have a sharp outline, and that the storage stability as a recording liquid be excellent.
• the solvent that can be used for the recording liquid is significantly limited.
• Dyes for recording liquids have sufficient solubility in the limited solvents described above, and are stable even when stored as recording liquids for a long period of time. It is required that the color saturation and density be high, and that it be excellent in water resistance, light resistance, and ozone resistance.
• Japanese Patent Application Laid-Open No. 57-42775 proposes a recording liquid containing a specific metal complex dye in a form in which a metal is coordinated near an azo group.
• the metal complex dye exemplified here is a specific 6-membered aromatic ring having a carbon or nitrogen atom having an orthohydroxy group for coordination bond formation in contact with the bonding carbon of the azo group. It is produced by using a compound as a diazo component and using a 5-membered pyrazole derivative having a hydroxyl group at a carbon adjacent to the carbon bonded to the azo group as a coupling component.
• gas resistance refers to the undesirable phenomenon of dye fading due to various active species gases such as nitrogen oxides, sulfur oxides, other acidic gases and ozone in the air. It is a property that is not allowed.
• This gas fading phenomenon is known to be highly correlated with, for example, accelerated tests in which images are exposed to ozone-containing air at concentrations of 3 ppm or 10 ppm. For this reason, gas resistance is generally referred to as ozone resistance.
• ozone resistance Therefore, in this specification, hereinafter, the degree of fading of test specimens subjected to ozone exposure is evaluated as a measure of gas resistance. The evaluation is made by using the index (ie, the ozone resistance evaluation result) obtained by the above.
• Japanese Patent Application Laid-Open No. 11-293168 discloses that a dye similar to the dye described in Japanese Patent Application Laid-Open No. 57-42775 described above is adjacent to a carbon bonded to an azo group.
• a specific aromatic compound having a hydroxy group-containing carbon or a specific aromatic compound having a sulfo group-substituted carbon adjacent to the azo group-bonding carbon is used as a diazo component and has a 5-membered ring. Examples of compounds produced using a certain pyrazole derivative or a 6-membered pyridone derivative as a coupling component are described.
• the publication states that a clear magenta pigment having good lightfastness and a color tone, a * value indicating reddish color is 50 or more, and b * value indicating yellowish color is close to 0 can be obtained. Have been. However, the publication does not describe anything about the ozone resistance of the dye, and these dyes are still compounds that form a coordination bond via the hydroxy group of the diazo component. Thus, it is assumed that the ozone resistance is not good.
• Japanese Patent Application Laid-Open No. H07-072560 proposes a specific metal complex dye in which a metal is not in the vicinity of an azo group but is bidentately coordinated with a part of a coupler.
• the feature of the metal complex dye exemplified here is that the metal coordination bond is not located near the so-called chromophore such as azo group or methine group, but is at least bidentate at a position away from it. This is where the position bond is formed.
• chromophore such as azo group or methine group
• the present invention relates to a water-soluble complex dye which is excellent in light resistance and ozone resistance and can form an image having high chroma in an ink jet recording method, an aqueous recording liquid using the same, and especially an ink jet recording liquid. It is an object to provide an ink set using the recording liquid, and an ink jet recording method. Disclosure of the invention The inventors of the present invention have conducted studies on a colorant that satisfies all of the above three characteristics, that is, light fastness, ozone fastness, and saturation. The present inventors have found that the water-soluble metal complex dye has excellent light fastness, ozone fastness and chroma, and achieved the present invention. ''
• the gist of the present invention includes a water-soluble complex dye formed from an azo compound represented by the following general formula (1) or a tautomer thereof and a transition metal ion, and at least one of the dyes.
• the present invention relates to an aqueous recording liquid, particularly a recording liquid for inkjet, an ink set using the recording liquid, and an ink jet recording method using the recording liquid.
• a 1 is a 5- to 7-membered monocyclic ring having 3 or 4 hetero atoms in the ring-constituting atoms or a condensed ring containing the heterocyclic ring bonded to an azo group.
• Ring X 1 is a fused heterocyclic ring containing a 6-membered heterocyclic ring, and represents a group in which the 6-membered heterocyclic ring is bonded to an azo group, and may have an arbitrary substituent.
• R 1 and R 2 independently represent a hydrogen atom or a monovalent substituent.
• the metal complex dye useful in the aqueous recording liquid of the present invention is formed from the azo compound represented by the general formula (1) or a tautomer thereof and a transition metal ion. It is a water-soluble complex dye having a specific structure.
• a 1 represents a 5- to 7-membered monocyclic ring having 3 or 4 hetero atoms in the ring-constituting atoms or a fused heterocyclic ring containing the heteromonocyclic bonded to an azo group. It is a ring and may have an arbitrary substituent, but does not have a hydroxyl group at a position adjacent to the carbon bonded to the azo group.
• Examples of the heterocyclic monocyclic ring and the condensed heterocyclic ring represented by A 1 include a triazole ring, a thiadiazolic ring, an oxadiazole ring, a triazine ring, a benzotriazoyl ring, a tetrazole ring, an oxadiazine ring, a thiadiazine ring, and a triazolopyrimidine And a triazolotriazine ring or a triazo quinoxaline ring.
• a ring containing at least one nitrogen atom as a hetero atom is preferable, and a ring having three hetero atoms, more preferably a 5-membered ring is preferable.
• a triazole ring or a thiadiazole ring is preferable, and particularly, a ring having three nitrogen atoms, specifically, a triazole ring is preferable.
• the bonding position is such that the azo group is bonded at a carbon atom among the ring-forming atoms, and at least one of the ring-forming atoms adjacent to the bonded carbon atom is a nitrogen atom, an oxygen atom or a sulfur atom. It is preferable that the carbon atoms are bonded to form a carbon atom having a substituent capable of coordinating with a metal atom other than a hydroxyl group, or a ring-forming atom adjacent to the bonded carbon atom is a nitrogen atom So that More preferably.
• the heterocyclic ring represented by A 1 may have one or more substituents on the heterocyclic ring, and any substituent on the heterocyclic ring may be any group that does not adversely affect the performance of the dye. Although it is not particularly limited, it is usually a group having a substituent of about 10 to 1000 in terms of molecular weight, and specifically, a halogen atom such as a chlorine atom, a bromine atom and a fluorine atom; a hydroxyl group; a mercapto group; A cyano group; a carboxyl group; a sulfo group; a phosphono group; an optionally substituted straight-chain, branched-chain or cyclic group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
• a halogen atom such as a chlorine atom, a bromine atom and a fluorine
• Alkyl group linear, branched or cyclic alkenyl group such as vinyl group, 2-propenyl group, isopropyl group, 2-butenyl group which may be substituted; phenyl group which may be substituted; Group, naphthyl group, etc.
• alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group or an n-butoxy group; an optionally substituted vinyloxy group or a 2-propenyloxy group; Alkenyloxy groups such as isopropenyloxy and 2-butenyloxy; aryloxy such as phenoxy and naphthyloxy which may be substituted; acetyl, propionyl, propylcarbonyl and butylcarbonyl , Vinylcarbonyl, isopropylylcarbonyl, benzoyl, benzylcarbonyl and other acyl groups; acetyloxy, propionyloxy, isoptyryloxy, bivaloyloxy, acryloyloxy, methacryloyloxy, Acylo such as benzoyloxy group
• An optionally substituted alkoxycarboxy group such as a methoxycarbyl group, an ethoxycarbonyl
• a carboxylate group comprising an aryloxycarbonyl group; an amino group which may be substituted; an alkylthio group which may be substituted, such as a methylthio group, an ethylthio group, a propylthio group and a butylthio group; Optionally substituted, vinylthio group, 2-probenylthio An alkenylthio group such as an isopropylthio group; an optionally substituted arylthio group such as a phenylthio group or a naphthylthio group; an optionally substituted methylsulfinyl group, an ethylsulfinyl group; Alkylsulfinyl groups such as propylsulfenyl group and isopropylsulfenyl group; arylsulfinyl groups such as phenylsulfinyl group and naphthylsulfinyl group which may be substitute
• alkyl group which may be substituted alkenyl group which may be substituted, alkoxy group which may be substituted, alkenyloxy group which may be substituted, acyl group, acyloxy group, which may be substituted Good rubamoyl group, carboxylate group, may be substituted Mino group, alkylthio group which may be substituted, alkenylthio group which may be substituted, alkylsulfinyl group which may be substituted, alkylsulfonyl group which may be substituted, sulfamoyl which may be substituted
• the group and the sulfonic acid ester group preferably have 10 or less carbon atoms, more preferably 6 or less, and still more preferably 4 or less, and the above-mentioned substituted aryl group,
• Substituents for the sulfonyl group, arylsulfonyl group and sulfamoyl group include: halogen atom; hydroxyl group; cyano group; carboxyl group; sulfo group; phosphono group; and hydroxyl group, carboxyl group, sulfo group, and phosphono group.
• a methyl group preferred are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a hydroxyethyl group, a carboxymethyl group, a lipoxetyl group, and a trifluoro group.
• It is an alkyl group which may be substituted with a substituent selected from the group consisting of halogen atoms such as a lomethyl group, a benzyl group and a phenethyl group, a hydroxyl group, a propyloxyl group and an aryl group.
• alkenyl groups which may be substituted, a hydroxyalkenyl group or an unsubstituted alkenyl group is preferred.
• aryl groups which may be substituted preferably an aryl group which may be substituted with a substituent selected from the group consisting of a carboxyl group and a sulfo group such as a phenyl group, a naphthyl group, a carboxyphenyl group and a sulfophenyl group It is.
• a hydroxyalkoxy group or an unsubstituted alkoxy group is preferred.
• alkenyloxy groups which may be substituted, a hydroxyalkenyloxy group or an unsubstituted alkenyloxy group is preferred.
• aryl group of the optionally substituted aryloxy group examples include the same as those described in the section of the above-mentioned aryl group.
• optionally substituted rubamoyl groups preferred are rubamoyl group, N, N-dimethylcarbamoyl group, hydroxyethylaminocarbonyl group, lipoxyxethylaminocarbonyl group, and sulfoethyl Substituted with a substituent selected from the group consisting of an optionally substituted alkyl group and aryl group, such as an aminocarbonyl group, a phenylcarbamoyl group, a carboxyphenyl group, a carbamoyl group, a sulfophenylcarbamoyl group, and a phosphonophenylcarbamoyl group.
• an alkyl group or a hydroxyl group substituted with a hydrophilic group represented by a hydroxyl group, a carboxyl group, a sulfo group and a phosphono group, a hydroxyl group, a sulfoxy group and a phosphono group Substituted with a phenyl group substituted with a hydrophilic group represented by Is a good force Rubamoiru group optionally, particularly preferably Karubokishifue carbamoylmethyl group or Suruhofue carbamoylmethyl group.
• an alkoxycarboxy group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbyl group, a hydroxyethylcarbonyl group, or , Phenoxycarbonyl group, naphthyloxycarbonyl group, methylphenoxycarbonyl group, methoxyphenoxycarbonyl group, carboxyphenoxycarbonyl group, sulfoxyphenoxycarbonyl group, alkyl such as phosphonophenoxycarbonyl group
• An aryloxycarbonyl group which may be substituted with a substituent selected from the group consisting of a group, an alkoxy group, a carboxyl group, a sulfonic acid group and a phosphono group, and particularly preferably a group consisting of a sulfoxy group and a sulfoxy group. More chosen Substituted
• alkyl groups such as methylamino, ethylamino, dimethylamino, acetylamino, hydroxyethylamino, acetylamino, trichloroacetylamino, benzoylamino and the like are preferable.
• an amino group which may be substituted with an acyl group is preferable.
• a hydroxyalkylthio group or an unsubstituted alkylthio group is preferred.
• a hydroxyalkenylthio group or an unsubstituted alkenylthio group is preferred.
• the above-mentioned optionally substituted arylthio group is preferably a phenyloxy group such as a phenylthio group, a methylphenylthio group, a carboxyphenylthio group, a sulfophenylthio group, a phosphonophenylthio group, a methoxyphenylthio group, or a sulfo group.
• an arylthio group which may be substituted with a substituent selected from the group consisting of a phosphono group, an alkyl group and an alkoxy group, and more preferably a substituent selected from the group consisting of a carboxyl group and a sulfo group.
• a hydroxyalkylsulfinyl group or an unsubstituted alkylsulfinyl group is preferred.
• arylsulfenyl groups preferred are phenylsulfinyl, methylphenylsulfenyl, naphthylsulfinyl, carboxyphenylsulfinyl, sulfophenylsulfinyl, and phosphonoff
• An alkyl group such as an enylsulfinyl group, A arylsulfinyl group which may be substituted with a substituent selected from the group consisting of a carboxy group, a sulfo group and a phosphono group, and more preferably a substituent selected from the group consisting of a carboxyl group and a sulfo group Is an arylsulfinyl group substituted with
• a hydroxyalkylsulfonyl group or an unsubstituted alkylsulfonyl group is preferred.
• arylsulfonyl groups preferred are phenylsulfonyl, methylphenylsulfonyl, naphthylsulfonyl, carboxyphenylsulfonyl, sulfophenylsulfonyl, and phosphonophenyl Alkyl group such as a sulfonyl group, a carboxy group, an arylarylsulfonyl group which may be substituted with a substituent selected from the group consisting of a sulfo group and a phosphono group, and more preferably a group consisting of a sulfoxy group and a sulfo group. It is an arylsulfonyl group substituted with the selected substituent.
• sulfamoyl groups preferred are a sulfamoyl group, an N, N-dimethylsulfamoyl group, a hydroxyethylaminosulfonyl group, a carboxyethylaminosulfonyl group, a sulfoethylaminosulfonyl group, a phenyl Substituted with a substituent selected from the group consisting of an optionally substituted alkyl group and aryl group such as a nylsulfamoyl group, a carboxyphenylsulfamoyl group, a sulfophenylsulfamoyl group, and a phosphonophenylsulfamoyl group.
• an alkoxysulfonyl group such as a methoxysulfonyl group, an ethoxysulfonyl group, a hydroxyethoxysulfonyl group, a propoxysulfonyl group, an isopropoxysulfonyl group, a butoxysulfonyl group, or a phenoxysulfonyl group
• Alkyl groups such as naphthyloxysulfonyl group, methylphenoxysulfonyl group, methoxyphenoxysulfonyl group, carboxyphenoxysulfonyl group, sulfophenoxysulfonyl group, alkoxy group, carboxyl group and sulfonic acid group
• An aryloxysulfonyl group which may be substituted with a substituent selected from the group consisting of
• substituents of the above heterotube preferably a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an optionally substituted alkyl group, an optionally substituted alkenyl group, and an optionally substituted Aryl group, optionally substituted alkoxy group, optionally substituted carbamoyl group, carboxylate group, optionally substituted amino group, optionally substituted alkylthio group, substituted An optionally substituted arylthio group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted sulfamoyl group or a thiocyanato group, more preferably Is a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an optionally substituted alkyl group, an optionally substituted Alkenyl group
• the substituent of the alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, arylthio group, alkylsulfonyl group and arylsulfonyl group is not particularly limited, but is preferably a halogen atom, a hydroxyl group.
• the substituent of the amino group, the sulfamoyl group and the sulfamoyl group include an alkyl which may be substituted with a substituent selected from the group consisting of a halogen atom, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group and a nitro group. At least one group selected from a group, an alkenyl group and an aryl group.
• heterocyclic ring represented by A 1 especially the following general formula (2) or preferably a group you express in any one of (3).
• R 3 to R 5 each independently represent a hydrogen atom or a monovalent substituent, and these may each form a condensed ring.
• Examples of the monovalent substituent represented by R 3 to R 6 include the same substituents as the substituents that the heterocyclic ring represented by A 1 may have.
• R 3 and R 5 are preferably a hydrogen atom or an optionally substituted alkyl group.
• the substituent of the alkyl group is not particularly limited, but preferably includes a water-soluble group such as a hydroxyl group, a carboxyl group, a sulfo group, and a phosphono group, and among them, a carboxyl group or a sulfo group is preferable.
• R 4 and R 6 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, Poxyl group, sulfo group, alkyl group which may be substituted, alkenyl group which may be substituted, aryl group which may be substituted, alkoxy group which may be substituted, rubamoyl which may be substituted Group, optionally substituted alkoxycarbonyl group, carboxylate group, optionally substituted amino group, optionally substituted alkylthio group, optionally substituted arylthio group, substituted An alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted sulfamoyl group or a thiocyanato group, and more preferably an amino group, a nitro group, a carboxyl group, or a sulfo group.
• An optionally substituted alkylthio group or an optionally substituted alkylsulfonyl group particularly preferably a nitro group, a carboxyl group, an optionally substituted alkyl group or an optionally substituted alkylsulfonyl group. is there.
• the ring represented by X 1 in the general formula (1) is a condensed heterocyclic ring containing a 6-membered heterocyclic ring. That is, next to the carbon atom bonded to the azo group is a carbon atom which may have a substituent capable of forming a coordination bond, and a nitrogen atom which may be substituted is present next to the carbon atom. And a ring containing these atoms is a 6-membered ring, and the hetero 6-membered ring has a condensed ring.
• R 1 and R 2 in the general formula (1) each independently represent a hydrogen atom or a monovalent substituent.
• the monovalent substituent of R 1 is not particularly limited as long as it does not adversely affect the performance of the dye, and specifically, may have 1 to 9 carbon atoms which may be substituted.
• substituent of the alkyl group and the alkenyl group preferably, a halogen atom, a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, a cyano group, a nitro group, an optionally substituted amino group and the like are mentioned.
• Examples of the substituent capable of forming a coordination bond of R 1 include a group capable of coordinating to a metal atom including an atom having one long electron (lone electron pair) such as an oxygen atom, a sulfur atom, and a nitrogen atom, Specifically, a halogen atom; a hydroxyl group; a mercapto group; a nitro group; a cyano group; a carbonyl group; a sulfonate group; an alkyl group such as a carbamoyl group, a methylcarbamoyl group, and a phenylcarbamoyl group; A sulfamoyl group; a sulfamoyl group, a sulfamoyl group which may be substituted with an alkyl group such as a methylsulfamoyl group, a phenylsulfamoyl group or an aryl group; an amino group, a methylamin
• an amino group (the alkyl group is Or an amino group which may be substituted with a hydroxyl group or an alkyl group (the alkyl group may be a sulfo group, May be substituted selected from the group consisting of a carboxyl group and a hydroxyl group), and particularly preferably a hydroxyl group.
• R 2 is a hydrogen atom or a monovalent substituent, and the monovalent substituent is not particularly limited as long as it is a group that does not adversely affect the performance of the dye and can be bonded to a nitrogen atom. but compound in adjacent carbon atom connected to the nitrogen atom on X 1 ring when a heteroatom, the metal in this portion when complexing is coordinated as 2-pyridyl group is generated This is not preferable because it is incompatible with the compound of the present invention which essentially forms a coordination bond near the azo group.
• the monovalent substituent of R 2 is preferably an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, or an aryl group which may be substituted. More preferably, the substituent of the alkyl group, alkenyl group, alkoxy group and aryl group includes a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an optionally substituted alkyl group, An optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an acyl group, an acyloxy group, an optionally substituted carbamoyl group, a carboxylic acid ester group, a substituted Optionally substituted amino group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted alkylsulfonyl group
• alkyl group which may be substituted aryl group which may be substituted, alkoxy group which may be substituted, aryloxy group which may be substituted, acyl group, acyloxy group, which may be substituted Carbamoyl group, carboxylate group, amino group which may be substituted, alkylthio group which may be substituted, arylthio group which may be substituted, alkylsulfonyl group which may be substituted, substituted have good ⁇ reel sulfonyl group, examples of the optionally substituted sulfamoyl Moto ⁇ beauty sulfonate group, include the same groups as those exemplified in the description of the substituents in the heterocyclic ring a 1 of the above Can be
• R 2 is more preferably a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted or an aryl group which may be substituted (here, Examples of the substituent of the alkyl group, the alkenyl group, the alkoxy group and the aryl group include a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group and an optionally substituted amino group, preferably a halogen atom, a hydroxyl group.
• a cyano group, a carboxyl group or a sulfo group particularly preferably a hydroxyl group, a cyano group, a carbonyl group or a sulfo group.
• An alkyl group which may be substituted with a substituent selected from the group consisting of Kishiarukokishi group; or a hydroxyl group, a Shiano group, may be substituted with a substituent selected from the group consisting of forces Rupokishiru group and sulfo group Ariru group.
• ring represented by X 1 include a quinoline ring and a benzopyridine ring, and more preferably a group represented by any of the following general formulas (4) and (5) and Its tautomers are mentioned.
• R 7 to R 13 independently represent a hydrogen atom or a monovalent substituent (including tautomerism).
• examples of the monovalent substituent of R 7 to R 13 include the same groups as those described in the description of R 1 and R 2 above.
• Y is a heterocyclic ring composed of 5 to 7 atoms formed by linking R 2 which is a substituent of a nitrogen atom in the general formula (1) and a substituent of a carbon atom adjacent to the nitrogen atom to each other. And these rings may be substituted with any substituents.
• Preferred examples of the substituent R 7 include a hydrogen atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, an alkenyl group optionally having 2 to 9 carbon atoms or an optionally substituted aryl.
• the alkyl, alkenyl, and aryl groups are preferably a halogen atom, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted amino group. And the like.
• R 7 is a hydrogen atom; an alkyl group having 1 to 9 carbon atoms, which is substituted by a substituent selected from the group consisting of a halogen atom, a sulfo group, a carboxyl group, and a cyano group; A phenyl group substituted with a substituted amino group (the substituent of the amino group is an alkyl having 1 to 9 carbon atoms substituted with a substituent selected from the group consisting of a halogen atom, a sulfo group, a carboxyl group and a cyano group); And more preferably a hydrogen atom; or a group having 1 to 9 carbon atoms which is substituted by a substituent selected from the group consisting of a halogen atom, a sulfo group, a sulfoxy group and a cyano group. Is an alkyl group having 1 to 2 carbon atoms.
• substituents R 8 to R 13 include a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a phosphono group, a cyano group, a nitro group, a hydroxyl group, an optionally substituted alkyl group, and a substituted alkyl group.
• the substituent of the alkyl group, the alkenyl group and the alkoxy group is at least one selected from a halogen atom, a sulfo group, a hydroxyl group, a hydroxyl group, a cyano group, a nitro group and an amino group which may be substituted.
• the substituent of the amino group and the carbamoyl group may be substituted with a substituent selected from the group consisting of a halogen atom, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group and a nitro group.
• At least one group selected from an alkyl group and an alkenyl group is preferred.
• adjacent substituents of R 8 to R 13 may further form a ring via a nitrogen atom, a carbon atom, or the like.
• R 7 and R 1 (1 is preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, And a substituted or unsubstituted alkyl group, more preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or a substituted Or an optionally substituted alkyl group, and more preferably a hydrogen atom or an optionally substituted alkyl group.
• the substituent of the alkyl group, the alkenyl group and the alkoxy group includes a halogen atom, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group and a nitro group.
• R 8 and R 9 are preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, a phosphono group, an optionally substituted alkoxy group, an amino group, and an optionally substituted alkyl
• Examples include an amino group, a carbamoyl group or an optionally substituted alkyl rubamoyl group, and more preferably a hydrogen atom, a cyano group, a nitro group, a propyloxyl group, a sulfo group, a phosphono group, or a substituted group. It is an alkoxy group, an optionally substituted alkylamino group or an optionally substituted alkyl group.
• R 11 is preferably a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, an amino group, an optionally substituted alkylamino group, a carbamoyl group or an optionally substituted alkylcarbamoyl group. And more preferably a hydrogen atom, a hydroxyl group, a hydroxyl group or an amino group.
• R 12 is preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, a propyloxyl group, a sulfo group, a phosphono group, an optionally substituted alkoxy group, an amino group, an optionally substituted alkylamino And a substituted rubamoyl group or an optionally substituted alkyl rubamoyl group, more preferably a hydrogen atom, a cyano group, a nitro group, a lipoxyl group or a sulfo group.
• the ring Y is not particularly limited as long as it does not adversely affect the performance of the dye.
• a ring having a hetero atom adjacent to the nitrogen atom described in the general formula (4) or further adjacent thereto is a metal ion
• a compound coordinated to a metal ion may be generated at this portion, which is not preferable because it is incompatible with the compound of the present invention, which essentially forms a coordination bond near an azo group.
• the ring Y is preferably a ring in which the hetero atom is not present at the peri-position of the carbon atom substituted by the hydroxyl group specified in the general formula (4), or a ring in which no chelating group is present.
• transition metal atom used in the water-soluble complex dye of the present invention examples include silver (I), aluminum (III), gold (111), cerium (111, IV), cobalt (11, 111), and chromium (111). ), Copper (1, II), palladium (111), iron (11, III), gallium (111), germanium (IV), indium (111), lanthanum (111), manganese (II), nickel (II), palladium (II), platinum (11, IV), rhodium (11, 111), ruthenium (11, III, IV), scandium (111), silicon (IV), samarium (111), titanium ( IV), uranium (IV), zinc (II), zirconium (IV) and the like.
• preferred examples of the transition metal ion used in the present invention include Cu, Ni, Co, Zn, and Fe.In particular, Cu and Ni are preferred in terms of robustness, and particularly preferred. Nickel.
• the structure of the water-soluble complex dye formed from the azo compound represented by the above general formula (1) or a tautomer thereof and a transition metal ion according to the present invention has, for example, the form of the following general formula (6) Are more specifically represented.
• M represents an arbitrary transition metal ion.
• a 2 is a 5- to 7-membered heteromonocycle containing 3 or 4 heteroatoms in the ring-constituting atoms or a fused heterocycle containing the heteromonocycle bonded to an azo group; and A group which may have a group but does not have a hydroxyl group at a site adjacent to the carbon atom bonded to the azo group.
• Ring X 2 is a fused heterocyclic ring containing a 6-membered heterocyclic ring, and represents a group in which the 6-membered heterocyclic ring is bonded to an azo group, and may have an arbitrary substituent.
• R M represents a substituent capable of forming a coordination bond (including a tautomer);
• R 15 represents a hydrogen atom or a monovalent substituent; a substituent adjacent to the nitrogen atom to which the substituent is bonded;
• a heterocyclic ring consisting of 5 to 7 atoms may be formed together with the carbon atoms.
• a 2 include the same groups as those described in the description of A 1 above, and specific examples of the substituent capable of forming a coordination bond of R 14 include the above R 1
• the same groups as those described in the description section of R 2 are specifically exemplified as the monovalent substituent of R 15. .
• Examples of the ligand in this case include a halogen ion, a hydroxyl ion, a water molecule, an acetate ion, an acetyl acetonato ion, a viviridyl ion, or another molecule of the same or different azo dye ligand. And the like.
• the molecular weight of the azo compound used in the present invention, in the form of a free acid, is preferably in the range of 200 to 300, more preferably in the range of 300 to 150.
• Complex color of the present invention The element is formed from the above-mentioned azo compound and the above-mentioned metal salt, and the ratio of the metal atom to the azo compound is 1:
• the metal chelate dye may form a hydrate or an acid addition salt.
• the water-soluble complex dye of the present invention can be produced by performing a usual diazotization, coupling reaction and complexation according to a known method.
• a usual diazotization, coupling reaction and complexation for example, an azo compound obtained by diazotizing an amino compound having a heteromonocyclic or condensed heterocyclic ring represented by A 1 and subjecting the azo compound to a coupling reaction with a condensed heterocyclic compound containing a 6-membered heterocyclic ring having ring X 1 .
• a metal salt solution for example, an azo compound obtained by diazotizing an amino compound having a heteromonocyclic or condensed heterocyclic ring represented by A 1 and subjecting the azo compound to a coupling reaction with a condensed heterocyclic compound containing a 6-membered heterocyclic ring having ring X 1 .
• the heterocyclic compound is a diazo component
• the condensed heterocyclic compound containing a 6-membered heterocycle is a coupler
• the metal bond of the coupler is close to the azo-group bond of the 6-membered heterocycle. Therefore, it is considered that the coordination bond forms a bond between the heteroatom of the diazo component, the bonding group (coordination bond forming group) of the 6-membered heterocyclic portion of the coupler, and the metal.
• the dye of the present invention is a dye synthesized using a 5-membered heterocyclic coupler, as described in JP-A-57-42775 and JP-A-2-84070. The reason why the dye of the present invention exhibits excellent performance as compared with the above, that is, the mechanism whereby the dye of the present invention exhibits all three properties of chroma, light fastness and ozone fastness at a high level is unclear.
• metal complex dyes have a high molecular cohesion on a printing medium, and the solidity is improved, but the chroma tends to be reduced. It is considered that the intermolecular aggregation occurs with an appropriate strength due to the presence of the position bond and the 6-membered heterocyclic structure in the vicinity of the metal, thereby satisfying both the chroma, light fastness and ozone fastness.
• Japanese Patent Application Laid-Open No. 11-293168 describes a metal complex dye using a carbon aromatic ring compound as a diazo component and a 6-membered heterocyclic compound in a coupler.
• the dye using a carbon aromatic ring as the diazo component is extremely inferior in ozone resistance, which indicates that the bond between the complex atom of the diazo component and the metal in the present dye is resistant. It is presumed to have contributed to improving ozone properties.
• the dye in a recording liquid (hereinafter, also referred to as ink)
• the dye may be used as it is in a free acid form. It may be used or converted into a desired salt form.
• a method for exchanging the salt form any known method can be used. For example, the following method can be used.
• a strong acid such as hydrochloric acid is added to an aqueous solution of the dye obtained in the salt form, and the dye is acid-precipitated in the form of a free acid. Then, the dye is treated with an alkaline solution having a desired counter ion (for example, aqueous lithium hydroxide).
• a desired counter ion for example, aqueous lithium hydroxide.
• the dye used in the recording liquid of the present invention may have a part of acid groups in a salt form, and may have a mixture of a salt form dye and a free acid form dye.
• the acidic group takes a free acid form or a salt form depends on the pKa of the dye and the pH of the ink.
• the sulfo group has a salt form and the carboxyl group has a larger salt form in terms of the difficulty of ink clogging.
• a dye having a carboxyl group in an acid form is preferably used when emphasis is placed on water resistance and bleeding resistance.
• the salt type include salts of alkali metals such as Na, Li, and K, salts of ammonium which may be substituted with an alkyl group or a hydroxyalkyl group, and salts of organic amines.
• organic amines examples include lower alkylamines, hydroxy-substituted lower alkylamines, hydroxyl-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms.
• these salt forms the kind is not limited to one kind, and plural kinds may be mixed.
• the type of the counter ion of the acid group is freely selected according to the important characteristics of the ink.
• intermediates and reagents for dye synthesis often contain Na, so water-soluble dyes are generally obtained in the form of Na salts, but when water resistance is important, they are converted to NH 4 salts.
• a Li salt or an alkanolamine salt represented by triethanolamine when it is necessary to increase the solubility of the dye and maintain the clogging of the ink at a higher level, it is necessary to use a Li salt or an alkanolamine salt represented by triethanolamine. Sometimes converted.
• the plurality of acid groups when one molecule contains a plurality of acid groups, the plurality of acid groups may be of a salt type or an acid type and may be different from each other.
• more preferred specific examples include those described in Tables 3-1 to 3-4.
• the water-soluble complex dye of the present invention gives a yellow to orange color tone when used in a recording liquid as a coloring material of the recording liquid. That is, a yellow to orange hue corresponding to a maximum absorption wavelength (Aniax) of the dye of 380 to 500 ⁇ m is provided.
• a maximum absorption wavelength (Aniax) of the dye of 380 to 500 ⁇ m is provided.
• an electron-withdrawing substituent for the diazo component or by chemical modification such as increasing the electron-donating property of the coupling component it is possible to maintain the same robustness as in the example, while maintaining good robustness such as magenta, violet or cyan. It is expected that a wide variety of clear pigments will be synthesized.
• the water-soluble complex dye of the present invention is used at any concentration.
• the total dye concentration in the recording liquid is usually about 0.1 to 10% by weight, preferably about 0.5 to 7% by weight, and more preferably about 0.5 to 7% by weight based on the total amount of the recording liquid. It is preferably about 2 to 5% by weight.
• a recording solution may be prepared by using the water-soluble complex dye of the present invention and another dye in combination.
• the ink containing the water-soluble complex dye of the present invention is produced according to a method for preparing an ink used in a usual ink jet recording method.
• water can be used, but water containing a water-soluble organic solvent is preferably used.
• water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (weight average molecular weight of about 190 to 400), and glycerin.
• Heterocycles such as 1-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone; thiojetanol; sulfoxides such as dimethylsulfoxide; ethylene glycol monoallyl ether; ethylene glycol Ethers such as monomethyl ether and diethylene glycol monomethyl ether; sulfones such as sulfolane; and alcohols such as ethyl alcohol and isopropanol.
• These water-soluble organic solvents are usually used in the range of 1 to 50% by weight based on the total amount of the recording liquid. On the other hand, water is used in the range of 45 to 95% by weight based on the total amount of the recording liquid.
• the recording liquid of the present invention may contain a dye other than the metal chelate dye of the present invention, and other additives.
• the recording liquid of the present invention contains a compound selected from urea, thiourea, biuret, and semicarbazide in an amount of about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight based on the total amount thereof.
• a surfactant or adding about 0.01 to 5% by weight of a surfactant, quick drying after printing and print quality can be further improved.
• the pH value of the recording liquid of the present invention is usually 2 or more, preferably 4 or more, more preferably 6.5 or more, and most preferably 7 or more.
• the upper limit of the pH value is usually 12 or less, preferably 11 or less, and more preferably 9.5 or less.
• the compound is neutral to slightly alkaline.
• the azo metal chelate of the dye will have reduced solubility stability, and the dye will precipitate during storage or the metal chelate will come off.
• the discoloration is raw.
• an alcoholic organic solvent and a metal chelate may form an alcohol in the recording liquid, which may cause deterioration of ink performance.
• the recording liquid of the present invention since the recording liquid of the present invention has a high possibility of touching the human body, it is desirable to prepare the recording liquid while avoiding high pH from the viewpoint of safety.
• the pH of the recording liquid can be adjusted using a pH adjusting agent.
• the pH adjusting agent can control the pH within a predetermined range without adversely affecting the prepared recording liquid.
• any substance can be used.
• hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide; sodium carbonate, sodium hydrogen carbonate, potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, Alkali metal inorganic salts such as lithium phosphate, dihydrogen phosphate phosphate, and sodium hydrogen phosphate; sodium acetate, potassium acetate, lithium acetate, sodium oxalate, potassium oxalate, lithium oxalate, sodium borate Alkali metal organic acid salts such as sodium tetraborate, potassium hydrogen borate, potassium hydrogen tartrate; ammonia; methylamine, ethylamine, getylamine, tris (hydroxymethyl) aminoaminohydrochloride, diethanolamine, triethanolamine
• buffers exhibiting a buffering action are more preferable.
• the buffer include a weak acid and its salt, or a combination (mixture) of a weak base and its salt, and specifically, sodium acetate, lithium acetate, sodium phosphate, lithium phosphate, and dihydrogen phosphate.
• the buffer is used in a concentration of usually 0.01 to 3% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on the total weight of the recording liquid. .
• the pH of the recording solution may be adjusted using a buffer solution.
• various buffers are generally used for the purpose of preventing a decrease in ⁇ ⁇ ⁇ ⁇ due to mixing of hydrogen ions.
• each is mixed in an appropriate amount in the following combinations and the like, and these can be appropriately selected and used.
• a combination of tartaric acid and sodium tartaric acid is provided.
• borax sodium tetraborate
• sodium hydroxide sodium hydroxide
• tris (hydroxymethyl) amino methane and hydrochloric acid is particularly preferable.
• the buffer is used in a concentration of usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight, based on the total weight of the recording liquid.
• the method of performing ink jet recording using the aqueous recording liquid (ink) of the present invention is not particularly limited, and a commonly used method can be used.
• on-demand methods include electric-heat conversion methods (eg, thermal ink jet type, bubble jet type, etc.), electric-mechanical conversion methods (eg, single-cavity type 1, double-cavity type, vendors). Type, piston type, share one mode type, shared wall type, etc.), other electrostatic suction type, discharge type, etc.
• recording may be performed using the above-described metal chelate dye-containing recording solution.
• a method of recording by forming the above-mentioned metal chelate dye can also be performed.
• the ink set of the present invention uses the recording liquid of the present invention as a yellow ink, and combines three primary colors such as magenta ink and cyan ink, and further includes black ink if necessary. Link.
• magenta pigments such as basic violet 1, 2, 3, 7, 10, 1 5, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, etc.
• a 1 Q 1 to E 1 G 1 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a lipoxyl group, a sulfo group, a phosphono group, May be Alkyl group, alkenyl group which may be substituted, aryl group which may be substituted, alkoxy group which may be substituted, alkenyloxy group which may be substituted, aryloxy group which may be substituted An acyl group, an acyloxy group, an optionally substituted rubamoyl group, a carboxylate group, an optionally substituted amino group, an optionally substituted alkylthio group, an optionally substituted alkenylthio group, An optionally substituted arylthio group, an optionally substituted alkylsulfinyl group, an optionally substituted arylsulfenyl group, an optionally substituted phospho
• R MA 1 , R MA 2, and R MA 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxyl group, a nitro group, or a carbon number of 1 to 9 which may have a substituent.
• a represents M S 0, 1 or 2.
• E MA 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• G MA1 and G MA 2 R are each independently a halogen atom, a group represented by NR MA 4 R MA 5 or OR MA 6 , and R MA 4 , R MA 5 and R MA 6 are each independently , A hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aromatic hydrocarbon ring group or a heterocyclic group. May be provided. )
• R MB1 and R MB2 is, - OR Mbl, - NR Mb2 R Mb3 or a chlorine atom
• R MBL, R Mb2 and R Mb3 represents a hydrogen atom, a linear or branched chain having 1 to 8 carbon atoms
• R Mb 2 and R Mb 3 may form a 5- or 6-membered ring together with the nitrogen atom to be bonded.
• Y MB1 represents a divalent linking group selected from the groups represented by the following general formulas ( MB1 ) to (MB4) and the groups represented by the following structural formulas (MB5) to ( MB8 ). ( ⁇ 1 )
• Y MB10 is a linear or branched chain having 1 to 12 carbon atoms
• B MB represents an integer of 0 to 20.
• R MB11 and R MB12 represent a hydrogen atom or a methyl group.
• R MB13 and R MB14 each independently represent a hydrogen atom, a methyl group, or a methoxy group.
• Ar MB1 and Ar MB2 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent.
• Ar MC1 -N -Y MC -Y MC2- (R MC ⁇ -Y MC -NR MC ⁇ -Y MC2 )
• One Y MC — N N-Ar C2
• Ar MC1, A r MC2 each independently represent a may have a substituent group Ariru group, at least one of A r MC1, A r MC2 is selected from a COOH and single COSH as substituents It has at least one substituted substituent.
• R MG1 and R MG2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
• Y MC represents the following group. HO NH
• Y MC1 represents a bivalent organic linking group, c MC is 0 or 1
• Y MC 2 represents a group represented by the formula 1 ⁇ 3 carbonyl group or the following.
• Z MC11 represents NR MC21 R MC22, SR MC23 or OR MC23
• Z MC12 represents a group represented by a hydrogen atom, a chlorine atom or Z MC11
• Z MC 13 represents a chlorine atom or a Shiano group
• RMC, RMC22 and RMC23 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent Or an aralkyl group which may have a substituent
• R MC21 and R MC22 may form a 5-membered ring or a 6-membered ring together with the bonded nitrogen atom.
• R MD1 represents a hydrogen atom, a methyl group, a methoxy group, they may form a benzene ring together with the 3-position carbon atom of the force benzene ring d which represents the Asechiruamino group or a nitro group.
• R MD2 represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, or a 4-chloro-6-hydroxy-1,3,5-triazine-12-yl group.
• R ME1 represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms.
• R ME2 is a hydrogen atom; a cyano group, a COOR Me group (R Me represents a hydrogen atom, a metal atom, or an optionally substituted ammonium group), a hydroxyl group, a COOCH 3 group, and a COOCH 2 CH 3 group Represents an alkyl group having 1 to 6 carbon atoms which may have a substituent selected from the group consisting of: or an aryl group which may have a substituent with a methyl group.
• e ME represents an integer of 2 to 4.
• R ME3 represents an amino group, an alkylthio group, a hydroxyl group or an alkoxy group which may have a substituent.
• Y MF2 represents a carbonyl group or a sulfonyl group
• R MF6 is an aliphatic hydrocarbon group having 1 to 18 carbon atoms or a group represented by the following formula (F1).
• R MF6A represents a hydrogen atom, a halogen atom, a propyloxyl group, a nitro group, a cyano group, a lower alkyl group having 1 to 4 carbon atoms or a lower alkoxy group having 1 to 4 carbon atoms
• R MF6B represents a hydrogen atom.
• Q MG1 represents N, C-C l, C-one CN or C- N0 2
• R MG 1 represents an alkyl group which may be hydrogen atom or a substituent
• R MG2 is a hydrogen atom or Represents an alkyl group
• Y MG1 represents —O—, —S—, or one NR MG6 — (R MG6 represents a hydrogen atom or an optionally substituted alkyl group.)
• RMG3 represents an co 2 H or one S0 3 H
• R MG4 represents an amino group which may be substituted
• R MG 5 is a halogen atom, a hydroxyl group, a thiol group, a nitro group, Shiano group, optionally substituted Good alkyl group, optionally substituted alkenyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted carbamoyl group, acyl group or acyloxy group
• R MG3, R MG4, and the R MG 5 there are a plurality each of R MG3, R MG4, and R MG 5 may be the same or different.
• the magenta dye used in the ink set of the present invention is preferably a water-soluble azo metal chelate compound, and a preferable specific example of the compound is a compound represented by the following general formula (102)-( The compound formed from the azo compound represented by the formula (105) and a metal atom can be mentioned, and particularly preferably the compound formed from the azo compound represented by the following general formula (103) and a metal atom. is there.
• X 102 , Y 102 and Z 102 are each independently a halogen atom; a cyano group; A hydroxyl group; a sulfoxy group; a sulfo group; a phospho group; a peridode group; an optionally substituted alkyl group having 1 to 6 carbon atoms; an optionally substituted alkoxy group having 1 to 6 carbon atoms; An aryl group having 6 to 10 carbon atoms; an optionally substituted heteroaryl group; an optionally substituted alkoxycarbonyl group; an optionally substituted alkyl group, an optionally substituted An amino group which may be substituted with 1 or 2 substituents selected from the group consisting of a reel group, an acyl group, an alkylsulfonyl group and an arylsulfonyl group; an alkyl group which may be substituted and A carbamoyl group which may be substituted with a substituent selected from the group consisting of
• the general formula (103) is an azo compound having at least one hydrophilic group in the molecule
• X 1G3 is a compound required to form at least one 5- to 7-membered heterocyclic ring.
• the heterocyclic ring containing the represents an atom.
• X 1 03 may have a substituent on the heterocyclic ring, the substituents on the heterocyclic ring may be condensed to form a condensed ring.
• X 1Q3 Ar 1 Q3 represents a substituted naphthyl group selected from the following formulas (103-1) to ( 103-3) :
• Y 1G3 is a chelating compound . Represents a group, Z 1 Q3 represents an optional substituent which may be different from each other, and a 1Q3 represents an integer of 0 to 6.
• X 1Q4 represents a hydrogen atom, a halogen atom, a nitro group, a carboxyl group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkylsulfonylamino having 1 to 4 carbon atoms.
• X 1 Q4 ′ represents a hydrogen atom or a sulfo-go.
• Q 1 D4 is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an acylamino group having 2 to 7 carbon atoms, a substituted or unsubstituted triazinyl amino group, and a substituted or unsubstituted rubamoyl group
• 11 1 1) 4 represents an integer of 0 to 3.
• ⁇ 1 () 5 represents a benzene ring or a naphthalene ring having at least a sulfonyl group as a substituent
• ⁇ 105 represents a sulfo group or a substituted amino group
• n 1 Q5 is an integer of 0 to 2.
• ureido group represented by X 1 () 2 , Y 1 Q 2 and Z 1G2 include a ureide group, an n- methylureide group, and 3,5 —
• Preferred specific examples of the optionally substituted alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a 3- (N, N-dimethylamino) propyl group, a sulfatoethyl group And a straight-chain or branched-chain alkyl group which may be substituted with a substituent selected from the group consisting of a hydroxy group such as benzyl group, an optionally substituted amino group, a sulfato group and an aryl group.
• alkoxy group in the optionally substituted alkoxy group and the optionally substituted alkoxycarbonyl group include a hydroxy group such as a methoxy group, an isopropoxy group, a 2-hydroxyethoxy group and a carboxymethoxy group. And an alkoxy group which may be substituted with a substituent selected from the group consisting of carboxyl groups.
• aryl group having 6 to 10 carbon atoms which may be substituted include a halogen atom such as a phenyl group, a naphthyl group, a 4-chlorophenyl group and a 2-carboxyphenyl group; And a phenyl group or a naphthyl group which may be substituted with a substituent selected from the group consisting of:
• Preferred specific examples of the optionally substituted heteroaryl group include a pyridyl group, an imidazolyl group and a quinolyl group.
• amino group which may be substituted by 1 or 2 with a substituent selected from the group consisting of a sulfonyl group and an arylsulfonyl group include a methylamino group, an N, N-dimethylamino group, and a carboxymethylamino group.
• Preferred specific examples of the carbamoyl group which may be substituted with a substituent selected from the group consisting of an alkyl group which may be substituted and an aryl group which may be substituted include an N-methylcarbamoyl group and an N- Examples include a methyl-N- (3-sulfophenyl) -l-rubamoyl group, an N-p- (trimethylammonium) phenylcarbamoyl group or an N, N-bis (4-carboxyphenyl) -lumbamoyl group.
• Preferred specific examples of the sulfamoyl group which may be substituted with a substituent selected from the group consisting of an alkyl group which may be substituted and an aryl group which may be substituted include N-methylsulfamoyl group, N-methyl- N— (3-sulfophenyl) —sulfamoyl group, N—p—
• Preferred specific examples of the quaternary ammonium group include a trimethylammonium group and a benzyldimethylammonium group.
• Preferred specific examples of the phosphonium group include a triphenylphosphonium group and a trimethylphosphonium group.
• heterocyclic 5- or 6-membered represented by Q 1 0 2, pyridine ring, pyrazine ring, quinoline ring, thiazole ring, include benzothiazole Ichiru ring or pyrazole ring, of which preferably pyridine down ring is there.
• a condensed ring such as a ring, a benzoxazole ring or a benzimidazole ring may be formed.
• those containing at least two nitrogen atoms as hetero atoms are more preferred, more preferably an imidazole ring, a pyrazole face, a thiadiazole ring or a triazole ring, and further preferably an imidazole ring.
• a triazole ring particularly preferably an imidazole ring.
• the 5- to 7-membered heterocyclic ring and fused heterocyclic ring containing X 1 Q 3 include a halogen atom such as a chlorine atom, a bromine atom and a fluorine atom; a hydroxyl group; a mercapto group; a nitro group; a cyano group; a carboxyl group; A phosphono group; a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group; which may be substituted; A linear, branched or cyclic alkenyl group such as a vinyl group, a 2-propenyl group, an isopropyl group or a 2-butenyl group; an aryl group such as a phenyl group and a naphthyl group which may be substituted; An alkoxy group such as a methoxy group
• a carboxylate group consisting of an optionally substituted aryloxycarbonyl group such as a bonyl group or a sulfoxyphenoxycarbonyl group; an optionally substituted amino group; an optionally substituted methylthio group; Alkylthio groups such as tylthio group, propylthio group, butylthio group, vinylthio group, 2-probenylthio group and isobutenylthio group; and arylthio groups such as optionally substituted phenylthio group and naphthylthio group; An alkylsulfyl group such as a methylsulfinyl group, an ethylsulfinyl group, a propylsulfiel group, or an isopropylsul
• alkyl group which may be substituted an alkenyl group which may be substituted, an alkoxy group which may be substituted, an acyl group, an acyloxy group, a rubamoyl group which may be substituted, a carboxylate group, Amino group which may be substituted, alkylthio group which may be substituted, alkylsulfinyl group which may be substituted, alkylsulfonyl group which may be substituted, sulfamoyl group which may be substituted, and sulfonic acid
• the ester group preferably has 10 or less carbon atoms, more preferably has 6 or less carbon atoms, and still more preferably has 4 or less carbon atoms.
• the Le group and the optionally substituted ⁇ reel sulfonyl group, preferably of 1 5 or less carbon atoms, yo Ri preferably is 1 2 or less, more preferably 8 or less.
• Examples include a ter group, a sulfonic ester group, and an amino group which may be alkyl-substituted.
• a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group are exemplified. Groups are preferred.
• alkyl groups preferred are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a carboxymethyl group, a carboxyethyl group, a trifluoromethyl group, a benzyl group and a phenethyl group.
• alkenyl groups which may be substituted, unsubstituted ones are preferred.
• alkyl groups such as phenyl, naphthyl, tolyl, methoxyphenyl, carboxyphenyl and sulfoxyphenyl, alkoxy, and alkoxyl are preferred.
• alkyl groups such as phenoxy group, naphthyloxy group, tolyloxy group, methoxyphenoxy group, carboxyphenoxy group, sulfoxyphenoxy group, alkoxy group, and alkoxyl group.
• an aryloxy group which may be substituted with a substituent selected from the group consisting of sulfonic acid groups.
• carbamoyl groups preferably a group consisting of an alkyl group such as a carbamoyl group, an N, N-dimethylcarbamoyl group, a phenylcarbamoyl group, a 3-sulfonylcarbamoyl group, and an aryl group.
• an alkyl group such as a carbamoyl group, an N, N-dimethylcarbamoyl group, a phenylcarbamoyl group, a 3-sulfonylcarbamoyl group, and an aryl group.
• It is a force-rubamoyl group which may be substituted with a substituent selected from the above, more preferably a force-rubamoyl group.
• alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, or phenoxycarbonyl group, naphthyloxy group.
• Consists of alkyl, alkoxy, carboxyl, and sulfonic acid groups such as carbonyl, methylphenoxycarbonyl, methoxyphenoxycarbonyl, carboxyphenoxycarbonyl, and sulfoxyphenoxycarbonyl.
• An aryloxycarbonyl group which may be substituted with a substituent selected from the group.
• an amino group which may be substituted with an alkyl group or an acyl group such as a methylamino group, an ethylamino group, a dimethylamino group, a acetylamino group, an acetylamino group, a benzoylamino group, is preferable. is there.
• arylthio groups a group consisting of a carboxyl group such as a phenylthio group, a methylphenylthio group, a carboxyphenylthio group, a methoxyphenylthio group, an alkyl group and an alkoxy group is preferable.
• An arylthio group which may be substituted with a substituent selected from the above is preferable, and an unsubstituted arylthio group is more preferable.
• optionally substituted alkylsulfinyl groups unsubstituted ones are preferred.
• optionally substituted arylsulfinyl groups preferred are aryls which may be substituted with alkyl groups such as phenylsulfinyl, methylphenylsulfinyl and naphthylsulfiel. And more preferably an unsubstituted arylsulfinyl group. Group.
• alkylsulfonyl groups unsubstituted ones are preferred.
• arylsulfonyl groups which may be substituted, preferably substituted with a substituent selected from the group consisting of an alkyl group and an alkoxy group such as a phenylsulfonyl group, a methylbenzenesulfonyl group and a methoxybenzenesulfonyl group.
• an unsubstituted arylsulfonyl group is more preferable.
• sulfamoyl groups preferred are a sulfamoyl group, an N, N-dimethylsulfamoyl group, a hydroxyethylaminosulfonyl group, a carboxyethylaminosulfonyl group, a sulfoethylaminosulfonyl group, Substituted with a substituent selected from the group consisting of an optionally substituted alkyl group and aryl group such as a nylsulfamoyl group, a carboxyphenylsulfamoyl group, a sulfophenylsulfamoyl group, and a phosphonophenylsulfamoyl group.
• a hydrophilic group represented by a group It is also good sulfamoyl group optionally substituted by enyl group, particularly preferably a carboxymethyl Hue Nils Alpha Moi group or sulfo Hue acylsulfamoyl group.
• alkoxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, isopropoxysulfonyl group, butoxysulfonyl group, and the like, or phenoxysulfonyl group, naphthyl Consists of alkyl, alkoxy, carboxyl, and sulfonic acid groups such as xylsulfonyl group, methylphenoxysulfonyl group, methoxyphenoxysulfonyl group, carboxyphenoxysulfonyl group, and sulfoxyphenoxysulfonyl group
• An aryloxysulfonyl group which may be substituted with a substituent selected from the group;
• substituents on the heterocyclic ring preferably a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group, an optionally substituted alkyl group, an optionally substituted aryl group
• a r 103 in the general formula (103), the general formula (103 - 1) - (103 - 3) is a substituted naphthyl group represented by.
• Y 103 is a chelating group
• the chelating group is a group capable of forming an arrangement bond in the description of the substituent R 1 in the water-soluble complex dye of the present invention represented by the general formula (1).
• the same groups as mentioned above can be mentioned.
• Z 103 in the general formulas (103-1) to (103-3) is a monovalent group, and is particularly limited as long as the azo compound represented by the general formula (103) has a function as a water-soluble dye. It is not, and specific examples thereof include groups such as have been exemplified as the substituents of the heterocycle Ru mentioned in the description of the a 1.
• a halogen atom a hydroxyl group, a propyloxyl group, a sulfonic acid group, a phosphono group, a nitro group, a ureido group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, and a substituted Carboxy group, optionally substituted rubamoyl group, sulfonic acid ester group, optionally substituted amino group, sulfamoyl group, optionally substituted alkylsulfamoyl group or arylsulfamoyl group And more preferably a halogen atom, a carboxyl group, a nitro group or an arylsulfamoyl group.
• an alkoxy group which may be substituted an aryloxy group which may be substituted; an acyloxy group which may be substituted, a rubamoyl group which may be substituted, a carboxylic acid ester group and a substituted
• the amino group T examples include the same groups as those exemplified in the description of the substituent of the heterocyclic ring.
• the alkoxy group which may be substituted preferably includes an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group.
• the above-mentioned optionally substituted aryloxy group is preferably a phenoxy group.
• the above-mentioned optionally substituted acyloxy group is preferably a carbon number such as an acetyloxy group.
• the above-mentioned optionally substituted carbamoyl group is preferably an unsubstituted carbamoyl group.
• the carboxylic acid ester group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group, or an aryloxy group such as a phenoxycarbonyl group or a naphthy ⁇ ) rethoxycarbonyl group. And a carbonyl group.
• the above-mentioned optionally substituted amino group is preferably an alkylamino group having 1 to 6 carbon atoms such as an amino group or a methylamino group; an alkylamino group or a benzoylamino group having 2 to ⁇ carbon atoms such as an acetylamino group.
• C1 to C6 alkylsulfonylamino group such as methylsulfonylamino group; or arylsulfonylamino group such as phenylsulfonylamino group and 4-methylphenylsulfonylamino group.
• Preferred examples of the optionally substituted alkylsulfamoyl group include a ⁇ , ⁇ -bis (carboxymethyl) sulfamoyl group.
• the aromatic carbocyclic ring and aromatic heterocyclic ring forming the arylsulfamoyl group include an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted anthryl group, An optionally substituted phenylenyl group, an optionally substituted anthraquinolyl group, an optionally substituted penquinenolyl group, an optionally substituted triazinyl group, an optionally substituted quinolyl group, an optionally substituted Optionally substituted imidazolyl group, optionally substituted pyrazolyl group, optionally substituted isoxazolyl group, optionally substituted thiazolyl group, optionally substituted thiadiazolyl group, optionally substituted Pyridazinyl group, optionally substituted pyrimidinyl group, optionally substituted birazinyl group, Benzothiazolyl group which may be substituted, benzoxazolyl group which may be substituted, benz
• the aromatic ring is a benzene ring
• the dye solubility is high, so that it is preferable from the viewpoint of maintaining the storage stability and reliability of the recording liquid, and when the naphthalene ring is used, the dye cohesion is further improved and the solidity is high.
• the pyridine ring is preferable from the viewpoint of improving the robustness due to the salt-forming aggregation effect.
• the substituent for the aromatic carbocycle and the aromatic heterocycle is not particularly limited as long as the azo compound represented by the general formula (103) has a function as a water-soluble dye.
• Specific examples thereof include: groups such as have been exemplified as the substituents of the heterocyclic ring are exemplified in the description of the above a 1. Of these, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, a nitro group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms are preferable.
• the number of these substituents on the aromatic carbocycle and the aromatic heterocycle is preferably 0 to 3, more preferably 0 to 2.
• the substituent on the nitrogen atom in the arylsulfamoyl group is usually a hydrogen atom, an alkyl group, a hydroxyalkyl group or a mercaptoalkyl group, preferably a hydrogen atom or a methyl group.
• the alkyl group, hydroxyalkyl group or mercaptoalkyl group preferably has 4 or less carbon atoms, and more preferably has 2 or less carbon atoms.
• a103 represents an integer of 0 to 6, preferably 0 to 3, and particularly preferably 0 to 2.
• heterocycle containing Ar 103 preferred examples include JP-A-2002-080765 (corresponding English publication: European Patent Publication No. 1241232) and JP-A-2003-096323 ( Corresponding English gazettes: those described in European Patent Publication No. 1270676) and those described in Tables 5-1 to 5-10 below.
• X 1Q4 represents a hydrogen atom, a halogen atom, a nitro group, a carboxyl group, a sulfo group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Alkylsulfonylamino group, arylsulfonylamino group having 6 to 10 carbon atoms, acylamino group having 2 to 7 carbon atoms, substituted or unsubstituted triazinylamino group, or substituted or unsubstituted sulfa
• X represents a moyl group
• X 1Q4 ′ represents a hydrogen atom or a sulfo group.
• Q1Q4 has a hydroxyl group, and further has an alkoxy group having 1 to 4 carbon atoms, an acylamino group having 2 to 7 carbon atoms, a hydroxyl group, a substituted or unsubstituted triazinylamino group and a substituted or unsubstituted group.
• a phenyl or naphthyl group which may have a substituent selected from the group consisting of unsubstituted rubamoyl groups, wherein the hydroxyl group is a ring-constituting atom adjacent to the carbon atom to which the azo group is bonded; Is to combine with n 10 4 represents 0, 1, 2 or 3.
• Z 1 Q5 represents a benzene ring or a naphthalene ring having at least a sulfo group as a substituent
• Y 1Q5 represents a sulfo group or a substituted amino group.
• the substituent on the benzene ring and the naphthalene ring include a halogen atom, a nitro group, a carboxyl group and an acylamino group.
• substituent of the amino group include an acyl group, a 3,5-diaminotriazinyl group, Examples thereof include an alkoxysulfonyl group and an aryloxysulfonyl group.
• n I Q5 is an integer between 0 and 2
• Examples of the metal atom used for the chelate dye include silver (I) and aluminum.
• nickel (II), cobalt (11, 111) and copper are preferred.
• Preferable specific examples of the water-soluble metal chelate compounds include JP-A-2000-160079 (corresponding US Pat. No. 600-161), JP-A-2000-265099, and JP-A-2002-080765. Gazettes (corresponding English gazette: European Patent Publication No. 1241232) and Japanese Patent Application Laid-Open No. 2003-096323 (corresponding English gazette: European Patent Publication No.
• the magenta ink may be a combination of two types of ink, dark ink and light ink.
• Examples of the cyan ink include those containing a known cyan dye arbitrarily in an aqueous medium, preferably CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15 : 4, 15: 6, 16, 27, 29, 61 and 62, and pigments such as Pigment Green 7, 17. 18, 36, or dyes represented by the following general formulas (201) and (202) It is preferably used.
• a known cyan dye arbitrarily in an aqueous medium preferably CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15 : 4, 15: 6, 16, 27, 29, 61 and 62, and pigments such as Pigment Green 7, 17. 18, 36, or dyes represented by the following general formulas (201) and (202) It is preferably used.
• the dyes represented by the following general formulas (201) and (202) those having a molecular weight of 5,000 or less are usually preferable, and those having a molecular weight of about 300 to 3,000 are particularly preferred. It is preferable to consider such factors comprehensively.
• R CI represents a hydrogen atom or an arbitrary substituent, a plurality of may be the same or different, and M ′′ represents a metal atom.
• R represents a hydrogen atom or an arbitrary substituent, and a plurality of R e2 may be the same or different.
• Xc represents a hydrogen atom, a sulfo group, a carboxyl group, a phosphono group, an amino group, or an optionally substituted alkyl group.
• the optional substituents for R ′′ and R C2 include, for example, a halogen atom, a carboxyl group, a sulfo group, a phosphono group, a sulfo group which may be substituted.
• Amoyl group optionally substituted (: alkyl group, optionally substituted to alkoxy group, optionally substituted phenyl group, optionally substituted amino group, optionally substituted alkyl
• Examples include a sulfonyl group, an optionally substituted arylsulfonyl group, a sulfonate ester group, an acyl group, a carboxylate group, and an optionally substituted triazinyl group.
• R CI represented by the general formula (201) includes a hydrogen atom; a halogen atom; a sulfo group; an optionally substituted alkyl group; or an optionally substituted alkyl group and a substituted A sulfamoyl group which may be substituted with a substituent selected from the group consisting of aryl groups (here, preferably, a substituent of the alkyl group and aryl group is a hydroxyl group, a sulfo group, a carboxyl group, an alkylsulfonyl Or a triazinylamino group.) Is preferably used.
• the metal thickness of M cl is preferably nickel or copper, and particularly preferably copper.
• R C2 represented by the general formula (202) represents a hydrogen atom, a sulfo group, or an amino group which may be substituted with an alkyl group (where the alkyl group is substituted with a sulfoaryl group. May be suitably used.
• X c is preferably a hydrogen atom, a sulfo group, an amino group or an alkyl group having 1 to 4 carbon atoms.
• Preferred specific examples of these cyan dyes include CI Acid Blue 9, CI Direct Blue 86, CI Direct Blue 199, CI Reactive Blue 5, 7, 11, 11, 14, 15:01, 18 , 21, 23, 25, 35, 38, 41, 48, 63, 71, 72, 77, 80, 85, 92, 95, 105, 107, 1 18: 1, 123, 124, 1 36, 138 , 140, 143, 148, 152, 153, 159, 174, 197, 207, 215, 227, 229, 231 or a hydrolyzate thereof, or R cl in the general formula (201)
• R c 2 and X c in the compound represented by the following R cl — 1 to R C 1 _ 10 or the general formula (202) are each represented by the following R c 2 —:! ⁇ R
• the above-mentioned black ink contains a pigment such as CI Pigment Black 1, 7, 11 or 31 or a known pigment dye represented by carbon black or a known dye dye in an aqueous medium. Are included.
• preferred carbon blacks include various carbon blacks such as acetylene black, channel black, and furnace black, which are usually used for inkjet recording, and more preferably channel black or furnace black. Particularly preferred is furnace black.
• the DBP oil absorption of the above carbon black is preferably 100 ml 100 g or more, more preferably 120 m 1/100 g or more, and particularly preferably 14 Om 1 100 g or more.
• the volatile content is preferably 8% by weight or less, particularly preferably 4% by weight or less.
• the pH is usually 1 to 14, but from the viewpoint of storage stability of the recording solution, 3 to 11 is preferable, and 6 to 9 is particularly preferable.
• the BET specific surface area is usually 200 m 2 / g or more, preferably 250 to 600 m 2 Zg, particularly preferably 250 to 500 m 2 / g.
• the DBP oil absorption is a value measured by the JIS K6221 method
• the volatile content is a value measured by the JIS K6221 method
• the primary particle diameter is an arithmetic mean diameter (number average) measured by an electron microscope.
• Specific examples of the carbon black include the following products (1) to (4).
• the dye-based dye is preferably represented by the following general formulas (30 1) and (302).
• Water-soluble compounds Its molecular weight is preferably 4,000 or less, and among them, those having a molecular weight of 300 or more and 2000 or less are preferable in consideration of solubility, storage stability, print density and the like.
• B B1 8 1 and 0 8 1 each independently represent an aromatic ring, aromatic ring may have a substituent and m is 0:.
• each of B B1 represents a hydrogen atom or an arbitrary substituent in each independent may RB1 and RB2 which be the same or different.
• ⁇ 1 CC ⁇ 1 ′ and D B1 ′ each independently represent an aromatic ring, and the aromatic ring may have an arbitrary substituent.
• M B 1 is 0 n.
• alpha is an integer of 0 ⁇ 4.
• ⁇ ⁇ 1' if there are a plurality, each of the beta .beta.1 'may be the same or different.
• M B1 represents a hydrogen atom or any substituent represents a metal atom.
• M B 1 can also take a coordination of three or more seats, in which case, M B1 general formula (302) in from any substituent or bond portion, or by any ligand, optionally may Kuraisure distribution at a ratio of specific ligand to metal of said M B1 has. also, beta .beta.1 'there are a plurality of In this case, a metal ion may be further coordinated in the form of O—M B1 —O— between ⁇ ⁇ 1 'or ⁇ ⁇ 1 ' and C B1 'adjacent to each other with the azo group interposed therebetween. )
• examples of the optional substituent in R BI and R B2 include a hydrogen atom, an optionally substituted sulfamoyl group, and an optionally substituted alkyl.
• An alkoxy group or a phenyl group which may be substituted is preferably used.
• m B1 is especially preferable is 1
• n B1 is particularly preferably has 1 or a 2
• p B1 is especially preferable is 1
• R BI and R B2 are independently water atom, it is particularly preferable good be good phenyl group or a substituted optionally substituted C! -C 4 alkyl group.
• q B1 preferably those which are 0-2, particularly Q B1 is the aromatic rings represented by the D B1 if a 0 is also preferably used to further substituted by an aromatic ring substituent ⁇ zone group, in particular q B1 But
• aromatic rings represented by the B B1 is a sulfo group, a carboxyl group, Hue sulfonyl group or naphthyl group substituted with a phosphono group.
• the aromatic ring represented by C B1 is substituted with a sulfo group, a sulfoxyl group, an optionally substituted alkyl group, an optionally substituted ⁇ (: 4 substituted with an alkoxy group, an acetoamino group, a substituted alkylsulfonyl group, etc.
• the left end B B1 is represented by the following formula: It is preferably a phenyl group or a naphthyl group substituted with a sulfo group, a carboxyl group, or a phosphono group, and the other BB 1 and CB 1 are a sulfo group, a carboxyl group, or a substituted (: alkyl group A phenylene group or a naphthylene group substituted with an alkoxy group, an acetoamino group, a substituted alkylsulfonyl group, or the like; More preferably used.
• m B1 ′ is particularly preferably 0, ⁇ ⁇ 1 ′ is particularly preferably 1 or 2, ⁇ ⁇ 1 ′ is particularly preferably 1, and R B1 and R B2 is independently a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted ⁇ (: 4 alkyl group is particularly preferable.
• Q B1 ' is more preferably 0 to 2 When q B1 ′ is 0 or 1, particularly when q B1 ′ is 0, the aromatic ring represented by D B1 ′ is preferably further substituted with an aromatic ring-substituted azo group.
• the aromatic ring represented by ⁇ ⁇ 1 ' is a phenyl group or a naphthyl group substituted with a substituent selected from the group consisting of a sulfo group, a carboxyl group and a phosphono group.
• the aromatic ring represented by C B1 ' is a sulfo group, a carboxyl group, Optionally substituted ( ⁇ -( ⁇ alkyl group, optionally substituted Ci ⁇ alkoxy group, acetamino group, phenylene group or naphthylene group substituted with substituted alkylsulfonyl group, etc.
• Q B1 ' is 2 or more, among the plurality of B's in the general formula (302), for the left-end ⁇ 1 ', a group consisting of a sulfo group, a carboxyl group and a phosphono group It is preferably a phenyl group or a naphthyl group substituted with a substituent selected from the group consisting of: ⁇ '1 ⁇ and C B1 ⁇ are a sulfo group, a carboxyl group, and optionally substituted C! To C!
• alkyl group optionally substituted C ⁇ C ⁇ alkoxy group, Asetamino group, preferred more is what is phenylene group or a naphthylene group substituted with a substituted alkyl sulfonyl group such as It is Iraq for.
• dyes include CI Food Black 2, CI Direct Black 19, CI Direct Black 154, CI Direct Black 195, C.I.Direct Black 200, Reactive Black 31 and their hydrolysates.
• Decomposition products or dyes represented by the following general formulas (301 ′) and (302 ′) are exemplified, but the present invention is not limited to these.
• n 1 to 2
• B is the same or different.
• m is preferably 0 to 1
• n is 0 to 2.
• B may be the same or different.
• Table 13 specifically illustrates black dyes particularly preferably used in the dye set of the present invention.
• M ′ in the table is a metal atom selected from the group consisting of Na, Li, K and NH 4. . 13
• Table 13 specifically illustrates black dyes particularly preferably used in the dye set of the present invention.
• M in the table ' is a metal atom selected from the group consisting of N a, L i, K and NH 4.
• the above-mentioned magenta dye, cyan dye and black dye may be arbitrarily manufactured using known methods or according to them.
• magenta dye, cyan dye, and black dye have an acid group such as a carboxyl group or a sulfo group, the same as described in the description of the recording solution using the water-soluble complex dye of the present application.
• a salt may be arbitrarily formed, and the type of the salt may be arbitrarily changed.
• Table 14 shows examples of combinations with magenta, cyan and black dyes, which are preferable as the ink set of the present invention.
• c. I. is an abbreviation for color index.
• the numbers described in the yellow column correspond to the respective compounds described in Tables 3-1 to 3-4.
• MM—:! MM-10 are the following compounds, and MM-11 is a compound in which the reactive group of C.I. Reactive Red 180 is hydrolyzed and stabilized.
• 6-1 is It is a compound represented by No. 1.
• the numbers described in the black columns correspond to the compound numbers described in Table 13 above.
• magenta dye, cyan dye and black dye are specified in water containing a water-soluble organic solvent and optional additives in the same manner as described in the description of the recording liquid using the water-soluble complex dye of the present invention. It may be contained at a concentration of.
• the pigment concentration in the dark ink is 0.1 to 10% by weight in total with respect to the total amount of the recording liquid, preferably The content is preferably about 0.5 to 7% by weight, particularly about 2 to 5% by weight, and the pigment concentration in the light-colored ink is about 0.1 to 2% by weight, preferably about 0.1 to 1.5% by weight.
• the ink may contain a plurality of dyes in addition to the above-described dyes.
• the following components are mixed, the total amount is adjusted to 100 parts by weight with water, mixed well to dissolve the dye, filtered through a Teflon (registered trademark) filter having a pore size of 0.45, and then subjected to ultrasonic cleaning.
• the ink was prepared by degassing with a machine. The composition of the ink is shown in the table below. Ink composition
• Color tone of recorded image The clarity (C * value) of the color tone of the obtained printed matter was quantified using a colorimeter Spectro Eye (Daletag Macbeth). Where the C * value is an indicator of saturation.
• a sharp yellow or magenta print on ink-jet special paper as in this embodiment often takes a value of 80 or more. In this application, the goal was set at 80 or more.
• ⁇ E value was measured with the colorimeter described above.
• the ⁇ value indicates the degree of discoloration, and the smaller the numerical value, the smaller the degree of discoloration.
• a value of 6 was obtained.
• the target value is set to 3 or less with the aim of achieving a discoloration degree of 1 Z 2 or less, that is, light resistance that is at least twice as good as that of a general-purpose inkjet dye.
• ⁇ E value was measured with the colorimeter described above.
• the ⁇ value indicates the degree of discoloration, and the smaller the numerical value, the smaller the degree of discoloration.
• DY-132 C.I. Direct Yellow 132
• ⁇ ⁇ about 1 to 3 can be regarded as equally good. Therefore, in this application, the target value was set to 3 or less, aiming at good ozone resistance comparable to DY-132. .
• a recording liquid (ink) was prepared in the same manner as in Example 1 except that the dye was changed to the dye obtained in Synthesis Example 2 or 3, and the ink was evaluated. Table 15 shows the results.
• Example 15 An ink was prepared in the same manner as in Example 1 except that the dye was changed to the dye shown in Table 15 and the amount was changed to triple parts so that the absorbance of the ink was adjusted to that in Example 1.
• An evaluation test of the ink was performed by the evaluation method, and the results are shown in Table 15.
• the dyes listed in Table 5 are compounds having a similar structure to the dyes of the present invention, but differ in that they form a coordination bond with a metal via the hydroxyl group of the diazo component. As shown in Table 15, this dye was 3 to 7 times worse in light fastness than the dye of the present invention and nearly 10 times worse in ozone resistance than the dye of the present invention.
• Example 15 An ink was prepared in the same manner as in Example 1 except that the dye was replaced with the dye shown in Table 15 and the amount was changed to a quadruple part in order to adjust the absorbance of the ink to that of Example 1.
• An evaluation test of the ink was performed by the evaluation method, and the results are shown in Table 15.
• the dyes listed in Table 5 are compounds having a similar structure to the dyes of the present invention, but differ from the dyes of the present invention in that the coupler component is a 5-membered heterocyclic ring. This dye had good chroma and light fastness, but had ozone fastness nearly 10 times worse than the dye of the present invention.
• the ink was prepared in the same manner as in Example 1 except that the dye was changed to DY-1 32, and the amount was changed to 2 parts by weight to adjust the absorbance of the ink to that in Example 1.
• An ink evaluation test was performed, and the results are shown in Table 15.
• the DY-132 dye in Table 5 is one of the most commonly used yellow inkjet dyes. As shown in Table 15, the chroma and ozone resistance of this dye were good, but the light resistance was about 3 to 6 times worse than that of the dye of the present invention.
• magenta and cyan inks having the respective compositions shown in the following table were prepared.
• Example 1 Water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Ink
• Red which is a mixture of magenta ink and yellow ink
• inkjet paper product name: MJA 4 SP1, a product of Seiko Epson Corporation
• Green printing that mixes ink was performed.
• Red and green printing were performed in the same manner as in Example 4 except that the ink obtained in Example 2 was used as the yellow ink, and the light resistance was evaluated in the same manner. The results are shown in Table 16.
• the image recorded by the recording liquid using the water-soluble metal complex composed of the azo compound having a specific structure and a metal according to the present invention has all three characteristics of light fastness, gas fastness, and chroma. Since it has excellent properties to satisfy, the dye of the present invention has extremely excellent suitability as a dye for recording liquid.
• the contents of all the specifications of Japanese Patent Application No. 2002-207711 and Japanese Patent Application No. 2003-099932, which are the basis of the priority claim of the present application are cited and incorporated.

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• 2003
  • 2003-07-17 CN CNB03816907XA patent/CN100345911C/zh not_active Expired - Lifetime
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