WO2012081637A1 - Composition d'encre, procédé d'enregistrement par jet d'encre et corps coloré - Google Patents

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

Info

Publication number
WO2012081637A1
WO2012081637A1 PCT/JP2011/078955 JP2011078955W WO2012081637A1 WO 2012081637 A1 WO2012081637 A1 WO 2012081637A1 JP 2011078955 W JP2011078955 W JP 2011078955W WO 2012081637 A1 WO2012081637 A1 WO 2012081637A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
dye
sulfo
carboxy
ink composition
Prior art date
Application number
PCT/JP2011/078955
Other languages
English (en)
Japanese (ja)
Inventor
彬 川口
隆志 吉本
大島　賢司
弘和 北山
Original Assignee
日本化薬株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Priority to JP2012548821A priority Critical patent/JP5814260B2/ja
Publication of WO2012081637A1 publication Critical patent/WO2012081637A1/fr

Links

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
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/04—Disazo dyes in which the coupling component is a dihydroxy or polyhydroxy compound
    • C09B33/056—Disazo dyes in which the coupling component is a dihydroxy or polyhydroxy compound the coupling component being a bis-(naphthol-urea)
    • 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
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/18—Trisazo or higher polyazo dyes
    • C09B33/28—Tetrazo dyes of the type A->B->K<-C<-D
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
    • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
    • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes

Definitions

  • the present invention relates to an ink composition containing dyes (I) and (II), which are at least two specific kinds of dyes, an ink jet recording method using the ink composition, and a colored body colored by the ink composition About.
  • a recording method using an ink jet printer which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is.
  • This method is quiet because it does not generate sound because the recording head and the recording material are not in direct contact.
  • water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks for fountain pens, felt pens, and the like and inks for ink-jet recording.
  • a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
  • These inks provide a recorded image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on recording materials, have little bleeding, and have storage stability. It is required to be excellent.
  • the water-soluble dye used is required to have particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink.
  • the formed image is required to have image fastness such as water resistance, light resistance, gas resistance and moisture resistance.
  • the gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action existing in the air acts on the dye in the recording material and causes the printed image to discolor.
  • examples of the oxidizing gas having this kind of action include NOx, SOx, etc.
  • ozone gas is a main causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recording images. It is said that. Therefore, ozone gas resistance tends to be regarded as the most important among gas resistances.
  • Ink receiving layers provided on the surface of photographic image-dedicated inkjet paper often use materials such as porous white inorganic materials in order to speed up ink drying and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on such recording paper. Since the color fading phenomenon due to the oxidizing gas is characteristic of an ink jet recording image, improvement of ozone gas resistance is one of the most important issues in the ink jet recording method.
  • the ink composition used for ink jet recording and the colored bodies colored thereby will be further improved in light resistance, ozone gas resistance, moisture resistance and water resistance. Is strongly demanded.
  • Ink of various hues is prepared from various pigments, and among them, black ink is an important ink used for both monocolor and full-color images.
  • black ink is an important ink used for both monocolor and full-color images.
  • a black ink is prepared by blending a plurality of various pigments.
  • the hue differs depending on the medium (recording material) as compared to the case where the ink is prepared with a single dye.
  • Decomposition of the dye by light or ozone gas In particular, there is a problem that discoloration becomes large.
  • the bronzing phenomenon refers to a phenomenon in which the dye becomes flakes on the surface of the recording material due to the association of the dyes or poor ink absorption.
  • the gloss, print quality, and print density are all inferior.
  • it often appears as a “red floating phenomenon” in a portion printed using a metal phthalocyanine dye or a polyazo dye as a dye, resulting in nonuniform color balance as a whole image and lowering its quality.
  • glossy paper is often used as a recording material having a texture similar to that of a photographic tone.
  • the bronze phenomenon occurs, the glossiness on the surface of the recorded material varies and the texture of the image is significantly impaired. . From such a viewpoint, a pigment that does not cause bronzing is strongly desired.
  • Patent Document 1 examples of the black ink composition for inkjet having various durability of the printed material include the ink of Patent Document 1.
  • Patent Document 2 proposes an ink that further improves ozone resistance and has a good hue as black.
  • these inks are ink compositions in which the image fastness of printed matter has been greatly improved.
  • further improvement in ozone gas resistance has been demanded, and products that still satisfy market demands are still required. It has not been provided.
  • the present invention is stable even when stored for a long time, exhibits a neutral black to gray color with low saturation and no tint in both dark and light color printing, and the density of the printed image is high.
  • An object of the present invention is to provide a water-based black ink composition that gives a black recorded image that is very excellent in various fastnesses of recorded images, in particular, ozone gas resistance.
  • the present inventors have found that at least one kind of the dye represented by the specific formula (1), a tautomer thereof, or a salt thereof ( The present inventors have found that an ink composition containing the dye (I)), the dye represented by the formula (2) or a salt thereof (dye (II)) can solve the above-mentioned problems.
  • the present invention 1) At least one dye represented by the following formula (1), a tautomer thereof, or a salt thereof (I), and at least one dye represented by the following formula (2) or An ink composition containing a dye (II) which is a salt thereof;
  • R 1 represents a (C1-C4) alkyl group; a (C1-C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group
  • R 3 and R 4 each independently represent a hydrogen atom; a (C1-C4) alkyl group; a halogen atom; a (C1-C4) alkoxy group; or a sulfo group
  • R 5 represents a (C1-C4) alkylthio group; or a (C1-C4) alkylthi
  • a and B are each independently a phenyl group optionally substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, a carboxy group, and a (C1-C4) alkylcarbonylamino group.
  • R 1 is a methyl group; or a phenyl group
  • R 2 is a cyano group; or a carbamoyl group
  • R 3 is a hydrogen atom; a methyl group; or a methoxy group
  • R 4 is a sulfo group
  • R 6 is a (C1-C4) alkylcarbonylamino group
  • R 8 is a (C1-C4) alkylcarbonylamino group
  • R 9 is a sulfo (C1-C4) alkoxy group
  • R 10 is a (C1-C4) alkyl group; or an acetylamino group
  • R 11 to R 13 are each independently substituted with a hydrogen
  • a dye (III) which is a dye represented by the following formula (3) or a salt thereof, and 1 to 2 azo groups in one molecule not included in the dyes (I) to (III)
  • the proportion of the coloring matter (I) is 50 to 90% by mass, and the proportion of the coloring matter (II) is 1 to 10% by mass.
  • the total content of the pigment (I) and the pigment (II) is 0.1 to 20% by mass with respect to the total mass of the ink composition, according to any one of 1) to 7) above
  • the ratio of the dye (I) is 50 to 90% by mass
  • the ratio of the dye (II) is 1 to 10% by mass
  • the total content of the dye (I), the dye (II), the dye (III), and the dye (IV) is 0.1 to 20% by mass with respect to the total mass of the ink composition.
  • the ink composition of the present invention has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage.
  • the ink composition of the present invention is used as an ink and is recorded on ink jet dedicated paper, the printing density is high, and various fastness properties, particularly ozone gas resistance are excellent.
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids.
  • a description such as “dye, its tautomer, or a salt thereof” may be simply abbreviated as “pigment” for convenience in order to avoid complicated description. In some cases, it shall mean any one of a dye, a tautomer thereof, a salt thereof, and a mixture thereof.
  • a description such as “dye or salt thereof” may be simply abbreviated as “pigment” for the sake of convenience in order to avoid complicated description. It shall mean any of those mixtures.
  • the ink composition of the present invention comprises at least one kind of dye (I) represented by the above formula (1) and at least one kind of dye (II) represented by the above formula (2).
  • An aqueous black ink composition As will be described later, the effects of the present invention become more remarkable by further containing the dye (III) and / or the dye (IV). That is, it is possible to realize an ink composition that is extremely excellent in storage stability, print density, and various fastness properties.
  • the ink composition of the present invention further contains a dye other than the dye (I), the dye (II), the dye (III), and the dye (IV). Also good.
  • the ink composition of the present invention can obtain the effects of the present invention even if it does not contain a dye other than the dye (I), the dye (II), the dye (III), and the dye (IV). be able to.
  • the pigment (I) contained in the ink composition of the present invention is one or more pigments represented by the above formula (1). That is, the dye (I) may be a single dye represented by the above formula (1), but is usually represented by the above formula (1) from the viewpoint of ease of production, low cost, and the like.
  • the azo compound represented by the above formula (1) has a tautomer.
  • this tautomer in addition to the compound represented by the above formula (1), the following formulas (5), (6) and the like can be considered. These compounds are also included in the present invention.
  • R 1 to R 13 have the same meaning as in the above formula (1).
  • examples of the (C1 to C4) alkyl group in R 1 include a linear or branched unsubstituted group, and a linear group is preferable.
  • Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl;
  • Preferable specific examples include methyl and n-propyl, and methyl is particularly preferable.
  • Examples of the (C1-C4) alkyl group substituted with a carboxy group in R 1 include those in which any of the carbon atoms of the unsubstituted (C1-C4) alkyl group is substituted with a carboxy group.
  • the substitution position of the carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitution of the carboxy group is 1 or 2, preferably 1.
  • Specific examples include carboxymethyl and 2-carboxyethyl.
  • Preferred examples include carboxymethyl.
  • the phenyl group substituted with a sulfo group in R 1 includes a phenyl group substituted with 1 to 3, preferably 1 or 2, sulfo groups, and the substitution position of the sulfo group is not particularly limited. Specific examples include 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like. A preferred example is 4-sulfophenyl.
  • R 1 includes a (C1 to C4) alkyl group, a (C1 to C4) alkyl group substituted with a carboxy group, a phenyl group, and a phenyl group substituted with a sulfo group. More preferred is a phenyl group substituted with a (C1-C4) alkyl group, a phenyl group, or a sulfo group. More preferred are a (C1 to C4) alkyl group and a phenyl group. Particularly preferred is a (C1-C4) alkyl group, with methyl being most preferred.
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group. Among these, a cyano group and a carbamoyl group are preferable, and a cyano group is more preferable.
  • examples of the (C1 to C4) alkyl group in R 3 and R 4 include the same as the (C1 to C4) alkyl group in R 1 including preferable ones.
  • halogen atom in R 3 and R 4 a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a chlorine atom is preferable.
  • Examples of the (C1 to C4) alkoxy group in R 3 and R 4 include a linear or branched unsubstituted group, and a linear group is preferable. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy; Of these, methoxy is particularly preferred.
  • R 3 and R 4 are preferably each independently a hydrogen atom, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, or a sulfo group. More preferably, one is a combination of hydrogen atoms and the other is a sulfo group.
  • the substitution position of R 3 and R 4 is not particularly limited, but when either one is a hydrogen atom and the other is a sulfo group, the sulfo group is not adjacent to any nitrogen atom constituting the benzimidazolopyridone ring. It is preferable to substitute one of the two carbon atoms.
  • the compound represented by the above formula (1) of the present invention may be used as a mixture containing at least two kinds of positional isomers at the substitution positions of R 3 and R 4 from the viewpoint of ease of synthesis and low cost. Good.
  • R 1 is a (C1-C4) alkyl group or a phenyl group (preferably a (C1-C4) alkyl group, more preferably a methyl group)
  • R 2 Is a cyano group or a carbamoyl group (preferably a cyano group)
  • R 3 is a hydrogen atom, a methyl group, a methoxy group (preferably a methoxy group)
  • R 4 is a sulfo group.
  • examples of the (C1 to C4) alkylthio group in R 5 include those in which the alkyl moiety is a linear or branched unsubstituted group, and a linear group is preferred. Specific examples include straight chain such as methylthio, ethylthio, n-propylthio and n-butylthio; branched chain such as isopropylthio, isobutylthio, sec-butylthio and tert-butylthio;
  • the (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 5 is any carbon in the (C1-C4) alkylthio group. Those having these substituents in the atom can be mentioned.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
  • C1-C4 alkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropylthio, 3-hydroxypropylthio
  • sulfo (C1-C4) such as 2-sulfoethylthio, 3-sulfopropylthio and the like.
  • R 5 includes a sulfo (C1 to C4) alkylthio group or a carboxy (C1 to C4) alkylthio group, a sulfo (C1 to C4) alkylthio group is more preferable, and a sulfopropylthio group is particularly preferable.
  • examples of the (C1-C4) alkylcarbonylamino group in R 6 include those in which the alkyl moiety is a linear or branched unsubstituted group, and a linear group is preferred.
  • Specific examples include straight chain such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), n-propylcarbonylamino, n-butylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butyl Branched chain such as carbonylamino and pivaloylamino (tert-butylcarbonylamino); and the like.
  • a straight chain is preferable, and an acetylamino group is particularly preferable.
  • R 5 and R 6 is a combination of R 5 is a sulfo (C1-C4) alkylthio group, R 6 is an acetylamino group, R 5 is a sulfopropylthio group, and R 6 is an acetylamino group. Particularly preferred.
  • examples of the (C1 to C4) alkylthio group in R 7 include those in which the alkyl moiety is a linear or branched unsubstituted group, and a linear group is preferred. Specific examples include straight chain such as methylthio, ethylthio, n-propylthio and n-butylthio; branched chain such as isopropylthio, isobutylthio, sec-butylthio and tert-butylthio;
  • the (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 7 is any carbon in the (C1-C4) alkylthio group. Those having these substituents in the atom can be mentioned.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
  • C1-C4 alkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropylthio, 3-hydroxypropylthio
  • sulfo (C1-C4) such as 2-sulfoethylthio, 3-sulfopropylthio and the like.
  • R 7 includes a sulfo (C1 to C4) alkylthio group or a carboxy (C1 to C4) alkylthio group, a sulfo (C1 to C4) alkylthio group is more preferable, and a sulfopropylthio group is particularly preferable.
  • examples of the (C1 to C4) alkylcarbonylamino group in R 8 include those in which the alkyl moiety is a linear or branched unsubstituted group, and a linear group is preferred.
  • Specific examples include straight chain such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), n-propylcarbonylamino, n-butylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butyl Branched chain such as carbonylamino and pivaloylamino (tert-butylcarbonylamino); and the like.
  • a straight chain is preferable, and an acetylamino group is particularly preferable.
  • R 7 and R 8 is a combination of R 7 is a sulfo (C1-C4) alkylthio group, R 8 is an acetylamino group, R 7 is a sulfopropylthio group, and R 8 is an acetylamino group. Particularly preferred.
  • examples of the (C1 to C4) alkyl group in R 9 and R 10 include the same as the (C1 to C4) alkyl group in R 1 including preferable ones.
  • Examples of the (C1-C4) alkoxy group in R 9 and R 10 include the same groups as the (C1-C4) alkoxy group in R 3 and R 4 , including preferred ones.
  • the (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group in R 9 and R 10 is: Those having these substituents at any carbon atom in the (C1 to C4) alkoxy group are exemplified.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the oxygen atom in the alkoxy group is bonded.
  • hydroxy (C1 to C4) alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy
  • sulfo (C1 to C4) such as 2-sulfoethoxy, 3-sulfopropoxy and 4-sulfobutoxy.
  • R 9 includes a sulfo (C1 to C4) alkoxy group and a carboxy (C1 to C4) alkoxy group, more preferably a sulfo (C1 to C4) alkoxy group, and a sulfopropoxy group and a sulfobutoxy group. Is particularly preferred.
  • R 10 includes (C1 to C4) alkyl group, (C1 to C4) alkoxy group, sulfo (C1 to C4) alkoxy group, carboxy (C1 to C4) alkoxy group, and acetylamino group.
  • (C1-C4) alkyl groups are more preferred, and methyl groups are particularly preferred.
  • R 9 and R 10 is a combination of R 9 is a sulfo (C1-C4) alkoxy group, R 10 is a (C1-C4) alkyl group, and R 9 is a sulfopropoxy group (particularly a 3-sulfopropoxy group).
  • R 10 is preferably a combination of methyl groups, R 9 is a sulfobutoxy group (particularly preferably a 4-sulfobutoxy group), and R 10 is particularly preferably a methyl group.
  • examples of the (C1 to C4) alkyl group in R 11 to R 13 include the same as the (C1 to C4) alkyl group in R 1 including preferable ones.
  • Examples of the (C1 to C4) alkoxy group in R 11 to R 13 include the same groups as the (C1 to C4) alkoxy group in R 3 and R 4 , including preferred ones.
  • the (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group in R 11 to R 13 is as follows: A (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group in the above R 5 and R 6 ; The same thing is mentioned including a preferable thing.
  • Examples of the (C1 to C4) alkylsulfonyl group in R 11 to R 13 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl; branched chains such as isopropylsulfonyl and isobutylsulfonyl; Of the above, methylsulfonyl, ethylsulfonyl, and isopropylsulfonyl are preferable, and methylsulfonyl is particularly preferable.
  • Examples of the (C1 to C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 11 to R 13 include the above (C1 to C4) alkyl. What substituted the said group to the arbitrary carbon atoms in a sulfonyl group is mentioned, The number of this substituent is 1 or 2 normally, Preferably it is one. The position of the substituent is not particularly limited.
  • hydroxy-substituted compounds such as hydroxyethylsulfonyl and 2-hydroxypropylsulfonyl
  • sulfo-substituted compounds such as 2-sulfoethylsulfonyl and 3-sulfopropylsulfonyl
  • 2-carboxyethylsulfonyl and 3-carboxypropylsulfonyl 2-carboxyethylsulfonyl and 3-carboxypropylsulfonyl.
  • Carboxy-substituted ones such as;
  • R 11 includes a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, and a (C1 to C4) alkylsulfonyl group.
  • R 12 is a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, a sulfamoyl group, a (C1-C4) alkylsulfonyl group, or a carboxy (C1-C4) alkyl.
  • a sulfo group, a nitro group, a methyl group, a methoxy group, a sulfamoyl group, a sulfopropylsulfonyl group, or carboxyethyl A sulfonyl group is more preferred, and a sulfo group is particularly preferred. Good.
  • R 13 includes a hydrogen atom, a carboxy group, a sulfo group, a methoxy group, a nitro group, a chlorine atom, and a (C1 to C4) alkylsulfonyl group, and is a hydrogen atom or an electron-withdrawing substituent.
  • a carboxy group, a sulfo group, a nitro group, a chlorine atom, a (C1 to C4) alkylsulfonyl group, or a methoxy group is preferable, and a hydrogen atom is particularly preferable.
  • R 11 to R 13 is a combination of R 11 as a hydrogen atom, R 12 as a sulfo group, R 13 as a hydrogen atom, R 11 as a hydrogen atom, R 12 as a sulfamoyl group, and R 13 as a hydrogen atom, Or a combination of R 11 is a hydrogen atom, R 12 is a chlorine atom, R 13 is a sulfo group, R 11 is a hydrogen atom, R 12 is a chlorine atom, and R 13 is a sulfo group is particularly preferable.
  • R 1 is a methyl group; or a phenyl group
  • R 2 is a cyano group; or a carbamoyl group
  • R 3 is a hydrogen atom; a methyl group; or a methoxy group
  • R 4 is a sulfo group
  • R 6 is a (C1-C4) alkylcarbonylamino group
  • R 8 is a (C1-C4) alkylcarbonylamino group
  • R 9 is a sulfo (C1-C4) alkoxy group
  • R 10 is
  • R 1 is a methyl group; R 2 is a cyano group; R 3 is a hydrogen atom; or a methoxy group; R 4 is a sulfo group; R 5 is a sulfo (C1-C4) alkylthio group; R 6 is an acetylamino group; R 7 is a sulfo (C1-C4) alkylthio group; R 8 is an acetylamino group; R 9 is a sulfopropoxy group; or a sulfobutoxy group; R 10 is a (C1-C4) alkyl group; R 11 is a hydrogen atom; or a sulfo group; R 12 is a sulfo group; or a chlorine atom; A combination in which R 13 is a hydrogen atom; or a sulfo group.
  • the azo compound represented by the above formula (1) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid. In the following formulas (7) to (14), R 1 to R 13 have the same meaning as in the above formula (1).
  • a compound represented by the following formula (7) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (8) are subjected to a coupling reaction by a conventional method to obtain a compound represented by the following formula (9). To obtain the compound.
  • the obtained compound represented by the above formula (9) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (10) are subjected to a coupling reaction by a conventional method.
  • the compound represented by (11) is obtained.
  • the obtained compound represented by the above formula (11) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (12) are subjected to a coupling reaction by a conventional method.
  • the compound represented by (13) is obtained.
  • azo compound represented by the above formula (1) are not particularly limited, but include compounds represented by the structural formulas listed in Tables 1 to 16 below. In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience.
  • the diazotization of the compound represented by the formula (7) is carried out by a method known per se, for example, a nitrite such as -5 to 30 ° C, preferably 0 to 15 ° C in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the above formula (7) and the compound represented by the above formula (8) is also carried out under known conditions. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C., preferably 0 to 25 ° C., and at an acidic to neutral pH value, for example pH 1 to 6.
  • the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines.
  • the compound represented by the above formula (7) and the compound represented by the above formula (8) are used in a substantially stoichiometric amount.
  • the diazotization of the compound represented by the above formula (9) is carried out by a method known per se, for example, a nitrite such as, for example, -5 to 40 ° C., preferably 5 to 30 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized product of the compound represented by the above formula (9) and the compound represented by the above formula (10) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 40 ° C., preferably 10 to 30 ° C., and at an acidic to neutral pH value, for example pH 2-7.
  • a nitrite such as, for example, -5 to 40 ° C., preferably 5 to 30 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite.
  • the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base.
  • the same base as described above can be used.
  • the compound represented by the above formula (9) and the compound represented by the above formula (10) are used in a substantially stoichiometric amount.
  • the diazotization of the compound represented by the above formula (11) is carried out by a method known per se, for example, a nitrite such as -5 to 50 ° C., preferably 5 to 40 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the above formula (11) and the compound represented by the above formula (12) is also carried out under known conditions. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 50 ° C., preferably 10 to 40 ° C., and at an acidic to neutral pH value, for example pH 2 to 7.
  • the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base.
  • the same base as described above can be used.
  • the compound represented by the above formula (11) and the compound represented by the above formula (12) are used in a substantially stoichiometric amount.
  • the diazotization of the compound represented by the above formula (13) is also carried out by a method known per se, for example, a nitrite such as, for example, -5 to 50 ° C., preferably 10 to 40 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound represented by the above formula (13) and the compound represented by the above formula (14) is also carried out under known conditions. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 50 ° C., preferably 10 to 40 ° C., and at a weakly acidic to alkaline pH value.
  • a nitrite such as, for example, -5 to 50 ° C., preferably 10 to 40 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite.
  • the pH value is adjusted by adding a base.
  • a weakly acidic to weakly alkaline pH value for example, pH 5 to 10
  • the same base as described above can be used.
  • the compound represented by the above formula (13) and the compound represented by the above formula (14) are used in a substantially stoichiometric amount.
  • the pigment (II) contained in the ink composition of the present invention is one or more pigments represented by the above formula (2). That is, the dye (II) may be a single dye represented by the above formula (2) or a mixture of a plurality of dyes represented by the above formula (2). One dye is preferred.
  • a and B are each independently substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, a carboxy group, and a (C1-C4) alkylcarbonylamino group.
  • a and B are each independently a group having at least one substituent selected from the group consisting of a sulfo group and a carboxy group, and having one azo bond.
  • the substituents A and B in the above formula (2) may be independent from each other, but preferably the same combination of substituents, that is, the dye (II) preferably has a symmetric structure.
  • C.I. I. Direct Orange 26, C.I. I. Direct Orange 29, C.I. I. Direct Red 4, C.I. I. Direct Red 23, C.I. I. Direct Red 80 is available as a commercially available dye, and is suitable because it is excellent in color development, fastness, and solvent solubility when used as a black ink. Furthermore, C.I. I. Direct Red 80 is particularly useful.
  • Numbered dyes can be purchased from commercially available dyes and purified to a purity suitable for inkjet using a known method, but they are commercially available according to the synthesis method described in Commentary dye chemistry (issued by Color dyeing company). It is also easy to synthesize from these raw materials.
  • the ink composition of the present invention may contain one or more dyes represented by the above formula (3) as the dye (III). That is, the dye (III) may be a single dye represented by the above formula (3) or a mixture of a plurality of dyes represented by the above formula (3). It is preferable that it is a pigment
  • examples of the unsubstituted (C1 to C4) alkyl group for R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl; Of these, methyl, ethyl, and n-propyl are preferable, and methyl is particularly preferable.
  • Examples of the (C1-C4) alkyl group substituted with a hydroxy group or a (C1-C4) alkoxy group in R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include hydroxy-substituted ones such as 2-hydroxyethyl; methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl and the like (C1 ⁇ C4) alkoxy-substituted ones;
  • Examples of the unsubstituted (C1-C4) alkoxy group for R a include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy; Of these, methoxy, ethoxy and n-propoxy are preferable, and methoxy is particularly preferable.
  • Examples of the (C1-C4) alkoxy group substituted with a hydroxy group or a (C1-C4) alkoxy group in Ra include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxy Linear or branched, preferably linear (C1-C4) alkoxy substituted, such as propoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy and alkoxy, such as 2-hydroxyethoxyethoxy, combined And the like.
  • hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy
  • Examples of the unsubstituted (C1 to C4) alkylamino group in Ra include mono (unsubstituted linear or branched chain) such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, etc. Alkyl) amino group; di (unsubstituted straight chain) such as N, N-dimethylamino, N, N-diethylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino, etc. Branched chain alkyl) amino group; and the like.
  • Examples of the (C1-C4) alkylamino group substituted with a hydroxy group or a (C1-C4) alkoxy group in R a include mono (hydroxy-substituted) such as hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino, etc.
  • Alkyl) amino group bis (hydroxy-substituted alkyl) amino group such as bis (hydroxyethyl) amino; mono (alkoxy-substituted alkyl) amino group such as methoxyethylamino, ethoxyethylamino; bis (methoxyethyl) amino, bis (2 -Bis (alkoxy-substituted alkyl) amino groups such as ethoxyethyl) amino; and the like.
  • Examples of the carboxy (C1-C5) alkylamino group for R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino and the like.
  • Examples of the bis (carboxy (C1-C5) alkyl) amino group for R a include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include bis (carboxymethyl) amino, bis (carboxyethyl) amino, bis (carboxypropyl) amino, and the like.
  • Examples of the unsubstituted (C1-C4) alkanoylamino group in R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples thereof include linear ones such as acetylamino and n-propionylamino; branched ones such as isopropionylamino;
  • (C1-C4) alkanoylamino group substituted with a hydroxy group or a (C1-C4) alkoxy group in R a a linear or branched one can be mentioned, and a straight-chain one is preferred.
  • hydroxy-substituted ones such as hydroxyacetylamino, 2-hydroxy-n-propionylamino, 3-hydroxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino; 2 Alkoxy-substituted ones such as -methoxy-n-propionylamino, 3-methoxy-n-propionylamino, 2-methoxy-n-butyrylamino, 3-methoxy-n-butyrylamino, and the like.
  • Examples of the phenylamino group in which the benzene ring in R a is substituted with at least one group selected from the group consisting of a carboxy group, a sulfo group, and an amino group include 2-, 3-, or 4- Carboxy-substituted ones such as carboxyphenylamino and 3,5-biscarboxyphenylamino; sulfo-substituted ones such as 2-, 3- and 4-sulfophenylamino; 2-aminophenylamino and 3,5-diaminophenylamino Amino-substituted ones such as diaminosulfophenylamino and the like substituted with sulfo and amino respectively.
  • R a unsubstituted (C1 ⁇ C4) alkyl group of the above are preferred, among which methyl is particularly preferred.
  • aliphatic amino group substituted with a carboxy group or a sulfo group in X all are linear or branched, preferably a linear sulfo (C1-C5) alkylamino group; A carboxy (C1-C5) alkylamino group; a di (sulfo (C1-C5) alkyl) amino group; a di (carboxy (C1-C5) alkyl) amino group; (C1-C5) alkylamino group or di ((C1-C5) alkyl) amino group;
  • the range of carbon number is usually C1 to C5, preferably C1 to C4, more preferably C1 to C3, and further preferably C1 to C2.
  • sulfo (C1-C5) alkylamino groups such as sulfomethylamino, sulfoethylamino, sulfopropylamino, sulfobutylamino, sulfopentylamino; carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxybutyl Carboxy (C1-C5) alkylamino groups such as amino and carboxypentylamino; Di (sulfo (C1-C5) alkyl) amino groups such as di (sulfomethyl) amino, di (sulfoethyl) amino, di (sulfopropylamino); A di (carboxy (C1-C5) alkyl) amino group such as di (carboxymethyl) amino; and the like.
  • X is preferably a sulfo (C1-C5) alkylamino group or a di (carboxy (C1-C5) alkyl) amino group, more preferably the former, and particularly preferably sulfoethylamino among the former.
  • dyes (III) represented by the above formula (3) preferred are the dyes represented by the above formula (4).
  • X represents the same meaning as in formula (3), including preferred ones.
  • the most preferable one is a dye represented by the following formula (15).
  • the dye (III) represented by the above formula (3) can be obtained according to the method described in Patent Document 3.
  • the ink composition of the present invention may contain a water-soluble yellow dye having 1 to 2 azo groups in one molecule as the pigment (IV). However, the dyes contained in the dyes (I) to (III) are excluded.
  • the water-soluble yellow dye is a dye which has a sulfo group and a carboxy group in the molecule and has water solubility, and specifically has a water solubility of 50 g / kg or more.
  • Dyes exhibiting the solubility of The dye having the solubility is preferably a dye exhibiting a solubility of 80 g / kg or more, and more preferably 100 g / kg or more.
  • the dye (IV) include known yellow dyes (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 120, C CI direct yellow 132, CI direct yellow 142, etc.) can be used, but among the dyes listed above, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132, C.I. I. Direct Yellow 142, more preferably C.I. I. Direct yellow 132.
  • known yellow dyes for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 120, C CI direct yellow 132, CI direct yellow 142, etc.
  • dye (IV) a dye represented by the following formula (16) or a salt thereof (hereinafter, for the same reason as described above, it is simply referred to as “dye” including both “the dye or a salt thereof”) Is preferable).
  • an ink using a dye represented by the following formula (16) is the above-mentioned C.I. I. Compared with each dye to which a number is assigned, it is preferable because it can provide a printed matter having excellent light resistance and ozone resistance, and particularly excellent moisture resistance.
  • R represents a hydrogen atom, an unsubstituted (C1-C4) alkyl group, an unsubstituted (C1-C4) alkoxy group, or a sulfo group
  • n is 1 or 2
  • m is 1 to An integer of 3
  • q is an integer of 2 to 4
  • y is an integer of 1 to 3
  • a ring substituted by — (SO 3 H) m is not present when there is no ring represented by a broken line A benzene ring; and a naphthalene ring when a ring represented by a broken line is present.
  • the dye represented by the formula (16) may be a single dye or a mixture of a plurality of dyes represented by the formula (16), but is a single dye. Is preferred.
  • the unsubstituted (C1 to C4) alkyl group in R is the same as the unsubstituted (C1 to C4) alkyl group in R a in the above formula (3), including preferable ones. Can be mentioned.
  • Examples of the unsubstituted (C1 to C4) alkoxy group in R include the same ones as preferred, including the unsubstituted (C1 to C4) alkoxy group in R a of the above formula (3).
  • R is preferably an unsubstituted (C1 to C4) alkoxy group, particularly preferably a methoxy group.
  • n is 1 or 2, preferably 1.
  • the substitution position on the benzene ring of “— (SO 3 H) n” whose substitution position is not specified is not particularly limited, but when n is 2 with the substitution position of the nitrogen atom on the benzene ring being the 1st position The 2nd and 4th positions are preferred. Similarly, when n is 1, the 4-position is preferred.
  • m is an integer of 1 to 3, preferably 1 or 2.
  • substitution position on the ring that is substituted by “— (SO 3 H) m” whose substitution position is not specified.
  • m is 1 and the substitution position of the nitrogen atom on the benzene ring is defined as the 1-position, “— (SO 3 H) More preferably, “m” is substituted at the 3-position.
  • the ring has a ring represented by a broken line, that is, a naphthalene ring
  • m is 2 and the substitution position of the nitrogen atom of the naphthalene ring is defined as the 2-position, and “— (SO 3 H M) is more preferably substituted at the 5th and 7th positions, the 6th and 8th positions, or the 4th and 8th positions.
  • q is an integer of 2 to 4, preferably 3.
  • Y is an integer of 1 to 3, preferably 2.
  • a preferable pigment represented by the above formula (16) is a pigment represented by the following formula (17).
  • R represents the same meaning including those preferred in the above formula (16), and L represents 1 or 2, preferably 1.
  • the most preferable one is the dye represented by the following formula (18).
  • the salt of the dye (I), the dye (II), the dye (III), and the dye (IV) used in the ink composition of the present invention is a salt with an inorganic or organic cation.
  • the salt with an inorganic cation include alkali metal salts, alkaline earth metal salts, and ammonium salts, and lithium, sodium, potassium salts, and ammonium salts are preferable.
  • examples of the salt with an organic cation include, but are not limited to, a salt with a quaternary ammonium represented by the following formula (19). Further, the free acid, its tautomer, and various salts thereof may be a mixture.
  • any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used.
  • the physical properties such as solubility may differ, and by selecting the type of salt as appropriate, or by changing the ratio when containing multiple salts, etc. It is also possible to obtain a mixture having physical properties suitable for the above.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group. , At least one of them represents a group other than a hydrogen atom.
  • Specific examples of the alkyl group of Z 1 , Z 2 , Z 3 , Z 4 in the above formula (19) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, etc.
  • hydroxyalkyl group examples include hydroxy (C1-C4) such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
  • Alkyl group, and specific examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl.
  • 2-hydroxye And hydroxy (C1-C4) alkoxy (C1-C4) alkyl groups such as toxibutyl.
  • hydroxyethoxy (C1-C4) alkyl is preferred. Particularly preferred is a hydrogen atom; methyl; hydroxy (C1-C4) alkyl such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc. Groups: hydroxyethoxy (C1-C4) such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. Alkyl group; and the like.
  • the ink composition of the present invention will be described.
  • the ink composition of the present invention containing the dye (I), the dye (II), and, if necessary, the dye (III) and the dye (IV) can color a material made of cellulose. Further, it is possible to color a material having a carbonamide bond, and it can be widely used for materials such as leather, fabric and paper.
  • each reaction solution after the final step is directly used for producing the ink composition of the present invention.
  • the reaction solution containing each dye is individually dried, for example, spray dried; salted out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; hydrochloric acid, sulfuric acid, nitric acid
  • Each of the dyes is isolated by mixing acid salting out by adding a mineral acid such as acid salting; or acid salting out by combining salting-out and aciding-out as described above, and mixed to prepare an ink composition. You can also
  • the ink composition of the present invention contains dye (I) and dye (II) as the dye. Moreover, in order to acquire a more remarkable effect, pigment
  • Each of the dye (I), the dye (II), and the dye (III) may be a single dye or a mixture of a plurality of dyes as long as the above specific conditions are satisfied.
  • Pigment (IV) is a compound having 1 to 2 azo groups in one molecule, and is a water-soluble yellow dye. Therefore, the ink composition of the present invention is one in which at least two kinds of pigments are blended, and four or more pigments are blended as necessary.
  • the ratio of the dye (I) is 50 to 90% by mass, preferably 50 to 80% by mass, and the ratio of the dye (II) is 1 to 10% by mass.
  • the content is preferably 1 to 8% by mass.
  • the ratio of the dye (III) is 5 to 20% by mass, preferably 5 to 15% by mass, and the ratio of the dye (IV) is 4 to 20% by mass. %, Preferably 4 to 15% by mass.
  • the total content of the dye (I), the dye (II), and the dye (III) and the dye (IV) when necessary is usually 0.1 to 20% by mass with respect to the total mass of the ink composition.
  • the content is preferably 1 to 10% by mass, more preferably 2 to 8% by mass.
  • the ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent, for example, 0 to 20% by mass of an ink preparation agent, and the balance is water.
  • the pH of the ink composition of the present invention is preferably pH 5 to 11 and more preferably pH 7 to 10 for the purpose of improving storage stability.
  • the surface tension of the ink composition is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m.
  • the viscosity of the ink composition is preferably 30 mPa ⁇ s or less, and more preferably 20 mPa ⁇ s or less.
  • the pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.
  • the dye (I), the dye (II), the dye (III), and the dye (IV) are dissolved in water or a water-soluble organic solvent (an organic solvent miscible with water).
  • An ink preparation agent is added as necessary.
  • the metal cation in the dye (I), dye (II), dye (III), and dye (IV) contained in the ink composition of the present invention is used. It is preferable to use a low content of inorganic impurities such as chloride (for example, sodium chloride) and sulfate (for example, sodium sulfate).
  • the standard of the inorganic impurity content is about 1% by mass or less with respect to the total mass of the dye, and the lower limit may be the detection limit of the analytical instrument or less, that is, 0%.
  • a method using a reverse osmosis membrane a dried pigment product or a wet cake is stirred in a mixed solvent of (C1-C4) alcohol such as methanol and water, and the precipitate is separated by filtration. Then, a desalting treatment may be performed by a method such as drying;
  • Examples of the ink preparation agent suitably used in the preparation of the ink composition of the present invention include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, and dye-dissolving agents. , Antioxidants, surfactants and the like.
  • these ink preparation agents will be described.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof.
  • preservative examples include organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole, Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl brom Acetate-based and inorganic salt-based compounds are exemplified.
  • organic halogen compounds include sodium pentachlorophenol
  • pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide.
  • isothiazoline compounds Are, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -Methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.
  • antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, trade name, Proxel RTM GXL (S), Proxel RTM XL-2 (S), and the like.
  • RTM means a registered trademark.
  • any substance can be used as long as it can control the pH of the ink in the range of, for example, 5 to 11 without adversely affecting the prepared ink.
  • specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Alkaline metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate;
  • chelating reagent examples include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
  • rust preventive examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
  • water-soluble ultraviolet absorbers examples include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
  • water-soluble polymer compounds examples include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.
  • dye solubilizer examples include ⁇ -caprolactam, ethylene carbonate, urea and the like.
  • organic and metal complex anti-fading agents can be used.
  • organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and the like.
  • surfactant examples include known surfactants such as anionic, cationic, and nonionic surfactants.
  • anionic surfactants include alkyl sulfonates, alkyl carboxylates, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurates, alkyls Sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonic acid Examples thereof include salts, diethylsulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.
  • cationic surfactants examples include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • amphoteric surfactants include: lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline Derivatives and the like.
  • nonionic surfactants include ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether.
  • Polyesters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate System; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5- Acetylene glycol (alcohol) type such as methyl-1-hexyn-3-ol; manufactured by Nisshin Chemical Co., Ltd., trade name Surfynol 104, 105, 82, 465, Olphine STG, etc .; Polyglycol ether type (for example, SIGMA-ALDRICH) TergItol 15-S-7 manufactured by The above ink preparation agents are used alone or in combination.
  • SIGMA-ALDRICH SIGMA-ALDRICH
  • the ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order.
  • the obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities.
  • the ink composition of the present invention includes the dye (I) and the dye (II). ), Pigment (III), and pigment (IV), other pigments having various hues may be contained within a range that does not impair the effects obtained by the present invention.
  • black having other hues for example, CI Acid Black 1, CI Direct Black 22, CI Direct Black 19, etc.
  • orange for example, CI Direct Orange 17
  • Brown, Scarlet eg, CI Direct Red 89, etc.
  • Red eg, CI Direct Red 62, CI Direct, etc.
  • magenta eg CI Direct Red 227 etc.
  • violet blue, navy, Lean
  • cyan e.g. C.I. Direct Blue 199, C.I. Acid Blue 9, C.I. Acid Blue 249, etc.
  • the ink composition of the present invention can be used in various fields, but is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink for ink-jet recording. It is suitably used in the ink jet recording method of the invention.
  • the ink jet recording method of the present invention performs recording by using the ink composition of the present invention as an ink, ejecting ink droplets of the ink in accordance with a recording signal, and attaching the ink droplets to a recording material.
  • the ink nozzles used for recording are not particularly limited and can be appropriately selected according to the purpose.
  • the recording method is a known method, for example, a charge control method for ejecting ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element; An acoustic ink jet method in which the ink is irradiated and the ink is discharged using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Etc. can be adopted.
  • a method called a photo ink in which a large number of inks having a low dye concentration (dye content) are ejected in a small volume; a plurality of dyes having substantially the same hue and different dye concentrations in the ink.
  • the colored body of the present invention is a substance colored with the ink composition of the present invention, and preferably a recording material colored with the ink composition of the present invention by an ink jet recording method using an ink jet printer.
  • the recording material that can be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters.
  • a transmission sheet is preferred.
  • the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer.
  • the ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are hydrophilic such as polyvinyl alcohol and polyvinyl pyrrolidone.
  • a sheet coated with a porous white inorganic material on the surface is particularly suitable for recording photographic images because of its high surface gloss and excellent water resistance.
  • the images recorded in these images are greatly discolored by ozone gas.
  • the ink composition of the present invention is excellent in ozone gas resistance, a great effect is exhibited even when ink jet recording is performed on such a recording material.
  • An example of a typical commercial product as a sheet coated on the surface with the porous white inorganic material as described above is manufactured by Canon Inc.
  • a container containing the above ink composition is set at a predetermined position of the ink jet printer, and recording is performed by a normal recording method. Record it on the material.
  • the inkjet recording method of the present invention includes the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color ink such as green, blue (or violet), and red (or orange).
  • a composition can also be used in combination.
  • the ink composition of each color is poured into each container, and each container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the black ink composition of the present invention, and used for ink jet recording.
  • the pigment contained in the ink composition of the present invention is easily synthesized and inexpensive. Further, since the solubility in a medium containing water as a main component is high and the solubility in water is excellent, the filterability by the membrane filter in the process of producing the ink composition is good.
  • the ink composition containing the compound or the ink prepared from the ink composition is also excellent in storage stability and ejection stability. That is, the ink composition of the present invention has good storage stability without solid precipitation, changes in physical properties, changes in hue, etc. after long-term storage.
  • the ink composition containing the coloring matter is suitably used for inkjet recording and writing instruments.
  • the ink composition of the present invention When used for recording on inkjet paper, it exhibits a neutral black to gray color with no hue in both dark and light color printing, and there is no change in hue for each medium.
  • the print density of the recorded image is very high, and even when a high-concentration solution is printed, no bronzing occurs in the image, and various fastnesses such as moisture resistance and water resistance, particularly light resistance and ozone gas resistance. Both are excellent.
  • full-color ink jet recording with excellent fastness and storage stability is possible, and of course can be used on plain paper. .
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • the obtained wet cake was dissolved in 300 parts of water, adjusted to pH 3.0 to 4.0 by adding 35% hydrochloric acid, salted out with sodium chloride, and the precipitated solid was collected by filtration, 205.3 parts of the compound represented by (21) was obtained as a wet cake.
  • pH 4 was obtained by adding a 25% aqueous sodium hydroxide solution.
  • An aqueous solution was obtained as 0 to 5.0.
  • This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes.
  • the mixture was reacted for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 15% aqueous sodium carbonate solution, and then salted out by adding sodium chloride.
  • the precipitated solid was collected by filtration to obtain 90 parts of a compound represented by the following formula (25) as a wet cake.
  • Step 6 To 250 parts of water, 45 parts of a wet cake of the compound represented by the formula (24) obtained in Example 1 (Step 4) was added and dissolved by stirring. After adding 16.5 parts of 35% hydrochloric acid, 4.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 5.5 parts of a compound of the following formula (26) obtained by the method described in JP-A-2004-083492 is added to 60 parts of water, and a pH of 4.5-5. An aqueous solution was obtained as 5.
  • This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 2.0 to 3.0 by adding a 15% aqueous sodium carbonate solution. After the pH was adjusted to 4.5 by adding a 15% aqueous sodium carbonate solution, 350 parts of methanol was added. The precipitated solid was collected by filtration to obtain 96.6 parts of a compound represented by the following formula (27) as a wet cake.
  • Step 7 To 170 parts of water, 32.2 parts of a wet cake of the compound represented by the formula (27) obtained in Example 1 (Step 6) was added, and dissolved by stirring. After adding 5.2 parts of 35% hydrochloric acid, 1.5 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 1.0 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
  • 2.2 parts of a compound represented by the following formula (28) obtained by the method described in Patent Document 1 was added to 60 parts of water, and a 25% aqueous sodium hydroxide solution was added to adjust the pH to 7.5 to 8.5. To obtain an aqueous solution.
  • the diazo reaction solution obtained above was added dropwise to this aqueous solution at 15 to 30 ° C. over about 30 minutes.
  • an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.5 to 8.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment.
  • Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 29.5 parts of a wet cake.
  • the obtained wet cake was dissolved in 100 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 80 parts of methanol was added, and the precipitated solid was collected by filtration.
  • Example 2 A sodium salt of 6.3 parts of the compound represented by the formula (29) obtained in Example 1 and 14 parts of lithium chloride were added to 140 parts of water and stirred to obtain an aqueous solution. 400 parts of 2-propanol was added, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake and 12.5 parts of lithium chloride were again added to 150 parts of water and stirred to obtain an aqueous solution. 350 parts of 2-propanol was added, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 80 parts of water, 150 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • the wet cake obtained again was dissolved in 40 parts of water, 100 parts of 2-propanol was added, and the precipitated solid was separated by filtration and dried to obtain the compound represented by the above formula (29) of the present invention. 5 parts were obtained as a mixed salt of sodium and lithium. ⁇ max: 586 nm.
  • Example 3 (Process 1) 15.2 parts of 2-methyl-6-nitroaniline were dissolved in 300 parts of methanol. The resulting solution was transferred into an autoclave, 2.0 parts of 5% Pd / carbon was added, and the mixture was reacted at 20 to 30 ° C. under a hydrogen pressure of 0.2 to 0.5 MPa until no hydrogen was absorbed. The reaction was further continued at the same temperature for 30 minutes. The catalyst (5% Pd / carbon) was separated by filtration to obtain a solution (filtrate) containing a compound represented by the following formula (30).
  • the methoxy group is at the position b and the sulfo group substitution position is a, c, or d, or the methoxy group is at the position c, and the sulfo group was a mixture of compounds in which the substitution position was a, b, or d.
  • Example 1 (Process 5) In Example 1 (Step 7), instead of using 2.2 parts of the compound represented by Formula (28), the wetness of the compound represented by Formula (33) obtained in Example 3 (Step 4) was used. Except for using 7.2 parts of cake, 6.3 parts of a compound represented by the following formula (34) of the present invention was obtained as a sodium salt in the same manner as in Example 1 (Step 7).
  • the methoxy group in the following formula (34) is at the position b and the substitution position of the sulfo group is a, c, or d, or the methoxy group is at the position c, and the sulfo group was a mixed dye composed of 2 to 6 types of compounds in which the substitution position was a, b, or d.
  • Example 4 In Example 2 above, instead of using 6.3 parts of the sodium salt of the compound represented by Formula (29), sodium of the compound represented by Formula (34) obtained in Example 3 above (Step 5) Except for using 8.8 parts of the salt, 4.5 parts of the compound represented by the above formula (34) of the present invention was obtained as a mixed salt of sodium and lithium. ⁇ max: 592 nm.
  • Example 5 (Process 1) 15.2 parts of 2-methyl-6-nitroaniline were dissolved in 300 parts of methanol. Transfer the resulting solution into an autoclave, add 2.0 parts of 5% Pd / carbon, and react under stirring at 20-30 ° C. under 0.2-0.5 MPa hydrogen pressure until no hydrogen is absorbed. Then, the reaction was further continued at the same temperature for 30 minutes. The catalyst (5% Pd / carbon) was separated by filtration to obtain a solution (filtrate) containing a compound represented by the following formula (35).
  • Example 5 In the above Example 1 (Step 7), instead of using 2.2 parts of the compound represented by Formula (28), wet the compound represented by Formula (39) obtained in Example 5 (Step 4). Except for using 6.0 parts of cake, 6.0 parts of the compound represented by the following formula (40) of the present invention was obtained as a sodium salt.
  • the methoxy group in the following formula (40) is at the position b
  • the substitution position of the sulfo group is a, c, or d
  • the methoxy group is at the position c
  • the sulfo group Was a mixed dye composed of 2 to 6 types of compounds in which the substitution position was a, b, or d.
  • Example 6 In Example 2 above, instead of using 6.3 parts of the sodium salt of the compound represented by Formula (29), sodium of the compound represented by Formula (40) obtained in Example 5 (Step 5) above Except for using 8.8 parts of the salt, 4.0 parts of the compound represented by the above formula (40) of the present invention was obtained as a mixed salt of sodium and lithium. ⁇ max: 590 nm.
  • Example 7 (Process 1) To 250 parts of water, 45 parts of a wet cake of the compound represented by the formula (24) obtained in Example 1 (Step 4) was added and dissolved by stirring. After adding 16.5 parts of 35% hydrochloric acid, 4.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid. On the other hand, 5.8 parts of a compound of the following formula (41) obtained by the method described in JP-A-2004-083492 is added to 60 parts of water, and a pH of 4.5-5. An aqueous solution was obtained as 5.
  • This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 2.0 to 3.0 by adding a 15% aqueous sodium carbonate solution. After the pH was adjusted to 4.5 by adding a 15% aqueous sodium carbonate solution, 350 parts of methanol was added. The precipitated solid was collected by filtration to obtain 94.0 parts of a compound represented by the following formula (42) as a wet cake.
  • the diazo reaction solution obtained above was added dropwise to this aqueous solution at 15 to 30 ° C. over about 30 minutes.
  • an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.5 to 8.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment.
  • Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 30.0 parts of a wet cake.
  • the obtained wet cake was dissolved in 100 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 80 parts of methanol was added, and the precipitated solid was collected by filtration.
  • the obtained wet cake was dissolved again in 60 parts of water, and 90 parts of methanol was added.
  • the precipitated solid was separated by filtration and dried to obtain 6.0 parts of a compound represented by the following formula (43) of the present invention as a sodium salt.
  • Example 8 A sodium salt of 6.0 parts of the compound represented by the formula (43) obtained in Example 7 and 14 parts of lithium chloride were added to 140 parts of water and stirred to obtain an aqueous solution. 400 parts of 2-propanol was added, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake and 12.5 parts of lithium chloride were again added to 150 parts of water and stirred to obtain an aqueous solution. 350 parts of 2-propanol was added, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 80 parts of water, 150 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • the wet cake obtained again was dissolved in 40 parts of water, 100 parts of 2-propanol was added, and the precipitated solid was separated by filtration and dried to obtain the compound 4. represented by the above formula (43) of the present invention. 3 parts were obtained as a mixed salt of sodium and lithium. ⁇ max: 590 nm.
  • Example 9 In Example 1 (Step 7), instead of using 2.2 parts of the compound represented by Formula (28), the wetness of the compound represented by Formula (33) obtained in Example 3 (Step 4) was used. 5.6 parts of a compound represented by the following formula (44) of the present invention was obtained as a sodium salt in the same manner except that 7.2 parts of cake was used.
  • the methoxy group in the following formula (44) is at the position b
  • the substitution position of the sulfo group is a, c, or d
  • the methoxy group is at the position c
  • the sulfo group was a mixed dye composed of 2 to 6 types of compounds in which the substitution position was a, b, or d.
  • Example 10 In Example 7 above, instead of using 6.0 parts of the sodium salt of the compound represented by Formula (43), 5.6 of the compound represented by Formula (44) obtained in Example 9 above. 4.0 parts of the compound represented by the above formula (44) of the present invention were obtained as a mixed salt of sodium and lithium in the same manner except that parts were used. ⁇ max: 597 nm.
  • the dyes obtained in Examples 1 to 10 were dissolved in ion-exchanged water to prepare solutions in which 5% of the dye was dissolved in water.
  • the obtained solution was put in a sealed container and allowed to stand for 1 week in a thermostatic oven at 60 ° C., but no decomposition of the pigment occurred.
  • ion-exchange water was used for water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with lithium hydroxide, and then ion-exchanged water was added to make a total amount of 100 parts.
  • a surfactant in the following Table 20 Nissin Chemical Co., Ltd. product name Surfinol 104PG50 was used.
  • the inks of Comparative Examples 1 to 8 were obtained by mixing the components shown in Table 20 below.
  • the ink for the comparative example was prepared in the same manner as the ink preparation of the above example.
  • R. 80 is C.I. I. Direct Red80.
  • the dye (III) represented by the formula (15) in the above table (20) was obtained by following the synthesis example described in Patent Document 3.
  • the dye (IV) represented by the formula (18) in the above table (20) was obtained by following the synthesis example described in Patent Document 4.
  • Comparative Example 1 As a black pigment to be compared, an ink was prepared using the pigment disclosed in Example 2 of International Publication No. 2007/077931, and this was used as the ink of Comparative Example 1. These dyes were obtained by following the synthesis methods described in the patent. The structures of the pigments (45) and (46) used in the ink of Comparative Example 1 are shown below.
  • Comparative Example 2 As a black pigment to be compared, an ink using a pigment disclosed in Example 1 of JP-A-2009-185133 was prepared, and this was used as the ink of Comparative Example 2. These dyes were obtained by following the synthesis methods described in the patent. The structure of the dye (47) used in the ink of Comparative Example 2 is shown below.
  • (F) Bronze property evaluation In order to evaluate the bronze property of the image recorded on the glossy paper 1 by ink jet, whether the bronze phenomenon has occurred by reflecting the light of the fluorescent lamp with the recorded image and visually checking the reflected light. An assessment of whether or not was made. The recorded image obtained should be free from bronzing. The results are shown in Table 21. A: Bronze phenomenon does not occur even at 100% duty. B: Bronze phenomenon occurs only at 100% duty. C: Bronze phenomenon occurs at 100% and 80% duty portions. D: A bronze phenomenon occurs at a duty portion of 60% duty or lower.
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the difference between L * , a * , and b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2 ⁇ : ⁇ E value is 3.5 or less ⁇ : ⁇ E value is 3.5 or more and less than 5.0 ⁇ : ⁇ E after 5.0 or more and less than 7.5 ⁇ : ⁇ E value is 7.5 or more
  • the black ink composition of the present invention is suitably used for black ink for various recordings such as writing instruments, particularly for inkjet recording.

Landscapes

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

Abstract

Cette composition d'encre contient un pigment (I) qui correspond à au moins un type de pigments représenté par la formule (1), un tautomère de ce pigment ou encore un sel du pigment ou tautomère, et un pigment (II) qui est au moins un type de pigment représenté par la formule (2) ou un sel de ce pigment. Dans la formule (1), R1 représente un groupe C1-C4 alkyle ou analogue ; R2 représente un groupe cyano ou analogue; R3 et R4 représentent indépendamment un atome d'hydrogène, un groupe sulfo, ou un groupe C1-C4 alkoxy ou analogue; R5 et R7 représentent indépendamment un groupe C1-C4 alkylthio ou analogue; R6 et R8 représentent indépendamment un groupe C1-C4 alkyl carbonyl amino; R9 et R10 représentent indépendamment un groupe C1-C4 alkoxy ou analogue; et R11 à R13 représentent indépendamment un atome d'hydrogène, un groupe sulfo ou analogue. Dans la formule (2), A et B représentent indépendamment un groupe phényle ou analogue pouvant avoir un substituant.
PCT/JP2011/078955 2010-12-17 2011-12-14 Composition d'encre, procédé d'enregistrement par jet d'encre et corps coloré WO2012081637A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012548821A JP5814260B2 (ja) 2010-12-17 2011-12-14 インク組成物、インクジェット記録方法及び着色体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-281298 2010-12-17
JP2010281298 2010-12-17

Publications (1)

Publication Number Publication Date
WO2012081637A1 true WO2012081637A1 (fr) 2012-06-21

Family

ID=46244733

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/078955 WO2012081637A1 (fr) 2010-12-17 2011-12-14 Composition d'encre, procédé d'enregistrement par jet d'encre et corps coloré

Country Status (3)

Country Link
JP (1) JP5814260B2 (fr)
TW (1) TWI477562B (fr)
WO (1) WO2012081637A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130321523A1 (en) * 2010-12-17 2013-12-05 Nippon Kayaku Kabushiki Kaisha Azo compound, ink composition, recording method and colored material
EP2674462A1 (fr) * 2012-06-15 2013-12-18 Canon Kabushiki Kaisha Encre, cartouche d'encre et procédé d'enregistrement à jet d'encre
US8864891B2 (en) 2010-12-17 2014-10-21 Nippon Kayaku Kabushiki Kaisha Ink composition, inkjet recording method and colored body
US20180074371A1 (en) * 2015-05-20 2018-03-15 Nippon Kayaku Kabushiki Kaisha Dye-based polarizer as well as polarizing plate and liquid crystal display device using the polarizer
US10323150B2 (en) * 2015-09-25 2019-06-18 Nippon Kayaku Kabushiki Kaisha Azo compound, ink composition, ink jet recording method, and colored article

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008169374A (ja) * 2006-11-08 2008-07-24 Nippon Kayaku Co Ltd アゾ化合物、インク組成物、記録方法及び着色体
JP2009263513A (ja) * 2008-04-25 2009-11-12 Nippon Kayaku Co Ltd アゾ化合物、インク組成物、記録方法及び着色体

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998591A (en) * 1997-05-22 1999-12-07 Sumitomo Chemical Company, Limited Fiber-reactive bisazo compound

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008169374A (ja) * 2006-11-08 2008-07-24 Nippon Kayaku Co Ltd アゾ化合物、インク組成物、記録方法及び着色体
JP2009263513A (ja) * 2008-04-25 2009-11-12 Nippon Kayaku Co Ltd アゾ化合物、インク組成物、記録方法及び着色体

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130321523A1 (en) * 2010-12-17 2013-12-05 Nippon Kayaku Kabushiki Kaisha Azo compound, ink composition, recording method and colored material
US8864891B2 (en) 2010-12-17 2014-10-21 Nippon Kayaku Kabushiki Kaisha Ink composition, inkjet recording method and colored body
US8932393B2 (en) * 2010-12-17 2015-01-13 Nippon Kayaku Kabushiki Kaisha Azo compound, ink composition, recording method and colored material
EP2674462A1 (fr) * 2012-06-15 2013-12-18 Canon Kabushiki Kaisha Encre, cartouche d'encre et procédé d'enregistrement à jet d'encre
JP2014015600A (ja) * 2012-06-15 2014-01-30 Canon Inc インク、インクカートリッジ、及びインクジェット記録方法
US8814341B2 (en) 2012-06-15 2014-08-26 Canon Kabushiki Kaisha Ink, ink cartridge and ink jet recording method
US20180074371A1 (en) * 2015-05-20 2018-03-15 Nippon Kayaku Kabushiki Kaisha Dye-based polarizer as well as polarizing plate and liquid crystal display device using the polarizer
US10007142B2 (en) * 2015-05-20 2018-06-26 Nippon Kayaku Kabushiki Kaisha Dye-based polarizer as well as polarizing plate and liquid crystal display device using the polarizer
US10323150B2 (en) * 2015-09-25 2019-06-18 Nippon Kayaku Kabushiki Kaisha Azo compound, ink composition, ink jet recording method, and colored article

Also Published As

Publication number Publication date
TW201237111A (en) 2012-09-16
TWI477562B (zh) 2015-03-21
JPWO2012081637A1 (ja) 2014-05-22
JP5814260B2 (ja) 2015-11-17

Similar Documents

Publication Publication Date Title
JP6218381B2 (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP5456666B2 (ja) トリスアゾ化合物、インク組成物、記録方法及び着色体
JP5925129B2 (ja) インク組成物、インクジェット記録方法及び着色体
JP2009132794A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP5814260B2 (ja) インク組成物、インクジェット記録方法及び着色体
JP2009185133A (ja) インク組成物、インクジェット記録方法及び着色体
JPWO2009136577A1 (ja) インク組成物、インクジェット記録方法及び着色体
JP2017061633A (ja) インク組成物、これを用いるインクジェット記録方法、及び着色体
WO2010143610A1 (fr) Matière colorante constituée d&#39;un composé trisazoïque, compositions d&#39;encre, procédé d&#39;impression et corps coloré
WO2014132926A1 (fr) Composé azo, composition d&#39;encre, procédé d&#39;impression et corps pigmenté
WO2017051923A1 (fr) Composé azoïque, composition d&#39;encre, procédé d&#39;impression par jet d&#39;encre et article coloré
JP2017061634A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP5456667B2 (ja) トリスアゾ化合物、インク組成物、記録方法及び着色体
JP2016172815A (ja) アゾ化合物、インク組成物、記録方法及び着色体
WO2010109843A1 (fr) Composé azo, composition d&#39;encre, procédé d&#39;impression et corps coloré
JP2016175996A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP5570506B2 (ja) インク組成物、インクジェット記録方法及び着色体
JP2015098572A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2015021032A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2019151784A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2019210360A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2017171842A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2017171841A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2017061635A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2017171843A (ja) アゾ化合物、インク組成物、記録方法及び着色体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11848861

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012548821

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11848861

Country of ref document: EP

Kind code of ref document: A1