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WO2007138925A1 - Composé azoïque, composition d'encre, procédé d'impression et matière colorée - Google Patents

Composé azoïque, composition d'encre, procédé d'impression et matière colorée Download PDF

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Publication number
WO2007138925A1
WO2007138925A1 PCT/JP2007/060431 JP2007060431W WO2007138925A1 WO 2007138925 A1 WO2007138925 A1 WO 2007138925A1 JP 2007060431 W JP2007060431 W JP 2007060431W WO 2007138925 A1 WO2007138925 A1 WO 2007138925A1
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Prior art keywords
group
sulfo
azo
groups
hydrogen atom
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PCT/JP2007/060431
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English (en)
Japanese (ja)
Inventor
Takashi Yoshimoto
Takahiko Matsui
Yoshiyuki Dejima
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Nippon Kayaku Kabushiki Kaisha
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Priority to JP2008517861A priority Critical patent/JPWO2007138925A1/ja
Publication of WO2007138925A1 publication Critical patent/WO2007138925A1/fr

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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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/50—Tetrazo dyes
    • C09B35/60—Tetrazo dyes of the type
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/50—Tetrazo dyes
    • C09B35/62—Tetrazo dyes of the type
    • 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
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents

Definitions

  • the present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product colored by these.
  • 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.). It is for recording.
  • This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact, so there is little noise generation and quietness, and the size and high speed are easy. Is expected.
  • water-based inks in which water-soluble dyes are dissolved in water-based media have been used as inks used for applications such as fountain pens and felt-tip pens, and inks for inkjet recording.
  • water-soluble organic solvents are added to prevent clogging of ink at the pen tip and the ink discharge nozzle. These inks provide a sufficiently dense recorded image, do not cause clogging of the pen tip and nozzles, good drying properties on the recording material, low bleeding, and storage stability. It is required to be excellent.
  • the water-soluble dye used is required to have a particularly high solubility in water and a 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, ozone gas resistance and moisture resistance.
  • the ozone gas resistance refers to a phenomenon in which ozone gas having an oxidizing action that exists in the air acts on the dye in the recording paper and discolors the printed image. It is resistance to do.
  • NOx, SOx, etc. are examples of acidic gases that have this type of action.
  • ozone gas promotes the discoloration and fading phenomenon of inkjet recording images. It is said to be the main causative substance.
  • the ink-receiving layer provided on the surface of the photographic image ink jet paper is made of a porous white inorganic material to accelerate ink drying and reduce image bleeding in high-quality recording.
  • the ink composition used for inkjet recording and the colored bodies colored thereby should be expanded in the field of use of printing methods using ink.
  • Light resistance, ozone gas resistance, moisture resistance Further improvement in water resistance and water resistance is strongly demanded.
  • Patent Document 1 As a compound (black pigment) used in an inkjet black ink which has been improved most recently in recent years and has become the most important issue in recent years, for example, a disazo compound described in Patent Document 1 can be used. Is mentioned. However, the ozone gas resistance of these compounds does not fully meet the market requirements. Patent Documents 2, 3 and 4 disclose trisazoy compounds, and Patent Documents 5, 6 and 7 disclose tetrakisazo compounds.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-183545
  • Patent Document 2 Japanese Patent Laid-Open No. 62-109872
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2003-201412
  • Patent Document 4 WO2005Z054374
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2005-68416
  • Patent Document 6 WO2005Z 097912
  • Patent Document 7 WO2005Zl08502
  • the present invention is stable even when a high-concentration aqueous solution or ink having high solubility in a medium containing water as a main component is stored for a long period of time, and a photograph in which the density of a printed image is very high. Even when a high-concentration solution is printed on inkjet paper, it does not cause bronzing, gives a printed black image with excellent fastness, especially ozone gas resistance, and is easy to synthesize. It is an object of the present invention to provide a black ink coloring matter and an ink composition thereof which are inexpensive.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, an N-phenylaminosulfo group.
  • (C1-C4) alkylsulfonyl group (the alkyl group may be substituted with a hydroxy group), phosphono group, nitro group, acyl group, ureido group, (C1-C4) alkyl group (hydroxy group) Group (which may be substituted with a group selected from the group consisting of (C1-C4) alkoxy groups), (C1-C4) alkoxy groups (hydroxy groups, (C1-C4) alkoxy groups, sulfo groups and carboxyl groups Substituted with a group selected from the group consisting of an acylamino group, an alkylsulfo-lumino group, or a phenylsulfo-lumino group (phenol).
  • The-group may be substituted with a group selected from the group consisting of a halogen atom, an alkyl group and a -tro group).
  • R 9 and R 1q are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, or an N-phenylaminosulfol group.
  • (C1-C4) alkylsulfonyl group (the alkyl group may be substituted with a hydroxy group), phosphono group, nitro group, acyl group, ureido group, (C1-C4) alkyl group (hydroxy group or (Cl-C4) may be substituted with an alkoxy group), (C1-C4) alkoxy group (substituted with a hydroxy group, (C1-C4) alkoxy group, a sulfo group or a carboxyl group!
  • a acylamino group, an alkylsulfo-lumino group or a phenylsulfo-lumino group (the phenol group may be substituted with a halogen atom, an alkyl group or a -tro group), n is 0 or 1 , Respectively.
  • At least one of R 3 to R 6 is a group other than a hydrogen atom, at least two of R 7 to R 1Q are sulfo groups, and the total number of sulfo groups included in formula (1) is 8 to 10
  • R 3 , R 5 and R 6 are each independently a carboxyl group, a sulfo group, or a (C1-C4) alkyl group (substituted with a hydroxy group or a (C1-C4) alkoxy group !, may be!), (C 1 to C4) an alkoxy group (which may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group), or an acylamino group according to (1) or (2) Azo compounds or salts thereof,
  • R 1 is a sulfo group or a carboxyl group
  • the substitution position of R 1 is ortho to the azo group
  • the substitution position of the nitro group is para to the azo group
  • the substitution of R 1 When the position is para to the azo group, the substitution position of the nitro group is ortho to the azo group
  • R 2 is a hydrogen atom (1) to (3) Azo compound or its salt
  • R 1 is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R 2 is a hydrogen atom, and n is 1 (1) to ( 4) the azo compound or salt thereof according to any one of
  • R 1 is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R 2 is a hydrogen atom, R 7 is a hydrogen atom, R 8 and The azo compound or salt thereof according to any one of (1) to (8), wherein R 9 is a sulfo group, R 1Q is a hydroxy group, the substitution position is peri to the azo group, and n is 1.
  • R 1 is a sulfo group, a carboxy group or a cyano group, and the substitution position of R 1 is ortho to the azo group, the force at which the substitution position of the nitro group is para to the azo group or
  • R 1 is a sulfo group or a cyano group, and the substitution position of R 1 is para to the azo group, the substitution position of the -together group is ortho to the azo group
  • R 2 is a hydrogen atom
  • R 3 and R 5 are sulfo- or hydroxy-substituted (C1-C4) alkoxy groups
  • R 4 and R 6 are hydrogen atoms, (C1-C4) alkyl groups or hydroxy-substituted (C1-C4) alkoxy group
  • R 7 is a hydrogen atom
  • R 8 and R 9 are sulfo groups
  • R 1Q is a hydroxy group or a sulfo group
  • the substitution position of R 1Q is an azo
  • R 1 is a sulfo group, the substitution position is ortho to the azo group, the nitro substitution position is para to the azo group,
  • R 2 is a hydrogen atom,
  • R 3 and R 5 are sulfo substitution (C1 -C4) alkoxy group,
  • R 4 and R 6 are (C1 -C4) alkyl group,
  • R 7 is a hydrogen atom,
  • R 8 and R 9 is a sulfo group, the substitution position R 1Q is in hydrate proxy group to ⁇ zone group The peri-position, and n is 1.
  • the azo compound of the present invention or a salt thereof (hereinafter collectively referred to simply as azo compound) is excellent in water-solubility, and therefore has good filterability with a membrane filter in the process of producing an ink composition. Also, it has excellent stability during storage of recording liquid and ejection stability during ink jet recording. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition containing the azo compound of the present invention is suitably used for inkjet recording and writing instruments, and the recording density of recorded images when recorded on plain paper and ink jet paper is very high.
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • the alkyl group in the group is not particularly limited unless otherwise specified, but is usually an alkyl group having about 1 to 20 carbon atoms, and a carbon having about 1 to about: LO is preferred.
  • An alkyl group of about 1 to 4 is more preferable.
  • more preferable “alkyl” or “alkoxy” includes (C1-C4) alkyl or (C1-C4) alkoxy.
  • the term “halogen” is not particularly limited, but “chlorine atom” or “bromine atom” is usually preferable.
  • N-alkylaminosulfol groups include, for example, N-methylaminosulfol, N-ethylaminosulfol, N- (n —Propyl) aminosulfol, N— (n-butyl) aminosulfur, N, N-dimethylaminosulfurol, N, N-di (n-propyl) aminosulfol and the like N— (C1 ⁇ C4) an alkylaminosulfonyl group.
  • Examples of (C1-C4) alkylsulfol groups (wherein the alkyl group may be substituted with a hydroxy group ) in ⁇ -1 ⁇ 1 () in the above formula (1) include, for example, methylsulfo- , Ethinolesnorehoninole, propinolesnorehoninole, butinolesnorehoninole, hydroxyethinolesnorephonyl, 2-hydroxypropylsulfol and 3-hydroxypropylsulfol.
  • examples of the acyl group include acetyl, piool, butyryl, isobutyryl, benzoyl and naphthoyl.
  • examples of the (C1-C4) alkyl group which may be substituted with a hydroxy group or a (C1-C4) alkoxy group include, for example, methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyxetyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl, 2-ethoxyethyl, n -propoxychetyl, isopropoxychetyl, Examples include n -butoxetyl, methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, and n-propoxybutyl. Usually, unsubstituted (C1-C4) alkyl is preferred.
  • ⁇ to 1 ⁇ 1 () in the above formula (1) it may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group, and (C1 to C4) of the alkoxy group
  • a hydroxy group a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group, and (C1 to C4) of the alkoxy group
  • methoxy, ethoxy, n propoxy isopropoxy, n butoxy, sec butoxy, tert butoxy, 2 hydroxyethoxy, 2 hydroxypropoxy, 3 hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n propoxyethoxy, isopropoxyethoxy, n Butoxyethoxy, methoxypropoxy, ethoxypropoxy, npropoxypropoxy, isopropoxybutoxy, npropoxybutoxy, 2-hydroxyethoxyethoxy, carb
  • examples of the acylamino group include acetylamino, propionylamino-containing butyrylamino-containing isobutyrylamino-containing benzoylamino, naphthoylamino and the like.
  • alkylsulfo-lumino group examples include, for example, methylsulfo-amidoethylsulfo-ramino and propylsulfo-ramino.
  • a halogen atom, an alkyl group or a -tro group may be substituted.
  • the phenylsulfo-lumino group include benzenesulfo- Examples include benzene-sulfo-lumino, benzene-sulfo-lumino, and toluene-toluene-amido. Substituents on these ring rings can be substituted in the ortho, meta, or para positions on the ring ring relative to the sulforamino group! / It ’s okay.
  • R 1 and R 2 in the above formula (1) are each independently a hydrogen atom, a chlorine atom, a bromine atom, a carboxylated carboxyl, a sulfo, a sulfamoyl, an N-methylaminosulfonole, an N-phenenole.
  • R 1 and R 2 are each independently a hydrogen atom, a chlorine atom, a sialamosulfuramoyl, acetyl, methylsulfur, hydroxyethylsulfol, nitro, carboxyl, or sulfo, Preferably, they are a hydrogen atom, carboxyl, sulfo, or cyan, and in these cases, one is a hydrogen atom and the other is more preferably a group other than a hydrogen atom. Further preferred R 1 is carboxyl or sulfo, and sulfo is particularly preferred. R 2 is particularly preferably a hydrogen atom.
  • the substitution position is R 1 when the substitution position is ortho to the azo group, and the substitution position of the nitro group is the azo group. against a para position, when the substitution position of R 1 is para-position to ⁇ zone group, the substitution position is substituted position ⁇ zone of preferred instrument R 1 being ortho against the ⁇ zone group the nitro group It is more preferred that the position is ortho to the group, and the position of substitution of the -to-group is para to the azo group.
  • Preferred as the phenyl group substituted with NO, R 1 and R 2 in formula (1) is p
  • groups other than hydrogen atoms include carboxyl, sulfo, (C1-C4) alkyl (substituted with hydroxy or (C1-C4) alkoxy !, may be!), (C1-C4) alkoxy ⁇ Substitution with hydroxy, sulfo or carboxyl which may be substituted with hydroxy, (C1-C4) alkoxy, sulfo or carboxyl is preferred.
  • 1 to 3, preferably 2 to 3 of R 3 to R 6 are sulfo- or hydroxy-substituted (C 1 to C 4) alkoxy groups, and At least one is sulfo-substituted (C 1 to C4) alkoxy group, preferably 2 are sulfo-substituted (C1 to C4) alkoxy groups, the rest are hydrogen atoms or (C1 to C4) alkyl groups, preferably all the rest are (C1 to C4) alkyl The case where it is a group can be mentioned.
  • the (C1-C4) alkoxy group in the above an ethoxy group or a propoxy group is preferable.
  • R 3 , R 5 and R 6 are each independently a carboxyl group, sulfo group, (C1-C4) alkyl group (which may be substituted with a hydroxy group or a (C1-C4) alkoxy group), (C1-C4) Examples include an alkoxy group (which may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group), or an acylamino group, and more preferably 1 to 2 (C 1 to C4) alkyl group, the remaining 2 to 3 are (C1 to C4) alkoxy groups (hydroxy groups, (C1 to C4) alkoxy groups, sulfo groups or carboxyl groups may be substituted, preferably hydroxy groups , A sulfo group or a carboxyl group, and more preferably a hydroxy group or a sulfo group.
  • R 3 and R 5 are each independently (C 1 -C 4) alkoxy substituted with sulfo, carboxyl or hydroxy, more preferably sulfo-substituted (C 1 -C 4) alkoxy. 3-sulfopropoxy is most preferred.
  • R 4 and R 6 are each independently a hydrogen atom, (C1-C4) alkyl or hydroxy-substituted (C1-C4) alkoxy, and (C1-C4) alkyl is more preferred methyl. Most preferred.
  • R 3 to R 6 in the above formula (1) are, independently of each other, a hydrogen atom, a chlorine atom, a hydroxy, a carboxy-containing carboxyl, a sulfo, a sulfamoyl, an N-methinoaminoaminorehoninole, an N— Phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propynole, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3 Sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino-containing benzoylamino, and the like, more preferably hydrogen atom, methyl, e
  • R 3 and R 5 preferred are those independently contained in (C1-C4) alkoxy substituted with either sulfo, carboxyl or hydroxy, and more preferred. Is included in sulfo-substituted (C1-C4) alkoxy.
  • preferable R 4 and R 6 are each independently a hydrogen atom or (C1-C4) alkyl or hydroxy-substituted (C1-C4) alkoxy, more preferably (C1-C4 ) It is included in alkyl.
  • R 3 to R 6 a combination, preferably the R 3 ⁇ R 6! /, A combination between ones are those more preferred one of preferred instrument R 3 to R 6 is the rest are preferable Combinations that are more preferable are combinations of R 3 to R 6 that are more preferable.
  • R 7 to R 1C> in the above formula (1) are a hydrogen atom, a chlorine atom, a bromine atom, a hydroxy, a carboxylated carboxyl, a sulfo, a sulfamoyl, an N-methylaminosulfol, and an N-phenol.
  • R 7 includes a hydrogen atom.
  • R 8 and R 9 include sulfo.
  • Preferred R 1G includes sulfo or hydroxy, more preferably hydroxy.
  • the substitution position of R 1C) is preferably the peri-position (8-position) relative to the azo group.
  • R 7 to R 1G is when R 7 is a hydrogen atom, R 8 and R 9 are sulfo, R 1C) is hydroxy, and the substitution position of R 1G is peri to the azo group It is.
  • n 0 or 1 !, it can be shifted! /, but 1 is preferred! /.
  • 1 ⁇ to 1 ⁇ substituents and n are preferably and , R 1 and R 2 , R 3 to R 6 and R 7 to R 1G are preferably combined with each other, and more preferable combinations are (l) R 1 and R 2 , (2) R 3 to R 6.
  • the more preferable combination of (1) to (3) is more preferable (1) to More preferred in (3) is a combination of 1 to 2 and other more preferred. More preferred in (1) to (3), or more preferred U, most preferred, a combination of things. Is the most preferred.
  • R 1 is preferably sulfo, carboxy, or cyan as a combination of the substituents in the above formula (1), and the substitution position of R 1 is at the ortho position with respect to the azo group. and - force the substitution position of Toro is para to ⁇ zone group or, R 1 is sulfo or Shiano, para substitution position of R 1 Whereas ⁇ zone group, and - substitution position Toro Is ortho to the azo group, R 2 is a hydrogen atom, and R 3 and R 5 are (C1-C4) alkoxy substituted by either sulfo, carboxy or hydroxy, preferably sulfo Or (C1-C4) alkoxy substituted by either hydroxy, R 4 and R 6 are each a hydrogen atom, (C1-C4) alkyl, or hydroxy-substituted (Cl-C4) alkoxy, preferably one Is a hydrogen atom and the other is (C1-C4) alkyl Or hydrate proxy substituted (C 1
  • R 1 is sulfo and the substitution position is ortho to the azo group, the nitro substitution position is para to the azo group, R 2 is a hydrogen atom, R 3 and R 5 are sulfo substitution (C1 ⁇ C4) alkoxy, R 4 and R 6 are (C1-C4) alkyl, R 7 is a hydrogen atom, R 8 and R 9 are sulfo, R 1G is hydroxy, and the substitution position is peri-position to the azo group, n Is a compound in which 1.
  • R 1 is sulfo
  • the substitution position is ortho to the azo group
  • the nitro substitution position is para to the azo group
  • R 2 is a hydrogen atom
  • R 3 and R 5 are 3-sulfopropoxy
  • R 7 is a hydrogen atom
  • R 8 and R 9 are sulfo
  • R 1G is hydroxy
  • R 1G is substituted at the peri position relative to the azo group
  • n is 1. Is mentioned.
  • R 7 to R 1C are sulfo groups, and the formula (1)
  • the total number of sulfo groups possessed by the compound is preferably 8 to 10, more preferably 9 to 10, and most preferably 9.
  • the salt of the azo compound represented by the formula (1) is an inorganic or organic cation salt.
  • inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts.
  • Preferred salts are lithium, sodium, potassium, and ammonium salts, and
  • organic cation salts include, but are not limited to, salts of compounds represented by the following formula (2).
  • Z 2 , Z 3 and Z 4 each independently represent a group selected from a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.
  • alkyl group of Z 3 or Z 4 include (C1-C4) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec butyl, tert butyl, etc.
  • Specific examples include hydroxy- (C1-C4) alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxypropyl, 3-hydroxybutyl, 2-hydroxybutyl, and hydroxyalkoxyalkyl groups.
  • hydroxymethyl such as hydroxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl (C1-C4 ) Alkoxy— (C 1 -C 4 ) Alkyl groups, among which hydroxyethoxy (C1-C4) alkyl groups are preferred.
  • Particularly preferred are a hydrogen atom; methyl; hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl.
  • C1-C4 alkyl groups such as til and 2-hydroxybutyl; hydroxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3- And hydroxyethoxy- (C1-C4) alkyl groups such as hydroxyethoxybutyl and 2-hydroxyethoxybutyl.
  • ZZ 2 , Z 3 and Z 4 either two are a hydrogen atom and Z or an alkyl group, and the other two are a hydroxy- (C1-C4) alkyl group, Alternatively, it is preferable that any one of them is a hydrogen atom or an alkyl group and the remaining three are hydroxy (C1-C4) alkyl groups! /.
  • the azo compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method.
  • the structural formula of the compound in each step is expressed in the form of a free acid.
  • the obtained compound represented by the above formula (4) was diazotized by a conventional method, and the diazoi compound was subjected to a coupling reaction with 4 amino-5-naphthol-1,7-disulfonic acid under an acidic condition.
  • the obtained compound represented by the above formula (13) is diazotized by a conventional method, and then the above diazo compound and the compound represented by the above formula (8) are subjected to a coupling reaction.
  • the azo compound of the present invention represented by the formula (1) or a salt thereof can be obtained.
  • Preferable specific examples of the compound of the present invention represented by the formula (1) include, but are not limited to, compounds described in Table 2 and Table 3 below. In each table, the sulfo group and carboxyl group are expressed in the form of free acid.
  • the esterification reaction between the compound of formula (3) and p-toluenesulfuryl chloride is carried out by a method known per se.
  • the esterification reaction may be carried out in water or an aqueous organic medium, for example at a temperature of 20-100 ° C, preferably 30-80 ° C, and a neutral force alkaline pH value, more preferably neutral to weakly alkaline,
  • the pH value is preferably 7 to 10.
  • the pH value is adjusted by adding a base.
  • a base for example, hydroxylated Alkali metal hydroxides such as lithium or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, and acetates such as sodium acetate can be used.
  • the compound of formula (3) and p-toluenesulfuryl chloride are used in almost stoichiometric amounts.
  • the diazotization of the compound of the formula (4) is carried out by a method known per se.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • an inorganic acid medium for example at a temperature of 5-30 ° C., preferably 0-15 ° C.
  • Coupling of the diazotized compound of formula (4) with 4-amino-5-naphthol 1,7-disulfonic acid is also carried out under conditions known per se. That is, the coupling reaction is carried out in water or an aqueous organic medium, for example, at a temperature of 5 to 30 ° C, preferably 5 to 25 ° C, and an acidic to neutral, preferably acidic to weakly acidic pH value such as ⁇ 1. A pH value of ⁇ 4 is good. Since the inside of the coupling reaction system is usually acidic, it is preferable to keep the reaction system preferably from acidic to weakly acidic, for example, ⁇ 1 to 4, by adding a base.
  • Examples of the base include lithium hydroxide or alkali metal hydroxide such as sodium hydroxide, alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, acetate such as sodium acetate, ammonia or Organic amines can be used.
  • the compound of formula (4) and 4-amino-5-naphthol-1,7-disulfonic acid are used in an almost stoichiometric amount.
  • Diazotization of the compound of formula (6) is also carried out by a method known per se.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • an inorganic acid medium for example at a temperature of 5-30 ° C., preferably 0-15 ° C.
  • the coupling of the diazotized compound of formula (6) and the compound of formula (5) is also carried out under conditions known per se.
  • the coupling reaction is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° C, and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, such as pH 5-10. Good to do.
  • the pH value is adjusted by adding base.
  • bases include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, or ammonia. Or organic amines can be used.
  • the compounds of formula (5) and formula (6) are used in an almost stoichiometric amount.
  • the production of the compound of the formula (8) by hydrolysis of the compound of the formula (7) is also carried out by a method known per se.
  • a method of heating in an aqueous alkaline medium is preferably used.
  • the pH value of the reaction solution is preferably maintained at 9.5 to L1.5.
  • the pH value is adjusted by adding a base.
  • the base those described above can be used.
  • Diazotization of the compound of the formula (9) is also carried out by a method known per se.
  • the diazotid is used, for example, in a mineral acid medium using, for example, a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. To be implemented.
  • the coupling of the diazotized compound of formula (9) and the compound of formula (10) is also carried out under conditions known per se. It may be carried out in water or an aqueous organic medium, for example at a temperature of 5-30 ° C., preferably 5-25 ° C. and an acidic to neutral pH value.
  • the coupling reaction is carried out, for example, at ⁇ 1 to 7, and the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, or ammonia. Or an organic amine etc. can be used.
  • the compounds of formulas (9) and (10) are used in almost stoichiometric amounts.
  • Diazotization of the compound of formula (11) is also carried out by a method known per se.
  • the diazotid is carried out in an inorganic acid medium, for example using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C. Is done.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • the coupling of the diazotized compound of formula (11) and the compound of formula (12) is also carried out under conditions known per se.
  • water or an aqueous organic medium for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, for example at a pH value of pH 6-10. It is advantageous to carry out a ring reaction.
  • the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or sodium carbonate, acetates such as sodium acetate, ammonia or Yes Machines can be used.
  • the compounds of formulas (12) and (11) are used in approximately stoichiometric amounts.
  • Diazotization of the compound of the formula (13) is also carried out by a method known per se.
  • the diazotium is carried out, for example, in a mineral acid medium, for example using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 5 to 25 ° C.
  • Coupling of the diazotized compound of formula (13) and the compound of formula (8) is also carried out under conditions known per se. It is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C, and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, for example at a pH value of pH 6 to 10. good.
  • the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, ammonia or organic amines. Etc. can be used.
  • the compounds of formulas (8) and (13) are used in almost stoichiometric amounts.
  • the compound represented by the formula (1) of the present invention is prepared by adjusting the pH of the reaction solution to neutral or acidic according to the purpose of acid precipitation after the coupling reaction, It can be obtained as a salt such as a sodium salt or a mixture of a salt and a free acid by salting out by adding a salt such as a salt.
  • the obtained compound is dissolved in water as necessary, and crystallization with addition of an alcohol such as methanol or 2-propanol V is carried out about 1 to 3 times as appropriate, so that the metal cation salt can be obtained. Soil and inorganic salts such as Z or sulfate can be removed, and the target azo compound having a low content of the inorganic salt can be obtained.
  • the compound represented by the formula (1) of the present invention can be isolated in the form of a free acid by adding a mineral acid to the reaction solution after the coupling reaction.
  • Inorganic salts can be removed by washing the isolated compound with water or acidified water.
  • the acid type dye (compound) having a low inorganic salt content thus obtained is neutralized with a desired inorganic or organic base in an aqueous medium to form a corresponding salt solution.
  • I can do it.
  • inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide or potassium hydroxide, ammonium hydroxide, lithium carbonate, carbonate, and the like.
  • organic bases include organic amines such as ethanolamine and triethanolamine, which are represented by the above formula (2). Force nor Examples include amines, but inorganic or organic bases are not limited to these.
  • the azo compound of the present invention can be used as a black pigment for dyeing various articles by a conventional method.
  • a typical use is one in which the compound is dissolved in a liquid medium, preferably an aqueous medium, and used as an aqueous composition for dyeing.
  • the aqueous composition containing the azo compound is capable of dyeing a material having a cellulose power.
  • the aqueous composition can be used for dyeing leather, woven fabric, paper, and the like because it can dye a material having a carbonamide bond.
  • a typical example of the aqueous composition is an ink composition.
  • a reaction solution containing the azoich compound of the present invention represented by the above formula (1) for example, the reaction before preparing to pH 6.0 to 7.5 with 35% hydrochloric acid in Example 1 (3) described later
  • the liquid can be used as it is in the production of the aqueous composition, particularly the ink composition.
  • the reaction solution is first dried, for example, spray-dried and isolated, and the pH is adjusted as necessary, as in the examples below.
  • salt praying with inorganic salts such as salt, sodium sulfate, sodium sulfate, etc.
  • mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. It is preferable to isolate, then remove inorganic salts as necessary, and then use this to prepare the aqueous composition, particularly the ink composition.
  • the content of the azo compound of the present invention in the aqueous composition can be variously changed according to the purpose, and is usually about 0.1 to 25% by mass with respect to the entire aqueous composition.
  • the aqueous composition may contain about 0 to 30% by mass of other water-soluble organic solvents and about 0 to 20% by mass of other additives, with the balance being water.
  • the ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the azo compound represented by the formula (1) of the present invention. It is a composition with water as the main medium.
  • the ink composition of the present invention further contains a water-soluble organic solvent, for example 0 to 30% by mass, preferably 2 to 25% by mass, more preferably 5 to 20% by mass of an ink preparation that may be contained, for example, 0 to 10% by mass, preferably 0 to 7% by mass. May be contained in an amount of 0 to 5% by mass.
  • the pH of the ink composition is preferably pH 7 to 10 and more preferably pH 7 to 10 from the viewpoint of improving storage stability.
  • the surface tension of the ink composition is preferably 25 to 70 mNZm, more preferably 25 to 60 mNZm. Further, the viscosity of the ink composition is preferably 30 mPa's or less, 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 described later.
  • the ink composition of the present invention dissolves the azo compound represented by the formula (1) in water or a water-soluble organic solvent (an organic solvent miscible with water), and the ink composition is used as necessary. A preparation is added.
  • this ink thread composite is used as an ink for an ink jet printer, the content of the inorganic compound such as a metal cation salt or an inorganic salt such as sulfate is low.
  • the preferred content is, for example, about 1% by mass or less based on the chromogen.
  • the conventional method using a reverse osmosis membrane or a dried product or wet cake of the azo compound of the present invention is applied to the above-described method for removing inorganic salts.
  • desalting may be performed by stirring in a mixed solvent of alcohol such as methanol and water, separating by filtration, and drying.
  • Al-Nol Carboxylic acid amides such as N, N dimethylformamide or N, N-dimethylacetamide; Ratatas such as 2-pyrrolidone or N-methylpyrrolidin 2one; 1,3 dimethylimidazolidin 2-one or 1, 3 Cyclic ureas such as dimethylhexahydropyrimido 2-one; ketones or keto alcohols such as acetonitrile, methyl ethyl ketone or 2-methyl-2-hydroxypentane-4-one; cyclic ethers such as tetrahydrofuran or dioxane; Ethylene glycol, 1, 2 propylene glycol, 1, 3 pro Glycol, 1, 2 butylene glycol, 1, 4-butylene glycol Honoré, 1, 6 hexylene glycol, diethylene glycidyl Mono-, oligo- or poly-alkylene glycols with (C2-C6) alkylene units such as cornole, triethylene glycol, tetraethylene
  • Ink preparations used for preparing the ink composition include, for example, antiseptic and antifungal agents, wrinkle adjusting agents, chelating reagents, antifungal agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dyes, and the like. Examples include solubilizers, antioxidants, and surfactants. These drugs are described below.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ⁇ -hydroxybenzoic acid ethyl ester, 1,2-benzisothiazoline 3-one and salts thereof. . These are preferably used in the ink composition in an amount of from 0.02 to 1.00% by mass.
  • Examples of the preservative include, for example, organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, halogenyl sulfone-based, odopropargyl-based, ⁇ ⁇ haloalkylthio-based, nitrile-based, pyridin-based, 8-oxyquinoline-based, Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brom
  • Examples include compounds such as Hihidanone, benzyl bromoacetate and inorganic salts.
  • organic halogen compounds include pentachlorophenol sodium
  • specific examples of pyridine oxide compounds include, for example, 2-pyridinethiol 1 oxide sodium
  • specific examples of inorganic salt compounds include sodium acetic anhydride.
  • isothiazoline compounds include 1,2- 3-isone thiazoline 3-one, 2-n-octinole 4-isothiazoline 3-one, 5-methyl 2-methyl 4-isothiazoline 3-one, 5-black 2-methyl 4-isothiazoline 1 -On magnesium chloride, 5-methyl 2-isothiazoline 3-on calcium chloride or 2-methyl 4-isothiazoline 3-on calcium chloride.
  • Specific examples of other antiseptic / antifungal agents include sodium sorbate and sodium benzoate.
  • the P H of the ink for example 5 Any substance can be used as long as it can control the range of L 1. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine or N-methylethanolamine or organic bases such as potassium acetate; or lithium hydroxide, sodium hydroxide or potassium hydroxide Alkali metal hydroxides such as lithium carbonate, sodium carbonate, sodium bicarbonate or potassium carbonate, etc., hydroxyammonium (ammonia), sodium silicate or phosphoric acid Inorganic bases such as disodium; and the like.
  • alkanolamines such as diethanolamine, triethanolamine or N-methylethanolamine or organic bases such as potassium acetate
  • Alkali metal hydroxides such as lithium carbonate, sodium carbonate, sodium bicarbonate or potassium carbonate, etc., hydroxyammonium (ammonia), sodium silicate or phosphoric acid Inorganic bases such as disodium; and the like.
  • chelating reagent examples include, for example, sodium ethylenediamine tetraacetate, sodium utrilotriacetate, sodium hydroxyethylethylenediamin triacetate, sodium diethylenetriaminepentaacetate, or sodium uracil diacetate.
  • antifungal agent examples include, for example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate or dicyclohexyl ammonium. -Umnite light.
  • water-soluble ultraviolet absorbers examples include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
  • water-soluble polymer compound examples include polybulal alcohol, cellulose derivative, polyamine or polyimine.
  • dye solubilizer examples include ⁇ -force prolatatam, ethylene carbonate or urea.
  • antioxidants include, for example, various organic and metal complex anti-fading agents. Can be used. Examples of the organic anti-fading agent include rhino, idroquinones, alkoxyphenols, dialkoxyphenols, phenols, arrines, amines, indanes, chromans, alkoxylins or And heterocyclic rings. Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants. Examples of cation surfactants include alkyl sulfonates, alkyl carboxylates, a-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-amino acids and their salts, N-acylmethyl taurine.
  • alkyl sulfate polyoxyalkyl ether sulfate alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid sarcophagus, castor oil sulfate ester, lauryl alcohol sulfate ester, alkyl phenol phosphate ester, alkyl phosphate ester , Alkylaryl sulfonate, jetyl sulfonate, jetyl hexyl sulfonate, dioctyl sulfonate, and the like.
  • the cationic surfactant include 2 vinyl pyridine derivatives and poly 4-vinyl pyridine derivatives.
  • amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkynole N canoleboxoxymethinole N hydroxyethyl imidazolium umbetaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, Octyl polyaminoethylglycine and other imidazoline derivatives.
  • non-ionic surfactant include polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether.
  • Ethers such as polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether or polyoxyethylene alkyl ether; polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxy Esters such as ethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, polyoxyethylene monooleate or polyoxyethylene stearate; 2, 4, 7, 9-tetramethyl- Acetylene glycols such as 5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6 diol, or 3,5 dimethyl-1-hexyne 3ol (eg, manufactured by Nissin Chemical Industry Co., Ltd.) ,Product : Such as Surfynol 104, 105, 82, 465 or Orufuin STG), and the like
  • 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.
  • other pigments having various hues may be mixed. In that case, black having other hues, yellow, magenta, cyan, and other colors can be mixed and used.
  • 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-jet ink. It is suitably used in the ink jet recording method of the present invention described later.
  • the ink jet recording method of the present invention is characterized by performing recording using the ink composition of the present invention.
  • the ink receiving ink containing the ink composition may be used for recording on the image receiving material by ink jet.
  • the ink nozzles There are no particular restrictions on the ink nozzles to be used at that time, and they can be appropriately selected according to the purpose.
  • a known ink jet recording method can be used.For example, a charge control method for discharging ink using electrostatic attraction force, a drop-on-demand method (pressure pulse using the vibration pressure of a piezo element), or the like.
  • an acoustic ink jet system that changes the electrical signal into an acoustic beam, irradiates the ink, and uses the radiation pressure to eject the ink, and forms a bubble by heating the ink to form a thermal ink jet that uses the generated pressure.
  • Bubble Jet (registered trademark)) method or the like can be adopted.
  • the ink jet recording method uses a low density called photo ink, a method that ejects a large number of inks by volume, and a plurality of inks having substantially the same hue and different densities, thereby improving image quality. This includes a method that uses a transparent and colorless ink.
  • the colored product of the present invention is colored with the above-described compound of the present invention or an aqueous composition containing the compound, preferably an ink composition. More preferably, it is colored by an ink jet printer using the ink composition of the present invention.
  • information transmission sheet such as paper or film, fiber or Z and cloth (raw materials may be cellulose, nylon or Z and wool, etc.), leather, base material for color filter, and the like.
  • the information transmission sheet is preferably a surface-treated sheet, and specifically, a sheet provided with an ink receiving layer on a substrate such as paper (including synthetic paper) or film.
  • the ink-receiving layer is formed by impregnating or coating the above-mentioned base material with a cationic polymer, and a porous white inorganic substance capable of absorbing pigments in ink such as porous silica, alumina sol and special ceramics. It is provided by coating on the surface of the base material together with a hydrophilic polymer such as alcohol or polyvinylpyrrolidone.
  • a paper provided with such an ink-receiving layer is usually called an inkjet paper (film) or a paper (film) or the like.
  • Pictorico (trade name, manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo Paper or matte photo paper (, slip is a trade name, manufactured by Canon Inc.), PM photo paper (gloss) or PM matte paper (, slip is a trade name, manufactured by Seiko Epson Corp.), premium plus photo paper, premium glossy paper
  • film or photo paper (trade name, Nippon Hewlett Packard Co., Ltd.) or Photolike QP (trade name, Co-Camino Norta Photo Imaging Co., Ltd.) are available.
  • plain paper can also be used.
  • the black ink composition of the present invention is converted into a publicly known magenta ink composition, cyan ink composition, yellow ink composition, and, if necessary, a green ink composition, blue ink composition. (Or violet) ink composition and red (orange) ink composition, etc., can be used in combination with one or more appropriately selected.
  • the ink composition of each color to be used together is injected into each container, and the container is used for the inkjet recording of the present invention. Similar to the container containing the aqueous black ink composition, it is used by being loaded into a predetermined position of the ink jet printer.
  • the azo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this azo compound is stable in storage without crystal precipitation, physical property change, color change, etc. after long-term storage. Sex is good. Further, the black ink composition containing the azo compound of the present invention is used for ink jet recording or for writing instruments, and when recorded on plain paper and ink jet dedicated paper, the recorded image has a high print density black. In addition, its ozone gas resistance, light resistance and bronzing properties are excellent. For the sake of convenience in this specification, the phrase “excellent bronzing property! /,” Means that bronzing is not caused or difficult to occur.
  • JP-A-2004-083492 The compound of the following formula (19) obtained by the method described in the above is dissolved in 30 parts of water to 30 parts of water to pH 4.5 to 5.5 by adding sodium hydroxide, and this solution is dissolved in 15 to 25 parts. The mixture was added dropwise to the above diazo reaction solution for about 30 minutes at ° C.
  • the above diazo suspension containing a diazo compound of the compound of formula (20) was added dropwise at 20-30 ° C.
  • the pH value was maintained at 8.0 to 9.0 by adding sodium carbonate.
  • the resulting solution was stirred at the same temperature for 2 hours to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of formula (21).
  • the obtained reaction solution was heated to 70 ° C, and reacted for 2 hours while maintaining ⁇ .8 ⁇ : L1.0 with sodium hydroxide. After the reaction, 35% hydrochloric acid is added to the reaction solution to adjust the pH to 6.0 to 7.5. Then, the mixture was salted and added with sodium chloride salt, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 200 parts of water, crystallized with 250 parts of methanol, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 170 parts of water, 250 parts of methanol was added for crystallization, the precipitate was separated by filtration, and dried to obtain the compound of the formula (22) of the present invention (No. 2 in Table 2). 15.) 4 parts were obtained as a sodium salt. The maximum absorption wavelength ( ⁇ max) of this compound in an aqueous solution having a pH of 7 to 8 was 625 nm, and the solubility was lOOgZL or more.
  • the compound of the following formula (181) obtained by using 4-amino-5-naphthol 1,7-disulfonic acid in place of 4-amino-5-naphthol 2,7-disulfonic acid in Example 1 (3) is represented by the formula (18
  • the compound of the following formula (23) of the present invention (No. 1 compound in Table 2) was obtained in the same manner as in Example 1 except that it was used in place of the compound of)) as a sodium salt.
  • the maximum absorption wavelength ( ⁇ max) of this compound in an aqueous solution having a pH of 7 to 8 was 615 nm, and the solubility was lOOgZL or more.
  • a black ink composition of the present invention was obtained, and impurities were removed by filtration through a 0.45 m membrane filter.
  • the water used was ion exchange water.
  • the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion-exchanged water was added to make the total amount 100 parts.
  • the ink composition thus obtained did not undergo precipitation separation during storage and did not change its physical properties even after long-term storage.
  • Example 4 except that the dye of Table 11 in Table 11 is used instead of the compound obtained in Example 1 as the water-soluble inkjet dye (Example (25)) in Example 4.
  • a comparative ink composition was prepared with the following composition.
  • a 2mm thick glass plate is installed so that an air layer is formed between the printed sample, and the humidity is 60% RH and the temperature is 24 ° C.
  • the printed sample was irradiated with light at 0.336 WZ square meter illumination for 50 hours. After the test was completed, color measurement was performed using the above colorimeter.
  • the dye residual ratio was determined by (reflection density after test Z reflection density before test) X 100 (%), and evaluated according to the following criteria.
  • the print sample was left for 4 hours at an ozone concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C.
  • the colorimetry was performed using the above-mentioned colorimeter, and the dye residual ratio was determined by (reflection density after test Z reflection density before test) X 1 00 (%) and evaluated according to the following criteria.
  • the image recorded by the ink composition containing the azo compound of the present invention is superior in fastness compared to the image of the conventional black dye (comparative example). Good results were obtained even when using special glossy paper of V and misalignment.
  • Comparative Example 1 is less than 60% (X), whereas Example 4 of the present invention is 70% or more ( ⁇ ) and showed high robustness.
  • An image recorded with the azo compound of the present invention is extremely excellent in both light fastness and anti-ozone gas fastness, and the azo compound of the present invention has high solubility and stability, so that a high density ink. Therefore, the azo compound of the present invention is extremely useful as a coloring matter for inkjet ink.

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

Abstract

L'invention concerne un composé azoïque représenté par la formule (1) ci-dessous ou un sel de celui-ci. L'invention concerne également une composition d'encre contenant un tel composé azoïque ou un sel de celui-ci. (1) (Dans la formule, R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe cyano, un groupe carboxyle, un groupe sulfo ou similaire ; R3, R4, R5 et R6 représentent chacun indépendamment un groupe carboxyle, un groupe sulfo ou similaire ; R7, R8, R9 et R10 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe hydroxy, un groupe cyano, un groupe carboxyle, un groupe sulfo, un groupe sulfamoyle, un groupe N-alkylaminosulfonyle ou similaire ; et n représente 0 ou 1.) Le composé azoïque peut être utilisé en tant que colorant pour du noir et présente une excellente solubilité dans un milieu contenant principalement de l'eau et une bonne stabilité au stockage en tant que liquide d'impression. Lorsque le composé azoïque ou la composition d'encre sont utilisés pour l'impression par jet d'encre ou pour un outil d'écriture, on peut obtenir une excellente matière imprimée ayant une résistance à la lumière élevée et une résistance à l'ozone gazeux élevée, l'image imprimée ne subissant pas de brunissage.
PCT/JP2007/060431 2006-05-29 2007-05-22 Composé azoïque, composition d'encre, procédé d'impression et matière colorée WO2007138925A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013035560A1 (fr) * 2011-09-05 2013-03-14 日本化薬株式会社 Composition d'encre noire à base aqueuse, procédé d'enregistrement par jet d'encre l'utilisant et corps coloré

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004078860A1 (fr) * 2003-03-05 2004-09-16 Nippon Kayaku Kabushiki Kaisha Composition d'encre noire a base d'eau et substance coloree
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004078860A1 (fr) * 2003-03-05 2004-09-16 Nippon Kayaku Kabushiki Kaisha Composition d'encre noire a base d'eau et substance coloree
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013035560A1 (fr) * 2011-09-05 2013-03-14 日本化薬株式会社 Composition d'encre noire à base aqueuse, procédé d'enregistrement par jet d'encre l'utilisant et corps coloré

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