WO2010109843A1 - Composé azo, composition d'encre, procédé d'impression et corps coloré - Google Patents

Composé azo, composition d'encre, procédé d'impression et corps coloré Download PDF

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Publication number
WO2010109843A1
WO2010109843A1 PCT/JP2010/002027 JP2010002027W WO2010109843A1 WO 2010109843 A1 WO2010109843 A1 WO 2010109843A1 JP 2010002027 W JP2010002027 W JP 2010002027W WO 2010109843 A1 WO2010109843 A1 WO 2010109843A1
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group
substituted
hydrogen atom
sulfo
carboxy
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PCT/JP2010/002027
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English (en)
Japanese (ja)
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松井貴彦
梶浦典子
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日本化薬株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/16—Trisazo dyes
    • C09B31/26—Trisazo dyes from other coupling components "D"
    • C09B31/28—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

  • the present invention relates to a novel azo compound or a tautomer thereof or a salt thereof, an ink composition containing them, and a colored body colored with 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.) for recording.
  • this method since the recording head and the recording material are not in direct contact with each other, there is little generation of sound and it is quiet. Moreover, since it has the feature that it is easy to reduce the size and increase the speed, it has been spreading rapidly in recent years, and is expected to grow greatly in the future.
  • inks for fountain pens, felt-tip pens and the like and inks for ink jet recording water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used.
  • a water-soluble organic solvent is generally added to these water-based inks in order to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
  • these inks it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and 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.
  • gas resistance refers to resistance to a phenomenon in which ozone gas or the like having an oxidizing action existing in the air acts on the dye on the recording material and discolors the recorded image.
  • examples of the oxidizing gas having this kind of action include NOx and SOx.
  • ozone gas is regarded as a main causative substance that promotes the discoloration phenomenon of ink jet recorded images, and particularly, ozone gas resistance is regarded as important.
  • Many ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper use a material such as a porous white inorganic material in order to expedite ink drying and to reduce bleeding at high image quality.
  • 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.
  • Many pigments for these black inks have been proposed to date, but they have not yet provided a pigment that sufficiently satisfies the market demand.
  • Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as poor water resistance and moisture resistance, insufficient light resistance and gas resistance, and poor metamerism.
  • a polyazo dye having an extended conjugated system generally has problems such as low water solubility, easily causing a bronzing phenomenon in which a recorded image has a partially metallic luster, and insufficient light resistance and gas resistance.
  • azo metal-containing dyes that have been proposed, some of them have good light resistance, but they contain metal ions, which is not preferable for safety and environmental problems to living organisms, and gas resistance. There are problems such as extremely weakness.
  • black compounds black pigments
  • ink jet recording examples include the compounds described in Patent Documents 1 and 7, for example. Although the gas resistance of these compounds has been improved, they do not fully meet market demands.
  • azo compounds having a benzimidazolopyridone skeleton which is one of the characteristics of the black pigment of the present invention, are disclosed in Patent Documents 2 to 6 and the like.
  • Patent Documents 3 and 4 also disclose trisazo compounds, but these trisazo compounds are obtained by further bonding two benzimidazolopyridone skeletons with azo structures to both ends of a linking group containing an azo structure.
  • Patent Document 6 discloses the use of a trisazo compound and a water-soluble black compound for inkjet recording. These compounds have high fastness but tend to have too high saturation as black, and are insufficient as achromatic and high-quality black.
  • the present invention has a high solubility in water, an azo compound used in black ink or a tautomer thereof or a salt thereof, and a hue containing these compounds and having a low saturation and more suitable for black ink.
  • Another object of the present invention is to provide an ink composition excellent in light resistance and ozone gas resistance, particularly suitable for ink jet recording, and a colored body colored with these.
  • n is 0 or 1;
  • 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 to R 7 are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group;
  • the substitution position of the azo group bonded to the benzimidazolopyridone ring substituted by R 1 to R 4 is the a-position or b-position, and the substitution position of — (SO 3 H) n is the b-position or c-position However, they are not replaced at the same position, R 8 and R 11 are each independently
  • R 9 is a hydrogen atom, the azo compound according to 1) or 2) or a tautomer thereof, or a salt thereof, 4)
  • R 5 is a C1-C4 alkoxy group substituted with a sulfo group
  • R 6 is a hydrogen atom
  • the substitution position of R 5 is para to the substitution position of R 7 ;
  • R 10 is a C1-C4 alkylcarbonyl group; a C1-C4 alkylcarbonyl group substituted with a carboxy group; a be
  • azo compound of the present invention including all of the “azo compound of the present invention or a tautomer thereof, or a salt thereof”, will be simply described.
  • the azo compound of the present invention and an ink composition containing the azo compound are suitably used as inks for ink jet recording, and when recorded on ink jet dedicated paper, both light resistance and ozone gas resistance are excellent.
  • the ink composition containing the azo compound of the present invention is extremely useful as a black ink for ink jet recording because it has a hue that is lower in saturation and more suitable for black ink.
  • the azo compound represented by the formula (1) has a tautomer, and examples of the tautomer include the following formulas (3) to (7) other than the compound represented by the formula (1). It is done. These compounds are also included in the present invention.
  • formulas (3) to (7) the substitution positions of R 1 to R 7 , n, and — (SO 3 H) n have the same meaning as in formula (1) above.
  • examples of the C1-C4 alkyl group for R 1 include a linear or branched unsubstituted group, and a linear group is preferable.
  • Specific examples thereof include, for example, linear ones such as methyl, ethyl, n-propyl and n-butyl; branched ones 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 carbon atom 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 substitutions of carboxy 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 having 1 to 3, preferably 1 or 2 substituted 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-C4 alkyl group, a C1-C4 alkyl group substituted with a carboxy group, a phenyl group, or a phenyl group substituted with a sulfo group. More preferred is a phenyl group substituted with a C1-C4 alkyl group, a phenyl group, or a sulfo group. More preferably, it is a C1-C4 alkyl group or a phenyl group. Particularly preferred is a C1-C4 alkyl group, and methyl is particularly preferred.
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group.
  • a cyano group or a carbamoyl group is preferable, and a cyano group is more preferable.
  • examples of the C1-C4 alkyl group in R 3 and R 4 include the same as the C1-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, or iodine atom, preferably a chlorine atom.
  • Examples of the C1-C4 alkoxy group for R 3 and R 4 include a linear or branched unsubstituted group, and a linear one is 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 is particularly preferred.
  • R 3 and R 4 are preferably each independently a hydrogen atom, a C1-C4 alkoxy group, or a sulfo group. More preferably, any one is a combination of a hydrogen atom or a C1-C4 alkoxy group, and the other is a sulfo group. More preferably, any one is a combination of a hydrogen atom and the other is a sulfo group.
  • the substitution position of R 3 and R 4 is not particularly limited. When either one is a hydrogen atom and the other is a sulfo group, the sulfo group is any carbon atom bonded to the nitrogen atom constituting the benzimidazolopyridone ring. It is preferable to substitute one of the two carbon atoms that are not adjacent to each other.
  • 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 3 and R 4 are groups other than hydrogen atoms, it is preferable to use them as a mixture.
  • R 1 to R 4 in the formula (1) is that R 1 is a C1-C4 alkyl group or a phenyl group, more preferably a C1-C4 alkyl group, particularly preferably a methyl group, and R 2 is a cyano group or A combination of a carbamoyl group, preferably a cyano group, R 3 is a hydrogen atom, and R 4 is a sulfo group.
  • examples of the C1-C4 alkyl group in R 5 to R 7 include the same as the C1-C4 alkyl group in R 1 including preferable ones.
  • Examples of the C1-C4 alkoxy group for R 5 to R 7 include the same C1-C4 alkoxy groups as those described above for R 3 and R 4 , including preferred ones.
  • the number of the substituents is usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but it is preferably substituted at the end of the alkoxy group.
  • hydroxy C1-C4 alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy C1-C4 alkoxy C1-C4 alkoxy groups such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; carboxymethoxy, Carboxy C1-C4 alkoxy groups such as 2-carboxyethoxy and 3-carboxypropoxy; sulfo-C1-C such as 2-sulfoethoxy, 3-sulfopropoxy and 4-sulfobutoxy Alkoxy group; and the like.
  • Examples of the C1-C4 alkylcarbonylamino group for R 5 to R 7 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight chain such as methylcarbonylamino (acetylamino), ethylcarbonylamino (propionylamino), propylcarbonylamino (butyrylamino); branched chain such as isopropylcarbonylamino; and the like.
  • C1-C4 alkylcarbonylamino group substituted with a carboxy group in R 5 to R 7 include, for example, a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropionylamino;
  • the number of substituents in the substituted C1-C4 alkylcarbonylamino group is usually 1 or 2, preferably 1.
  • C1-C4 alkyl substituted benzoylamino groups such as 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino; 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenyl Halogen atom (preferably chlorine atom) substituted benzoylamino group such as amino; C1 such as 2-methoxybenzoylamino, 4-methoxybenzoylamino, 3,5-dimethoxybenzoylamino, 2-ethoxybenzoylamino, 4-ethoxybenzoylamino, etc.
  • Substituted benzoylamino groups; carboxy-substituted benzoylamino groups such as 2-carboxybenzoylamino, 4-carboxybenzoylamino and 3,5-dicarboxybenzoylamino; sulfo-substituted benzoylamino groups such as 2-sulfobenzoylamino and 4-sulfobenzoylamino Group; etc. are mentioned.
  • substituents in the benzoylamino group substituted with a benzene ring one kind is preferable.
  • the number of substituents is usually 1 or 2, preferably 1.
  • substitution position of R 5 is not particularly limited, it is preferably substituted at the para position with respect to the substitution position of R 7 .
  • the substitution position of the azo group bonded to the naphthalene ring is position 1
  • the substitution position of the azo group bonded to the benzothiazole ring is position 4
  • the substitution position of R 7 is When the substitution position of 5-position and R 6 is 6-position, R 5 is preferably substituted at 2-position.
  • R 5 to R 7 are each independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group substituted with a sulfo group, or a C1-C4 alkoxy group substituted with a carboxy group. And more preferably a hydrogen atom, a C1-C4 alkyl group, and a C1-C4 alkoxy group substituted with a sulfo group.
  • a combination of R 5 to R 7 a combination in which any one is a hydrogen atom and the remaining two are groups other than a hydrogen atom is preferable.
  • R 6 is a hydrogen atom
  • R 5 and R 7 are groups other than hydrogen atoms. More preferably, C1-C4 alkoxy groups R 5 is substituted by a sulfo group, or a C1-C4 alkoxy group substituted by a carboxy group, R 6 is a hydrogen atom, R 7 is C1-C4 alkyl group, or a sulfo group A C1-C4 alkoxy group substituted with Particularly preferably, a C1-C4 alkoxy group in which R 5 is substituted with a sulfo group (preferably sulfopropoxy, more preferably 3-sulfopropoxy), R 6 is a hydrogen atom, and R 7 is a C1-C4 alkyl group (preferably Methyl).
  • the symbols “a”, “b”, and “c” given to the naphthalene ring are benzoimidazolo substituted with R 1 to R 4 , respectively, whose substitution positions are not specified.
  • the former group is substituted at the a-position or b-position, and the latter group is substituted at the b-position or c-position, but both groups are not substituted at the same position. It is preferable that the former group is substituted at the b-position and the latter group is substituted at the c-position.
  • examples of the C1-C4 alkyl group for R 8 and R 11 include the same as the C1-C4 alkyl group for R 1 including preferable ones.
  • Examples of the C1-C4 alkoxy group for R 8 and R 11 include the same C1-C4 alkoxy groups as those described above for R 3 and R 4 , including preferred ones.
  • Examples of the C1-C4 alkylsulfonyl group for R 8 and R 11 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl; branched chains such as isopropylsulfonyl and isobutylsulfonyl; Of the above, methylsulfonyl, ethylsulfonyl, and isopropylsulfonyl are preferable, and methylsulfonyl is particularly preferable.
  • the C1-C4 alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R 8 and R 11 is any of the above C1-C4 alkylsulfonyl groups
  • 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 at the end of the alkyl moiety.
  • 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 8 and R 11 each independently include a hydrogen atom or a sulfo group.
  • a preferable combination of R 8 and R 11 includes a combination in which one is a sulfo group and the other is a hydrogen atom. More preferably, R 8 is a sulfo group and R 11 is a combination of hydrogen atoms.
  • the substitution position of R 8 and R 11 is not particularly limited, as one of the position of the sulfur atom in the benzothiazole ring, R 8 is 4-position or 5-position, preferably 4-position, to replace the R 11 is 7-position Is preferred.
  • examples of the C1-C8 alkylcarbonyl group for R 9 and R 10 include straight-chain or branched-chain unsubstituted groups, and straight-chain groups are preferred.
  • the range of the carbon number is usually a C1-C8 alkylcarbonyl group, preferably C1-C6, more preferably C1-C5.
  • Specific examples include linear chains such as acetyl (methylcarbonyl), propionyl, butyryl, valeryl, hexanoyl, heptanoyl, octanoyl and nonanoyl; branched chains such as isobutyryl, pivaloyl, isovaleryl and 2-ethylhexanoyl; Can be mentioned.
  • acetyl, propionyl, pivaloyl, and isovaleryl are preferred, and acetyl is particularly preferred.
  • Examples of the C1-C8 alkylcarbonyl group substituted with a carboxy group in R 9 and R 10 include those in which a carboxy group is substituted on any carbon atom in the C1-C8 alkylcarbonyl group, and the number of the substituents is as follows. Usually 1 or 2, preferably 1.
  • the position of the substituent is not particularly limited, but is preferably substituted at the end of the alkyl moiety. Specific examples include 3-carboxypropionyl, 4-carboxybutyryl and the like.
  • the range of the number of carbon atoms includes the same ranges as described above including preferable ones, but 3-carboxypropionyl is particularly preferable.
  • a benzoyl group in which the benzene ring is substituted with at least one group selected from the group consisting of a C1-C4 alkyl group, a halogen atom, a C1-C4 alkoxy group, a carboxy group, and a sulfo group in R 9 and R 10 Substituted with a C1-C4 alkyl group such as 2-methylbenzoyl, 3-methylbenzoyl, 4-methylbenzoyl, 2,4,6-trimethylbenzoyl; 2-chlorobenzoyl, 3-chlorobenzoyl, 4-chloro Substituted by a halogen atom (preferably a chlorine atom) such as benzoyl; Substituted by a C1-C4 alkoxy group such as 2-methoxybenzoyl, 3-methoxybenzoyl, 4-methoxybenzoyl; 2-carboxybenzoyl, 2,5 -Substituted by a carboxy group
  • substituents in the benzoyl group substituted with a benzene ring one kind is preferable.
  • the number of substituents is usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • 4-methylbenzoyl, 2-chlorobenzoyl, 2-carboxybenzoyl, 2,5-dicarboxybenzoyl, and 2-sulfobenzoyl are preferred.
  • Examples of the C1-C4 alkylsulfonyl group for R 9 and R 10 include the same C1-C4 alkylsulfonyl groups as those described above for R 8 and R 11 , including preferred ones.
  • the number of the substituents is usually 1 to 3, preferably 1 or 2, and more preferably 1.
  • the position of the substituent is not particularly limited.
  • Specific examples include those substituted with a C1-C4 alkyl group such as 2-methylbenzenesulfonyl, 3-methylbenzenesulfonyl, 4-methylbenzenesulfonyl, 2,4,6-trimethylbenzenesulfonyl; 2-chlorobenzenesulfonyl, 3 -Substituted by halogen atoms (preferably chlorine atoms) such as chlorobenzenesulfonyl and 4-chlorobenzenesulfonyl; substituted by C1-C4 alkoxy groups such as 2-methoxybenzenesulfonyl, 3-methoxybenzenesulfonyl and 4-methoxybenzenesulfonyl Those having a carboxy group such as 2-carboxybenzenesulfonyl substituted; those having a nitro group substituted such as 4-nitrobenzenesulfonyl; Of the above, 4-methylbenzenesulfony
  • R 9 and R 10 are each independently a hydrogen atom, a C1-C4 alkylcarbonyl group; a C1-C4 alkylcarbonyl group substituted with a carboxy group; a benzoyl group; a C1-C4 alkyl group, a halogen A benzoyl group in which the benzene ring is substituted with one kind of group selected from the group consisting of an atom, a carboxy group, and a sulfo group; a C1-C4 alkylsulfonyl group; a benzenesulfonyl group; a C1-C4 alkyl group, and a halogen atom A benzenesulfonyl group in which the benzene ring is substituted with one kind of group selected from the group consisting of; or a naphthalenesulfonyl group.
  • a hydrogen atom, a C1-C4 alkylcarbonyl group, a C1-C4 alkylsulfonyl group, or a benzenesulfonyl group in which a benzene ring is substituted with a C1-C4 alkyl group is more preferable, and a hydrogen atom, C1-C4 More preferred is an alkylcarbonyl group or a C1-C4 alkylsulfonyl group.
  • R 9 is preferably a hydrogen atom, and R 10 is preferably a group other than a hydrogen atom.
  • R 9 is preferably a hydrogen atom
  • R 10 is preferably a group other than a hydrogen atom.
  • R 9 and R 10 include: R 9 is a hydrogen atom, R 10 is a C1-C4 alkylcarbonyl group; a C1-C4 alkylcarbonyl group substituted with a carboxy group; a benzoyl group; a C1-C4 alkyl group, a halogen A benzoyl group in which the benzene ring is substituted with one kind of group selected from the group consisting of an atom, a carboxy group, and a sulfo group; a C1-C4 alkylsulfonyl group; a benzenesulfonyl group; a C1-C4 alkyl group, and a halogen atom A combination of a benzenesulfonyl group in which a benzene ring is substituted with one kind of group selected from the group consisting of; or a naphthalenesulfonyl group.
  • R 9 is a hydrogen atom
  • R 10 is a C1-C4 alkylcarbonyl group, a C1-C4 alkylsulfonyl group, or a combination of benzenesulfonyl groups in which the benzene ring is substituted with a C1-C4 alkyl group.
  • R 9 is a hydrogen atom
  • R 10 is a C1-C4 alkylcarbonyl group or a combination of C1-C4 alkylsulfonyl groups.
  • substitution position of —NR 9 R 10 is not particularly limited. However, substitution at the 6-position is preferred, with the position of the sulfur atom in the benzothiazole ring being the 1-position.
  • preferable combinations in the formula (1) include the following combinations (i) to (iii).
  • (Ii) is preferable to (i), and (iii) is most preferable.
  • (I) n is 1, the substitution position of the azo group bonded to the benzimidazolopyridone ring is the b-position, the substitution position of the — (SO 3 H) n group is the c-position, and R 1 is a C1-C4 alkyl group Or a phenyl group, R 2 is a cyano group or carbamoyl group, R 3 is a hydrogen atom, R 4 is a sulfo group, and R 5 is a C1-C4 alkoxy group substituted with a sulfo group The substitution position is para to R 7 , R 6 is a hydrogen atom, R 7 is a C1-C4 alkyl group, R 8 is a sulfo group, and R 9 is a hydrogen atom.
  • R 10 is a C1-C4 alkylcarbonyl group; a C1-C4 alkylcarbonyl group substituted with a carboxy group; a benzoyl group; 1 selected from the group consisting of a C1-C4 alkyl group, a halogen atom, a carboxy group, and a sulfo group type A benzoyl group substituted with a benzene ring; a C1-C4 alkylsulfonyl group; a benzenesulfonyl group; or a C1-C4 alkyl group, and a single group selected from the group consisting of halogen atoms, A combination wherein R 11 is a hydrogen atom.
  • n 1,-(SO 3 H)
  • the substitution position of the n group is the c position
  • the substitution position of the azo group bonded to the benzimidazolopyridone ring is the b position
  • R 1 is a C1-C4 alkyl group Or a phenyl group
  • R 2 is a cyano group
  • R 3 is a hydrogen atom
  • R 4 is a sulfo group
  • R 5 is a C1-C4 alkoxy group substituted with a sulfo group.
  • R 6 is a hydrogen atom
  • R 7 is a C1-C4 alkyl group
  • R 8 is a sulfo group
  • R 9 is a hydrogen atom
  • R 10 is A C1-C4 alkylcarbonyl group; a C1-C4 alkylsulfonyl group; or a benzenesulfonyl group in which a benzene ring is substituted with a C1-C4 alkyl group; and a combination in which R 11 is a hydrogen atom.
  • n 1, the substitution position of the azo group bonded to the benzimidazolopyridone ring is the b position, the substitution position of the — (SO 3 H) n group is the c position, and 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
  • R 4 is a sulfo group
  • R 5 is a sulfopropoxy group
  • the substitution position is a para-position relative to R 7
  • R 6 is a hydrogen atom
  • R 7 is a methyl group
  • R 8 is a sulfo group
  • R 9 is a hydrogen atom
  • R 10 is an acetyl group, a methylsulfonyl group, or a toluenesulfonyl group. (Of these, a acetyl group or a methylsulfonyl group is prefer
  • the azo compound represented by the above formula (1) can be synthesized, for example, by the following method.
  • the structural formula of the compound in each process shall be represented in the form of a free acid, and in the following formulas (9) to (14), R 1 to R 11 , a, b, c, and n are each represented by the formula ( Has the same meaning as in 1).
  • a compound represented by the following formula (9) is diazotized by a conventional method, and this and a compound represented by the following formula (10) are subjected to a coupling reaction by a conventional method, and represented by the following formula (11). A compound is obtained.
  • the compound represented by the formula (11) thus obtained was diazotized by a conventional method, and this was then coupled with a compound represented by the following formula (12) by a conventional method. To obtain the compound.
  • the compound represented by the formula (13) thus obtained is diazotized by a conventional method, and then this and a compound represented by the following formula (14) are subjected to a coupling reaction by a conventional method, whereby the above formula (1)
  • the azo compound of this invention represented by these can be obtained.
  • the compound represented by the above formula (14) can be synthesized according to the method described in Patent Document 4.
  • the diazotization of the compound represented by the above formula (9) is carried out by a method known per se.
  • nitrosylsulfuric acid is used in an inorganic acid medium such as sulfuric acid and phosphoric acid, or in an organic acid medium such as acetic acid and propionic acid, for example, at a temperature of ⁇ 10 to 20 ° C., preferably 0 to 10 ° C.
  • Coupling of the diazotized compound of the compound represented by formula (9) and the compound represented by formula (10) 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 5 to 20 ° C.
  • the compound represented by formula (9) and the compound represented by formula (10) are used in approximately stoichiometric amounts.
  • the diazotization of the compound represented by the above formula (11) 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 to 30 ° C., preferably 5 to 20 ° C.
  • Coupling of the diazotized compound of the compound represented by the formula (11) and the compound represented by the formula (12) is also carried out under conditions known per se.
  • the pH value is adjusted by adding a base.
  • the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines.
  • the compound represented by formula (11) and the compound represented by formula (12) are used in approximately stoichiometric amounts.
  • the diazotization of the compound represented by the formula (13) is also carried out by a method known per se.
  • a nitrite for example an alkali metal nitrite such as sodium nitrite
  • Coupling of the diazotized compound of the compound represented by formula (13) with the compound represented by formula (14) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of 0 to 50 ° C., preferably 5 to 30 ° C., and at a weakly acidic to alkaline pH value.
  • the compound represented by the formula (13) and the compound represented by (14) are used in a substantially stoichiometric amount.
  • the salt of the azo compound represented by the above formula (1) is a salt with an inorganic or organic cation.
  • inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts.
  • Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts.
  • organic cation salt include, but are not limited to, salts with quaternary ammonium ions represented by the following formula (8).
  • the free acid of the azo compound of the present invention, 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 vary depending on the type of salt, and the physical properties that meet the purpose can be selected by selecting the type of salt as appropriate, or by changing the ratio when multiple salts are included. It is also possible to obtain a mixture having
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a group selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group. , At least one is a group other than a hydrogen atom.
  • Specific examples of the alkyl group of Z 1 to Z 4 in the formula (8) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
  • hydroxyalkyl group examples include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
  • hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc.
  • hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl,
  • hydroxyethoxy C1-C4 alkyl groups such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. It is done.
  • a desired inorganic salt or organic Obtained by adding a mineral acid such as hydrochloric acid to the reaction solution and isolating the azo compound from the reaction solution in the form of a free acid.
  • the free acid is washed with water, acidic water or an aqueous organic medium as necessary to remove impurities such as attached inorganic salts, and again in an aqueous medium (preferably in water).
  • a method of forming a salt by adding an organic base corresponding to the desired inorganic base or the above-described quaternary ammonium salt.
  • the salt of the target azo compound can be obtained in the form of a solution or a precipitated solid.
  • acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water.
  • the aqueous organic medium is an admixture of water and an organic substance and / or an organic solvent that are miscible with water. Examples of the water-miscible organic substance and organic solvent include water-soluble organic solvents described later.
  • Examples of inorganic salts used when the azo compound represented by the formula (1) is used as a desired salt include alkali metal halogen salts such as lithium chloride, sodium chloride and potassium chloride; lithium carbonate, sodium carbonate and potassium carbonate Alkali metal carbonates such as lithium hydroxide, sodium hydroxide, potassium hydroxide and other alkali metal hydroxides; ammonium ion halogen salts such as ammonium chloride and ammonium bromide; ammonium hydroxide (ammonia water), etc. And ammonium ion hydroxides.
  • Examples of organic cation salts include halogen salts of quaternary ammonium ions represented by the above formula (8) such as diethanolamine hydrochloride and triethanolamine hydrochloride.
  • the ink composition of the present invention will be described.
  • the azo compound of the present invention represented by the above formula (1) is an aqueous composition containing the compound, it is possible to dye a material made of cellulose.
  • materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabrics, paper, and the like.
  • a typical use of the compound of the present invention is an ink composition dissolved in a liquid medium, and is preferably used as an ink composition for inkjet recording.
  • the reaction liquid containing the compound represented by the above formula (1) for example, the reaction liquid after the final step in the synthesis reaction of the compound represented by the above formula (1) is directly used for the production of the ink composition. be able to.
  • the reaction solution is dried, for example, spray-dried; the reaction solution is salted out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; the reaction solution is treated with hydrochloric acid, sulfuric acid
  • the compound is isolated by a method of acid precipitation by adding a mineral acid such as nitric acid or the like; or a method of acid precipitation by a combination of the above-mentioned salting out and acid precipitation; Compositions can also be prepared.
  • the azo compound of the present invention is preferably used after being isolated.
  • the ink composition of the present invention is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass, using the azo compound of the present invention represented by the formula (1) as a pigment. It is a water-based ink composition containing.
  • the ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent and an ink preparation agent as necessary within a range that does not impair the effects of the present invention.
  • the water-soluble organic solvent may have a function as a dye-dissolving agent, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, etc., and the ink composition of the present invention It is preferable to contain them.
  • the ink preparation agent include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, antioxidants, and surfactants. These additives may be mentioned.
  • the ink composition of the present invention has a water-soluble organic solvent content of 0 to 30% by mass, preferably 5 to 30% by mass, and an ink preparation agent of 0 to 15% by mass, preferably 0 to 7% by mass, based on the total mass. % May be contained respectively.
  • the remainder other than the above is water.
  • the pH of the ink composition is preferably pH 5 to 11 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 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 ink composition of the present invention may appropriately contain other toning pigments and the like for the purpose of adjusting the subtle hue of black. Even in such a case, the total mass of the pigment contained in the ink composition of the present invention may be in the above range with respect to the total mass of the ink composition.
  • toning dyes include yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc.
  • Orange for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc.
  • Brown, Scarlet E.g., CI Direct Red 89
  • red e.g., CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226)
  • magenta for example, CI Direct Red 227), violet, blue, navy, cyan (for example, CI Direct Blue 199, CI Acid Blue 249, etc.), green, black, etc.
  • dye which has a hue is mentioned.
  • the ink composition of the present invention can be used by blending one or more of these toning dyes as long as the effects obtained by the azo compound of the present invention are not impaired. Even in this case, the total amount of the coloring matter contained in the ink composition may be in the above range.
  • the mixing ratio of the azo compound of the present invention to the toning dye is approximately 20: 1 to 1: 2, preferably 10: 1 to 1: 1, depending on the hue of the toning dye and the like. It is.
  • the standard of the content of the inorganic impurities is about 1% by mass or less with respect to the total mass of the pigment.
  • the lower limit may be equal to or lower than the detection limit of the analytical instrument, that is, 0%.
  • a method using a reverse osmosis membrane; or a dried product or wet cake of the azo compound of the present invention with an alcohol such as methanol, preferably a C1-C4 alcohol and water The mixture may be suspended and purified by stirring in a mixed solvent, and the salt may be desalted by a known method such as a method in which the precipitate is separated by filtration and dried;
  • C1-C4 alcohols such as methanol, ethanol, propanol
  • Ketone or ketoalcohol cyclic such as tetrahydrofuran, dioxane Ether; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol , Dipropylene glycol, polyethylene glycol, polypropylene glycol, mono-, oligo-, or polyalkylene glycols or thioglycols having a C2-C6 alkylene unit such as thiodiglycol or dithiodiglycol; trimethylolpropane, glycerin, hexane-1,2 Polyol (triol) such as, 6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl
  • the water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent for the sake of convenience.
  • antiseptic / antifungal agents pH adjusters, chelating reagents, rust preventives, water-soluble UV absorbers, water-soluble polymer compounds, dye dissolving agents, antioxidants, and surfactants that can be used as ink preparation agents Describe.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.
  • preservatives include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzothiazole. , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, Examples include benzyl bromacetate and inorganic salt compounds.
  • organic halogen compounds include, for example, pentachlorophenol sodium
  • specific examples of the pyridine oxide compounds include, for example, 2-pyridinethiol-1-oxide sodium
  • isothiazoline compounds include, 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- Examples include 4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, and 2-methyl-4-isothiazolin-3-one calcium chloride.
  • Specific examples of other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate and the like.
  • any substance can be used as long as it can control the pH of the ink within a range of about 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 potassium acetate; inorganic bases such as sodium silicate and disodium phosphate.
  • alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • Alkaline metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and
  • chelating reagent examples include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.
  • rust preventive examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
  • 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 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 their salts, N-acyl methyl taurates, alkyl sulfates 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 sulfonate, Examples thereof include diethylsulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.
  • Examples of the cationic surfactant 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, etc. Is mentioned.
  • Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl Acetylene glycol (alcohol) type such as lu-1-hexyn-3-ol (for example, trade name Surfinol 104, 105, 82,
  • the ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. If desired, the obtained ink composition may be subjected to microfiltration with a membrane filter or the like in order to remove impurities, and when used for ink jet recording, the filtration is preferably performed.
  • the pore diameter of the filter for performing microfiltration is usually 1 to 0.1 ⁇ m, preferably 0.8 to 0.1 ⁇ m.
  • the ink composition of the present invention can be used in 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 present invention.
  • the ink jet recording method of the present invention is a method for performing recording by using the ink composition of the present invention as ink and ejecting ink droplets of the ink in accordance with a recording signal to adhere to the recording material.
  • the ink jet recording method of the present invention there are no particular limitations on the ink head, ink nozzles, and the like used for recording, and the ink recording method can be appropriately selected according to the purpose.
  • This recording method is a known method, for example, a charge control method that ejects ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; An acoustic ink jet method that irradiates the ink instead of the ink and discharges the ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, a so-called bubble jet (registered trademark) method Etc. can be used.
  • the colored product of the present invention is colored by the azo compound of the present invention represented by the above formula (1) or an ink composition containing the same, and preferably by an inkjet recording method using an inkjet printer.
  • a substance colored by the ink composition containing the compound represented by the above formula (1) There are no particular restrictions on the substances that can be colored, but examples include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Sheets are preferred.
  • the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer.
  • the ink receiving layer is formed by, for example, impregnating or coating the above-described base material with a cationic polymer; porous white inorganic material capable of absorbing pigments in ink such as porous silica, alumina sol, and special ceramics, polyvinyl alcohol, polyvinyl pyrrolidone, and the like. Coating the surface of the substrate together with a hydrophilic polymer such as;
  • the information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like.
  • a container containing the above ink composition may be loaded at a predetermined position of an ink jet printer and recorded on the recording material by a normal method.
  • the ink jet recording method of the present invention comprises the black ink composition of the present invention and, for example, the known magenta, cyan, yellow, and as necessary, green, blue (or violet), red (or orange), etc. These ink compositions of the respective colors can also be used in combination.
  • the ink composition of each color is injected into each container, and each container is loaded into a predetermined position of the ink jet printer and used for ink jet recording in the same manner as the container containing the black ink composition of the present invention.
  • the azo compound of the present invention is a black pigment. This compound is easy to synthesize and inexpensive, and has a feature of low saturation, and therefore exhibits a more preferable hue as black. Moreover, since it is excellent in water solubility, the filterability by a membrane filter in the process of manufacturing an ink composition is good. Further, the ink composition of the present invention containing the azo compound is an aqueous black ink composition, and has good storage stability without solid precipitation, physical property change, color change, etc. after long-term storage. An image recorded with the ink composition of the present invention has a very high printing density and is excellent in various fastnesses such as light resistance, gas resistance, moisture resistance, and water resistance, particularly ozone gas resistance and light resistance.
  • the ink composition containing the azo compound of the present invention can be used as an ink for ink jet recording, a writing instrument, and the like, and has excellent ejection stability. Is preferred.
  • Example 1 (Process 1) To 320 parts of 30% fuming sulfuric acid, 77.6 parts of 2-amino-6-nitrobenzothiazole was added over about 1 hour, and the resulting solution was heated and reacted at 90-100 ° C. for 1.5 hours. The reaction solution was cooled to room temperature, and then added to a mixed solution of 900 parts of crushed ice and 200 parts of water over about 5 minutes. The precipitated solid was separated by filtration to obtain 221.2 parts of a wet cake of a compound represented by the following formula (15).
  • crushed ice was added to maintain a liquid temperature of 5 to 15 ° C., and after completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and the precipitated solid was separated by filtration and wetted with a compound represented by the following formula (19) 225.6 parts of cake were obtained.
  • Step 6 21.2 parts of the wet cake of the compound represented by the formula (20) obtained in the above (Step 5) was added to 330 parts of water and stirred for 1 hour to obtain an aqueous solution. After cooling this solution to 0-5 ° C in an ice bath, 3.0 parts of 35% hydrochloric acid and 1.4 parts of 40% aqueous sodium nitrite solution are added and reacted at the same temperature for 1 hour to obtain a diazo reaction liquid. It was. On the other hand, 2.2 parts of a compound represented by the following formula (21) obtained by the method described in Patent Document 7 is added to 200 parts of water, and a 25% aqueous sodium hydroxide solution is added to adjust the pH to 7.5 to 8.5.
  • Example 2 To 1200 parts of water, 5.0 parts of sodium salt of the compound represented by the formula (22) obtained in (Step 6) of Example 1 and 8.1 parts of lithium chloride were added to obtain a solution. This solution was heated to 60 to 70 ° C., stirred at the same temperature for 1 hour, cooled to 40 ° C., and 1000 parts of methanol and 500 parts of 2-propanol were added. This liquid was further cooled to room temperature, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 300 parts of water, 450 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • Example 3 (Process 1) A wet cake 120 of a compound represented by the following formula (23) is prepared in the same manner as in (Step 3) of Example 1 except that 31.1 parts of methylsulfonyl chloride is used instead of 22.2 parts of acetic anhydride. .2 parts were obtained.
  • the obtained wet cake was dissolved in 400 parts of water, 600 parts of methanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • the obtained wet cake was dissolved again in 250 parts of water, 250 parts of methanol and 100 parts of 2-propanol were added, and the precipitated solid was separated by filtration and dried, and expressed by the following formula (26) of the present invention. 7.2 parts of the compound obtained were obtained as the sodium salt. [lambda] max: 595.5 nm.
  • Example 4 instead of using 5.0 parts of the sodium salt of the compound represented by the formula (22), the same procedure as in Example 2 was conducted except that 5.0 parts of the sodium salt of the compound represented by the above formula (26) was used. The salt was exchanged to obtain 3.6 parts of the compound represented by the above formula (26) of the present invention as a mixed salt of sodium and lithium. ⁇ max: 595.0 nm.
  • Example 5 In the same manner as in all steps of Example 1 except that 40.0 parts of 4-toluenesulfonyl chloride was used instead of 22.2 parts of acetic anhydride in (Step 3) of Example 1, 6.2 parts of the compound represented by the formula (27) were obtained as a sodium salt. Next, in Example 2, instead of using 5.0 parts of the sodium salt of the compound represented by the formula (22), 5.0 parts of the sodium salt of the compound represented by the following formula (27) is used. Was subjected to salt exchange in the same manner as in Example 2 to obtain 3.9 parts of a compound represented by the following formula (27) of the present invention as a mixed salt of sodium and lithium. ⁇ max: 597.5 nm.
  • Example 6 instead of using 2.4 parts of the compound represented by the formula (21) in (Step 4) of Example 3, the compound 2 represented by the following formula (28) obtained by the method described in Patent Document 7 Except for using 9 parts, in the same manner as in all steps of Example 3, 6.0 parts of the compound represented by the following formula (29) of the present invention was obtained as a sodium salt. [lambda] max: 596.5 nm.
  • Example 7 [(A) Preparation of ink] An ink for evaluation was prepared by mixing the components shown in Table 8 below to obtain a black ink composition of the present invention and then filtering out impurities with a 0.45 ⁇ m membrane filter. This ink preparation is referred to as Example 7. Further, an ink for evaluation was prepared in the same manner as in Example 7 except that the compound obtained in Example 4 was used instead of the compound in Example 2. This ink preparation is Example 8. Ion exchange water was used as water for ink preparation. Further, at the time of ink preparation, the pH of the ink was adjusted to pH 7 to 9 with lithium hydroxide, and ion exchanged water was added to adjust the total amount to 100 parts.
  • the ink composition of the present invention and the ink obtained by microfiltration of the ink composition did not cause precipitation separation during storage and did not change physical properties even after long-term storage.
  • Comparative Example 2 A comparison was made in the same manner as in Examples 7 and 8 except that the dye of the following formula (31) disclosed in Example 2-6 of Patent Document 6 was used instead of the compound of the present invention obtained in each Example. An ink was prepared. This ink preparation is referred to as Comparative Example 2.
  • Glossy paper 1 manufactured by EPSON, product name: photographic paper Krispia (high gloss) Glossy paper 2: manufactured by EPSON, product name: photo paper (glossy) Glossy paper 3: manufactured by Canon Inc., trade name: Canon photo paper, Glossy Gold (GL101) Glossy paper 4: manufactured by Fuji Film Co., Ltd., product name: Painting photo finish Pro (Glossy paper 5: manufactured by Hewlett-Packard, trade name: Advanced Photo Paper)
  • an image pattern was prepared so that the reflection density was obtained in several gradations, a black gradation recorded matter was obtained, and the following evaluation test was performed using this as a test piece.
  • the color difference ⁇ E of the recorded image is a gradation portion where the black reflection density Dk value of the recorded image before the test is in the range of 1.1 to 1.3 using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye Was measured by measuring the color.
  • the reflection density was measured using DIN as a density reference and a viewing angle of 2 degrees.
  • Each evaluation was performed on all glossy papers 1 to 5.
  • the specific test method is as follows. The evaluation test results are shown in Table 9 below.
  • ⁇ E [( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ( ⁇ b * ) 2 ] 1/2
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the following values.
  • ⁇ L * difference in L * value before and after exposure
  • ⁇ a * difference in a * value before and after exposure
  • ⁇ b * difference in b * value before and after exposure
  • the test results were evaluated according to the following criteria.
  • Examples 7 and 8 showed results that were significantly better than Comparative Example 1 in terms of ozone gas resistance and light resistance. Further, in the color evaluation, it was revealed that Examples 7 and 8 had a saturation closer to 0 than that of Comparative Example 2 and an achromatic color and higher quality black than Comparative Example 2. Therefore, it was confirmed that the recorded image obtained with the ink containing the azo compound of the present invention has excellent ozone gas resistance and light resistance and, in addition, has a more preferable achromatic hue as black.
  • the compound and the ink composition containing the compound are extremely useful for recording, particularly for inkjet recording.
  • the ink composition containing the azo compound of the present invention is suitably used as a black ink liquid for ink jet recording and writing instruments.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract

L'invention porte sur un composé azo pour une encre noire, qui est très soluble dans un véhicule dans lequel le composant primaire est de l'eau, qui reste stable au stockage de longue durée d'une solution aqueuse hautement concentrée et d'encre, qui possède une excellente solidité d'image imprimée, en particulier une résistance à la lumière et une résistance à l'ozone gazeux, et qui est achromatique et confère une image imprimée noire de haute qualité. L'invention porte également sur une composition d'encre contenant le composé. Le composé est un composé azo représenté par la formule (1), un tautomère ou un sel de celui-ci. Dans la formule (1), n vaut 1 et similaire ; R1 représente un groupe alkyle en C1-C4 et similaire ; R2 représente un groupe cyano et similaire ; R3 et R4 représentent chacun indépendamment un atome d'hydrogène, un groupe sulfo et similaire ; R5 à R7 représentent chacun indépendamment des atomes d'hydrogène, des groupes sulfo alkyle en C1-C4, des groupes alkyle en C1-C4 et similaire ; R8 représente un groupe sulfo et similaire ; R9 représente un atome d'hydrogène et similaire ; R10 représente un groupe alkylcarbonyle en C1-C4 et similaire ; et R11 représente un atome d'hydrogène et similaire.
PCT/JP2010/002027 2009-03-27 2010-03-23 Composé azo, composition d'encre, procédé d'impression et corps coloré WO2010109843A1 (fr)

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JP6951366B2 (ja) * 2017-01-20 2021-10-20 日本化薬株式会社 アゾ化合物又はその塩、並びにこれを含有する染料系偏光膜及び染料系偏光板

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DE2023295A1 (en) * 1970-05-13 1971-11-25 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Water insoluble azo dyes for dyeing polyesters polyamides cellulose - esters and polypropylene
JPS50126716A (fr) * 1974-03-12 1975-10-06
JP2006509068A (ja) * 2002-12-05 2006-03-16 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド ベンゾイミダゾール−ピリドンをベースとするアゾ染料
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WO2008096697A1 (fr) * 2007-02-05 2008-08-14 Nippon Kayaku Kabushiki Kaisha Composé trisazo, composition d'encre, procédé d'impression et colorant
WO2009069279A1 (fr) * 2007-11-27 2009-06-04 Nippon Kayaku Kabushiki Kaisha Composé triazoïque, composition d'encre, procédé d'impression et corps coloré
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WO2009136576A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composé trisazo, composition d’encre, procédé d’impression et matériau colorant
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DE2004488A1 (en) * 1970-01-31 1971-08-05 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Water-soluble azo dyes for wool and poly-amide fibres
DE2023295A1 (en) * 1970-05-13 1971-11-25 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Water insoluble azo dyes for dyeing polyesters polyamides cellulose - esters and polypropylene
JPS50126716A (fr) * 1974-03-12 1975-10-06
JP2006509068A (ja) * 2002-12-05 2006-03-16 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド ベンゾイミダゾール−ピリドンをベースとするアゾ染料
JP2007517082A (ja) * 2003-11-20 2007-06-28 フジフィルム・イメイジング・カラランツ・リミテッド トリスアゾ染料
WO2008096697A1 (fr) * 2007-02-05 2008-08-14 Nippon Kayaku Kabushiki Kaisha Composé trisazo, composition d'encre, procédé d'impression et colorant
WO2009069279A1 (fr) * 2007-11-27 2009-06-04 Nippon Kayaku Kabushiki Kaisha Composé triazoïque, composition d'encre, procédé d'impression et corps coloré
WO2009078253A1 (fr) * 2007-12-14 2009-06-25 Nippon Kayaku Kabushiki Kaisha Composé trisazoïque, composition d'encre, procédé d'impression et corps coloré
WO2009136576A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composé trisazo, composition d’encre, procédé d’impression et matériau colorant
WO2009136575A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composé trisazo, composition d’encre, procédé d’impression et matériau colorant

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Publication number Priority date Publication date Assignee Title
WO2018135618A1 (fr) * 2017-01-20 2018-07-26 日本化薬株式会社 Composé azoïque ou sel de celui-ci, et film ainsi que plaque de polarisation à base de colorant comprenant ce composé
CN110114418A (zh) * 2017-01-20 2019-08-09 日本化药株式会社 偶氮化合物或其盐、以及含有偶氮化合物或其盐的染料系偏光膜及染料系偏光板
CN110114418B (zh) * 2017-01-20 2020-09-01 日本化药株式会社 偶氮化合物或其盐、以及含有偶氮化合物或其盐的染料系偏光膜及染料系偏光板

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