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WO2009136577A1 - Composition d'encre, procédé d'impression par jet d'encre et corps coloré - Google Patents

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

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Publication number
WO2009136577A1
WO2009136577A1 PCT/JP2009/058389 JP2009058389W WO2009136577A1 WO 2009136577 A1 WO2009136577 A1 WO 2009136577A1 JP 2009058389 W JP2009058389 W JP 2009058389W WO 2009136577 A1 WO2009136577 A1 WO 2009136577A1
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Prior art keywords
group
unsubstituted
substituted
sulfo
carboxy
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PCT/JP2009/058389
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English (en)
Japanese (ja)
Inventor
芳明 川井田
隆志 吉本
貴彦 松井
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日本化薬株式会社
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Priority to JP2010511058A priority Critical patent/JPWO2009136577A1/ja
Publication of WO2009136577A1 publication Critical patent/WO2009136577A1/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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/18—Trisazo or higher polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
    • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
    • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used

Definitions

  • the present invention relates to an ink composition containing at least two kinds of pigments, an ink jet recording method using the ink composition, and a colored body colored with the ink composition.
  • a recording method using an inkjet printer which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. Since this method has features that the recording head and the recording material are not in contact with each other, the generation of sound is low and the sound is quiet, and the size and speed are easily increased. Both are expected to grow significantly.
  • water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks such as fountain pens and felt-tip pens and inks for inkjet recording.
  • a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
  • a recording image With 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 and to have a bronze property that hardly occurs in a printed image.
  • the water-soluble dye used is required to have particularly high solubility in water and high solubility in a water-soluble organic solvent added to the ink.
  • the formed image is required to have image fastness such as water resistance, light resistance, oxidation resistance gas resistance and moisture resistance.
  • Bronze is a bronzing phenomenon (also called a bronzing phenomenon) in which pigments are formed into metal flakes on the surface of glossy paper due to association of pigments or poor ink absorption, resulting in glare with a metallic luster. It is easy to happen. When bronzing occurs, all aspects of gloss, print quality, and printing density are inferior to those without bronzing.
  • Oxidation-resistant gas properties are usually called gas-resistance, etc., but this is a phenomenon in which a gas with an oxidizing action that exists in the air reacts with the dye in the recording material, causing the printed image to fade and fade. It is resistance to.
  • Oxidizing gases having this type of action include ozone gas, NOx, SOx, etc. Of these oxidizing gases, ozone gas is considered to be a causative substance that further promotes the discoloration phenomenon of inkjet recording images. Ozone gas is used in the acceleration test for knowing the degree of these oxidation-resistant gas properties.
  • the ink receiving layer provided on the surface of the photographic image quality inkjet paper uses a porous material such as a white inorganic pigment in order to speed up drying of the ink and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is noticeable on such recording paper.
  • the moisture resistance is resistance to a phenomenon that a dye in a recording material bleeds when the colored recording material is stored in a high humidity atmosphere. If there is a blur of the dye, the image quality is remarkably deteriorated particularly in an image requiring a high-definition image quality such as a photographic tone. Therefore, it is important to reduce such a blur as much as possible. Therefore, moisture resistance is also an important issue required for ink-jet pigments, as with the aforementioned ozone gas resistance.
  • the ink composition used for ink jet recording and the colored body colored thereby will be further improved in water resistance, light resistance, moisture resistance and ozone gas resistance. There is a strong demand for improvement.
  • inks of various hues are prepared from various pigments, black ink among them is an important ink used not only for printing character information but also for color images.
  • a black ink is prepared by mixing a plurality of various pigments.
  • the hue differs depending on the medium (recording material) as compared to the case where the ink is prepared with a single dye.
  • Decomposition of the dye by light or ozone gas In particular, there is a problem that discoloration becomes large.
  • Patent Document 1 As a black ink composition for inkjet having various durability of printed matter, for example, one disclosed in Patent Document 1 has been proposed.
  • This ink composition has a very good hue as black, and is an ink composition in which the image fastness of the printed matter has been greatly improved.
  • the present invention is stable even when stored for a long period of time, exhibits a neutral black to gray color with no tint in both dark and light color printing, has a high density of printed images, and has a hue for each medium.
  • No change in image storage quality after printing that is, water resistance, light resistance, oxidation resistance gas resistance, moisture resistance, etc., especially water resistance that gives black recorded images with excellent ozone gas resistance and light resistance. It is an object to provide a black ink composition.
  • the present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that an ink composition containing at least two kinds of specific pigments can solve the above-mentioned problems, and has completed the present invention.
  • R a is a hydrogen atom; a hydroxy group; a carboxy group; a C1-C4 alkyl group optionally substituted by a hydroxy group or a C1-C4 alkoxy group; a C1-optionally substituted by a hydroxy group or a C1-C4 alkoxy group A C4 alkoxy group; a C1-C4 alkylamino group optionally substituted by a hydroxy group or a C1-C4 alkoxy group; a carboxy C1-C5 alkylamino group; a bis (carboxyC1-C5 alkyl) amino group; a hydroxy group or a C1- A C1-C4 alkanoylamino group optionally substitute
  • R 1 is a carboxy group; a C1-C4 alkyl group that is unsubstituted or substituted with a carboxy group; or a phenyl group that is unsubstituted or substituted with a sulfo group;
  • R 2 is a cyano group; a carbamoyl group; or a carboxy group,
  • R 3 and R 4 are each independently a hydrogen atom; a chlorine atom; a sulfo group; an unsubstituted C1-C4 alkyl group; or an unsubstituted C1-C4 alkoxy group;
  • the ring in which R 5 to R 7 are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present;
  • R 5 to R 7 are each independently hydrogen atom; chlorine atom; hydroxy group; sulfo group; carb
  • All of the dyes contained in the ink composition are the dye (I) represented by the formula (1) or a salt thereof, the dye (II) represented by the formula (2) or a tautomer thereof, or The ink composition according to 1), which is both a salt of 3) The ink composition according to 1) or 2), wherein the dye (I) is a dye represented by the following formula (3): [In formula (3), X has the same meaning as in formula (1). ] 4) 4. The ink composition according to any one of 1) to 3) above, wherein X is a mono C1-C5 alkylamino group or a diC1-C5 alkylamino group having a carboxy group or a sulfo group.
  • R 5 and R 7 are each independently a hydrogen atom; a chlorine atom; a C1-C4 alkylcarbonylamino group which is unsubstituted or substituted with a hydroxy group or a carboxy group; an unsubstituted C1-C4 alkyl group; or an unsubstituted or A C1-C4 alkoxy group substituted with a sulfo group or a hydroxy group;
  • R 6 represents a hydrogen atom;
  • R 8 and R 10 are each independently a hydrogen atom; a chlorine atom; a C1-C4 alkylcarbonylamino group which is unsubstituted or substituted with a hydroxy group or a carboxy group; a sulfo C1-C4
  • R 11 to R 14 are each independently a hydrogen atom; a chlorine atom; a sulfo group; a nitro group; a hydroxy group; a sulfamoyl group; unsubstituted or substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group, or a carboxy group And a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group; and a group selected from the group consisting of: ] 9) R 1 is a methyl group, R 2 is a cyano group or carbamoyl group, R 3 is a hydrogen atom, R 4 is a sulfo group, R 5 is a
  • Dye (II) or a tautomer thereof, or a ratio of the salt thereof is 70 to 90% by mass, the ink composition according to any one of 1) to 9) above, 11)
  • the total mass of the dye (I) or a salt thereof, and the dye (II) or a tautomer thereof or a salt thereof contained in the ink composition is 2 to 8% by mass based on the total mass of the ink composition
  • the ink composition of the present invention has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage.
  • the ink composition of the present invention is used for ink jet recording and writing instruments, and when printed on ink jet dedicated paper, the hue of the recorded image is neutral, and even when the ink has a low density, a black printed matter is produced.
  • the obtained print density is high, and various fastnesses, ie, water resistance, light resistance, oxidation gas resistance, moisture resistance, etc., especially ozone gas resistance and light resistance, and hue dependence on light source Is also small.
  • magenta, cyan, and yellow dyes full color ink jet recording excellent in light resistance and water resistance is possible.
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • the ink composition of the present invention contains at least both the dye (I) represented by the above formula (1) and the dye (II) represented by the above formula (2).
  • pigments other than these two types may be contained, but other than these two types may not be contained.
  • all of the pigments contained in the ink composition of the present invention may be both the pigment (I) represented by the above formula (1) and the pigment (II) represented by the above formula (2).
  • the pigment (I) contained in the ink composition of the present invention is a pigment represented by one or more formulas (1). That is, the dye (I) may be a single dye represented by the formula (1) or a mixture of a plurality of dyes represented by the formula (1). The pigment other than) is substantially not contained.
  • R a is a hydrogen atom; a hydroxy group; a carboxy group; a C1-C4 alkyl group optionally substituted by a hydroxy group or a C1-C4 alkoxy group; a hydroxy group or a C1-C4 alkoxy group C1-C4 alkoxy group which may be substituted; C1-C4 alkylamino group which may be substituted by hydroxy group or C1-C4 alkoxy group; carboxy C1-C5 alkylamino group; bis (carboxy C1-C5 alkyl) An amino group; a C1-C4 alkanoylamino group optionally substituted by a hydroxy group or a C1-C4 alkoxy group; a phenylamino group in which the benzene ring may be substituted by a carboxy group, a sulfo group, or an amino group; a sulfo group Halogen atom; or ure
  • C 1 -C 4 alkyl group optionally substituted by a hydroxy group or a C 1 -C 4 alkoxy group as R a include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, Unsubstituted, such as tert-butyl; Hydroxy-substituted, such as 2-hydroxyethyl; Methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl Alkoxy-substituted ones such as;
  • C 1 -C 4 alkoxy group which may be substituted by hydroxy group or C 1 -C 4 alkoxy group as R a include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert- Unsubstituted such as butoxy; hydroxy-substituted such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxy Alkoxy-substituted ones such as propoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, etc .; those in which hydroxy and alkoxy such as 2-hydroxyethoxyethoxy are combined and substituted; I can get lost.
  • C 1 -C 4 alkylamino group which may be substituted by hydroxy group or C 1 -C 4 alkoxy group as R a include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutyl
  • Unsubstituted monoalkylamino groups such as amino; unsubstituted dialkylamino such as N, N-dimethylamino, N, N-diethylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino;
  • Groups; mono (hydroxy-substituted alkyl) amino groups such as hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino; bis (hydroxy-substituted alkyl) amino groups such as bis (hydroxyethyl) amino; methoxyethylamino, ethoxy
  • Examples of the carboxy C1-C5 alkylamino group as R a include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino and the like.
  • Examples of the bis (carboxy C1-C5 alkyl) amino group as R a include bis (carboxymethyl) amino, bis (carboxyethyl) amino, bis (carboxypropyl) amino and the like.
  • C 1 -C 4 alkanoylamino group optionally substituted by a hydroxy group or a C 1 -C 4 alkoxy group as R a are unsubstituted ones such as acetylamino, n-propionylamino, isopropionylamino; Hydroxy-substituted ones such as amino, 2-hydroxy-n-propionylamino, 3-hydroxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino; 2-methoxy-n-propionylamino , Alkoxy-substituted ones such as 3-methoxy-n-propionylamino, 2-methoxy-n-butyrylamino, 3-methoxy-n-butyrylamino, and the like.
  • Examples of the phenylamino group in which the benzene ring may be substituted with a carboxy group, a sulfo group, or an amino group as Ra include unsubstituted ones such as phenylamino; carboxyphenylamino, biscarboxyphenylamino, etc.
  • X is an aliphatic amino group having a carboxy group or a sulfo group; a sulfo C1-C5 alkylamino group; a carboxy C1-C5 alkylamino group; a di (sulfo C1-C5 alkyl) amino group; a di (carboxy C1-C5 alkyl) And a mono C1-C5 alkylamino group or a di (C1-C5 alkyl) amino group having a carboxy group or a sulfo group.
  • a more preferable aliphatic carbon number is 1 or 2.
  • Preferable specific examples include a sulfo C1-C5 alkylamino group such as sulfoethylamino; a di (carboxyC1-C5 alkyl) amino group such as di (carboxymethyl) amino; among others, a sulfo C1 such as sulfoethylamino A -C5 alkylamino group is more preferred.
  • the most preferable dye (I) represented by the formula (1) is a dye represented by the following formula (7).
  • the dye (II) used in the present invention is a dye represented by one or more formulas (2). That is, the dye (II) may be a single dye represented by the formula (2) or a mixture of a plurality of dyes represented by the formula (2). The pigment other than) is substantially not contained.
  • the trisazo compound represented by the above formula (2) has a tautomer, and examples of the tautomer include the following formulas (8) and (9) in addition to the compound represented by the formula (2). Conceivable. These tautomers are also included in the present invention.
  • the rings substituted by the groups A and R 1 to R 10 have the same meaning as in the above formula (2) including the ring represented by the broken line. .
  • R 1 represents a carboxy group; a C1-C4 alkyl group which is unsubstituted or substituted with a carboxy group; or a phenyl group which is unsubstituted or substituted with a sulfo group.
  • R 1 in Formula (2) is an unsubstituted C1-C4 alkyl group
  • the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain.
  • Specific examples of the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.
  • the C1-C4 alkyl group has a carboxy group
  • the alkyl group moiety may be the same as described above including preferable ones.
  • R 1 is a C1-C4 alkyl group substituted with a carboxy group
  • preferred specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and the like.
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • R 1 in formula (2) is a phenyl group that is unsubstituted or substituted with a sulfo group
  • the sulfo group is usually substituted by 1 to 4, preferably 1 to 3, more preferably 1 to 2, such as disulfophenyl and 3,5-disulfophen
  • R 1 is more preferably an unsubstituted C1-C4 alkyl group; or an unsubstituted phenyl group, and particularly preferably an unsubstituted C1-C4 alkyl.
  • R 1 in the formula (2) are methyl, ethyl, n-propyl, tert-butyl, and phenyl, more preferably methyl, n-propyl, and phenyl, still more preferably methyl, n- Propyl.
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group. Any of R 2 is preferable, but cyano or carbamoyl is more preferable, and cyano is more preferable.
  • R 1 and R 2 in formula (2) is R 1 is methyl and R 2 is cyano, or R 1 is methyl and R 2 is carbamoyl.
  • the former combination is more preferable.
  • R 3 and R 4 each independently represent a hydrogen atom; a chlorine atom; a sulfo group; an unsubstituted C1-C4 alkyl group; or an unsubstituted C1-C4 alkoxy group.
  • R 3 and R 4 in formula (2) are unsubstituted C1-C4 alkyl groups
  • the alkyl group including the preferred ones may be the same as in the case where R 1 is an unsubstituted C1-C4 alkyl group .
  • R 3 and R 4 in the formula (2) are unsubstituted C1-C4 alkoxy groups
  • the alkoxy groups are preferably both linear and branched. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
  • R 3 and R 4 are more preferably a hydrogen atom; a sulfo group; or an unsubstituted C1-C4 alkyl group.
  • R 3 and R 4 in the formula (2) include a hydrogen atom, sulfo, methyl, ethyl, n-propyl, isopropyl, and tert-butyl, and more preferably a hydrogen atom, sulfo, methyl, and isopropyl. More preferably a hydrogen atom or sulfo.
  • R 3 and R 4 in the formula (2) are a hydrogen atom, methyl, or sulfo.
  • a preferred combination of R 3 and R 4 is that R 3 is a hydrogen atom and R 4 is sulfo, or R 3 is sulfo and R 4 is a hydrogen atom. The former combination is more preferable.
  • the ring in which R 5 to R 7 are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present; Respectively. It is preferable that there is no ring represented by a broken line, that is, the ring in which R 5 to R 7 are substituted is a benzene ring.
  • R 5 to R 7 are each independently hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; unsubstituted C1-C4 alkyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 C1-C4 alkoxy group substituted with an alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group, or carboxy group; mono- or di-C1-C4 alkyl unsubstituted or substituted with a hydroxy group, sulfo group, or carboxy group Amino group; C1-C4 alkylcarbonylamino group which is unsubstituted or substituted with a hydroxy group or a carboxy group; N'-C1-C4 alkylureido group which is unsubstituted or substituted with a hydroxy group, a sulfo group or
  • the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain.
  • the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.
  • a preferred embodiment is methyl or ethyl, more preferably methyl.
  • R 5 to R 7 in formula (2) are unsubstituted C1-C4 alkoxy groups
  • the alkoxy groups including preferred ones, are the same as when R 3 and R 4 are unsubstituted C1-C4 alkoxy groups. It's okay.
  • alkoxy group When the alkoxy group is substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxy Hydroxy C1-C4 alkoxy groups such as propoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, unsubstituted C1-C4 alkoxy C1-C4 alkoxy groups such as n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4- Sulfo C1-C4
  • R 5 to R 7 in Formula (2) are an unsubstituted mono- or di-C1-C4 alkylamino group
  • the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain.
  • Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chains such as butylamino, tert-butylamino, diisopropylamino; and the like.
  • the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as'-dihydroxydiethylamino; sulfo-substituted such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Mono- or di-C1-C4 alkylamino group; carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethy
  • R 5 to R 7 in formula (2) are an unsubstituted C1-C4 alkylcarbonylamino group
  • the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
  • C1-C4 alkylcarbonylamino group When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, 4 A hydroxy C1-C4 alkylcarbonylamino group such as hydroxybutanoylamino; a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.
  • R 5 to R 7 in the formula (2) are N′-C1-C4 alkylureido groups, those having a substituent are preferable to unsubstituted.
  • N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, N′-2-hydroxyethylureido, N′-3-hydroxy N′-hydroxy C1-C4 alkylureido group such as ethylureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethyl N′-carboxy C1-C4 alkylureido groups such as ureido, N′-2-carboxyethylureido, N′-3-
  • R 5 to R 7 in the formula (2) are each a phenylamino group, a benzoylamino group, or a phenylsulfonylamino group each having a substituent, which are sequentially described below, and the substituent of the benzene ring contained in each group
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl.
  • R 5 to R 7 in Formula (2) are unsubstituted or a phenylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • Specific examples thereof include, for example, unsubstituted phenylamino, or a chlorine atom-substituted phenylamino group such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, Unsubstituted C1-C4 alkyl-substituted phenylamino groups such as 4-tert-butylphenylamino; nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulf
  • R 5 to R 7 in Formula (2) are unsubstituted or a benzoylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • R 5 to R 7 in Formula (2) include unsubstituted benzoylamino, or chlorine atom-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoyl C1-C4 alkyl-substituted benzoylamino groups such as amino and 4-methylbenzoylamino; Nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino;
  • R 5 to R 7 in Formula (2) are unsubstituted or a phenylsulfonylamino group in which the benzene ring is substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • Specific examples include, for example, unsubstituted phenylsulfonylamino, or a chlorine atom-substituted phenylsulfonylamino group such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4- C1-C4 alkyl-substituted phenylsulfonylamino groups such as tert-butylphenylsulfonylamino; nitro-substitute
  • R 5 to R 7 in the formula (2) include a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy Carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2'-dihydroxy Diethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N′-carboxymethylureido, N′-2
  • R 5 is sulfopropoxy or sulfobutoxy, preferably 3-sulfopropoxy or 4-sulfobutoxy
  • R 6 is a hydrogen atom
  • R 7 is a hydrogen atom, chlorine atom Acetylamino, methyl or ethyl, methoxy or ethoxy, or sulfopropoxy or sulfobutoxy.
  • R 5 is sulfopropoxy
  • R 6 is a hydrogen atom
  • R 7 is methyl, methoxy, chlorine atom, or acetylamino.
  • the ring in which R 8 to R 10 are substituted is a benzene ring when a ring represented by a broken line is not present; a naphthalene ring when a ring represented by a broken line is present; Respectively. It is preferable that there is no ring represented by a broken line, that is, the ring in which R 8 to R 10 are substituted is a benzene ring.
  • R 8 to R 10 each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted group, a hydroxy group, or a C1-C4 alkoxy group A C1-C4 alkoxy group substituted with a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group; a C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group, or a carboxy group; an unsubstituted or hydroxy group; Mono- or di-C1-C4 alkylamino group substituted with a sulfo group or a carboxy group; unsubstituted or a C1-C4 alkylcarbonylamin
  • the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain.
  • the unsubstituted C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.
  • a preferred embodiment is methyl or ethyl, more preferably methyl.
  • R 8 to R 10 in the formula (2) are unsubstituted C1-C4 alkoxy groups, including the preferred alkoxy groups, the above R 3 and R 4 are unsubstituted C1-C4 alkoxy groups; It can be the same.
  • alkoxy group When the alkoxy group is substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy, 2-hydroxy Hydroxy C1-C4 alkoxy groups such as propoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, unsubstituted C1-C4 alkoxy C1-C4 alkoxy groups such as n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4- Sulfo C1-C4
  • R 8 to R 10 in Formula (2) are an unsubstituted C1-C4 alkylthio group
  • the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain.
  • Specific examples thereof include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, dimethylthio, diethylthio, di-n-propylthio, di-n-butylthio and the like; sec-butylthio, tert-butylthio, diisopropyl Branched chain such as thio;
  • the mono- or di-C1-C4 alkylthio group is substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, 2-hydroxyethylthio, 2-hydroxypropylthio, 2,2 ′ A hydroxy-substituted
  • R 8 to R 10 in formula (2) are an unsubstituted mono- or di-C1-C4 alkylamino group
  • the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain.
  • Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chains such as butylamino, tert-butylamino, diisopropylamino; and the like.
  • the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as'-dihydroxydiethylamino; sulfo-substituted such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Mono- or di-C1-C4 alkylamino group; carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethy
  • R 8 to R 10 in Formula (2) are an unsubstituted C1-C4 alkylcarbonylamino group
  • the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
  • C1-C4 alkylcarbonylamino group When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, 4 A hydroxy C1-C4 alkylcarbonylamino group such as hydroxybutanoylamino; a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.
  • R 8 to R 10 in the formula (2) are N′-C1-C4 alkylureido groups, those having a substituent are preferable to unsubstituted.
  • N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, N′-2-hydroxyethylureido, N′-3-hydroxy N′-hydroxy C1-C4 alkylureido group such as ethylureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethyl N′-carboxy C1-C4 alkylureido groups such as ureido, N′-2-carboxyethylureido, N′-3-
  • R 8 to R 10 in formula (2) are each a phenylamino group, benzoylamino group, or phenylsulfonylamino group each having a substituent, which are sequentially described below, and the substituents of the benzene ring contained in each group
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl.
  • R 8 to R 10 in Formula (2) are unsubstituted or a phenylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • Specific examples thereof include, for example, unsubstituted phenylamino, or a chlorine atom-substituted phenylamino group such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, Unsubstituted C1-C4 alkyl-substituted phenylamino groups such as 4-tert-butylphenylamino; nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulf
  • R 8 to R 10 in Formula (2) are unsubstituted or a benzoylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • R 8 to R 10 in Formula (2) include, for example, unsubstituted benzoylamino, or a chlorine atom-substituted benzoylamino group such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoyl C1-C4 alkyl substituted benzoylamino groups such as amino and 4-methylbenzoylamino; Nitro substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino; 2-s
  • Substituted benzoylamino group 2-carboxy benzoylamino, 4-carboxyphenyl benzoylamino, 3,5-carboxymethyl benzoyl carboxy-substituted benzoylamino group of the amino or the like; and the like.
  • R 8 to R 10 in Formula (2) are unsubstituted or a phenylsulfonylamino group in which the benzene ring is substituted with a chlorine atom, an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group
  • R 8 to R 10 in Formula (2) include, for example, unsubstituted phenylsulfonylamino, or a chlorine atom-substituted phenylsulfonylamino group such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, C1-C4 alkyl-substituted phenylsulfonylamino group such as 4-tert-butylphenylsulfonyla
  • R 8 to R 10 in the formula (2) include a hydrogen atom, a chlorine atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4 -Sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2 '-Dihydroxydiethylamino, 2,2'-dicarboxydiethylamino, 3,3'-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N'-carboxymethyl
  • R 8 to R 10 in formula (2) is that R 8 is sulfopropylthio or sulfobutylthio, preferably 3-sulfopropylthio or 4-sulfobutylthio, more preferably sulfopropylthio, and R 9 is A hydrogen atom, R 10 is a chlorine atom, an acetylamino group, a methyl or ethyl group, a methoxy group or an ethoxy group, or a sulfopropoxy group, preferably a chlorine atom, acetylamino, methyl, or methoxy, more preferably a chlorine atom .
  • a preferable compound represented by the above formula (2) is a compound represented by the above formula (4).
  • n, the group A, R 1 to R 10 , and R 8 to R 10 are substituted by the above formula (2) including the ring represented by the broken line and preferred ones. Same as
  • a preferable compound represented by the above formula (4) is a compound represented by the above formula (5).
  • the groups A and R 1 to R 4 may be the same as those in the formula (4), including preferable ones.
  • R 5 and R 7 are each independently a hydrogen atom; a chlorine atom; a C1-C4 alkylcarbonylamino group which is unsubstituted or substituted with a hydroxy group or a carboxy group; an unsubstituted C1-C4 alkyl group; or an unsubstituted or R 1 represents a C1-C4 alkoxy group substituted with a sulfo group or a hydroxy group, and R 6 represents a hydrogen atom.
  • R 8 and R 10 are each independently a hydrogen atom; a chlorine atom; a C1-C4 alkylcarbonylamino group which is unsubstituted or substituted with a hydroxy group or a carboxy group; a sulfo C1-C4 alkoxy group; an unsubstituted C1-C4 alkyl group
  • R 9 represents a hydrogen atom; or a C1-C4 alkoxy group substituted with a sulfo group or a C1-C4 alkylthio group substituted with a sulfo group or a carboxy group.
  • R 8 and R 10 in formula (5) including preferred ones, may be the same as those corresponding to R 8 and R 10 in formula (2).
  • R 11 to R 14 are each independently a hydrogen atom; chlorine atom; sulfo group; nitro group; hydroxy group; sulfamoyl group; unsubstituted or hydroxy group, unsubstituted C1-C4 alkoxy group, sulfo group A group selected from the group consisting of: a C1-C4 alkoxy group substituted with a group or a carboxy group; and a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group or a carboxy group; To express.
  • R 11 to R 14 in formula (6) are unsubstituted or a C1-C4 alkoxy group substituted with a hydroxy group, an unsubstituted C1-C4 alkoxy group, a sulfo group, or a carboxy group, the alkoxy group is Including the preferred ones, R 5 to R 7 in the above formula (2) may be the same as the corresponding C1-C4 alkoxy group.
  • R 11 to R 14 in formula (6) are unsubstituted or a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group
  • specific examples thereof include, for example, methylsulfonyl, ethylsulfonyl Linear or branched unsubstituted C1-C4 alkylsulfonyl groups such as propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl; 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl, etc.
  • a hydroxy C1-C4 alkylsulfonyl group a sulfo C1-C4 alkylsulfonyl group such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl; carboxymethylsulfonyl, 2-carboxyethyl Sulfonyl, carboxy C1-C4 alkylsulfonyl group such as 3-carboxypropyl sulfonyl; and the like.
  • R 11 to R 14 in the formula (6) include a hydrogen atom, a chlorine atom, sulfo, nitro, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, Carboxymethoxy, 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, 4-methylphenylsulfonyl 2,4-dimethylphenylsulfonyl, 4-nitrophenylsulfonyl, 4-sulfophenylsulfonyl, 2-carboxypheny
  • a preferable combination of R 11 to R 14 in the formula (6) is a combination of two sulfos and the other two hydrogen atoms, or three sulfos and the other one hydrogen atom, more preferably the latter combination.
  • the substitution positions of sulfo are more preferably the 4th, 6th and 8th positions of the naphthothiazole ring.
  • the salts of dyes (I) and (II) are inorganic or organic cation salts.
  • specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts
  • preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts.
  • organic cation salts include, but are not limited to, quaternary ammonium ions represented by the following formula (10).
  • the mixture of a free acid, its tautomer, and those various salts may be sufficient.
  • any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used.
  • the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate, or change the ratio when containing multiple salts, etc. Mixtures having suitable physical properties can also be obtained. Further, the dye (I) and the dye (II) do not have to be the same salt, and each may be a different salt.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group.
  • Specific examples of the alkyl group of Z 1 , Z 2 , Z 3 , Z 4 in the formula (10) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Can be mentioned.
  • hydroxyalkyl group examples include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
  • hydroxyalkoxyalkyl group examples include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. Hydroxy C1-C4 alkoxy C1-C4 alkyl group, and among them, hydroxyethoxy C1-C4 alkyl is preferable.
  • hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl,
  • hydroxyethoxy C1-C4 alkyl groups such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc. It is done.
  • the trisazo compound represented by the above formula (2) can be synthesized, for example, by the following method.
  • the acidic functional group of the compound in each process shall be represented in the form of a free acid for convenience.
  • each of the rings substituted by the groups A, R 1 to R 10 , and R 5 to R 10 includes the above formula ( Has the same meaning as in 2).
  • a compound represented by the following formula (11) is diazotized by a conventional method, and this and a compound represented by the following formula (12) are coupled by a conventional method to obtain a compound represented by the following formula (13). obtain.
  • the compound represented by Formula (11) is compoundable according to the method as described in the East German patent 223149 specification.
  • the compound represented by Formula (12) and (14) is compoundable by a conventional method.
  • the compound represented by the formula (13) thus obtained was diazotized by a conventional method, and this was then coupled with a compound represented by the following formula (14) by a conventional method to obtain a compound represented by the following formula (15). To obtain the compound.
  • the compound represented by the formula (15) thus obtained is diazotized by a conventional method, and then this and a compound represented by the following formula (16) are subjected to a coupling reaction by a conventional method, whereby the above formula (2)
  • the trisazo compound represented by these can be obtained.
  • the compound represented by the above formula (16) can be synthesized according to the method described in the specification of West German Patent No. 200000448.
  • the diazotization of the compound represented by the above formula (11) is carried out by a method known per se. For example, it is carried out using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of ⁇ 5 to 20 ° C., preferably 5 to 10 ° 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. For example, it is carried out in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of ⁇ 5 to 30 ° C., preferably 10 to 30 ° C.
  • 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.
  • an alkali metal nitrite such as a nitrite, for example sodium nitrite
  • an inorganic acid such as hydrochloric acid, sulfuric acid in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 40 ° C., preferably 5 to 30 ° C.
  • 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.
  • the reaction in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 50 ° C., preferably 10 to 30 ° C., and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6-10. Since the diazotization reaction solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base.
  • Examples of the base that can be used 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 (13) and the compound represented by formula (14) are used in approximately stoichiometric amounts.
  • the diazotization of the compound represented by the formula (15) is also carried out by a method known per se.
  • an alkali metal nitrite such as sodium nitrite.
  • the reaction in water or an aqueous organic medium, for example at a temperature of ⁇ 5 to 50 ° C., preferably 10 to 30 ° C., and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to 10, and the pH value is adjusted by adding a base.
  • a base the same ones as described above can be used.
  • the compound represented by the formula (15) and the compound represented by the formula (16) are used in a substantially stoichiometric amount.
  • the aqueous organic medium refers to water-containing organic materials miscible with water, so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later.
  • inorganic salts include alkali metal salts such as lithium chloride, sodium chloride, and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide.
  • organic cation salts include the above formula ( And halogenated salts of organic amines represented by 10).
  • inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate.
  • organic bases include organic amines such as quaternary ammoniums represented by the above formula (10) such as diethanolamine and triethanolamine, but are not limited thereto. Absent.
  • the ink composition of the present invention will be described.
  • the ink composition of the present invention containing both of the dyes (I) and (II) can dye a material made of cellulose.
  • other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabric and paper.
  • each reaction solution containing the dyes (I) and (II) can be used directly for the production of the ink composition of the present invention. That is, the ink composition of the present invention can also be produced by mixing two types of reaction liquids containing the dyes synthesized separately. However, first, the reaction solution containing each dye is individually dried, for example, spray-dried to isolate each dye; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, etc. Or by acidifying by adding a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; or by acidifying out a combination of salting out and aciding as described above; Thus, an ink composition can also be prepared.
  • the reaction solution containing each dye is individually dried, for example, spray-dried to isolate each dye; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, etc. Or by acidifying by adding a mineral acid such as
  • the ink composition of the present invention contains both of the two types of dyes (Dye (I) and (II)).
  • Each of the dyes (I) and (II) may be a single dye or a mixture of a plurality of dyes as long as the above specific conditions are satisfied. Therefore, the ink composition of the present invention is one in which at least two kinds of pigments are blended.
  • the total mass of the above-mentioned pigments (I) and (II) contained in the ink composition as a pigment is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, based on the total mass of the ink composition. More preferably, the ratio is 2 to 8% by mass, and the remainder in the ink composition other than that is water as a main medium.
  • the ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 10% by mass of an ink preparation agent, and preferably contains a water-soluble organic solvent. Further, if desired, other pigments may be included in the above range for the purpose of toning and the like.
  • 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. Furthermore, the viscosity of the ink composition is preferably 30 mPa ⁇ s or less, and more preferably 20 mPa ⁇ s or less.
  • the pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.
  • the ratio of each dye in the total mass of the dyes (I) and (II) contained in the ink composition as the dye is 10 to 30% by mass for the dye (I) and 70 to 90% by mass for the dye (II).
  • the pigment (I) is more preferably 15 to 25% by mass
  • the pigment (II) is more preferably 75 to 85% by mass.
  • the ink composition of the present invention contains a dye other than the dye (I) represented by the formula (1) and the dye (II) represented by the formula (2). You may add further in the range which does not inhibit the effect of.
  • the total amount of the pigments (I) and (II) is 70 to 99% by mass, and the total of other pigments is about 1 to 30% by mass in the total mass of the pigments contained in the ink composition. Is good.
  • other dyes than the dyes (I) and (II) may not be added to the ink composition of the present invention.
  • the dyes (I) and (II) are dissolved in water or a water-soluble organic solvent (an organic solvent miscible with water) together with other color-matching dyes as necessary.
  • an ink preparation agent is added as necessary.
  • other toning pigments and the like may be appropriately added to the ink composition of the present invention.
  • pigments (I) and (II) having a low content of inorganic impurities such as metal cation chlorides and sulfates.
  • the standard of the inorganic impurity content is about 1% by mass or less with respect to the total mass of the pigment.
  • a normal method using a reverse osmosis membrane, or a dried pigment product or a wet cake is stirred in a mixed solvent of alcohol such as methanol and water, and the precipitate is filtered and separated. Desalting treatment may be performed by a method such as drying.
  • the water-soluble organic solvent adjusts the viscosity of the ink, adjusts the drying property of the ink, and adjusts the permeability of the recording medium after printing and the ink receiving layer on the surface of the recording medium.
  • water-soluble organic solvents used for purposes such as Specific examples of water-soluble organic solvents that can be used include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol; N, N-dimethylformamide, N, N A carboxylic acid amide such as dimethylacetamide; a lactam such as 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2- Cyclic ureas such as ON, 1,3-dimethylhexahydropyrimido-2-one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane
  • Cyclic ether ethylene glycol, , 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 Mono-, oligo-, or poly-alkylene glycols or thioglycols having C2-C6 alkylene units such as glycol, polypropylene glycol, thiodiglycol, dithiodiglycol; trimethylolpropane, glycerin, hexane-1,2,6-triol, etc.
  • 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 in this specification for convenience.
  • ink preparation agent examples include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and antioxidants. Agents, surfactants and the like. These drugs are described below.
  • antifungal agent examples include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof Can be mentioned. These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.
  • preservative examples include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, and 8-oxyquinoline.
  • Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated Indanone-based compounds, benzyl bromacetate-based compounds, inorganic salt-based compounds, and the like can be given.
  • organic halogen compounds include sodium pentachlorophenol
  • pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide.
  • isothiazoline compounds Are, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -Methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.
  • 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 5 to 11, for example, without adversely affecting the prepared ink.
  • alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine
  • hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • 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.
  • chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.
  • rust preventive examples include, for example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.
  • water-soluble ultraviolet absorber 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.
  • the dye solubilizer include ⁇ -caprolactam, ethylene carbonate, urea and the like.
  • the antioxidant for example, various organic and metal complex antifading agents can be used.
  • the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. .
  • the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
  • Specific examples of the anionic surfactant include alkyl sulfonate, alkyl carboxylate, ⁇ -olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salt, N-acyl methyl taurate, Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfone Acid salts, diethylsulfosuccinate, diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.
  • cationic surfactant examples include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
  • amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, Examples include imidazoline derivatives.
  • nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and the like.
  • Ether type polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc.
  • Ester series 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, -Acetylene glycol (alcohol) type such as dimethyl-1-hexyn-3-ol; other specific examples include, for example, trade name Surfinol 104, 105, 82, 465, Olphine STG manufactured by Nissin Chemical Co., Ltd. . These ink preparation agents are used alone or in combination.
  • 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.
  • dye (I) and (II) you may mix the other pigment
  • the ink composition of the present invention can be used in various fields, but is suitable for a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink.
  • the ink jet recording method is preferably used.
  • the inkjet recording method of the present invention is characterized in that recording is performed using the ink composition of the present invention.
  • recording is performed on an image receiving material (recording material) using an ink jet ink containing the above ink composition, and there are no particular restrictions on the ink nozzles used at that time. And can be appropriately selected according to the purpose.
  • a known method for example, a charge control method that ejects ink using electrostatic attraction; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; an electric signal is converted into an acoustic beam and the ink is irradiated And adopting an acoustic ink jet method that discharges ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Can do.
  • a charge control method that ejects ink using electrostatic attraction
  • a drop-on-demand method pressure pulse method
  • an electric signal is converted into an acoustic beam and the ink is irradiated
  • adopting an acoustic ink jet method that discharges ink using the radiation pressure
  • a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method
  • a method called a photo ink in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentrations in the ink differ with substantially the same hue.
  • the colored body of the present invention is colored by an ink composition containing at least the pigments (I) and (II), and more preferably colored by the ink composition of the present invention by an ink jet recording method using an ink jet printer. It has been done.
  • sheets for information transmission such as paper and a film, fiber, cloth (cellulose, nylon, wool, etc.), leather, a base material for color filters, etc. are mentioned.
  • 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-mentioned base material with a cationic polymer; porous white inorganic material capable of absorbing pigments in inks such as porous silica, alumina sol and special ceramics, polyvinyl alcohol and polyvinylpyrrolidone. Coating on 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.
  • an image recorded on a sheet coated with a porous white inorganic substance on the surface is particularly prone to discoloration by ozone gas.
  • the ink composition of the present invention is excellent in ozone gas resistance, it is particularly effective when ink-jet recording is performed on such a recording material.
  • Specific examples of such a sheet coated with a porous white inorganic material include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photo Paper (Glossy), PM matte paper, Crispia; manufactured by Nippon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper; manufactured by Fuji Film Co., Ltd.
  • a container containing the above ink composition is loaded at a predetermined position of an inkjet printer, It may be recorded on a recording material by a method.
  • the inkjet recording method of the present invention comprises the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color such as green, blue (or violet), and red (or orange). It can also be used in combination as an ink set with an ink composition.
  • the ink composition of each color is injected into each container, and each container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the black ink composition of the present invention and used for ink jet recording.
  • the ink composition of the present invention does not cause crystal precipitation, change in physical properties, change in hue, etc. even when stored for a long period of time, it has good storage stability. Further, the ink composition of the present invention can be used for inkjet recording and writing instruments. Furthermore, when recording on an information recording sheet, particularly ink jet dedicated paper, the print density of the recorded image is high, and in addition, various durability of the recorded image, that is, water resistance, light resistance, oxidation resistance gas resistance, moisture resistance In particular, ozone gas resistance and light resistance are excellent.
  • combined in the Example showed the solubility of 100 g / L or more with respect to water.
  • An aqueous solution was obtained by adding 13.1 parts of the compound represented by the above formula (18), 7.0 parts of sulfamic acid and then sodium hydroxide to 200 parts of water to adjust the pH to 5.0 to 5.5.
  • the above diazo reaction solution was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 20 minutes. After completion of the dropping, the mixture was stirred at the same temperature for 1 hour, 800 parts of acetone was added, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound represented by the following formula (21).
  • aqueous solution was obtained by adding 110 parts of water to the wet cake obtained in the above (Step 4) and then sodium hydroxide to adjust the pH to 7.0 to 7.5.
  • aqueous solution 4.6 parts of 35% hydrochloric acid and then 4.6 parts of 40% sodium nitrite aqueous solution at a reaction temperature of 15 to 20 ° C. are dropped over about 5 minutes, and reacted for 1 hour to obtain a diazo reaction liquid. Obtained.
  • 5.4 parts of a compound represented by the following formula (22) was added to 35 parts of water, and then sodium hydroxide was added to adjust the pH to 5.0 to 5.5 to obtain an aqueous solution.
  • the diazo reaction liquid obtained as described above was added dropwise to this aqueous solution at a reaction temperature of 20 to 30 ° C. for 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 5.0 to 5.4. After completion of dropping, the mixture was stirred at the same temperature for 2 hours, salted out by addition of sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound represented by the following formula (23).
  • the compound represented by the following formula (22) was obtained by the method described in JP-A No. 2004-083492.
  • Step 6 The wet cake containing the compound represented by formula (23) obtained in the above (Step 5) is dissolved in 150 parts of water, 5.0 parts of 35% hydrochloric acid, and then 40% nitrous acid at a reaction temperature of 20 to 25 ° C.
  • a diazo reaction liquid was obtained by dropping 1.8 parts of an aqueous sodium solution over about 5 minutes and reacting for 1 hour.
  • the diazo reaction liquid obtained as described above was added dropwise to this aqueous solution at a reaction temperature of 20 to 30 ° C. for 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0. After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 160 parts of water, 350 parts of acetone was added, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 110 parts of water and 280 parts of acetone was added.
  • Example 1 The ink composition of the present invention was prepared by mixing the components shown in Table 14 below, and filtered through a 0.45 ⁇ m membrane filter to obtain an ink jet ink. The preparation of this ink is referred to as Example 1. Moreover, ion-exchange water was used for water. The pH of the ink composition was adjusted with 1.0% sodium hydroxide so that the pH was 8 to 10, and water was added so that the total amount was 100.0 parts. The obtained ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.
  • Example 2 The ink composition of the present invention was prepared by mixing the components shown in Table 15 below, and was filtered through a 0.45 ⁇ m membrane filter to obtain an ink jet ink. This ink preparation is Example 2. Moreover, ion-exchange water was used for water. The pH of the ink composition was adjusted with 1.0% sodium hydroxide so that the pH was 8 to 10, and water was added so that the total amount was 100.0 parts. The obtained ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.
  • Comparative Example 3 Preparation of an ink using only the dye (II) obtained in Synthesis Example 1 as a dye is Comparative Example 1, Comparative Example 2 is an ink preparation using only the dye (II) obtained in Synthesis Example 2, and Synthesis Example 3 Preparation of an ink using only the dye (I) obtained in Step 1 is referred to as Comparative Example 3.
  • Comparative Example 4 As Comparative Example 4, the ink disclosed in Example 3-2 of Patent Document 1 was prepared. This ink has the same composition as each example except that the blending ratios of the three types of pigment components are different. The water was ion-exchanged water, and the pH of the ink composition was adjusted with sodium hydroxide so that the pH was 8 to 10, and filtered through a 0.45 ⁇ m membrane filter. This ink preparation is referred to as Comparative Example 4.
  • Comparative Example 4 is a black ink in which three types of pigments containing two types of pigments different from pigment (II) and pigment (I) obtained in Synthesis Example 3 are blended. The compound obtained in Synthesis Example 4 of 1 is the same as the compound of Synthesis Example 3 in the present invention.
  • composition of the ink of Comparative Example 4 is shown in Table 19 below.
  • Table 19 the structural formulas of “the dye obtained in Example 2-6 of Patent Document 1” and “the dye obtained in Synthesis Example 1 of Patent Document 1” are the following formulas (29) and (30), respectively. It is represented by
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. The evaluation results are shown in Table 20 below. ⁇ : ⁇ E is less than 10 ⁇ : ⁇ E is 10 or more and less than 20 ⁇ : ⁇ E is 20 or more
  • ⁇ L *, ⁇ a *, and ⁇ b * mean differences between L *, ⁇ a *, and ⁇ b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. The evaluation results are shown in Table 20 below. ⁇ : ⁇ E is less than 10 ⁇ : ⁇ E is 10 or more and less than 20 ⁇ : ⁇ E is 20 or more
  • the saturation C * value was calculated using the following formula after measuring CIE a * and b *.
  • the light source was D65 and the viewing angle was 2 degrees.
  • C * (a * 2 + b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. The evaluation results are shown in Table 21 below. ⁇ C * is less than 15 ⁇ C * is 15 or more and less than 20 ⁇ C * is 20 or more
  • Comparative Example 4 is the most inferior in ozone gas resistance among all Examples and Comparative Examples. Moreover, Comparative Examples 1 and 3 were inferior to each Example in ozone gas resistance or light resistance, respectively. Furthermore, it was found that Comparative Example 2 had good fastness equivalent to each example in ozone gas resistance, light resistance, and moisture resistance. On the other hand, as is clear from the results of Table 21, Comparative Examples 1 and 2 that showed relatively good fastness were much higher in hue than each Example in terms of hue, and inferior to each Example in this respect. showed that.
  • the ink of each embodiment of the present invention had a good black hue with low saturation C * in both the high density portion and the low density portion.
  • the ink composition 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

L'invention porte sur un pigment pour encre noire et sur des compositions d'encre correspondantes qui sont hautement solubles dans des milieux ayant de l'eau comme composant principal, qui sont stables même lorsque des solutions aqueuses de concentration élevée sont stockées sur de longues durées, qui ont une densité élevée dans des images imprimées, qui ne produisent pas de bronzage dans des images dans lesquelles des solutions de concentration élevée ont été imprimées, qui ont un rendu de couleur favorable et qui produisent des images imprimées noires, lesdites images ayant une excellente solidité. Comme pigment pour l'encre noire, le pigment (I) représenté par la formule (1) ou des sels de celui-ci et le pigment (II) représenté par la formule (2) ou un tautomère de celui-ci, ou des sels de ceux-ci, sont utilisés. (1) [Dans la formule (1), Ra représente un groupe alkyle en C1-C4 et X représente un groupe amino aliphatique substitué par sulfo.] (2) [Dans la formule (2), R1 représente un groupe alkyle en C1-C4, R2 représente un groupe cyano, R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe sulfo, les noyaux dans lesquels R5 à R7 ou R8 à R10 sont substitués représentent des noyaux benzéniques lorsque les noyaux représentés par des lignes pointillées sont absents et des noyaux naphtalènes lorsque lesdits noyaux sont présents, R5 à R7 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-C4 ou un groupe alcoxy en C1-C4 substitué par sulfo, R8 à R10 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-C4 ou un groupe alkylthio en C1-C4 substitué par sulfo et le groupe A représente un groupe 2-naphtothiazolyle substitué par sulfo.]
PCT/JP2009/058389 2008-05-07 2009-04-28 Composition d'encre, procédé d'impression par jet d'encre et corps coloré WO2009136577A1 (fr)

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WO2010143610A1 (fr) * 2009-06-12 2010-12-16 日本化薬株式会社 Matière colorante constituée d'un composé trisazoïque, compositions d'encre, procédé d'impression et corps coloré
WO2011086974A1 (fr) * 2010-01-12 2011-07-21 日本化薬株式会社 Composition d'encre, procédé d'impression par jet d'encre et corps coloré
WO2012002317A1 (fr) * 2010-07-01 2012-01-05 日本化薬株式会社 Composition d'encre, procédé d'enregistrement à jet d'encre et corps coloré
KR101810272B1 (ko) 2010-07-01 2017-12-18 닛뽄 가야쿠 가부시키가이샤 잉크 조성물, 잉크젯 기록 방법 및 착색체

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JP5670893B2 (ja) * 2009-06-12 2015-02-18 日本化薬株式会社 トリスアゾ化合物からなる色素、インク組成物、記録方法及び着色体
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JPWO2010143610A1 (ja) * 2009-06-12 2012-11-22 日本化薬株式会社 トリスアゾ化合物からなる色素、インク組成物、記録方法及び着色体
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JP5690747B2 (ja) * 2010-01-12 2015-03-25 日本化薬株式会社 インク組成物、インクジェット記録方法及び着色体
CN103108924A (zh) * 2010-07-01 2013-05-15 日本化药株式会社 油墨组合物、喷墨记录方法及着色体
CN103108924B (zh) * 2010-07-01 2014-08-20 日本化药株式会社 油墨组合物、喷墨记录方法及着色体
WO2012002317A1 (fr) * 2010-07-01 2012-01-05 日本化薬株式会社 Composition d'encre, procédé d'enregistrement à jet d'encre et corps coloré
US8741046B2 (en) 2010-07-01 2014-06-03 Nippon Kayaku Kabushiki Kaisha Ink composition, inkjet recording method and colored body
TWI485204B (zh) * 2010-07-01 2015-05-21 Nippon Kayaku Kk Ink composition, ink jet recording method and chromosome
JP5939982B2 (ja) * 2010-07-01 2016-06-29 日本化薬株式会社 インク組成物、インクジェット記録方法及び着色体
KR101810272B1 (ko) 2010-07-01 2017-12-18 닛뽄 가야쿠 가부시키가이샤 잉크 조성물, 잉크젯 기록 방법 및 착색체
KR101810271B1 (ko) 2010-07-01 2017-12-18 닛뽄 가야쿠 가부시키가이샤 잉크 조성물, 잉크젯 기록 방법 및 착색체

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