WO2010143611A1 - Compositions d'encre, procédé d'impression par jet d'encre et corps coloré - Google Patents

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

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Publication number
WO2010143611A1
WO2010143611A1 PCT/JP2010/059633 JP2010059633W WO2010143611A1 WO 2010143611 A1 WO2010143611 A1 WO 2010143611A1 JP 2010059633 W JP2010059633 W JP 2010059633W WO 2010143611 A1 WO2010143611 A1 WO 2010143611A1
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Prior art keywords
group
unsubstituted
substituted
sulfo
carboxy
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PCT/JP2010/059633
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English (en)
Japanese (ja)
Inventor
順哉 柵木
隆志 吉本
貴彦 松井
彬 川口
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2011518534A priority Critical patent/JP5570506B2/ja
Publication of WO2010143611A1 publication Critical patent/WO2010143611A1/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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • 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
    • 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
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • 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 two specific types 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 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.
  • water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks for fountain pens, felt pens, and the like and inks for ink-jet recording.
  • a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle.
  • 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 fastness such as water resistance, light resistance, gas resistance and moisture resistance.
  • the gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action existing in the air acts on the dye in the recording material and causes the printed image to discolor.
  • examples of the oxidizing gas having this kind of action include NOx, SOx, etc.
  • ozone gas is a main causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recording images. It is said that. Therefore, ozone gas resistance tends to be regarded as the most important among gas resistances.
  • ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper use a material such as a porous white inorganic material in order to expedite ink drying and to reduce bleeding at high image quality.
  • Discoloration due to ozone gas is noticeable on such recording paper. Since the discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, the improvement of ozone gas resistance is one of the most important issues in the ink jet recording method.
  • the ink composition used for ink jet recording and the colored bodies colored thereby will be further improved in light resistance, ozone gas resistance, moisture resistance and water resistance. Is strongly demanded.
  • Ink of various hues is prepared from various pigments, and among them, black ink is an important ink used for both monocolor and full-color images.
  • black ink is an important ink used for both monocolor and full-color images.
  • a black ink is prepared by blending a plurality of various pigments.
  • the hue differs depending on the medium (recording material) as compared to the case where the ink is prepared with a single dye.
  • Decomposition of the dye by light or ozone gas In particular, there is a problem that discoloration becomes large.
  • 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 a black color, and is an ink composition that has been greatly improved in terms of image fastness of printed matter. However, there is still a demand for further improvement in ozone resistance, and it is still in the market. We have not yet provided products that fully satisfy the requirements of
  • the present invention is stable even when stored for a long period of time, exhibits a neutral black to gray color with low saturation and no tint in both dark and light color printing, and the printed image has a high density.
  • Another object of the present invention is to provide a water-based black ink composition that gives a black recorded image that is excellent in ozone gas resistance and light resistance of a recorded image without any change in hue for each medium.
  • the present inventors have found that at least one kind of the dye (I) represented by the specific formula (1) or a salt thereof, and the formula (3)
  • the present inventors have found that an ink composition containing the dye (II) represented by the formula (II), a tautomer thereof, or a salt thereof as a dye solves the above-mentioned problems.
  • the present invention is 1) At least one dye (I) represented by the following formula (1) or a salt thereof, and at least one dye (II) represented by the following formula (3) or a tautomer thereof, or a salt thereof
  • An ink composition containing both of them as a pigment [In Formula (1), R a is a hydrogen atom; a hydroxy group; a carboxy group; an unsubstituted C1-C4 alkyl group; a C1-C4 alkyl group substituted with a hydroxy group or a C1-C4 alkoxy group; an unsubstituted C1-C4 alkoxy group; a hydroxy group or C1 A C1-C4 alkoxy group substituted with a C4 alkoxy group; an unsubstituted C1-C4 alkylamino group; a C1-C4 alkylamino group substituted with a hydroxy group or a C1-C4 alkoxy group; a carboxy C1-C5
  • R 1 represents a carboxy group; an unsubstituted C1-C4 alkyl group; a C1-C4 alkyl group substituted with a carboxy group; an unsubstituted phenyl group; or a phenyl group substituted with a sulfo group;
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group;
  • R 3 represents a chlorine atom; an unsubstituted C1-C6 alkyl group; an unsubstituted C1-C6 alkoxy group; or an unsubstituted C1-C4 alkylcarbonylamino group;
  • a ring substituted by R 5 to R 7 represents 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 a hydrogen atom; a
  • 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; an unsubstituted C1-C4 alkoxy group; a hydroxy group, and an unsubstituted C1-C4 A C1-C4 alkoxy group substituted with an alkoxy group, a sulfo group, or a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; and a C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, or a carboxy group; A group selected from the group consisting of: ]
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group
  • R 3 is a chlorine atom, an unsubstituted C1-C6 alkyl group, or an unsubstituted C1-C6 alkoxy group
  • the ring in which R 5 to R 7 are substituted is a benzene ring in which there is no ring represented by a broken line;
  • R 5 is a C1-C4 alkoxy group substituted with a sulfo group,
  • R 6 is a hydrogen atom,
  • R 7 is an unsubstituted C1-C4 alkyl group,
  • the ring in which R 8 to R 10 are substituted is a benzene ring in which no ring represented by a broken line exists, R 8 is a C1-C4 alkylthio group substituted with a sulfo group, R 9 is a hydrogen atom, R
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group or a carbamoyl group
  • R 3 is an unsubstituted C1-C6 alkyl group or an unsubstituted C1-C6 alkoxy group
  • the ring in which R 5 to R 7 are substituted is a benzene ring in which there is no ring represented by a broken line
  • R 5 is a C1-C4 alkoxy group substituted with a sulfo group
  • R 6 is a hydrogen atom
  • R 7 is an unsubstituted C1-C4 alkyl group
  • the ring in which R 8 to R 10 are substituted is a benzene ring in which no ring represented by a broken line exists, R 8 is a C1-C4 alkylthio group substituted with a sulfo group, R 9 is a hydrogen atom, R 10 is an unsubstit
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group or a carbamoyl group
  • R 3 is an unsubstituted C1-C6 alkyl group or an unsubstituted C1-C6 alkoxy group
  • R 5 is a C1-C4 alkoxy group substituted with a sulfo group
  • R 6 is a hydrogen atom
  • R 7 is an unsubstituted C1-C4 alkyl group
  • R 8 is a C1-C4 alkylthio group substituted with a sulfo group
  • R 9 is a hydrogen atom
  • R 10 is an unsubstituted C1-C4 alkyl group
  • the ratio of the dye (I) or a salt thereof is 2 to 30% by mass in the total mass of the dye contained in the ink composition, and the ratio of the dye (II) or a tautomer thereof or a salt thereof
  • the ink composition according to any one of 1) to 10) above, wherein is from 60 to 90% by mass, 12)
  • the total content of the dye (I) or a salt thereof and the dye (II) or a tautomer thereof or a salt thereof in the total mass of the ink composition is 0 with respect to the total mass of the ink composition.
  • the ratio of the dye (I) or a salt thereof in the total mass of the dye contained in the ink composition is 2.0 to 20% by mass, the ratio of the dye (II) or a tautomer thereof, or a salt thereof.
  • 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 black color of the neutral and high-quality hue has low saturation and no tint regardless of the pigment concentration in the ink. A recorded image is obtained.
  • the printing density is high, and the ozone gas resistance and light resistance are excellent.
  • the ink composition of the present invention is extremely useful as a black ink for inkjet recording.
  • the ink composition of the present invention at least one kind of the dye (I) represented by the above formula (1) and at least one kind of the dye (II) represented by the above formula (3) are used as the dye.
  • It is an aqueous black ink composition characterized by containing.
  • the ink composition of the present invention may further contain a pigment other than the pigment (I) and the pigment (II) for the purpose of preparing a neutral and high-quality black.
  • the ink composition of the present invention can obtain the effects of the present invention even if it contains no dye other than the dye (I) and the dye (II).
  • 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). Is preferred.
  • examples of the unsubstituted C1-C4 alkyl group for R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include unsubstituted straight chain such as methyl, ethyl, n-propyl and n-butyl; unsubstituted branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl;
  • Examples of the C1-C4 alkyl group substituted with a hydroxy group or a C1-C4 alkoxy group in R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include hydroxy-substituted ones such as 2-hydroxyethyl; C1-C4 such as methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl, etc. Alkoxy-substituted ones; and the like.
  • Examples of the unsubstituted C1-C4 alkoxy group for R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include those having an unsubstituted linear chain such as methoxy, ethoxy, n-propoxy and n-butoxy; those having an unsubstituted branched chain such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy; .
  • Examples of the C1-C4 alkoxy group substituted with a hydroxy group or a C1-C4 alkoxy group in R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxy Linear or branched, preferably linear C1-C4 alkoxy substituted, such as propoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy and alkoxy such as 2-hydroxyethoxyethoxy are combined And the like.
  • Examples of the unsubstituted C1-C4 alkylamino group in R a include mono (unsubstituted linear or branched alkyl) amino such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, etc.
  • the C1-C4 alkylamino group substituted with a hydroxy group or a C1-C4 alkoxy group in R a is a mono (hydroxy-substituted alkyl) amino group such as hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino, etc.
  • Bis (hydroxy-substituted alkyl) amino groups such as bis (hydroxyethyl) amino; mono (alkoxy-substituted alkyl) amino groups such as methoxyethylamino and ethoxyethylamino; bis (methoxyethyl) amino and bis (2-ethoxyethyl) Bis (alkoxy-substituted alkyl) amino groups such as amino; and the like.
  • Examples of the carboxy C1-C5 alkylamino group for R a include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, carboxy-n-pentylamino and the like.
  • Examples of the bis (carboxy C1-C5 alkyl) amino group for R a include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include bis (carboxymethyl) amino, bis (carboxyethyl) amino, bis (carboxypropyl) amino, and the like.
  • Examples of the unsubstituted C1-C4 alkanoylamino group for R a include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include unsubstituted straight chain such as acetylamino and n-propionylamino; unsubstituted branched chain such as isopropionylamino; and the like.
  • a linear or branched one can be mentioned, and a linear one is preferred.
  • Specific examples include hydroxy-substituted ones such as hydroxyacetylamino, 2-hydroxy-n-propionylamino, 3-hydroxy-n-propionylamino, 2-hydroxy-n-butyrylamino, 3-hydroxy-n-butyrylamino; 2 Alkoxy-substituted ones such as -methoxy-n-propionylamino, 3-methoxy-n-propionylamino, 2-methoxy-n-butyrylamino, 3-methoxy-n-butyrylamino, and the like.
  • Examples of the phenylamino group in which the benzene ring in R a is substituted with a carboxy group, a sulfo group, or an amino group include 2-, 3-, or 4-carboxyphenylamino, 3,5-biscarboxyphenylamino, etc.
  • R a unsubstituted C1-C4 alkyl group of the above is preferable, and methyl is particularly preferred.
  • the aliphatic amino group substituted with a carboxy group or a sulfo group in X is either a linear or branched, preferably linear, sulfo C1-C5 alkylamino group; carboxy C1- A mono (C1-C5 alkyl) amino group; a di (sulfo C1-C5 alkyl) amino group; a di (carboxy C1-C5 alkyl) amino group; C1-C5 alkyl) amino group; and the like.
  • the range of carbon number is usually C1-C5, preferably C1-C4, more preferably C1-C3, and still more preferably C1-C2.
  • sulfo C1-C5 alkylamino groups such as sulfomethylamino, sulfoethylamino, sulfopropylamino, sulfobutylamino, sulfopentylamino; carboxymethylamino, carboxyethylamino, carboxypropylamino, carboxybutylamino, Carboxy C1-C5 alkylamino group such as carboxypentylamino; di (sulfoC1-C5 alkyl) amino group such as di (sulfomethyl) amino, di (sulfoethyl) amino, di (sulfopropylamino); di (carboxymethyl) amino A di (carboxy C1-C5 alkyl) amino group such as;
  • X is preferably a sulfo C1-C5 alkylamino group or a di (carboxy C1-C5 alkyl) amino group, more preferably the former, and particularly preferably sulfoethylamino among the former.
  • dyes (I) represented by the above formula (1) preferred are the dyes represented by the above formula (4).
  • X represents the same meaning as in formula (1), including preferred ones.
  • the most preferable one is a dye represented by the following formula (9).
  • the pigment (II) contained in the ink composition of the present invention is a pigment represented by one or more formulas (3). That is, the dye (II) may be a single dye represented by the above formula (3), but is usually represented by the formula (3) from the viewpoint of ease of production, low cost, and the like.
  • a mixed dye composed of several types of trisazo compounds roughly speaking, preferably 1 to 8 types, more preferably 1 to 7 types, and further preferably 2 to 6 types. Even if such a mixed dye is used, there is no problem in the effect obtained by the present invention. If the production is easy, the dye of the present invention may naturally consist of a single trisazo compound.
  • the dye (II) may be a mixed dye as described above, but does not substantially contain other dyes not represented by the formula (3).
  • the substitution positions of R 5 to R 7 or R 8 to R 10 may be different from each other within the specific range including the ring represented by a broken line.
  • R 1 is a methyl group
  • R 2 is a cyano group
  • R 1 is a carboxy group
  • R 2 is a carbamoyl group.
  • a mixed dye may be used.
  • each of the rings in which the dye (II) is substituted by R 1 to R 3 , R 5 to R 10 , group A, R 5 to R 7 or R 8 to R 10 in the above formula (3) is the same It is also possible to obtain a mixed dye composed of positional isomers of a plurality of trisazo compounds in which only the substitution positions of R 3 and sulfo group in a to d are different, and such a mixed dye is preferred.
  • the dye represented by the formula (3) has a tautomer, and examples of the tautomer include the following formulas (11) and (12) in addition to the formula (3). These tautomers are also included in the present invention.
  • the ring in which the group A, R 1 to R 3 , R 5 to R 10 , R 5 to R 7 or R 8 to R 10 is substituted is represented by a broken line. The same meaning as in the above formula (3) is also included including the ring.
  • examples of the unsubstituted C1-C4 alkyl group for R 1 include straight-chain or branched-chain groups, with straight-chain groups being preferred.
  • Specific examples of the unsubstituted C1-C4 alkyl group include, for example, straight chain such as methyl, ethyl, n-propyl, n-butyl, etc .; branched chain such as isopropyl, isobutyl, sec-butyl, t-butyl, etc. And the like.
  • methyl, ethyl, n-propyl and t-butyl are preferable, methyl and n-propyl are more preferable, and methyl is more preferable.
  • Examples of the C1-C4 alkyl group substituted with a carboxy group in R 1 include linear or branched ones. Specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl and the like.
  • Examples of the phenyl group substituted with a sulfo group in R 1 include those substituted with 1 to 4, preferably 1 to 3, more preferably 1 to 2 sulfo groups.
  • the position of the substituent is not particularly limited. Specific examples include 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like.
  • R 1 is preferably an unsubstituted C1-C4 alkyl group or an unsubstituted phenyl group, more preferably an unsubstituted C1-C4 alkyl group, and even more preferably a linear unsubstituted C1-C4 alkyl group.
  • R 2 represents a cyano group; a carbamoyl group; or a carboxy group.
  • R 2 is preferably a cyano group or a carbamoyl group, and more preferably a cyano group.
  • examples of the unsubstituted C1-C6 alkyl group for R 3 include straight-chain, branched-chain, and cyclic groups, and straight-chain or branched-chain groups are preferable, and straight-chain groups are more preferable. preferable.
  • the range of carbon number is usually C1-C6, preferably C1-C4, more preferably C1-C3. Specific examples include straight chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; branched chain such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl and isohexyl. Cyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • Examples of the unsubstituted C1-C6 alkoxy group for R 3 include straight-chain or branched-chain groups, and straight-chain groups are preferred.
  • the range of carbon number is usually C1-C6, preferably C1-C4, more preferably C1-C3.
  • Specific examples include straight-chain such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy; isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isopentyloxy, isohexyloxy, etc.
  • Examples of the unsubstituted C1-C4 alkylcarbonylamino group for R 3 include straight-chain or branched-chain groups, and straight-chain groups are preferred.
  • the range of the carbon number is usually C1-C4, preferably C1-C2, more preferably C1.
  • Specific examples include straight-chain ones such as methylcarbonylamino (acetylamino), ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino; isopropylcarbonylamino, isoptylcarbonylamino, t-butylcarbonylamino, etc.
  • R 3 is preferably a chlorine atom, an unsubstituted C1-C6 alkyl group, or an unsubstituted C1-C6 alkoxy group, and a chlorine atom, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C4 alkoxy group among the above. Is more preferable.
  • R 3 examples include a chlorine atom, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, methoxy, ethoxy, n-propoxy, and n-butoxy, more preferably a chlorine atom, Methyl, ethyl, methoxy and ethoxy are preferable, and chlorine atom, methyl and methoxy are 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.
  • the unsubstituted C1-C4 alkyl group in R 5 to R 7 may be the same as the unsubstituted C1-C4 alkyl group in R 1 , including preferred ones.
  • Examples of the unsubstituted C1-C4 alkoxy group for R 5 to R 7 include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, n-butoxy, sec-butoxy and t-butoxy; .
  • Examples of the C1-C4 alkoxy group substituted with a hydroxy group in R 5 to R 7 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy and the like.
  • Examples of the C1-C4 alkoxy group substituted with an unsubstituted C1-C4 alkoxy group in R 5 to R 7 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy and the like.
  • Examples of the C1-C4 alkoxy group substituted with a hydroxy C1-C4 alkoxy group in R 5 to R 7 include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include 2-hydroxyethoxyethoxy.
  • Examples of the C1-C4 alkoxy group substituted with a sulfo group in R 5 to R 7 include linear or branched ones, and linear ones are preferred.
  • the range of carbon number is usually C1-C4, preferably C3 or C4, more preferably C3. Specific examples include 3-sulfopropoxy, 4-sulfobutoxy and the like.
  • Examples of the C1-C4 alkoxy group substituted with a carboxy group in R 5 to R 7 include straight-chain or branched-chain groups, and straight-chain groups are preferred. Specific examples include carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy and the like.
  • Examples of the unsubstituted mono- or di-C1-C4 alkylamino group in R 5 to R 7 include linear or branched ones. Specific examples include linear mono-C1-C4 alkylamino groups such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino; dimethylamino, diethylamino, di-n-propylamino, di- linear diC1-C4 alkylamino groups such as n-butylamino; branched mono-C1-C4 alkylamino groups such as sec-butylamino and t-butylamino; branched diC1-C4 such as diisopropylamino Alkylamino group; and the like.
  • linear mono-C1-C4 alkylamino groups such as methylamino, ethylamino, n-propylamino, is
  • the mono- or di-C1-C4 alkylamino group substituted with a hydroxy group in R 5 to R 7 includes a hydroxy-substituted mono C1-C4 alkylamino group such as 2-hydroxyethylamino, 2-hydroxypropylamino; A di (hydroxy-substituted C1-C4 alkyl) amino group such as 2′-dihydroxydiethylamino; and the like.
  • the mono- or di-C1-C4 alkylamino group substituted with a sulfo group in R 5 to R 7 includes sulfo-substituted mono C1-C4 such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino and the like.
  • An alkylamino group; a di (sulfo-substituted C1-C4 alkyl) amino group such as 3,3′-disulfodipropylamino; and the like.
  • the mono- or di-C1-C4 alkylamino group substituted with a carboxy group in R 5 to R 7 includes carboxy-substituted mono C1-C4 alkylamino such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino and the like.
  • carboxy-substituted mono C1-C4 alkylamino such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino and the like.
  • Groups; di (carboxy-substituted C1-C4 alkyl) amino groups such as 2,2′-dicarboxydiethylamino; and the like.
  • the unsubstituted C1-C4 alkylcarbonylamino group for R 5 to R 7 may be the same as the unsubstituted C1-C4 alkylcarbonylamino group for R 3 , including preferred ones.
  • Examples of the C1-C4 alkylcarbonylamino group substituted with a hydroxy group in R 5 to R 7 include linear or branched ones, with linear ones being preferred. Specific examples include hydroxymethylcarbonylamino, 2-hydroxyethylcarbonylamino, 3-hydroxypropylcarbonylamino and the like.
  • Examples of the C1-C4 alkylcarbonylamino group substituted with a carboxy group in R 5 to R 7 include linear or branched ones, with linear ones being preferred. Specific examples include carboxymethylcarbonylamino, 2-carboxyethylcarbonylamino and the like.
  • Examples of the unsubstituted N′-C1-C4 alkylureido group in R 5 to R 7 include straight-chain or branched-chain groups, with straight-chain groups being preferred. Specific examples include methylureido, ethylureido, propylureido and the like.
  • N′-C1-C4 alkylureido group substituted with a hydroxy group in R 5 to R 7 examples include N′-2-hydroxyethylureido, N′-3-hydroxyethylureido and the like.
  • N′-C1-C4 alkylureido group substituted with a sulfo group in R 5 to R 7 examples include N′-2-sulfoethylureido and N′-3-sulfopropylureido.
  • N′-C1-C4 alkylureido group substituted with a carboxy group in R 5 to R 7 examples include N′-carboxymethylureido, N′-2-carboxyethylureido, N′-3-carboxypropylureido, And N′-4-carboxybutylureido.
  • the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom is substituted with one or two chlorine atoms such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino, etc. The thing which was done is mentioned.
  • Examples of the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group include 2-methylphenylamino, 4-methylphenylamino, 4-t-butylphenylamino and the like. And those substituted with an unsubstituted C1-C4 alkyl group in the chain.
  • Examples of the phenylamino group in which the benzene ring is substituted with a nitro group in R 5 to R 7 include those substituted with one nitro group such as 2-nitrophenylamino and 4-nitrophenylamino.
  • the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group includes 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, and 3,5-disulfophenyl. And those substituted with one or two sulfo groups, such as amino.
  • the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group includes 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, 3,5-dicarboxyphenyl Examples thereof include those substituted with one or two carboxy groups such as amino.
  • the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom includes one or two chlorine atoms such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino, etc. And those substituted with.
  • Examples of the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group include straight-chain such as 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino, etc. Examples thereof include those substituted with an unsubstituted C1-C4 alkyl group.
  • the benzoylamino group in which the benzene ring is substituted with a nitro group in R 5 to R 7 includes one or two nitro groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino, 3,5-dinitrobenzoylamino and the like. And those substituted with a group.
  • Examples of the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group include those substituted with one sulfo group such as 2-sulfobenzoylamino and 4-sulfobenzoylamino.
  • Examples of the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group include one or two of 2-carboxybenzoylamino, 4-carboxybenzoylamino, 3,5-dicarboxybenzoylamino, etc. The thing substituted by the carboxy group is mentioned.
  • the phenylsulfonylamino group in which the benzene ring is substituted with a chlorine atom in R 5 to R 7 includes those substituted with one or two chlorine atoms such as 2-chlorophenylsulfonylamino and 4-chlorophenylsulfonylamino. Can be mentioned.
  • the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group includes 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-t-butylphenylsulfonylamino And those substituted with a linear or branched, preferably linear, unsubstituted C1-C4 alkyl group.
  • the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a nitro group includes one nitro group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino and the like. And those substituted with.
  • the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group includes those substituted with one sulfo group such as 3-sulfophenylsulfonylamino and 4-sulfophenylsulfonylamino. It is done.
  • Examples of the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group include those substituted with one carboxy group such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino. It is done.
  • R 5 to R 7 are each independently a hydrogen atom, a C1-C4 alkoxy group substituted with a sulfo group, or an unsubstituted C1-C4 alkyl group, and at least 2 of R 5 to R 7 Is preferably a group other than a hydrogen atom, more preferably R 6 is a hydrogen atom, R 5 and R 7 are groups other than a hydrogen atom, and C 5 -C 4 alkoxy substituted with a sulfo group More preferably, R 6 is a hydrogen atom and R 7 is an unsubstituted C1-C4 alkyl group.
  • 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.
  • the unsubstituted C1-C4 alkyl group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkyl group in R 1 , including preferred ones.
  • the unsubstituted C1-C4 alkoxy group for R 8 to R 10 may be the same as the unsubstituted C1-C4 alkoxy group for R 5 to R 7 , including preferred ones.
  • the C1-C4 alkoxy group substituted with a hydroxy group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferable ones.
  • the C1-C4 alkoxy group substituted with the unsubstituted C1-C4 alkoxy group in R 8 to R 10 is the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferable ones. Good.
  • the C1-C4 alkoxy group substituted with a hydroxy C1-C4 alkoxy group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferable ones. .
  • the C1-C4 alkoxy group substituted with a sulfo group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferable ones.
  • the C1-C4 alkoxy group substituted with a carboxy group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferred ones.
  • the C1-C4 alkylthio group substituted with a hydroxy group, a sulfo group, or a carboxy group in R 8 to R 10 is any of the following linear or branched, preferably linear, unsubstituted C1-C4 alkylthio groups In which one or two, preferably one, of the above-described hydrogen atoms are substituted.
  • Examples of the unsubstituted C1-C4 alkylthio group include straight-chain groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, dimethylthio, diethylthio, di-n-propylthio, di-n-butylthio; sec-butylthio Branched chain such as t-butylthio and diisopropylthio;
  • any hydrogen atom other than the hydrogen atom of the carbon atom bonded to the sulfur atom is preferably substituted with the hydroxy group.
  • Examples of the C1-C4 alkylthio group substituted with a hydroxy group in R 8 to R 10 include 2-hydroxyethylthio, 2-hydroxypropylthio and the like.
  • Examples of the C1-C4 alkylthio group substituted with a sulfo group in R 8 to R 10 include 2-sulfoethylthio, 3-sulfopropylthio, 4-sulfobutylthio and the like.
  • Examples of the C1-C4 alkylthio group substituted with a carboxy group in R 8 to R 10 include carboxymethylthio, 2-carboxyethylthio, 3-carboxypropylthio and the like.
  • the unsubstituted mono- or di-C1-C4 alkylamino group in R 8 to R 10 may be the same as the unsubstituted mono- or di-C1-C4 alkylamino group in R 5 to R 7 including preferable ones.
  • the mono- or di-C1-C4 alkylamino group substituted with a hydroxy group in R 8 to R 10 is preferably a mono- or di-C1-C4 alkylamino group substituted with a hydroxy group in R 5 to R 7 above. It may be the same including things.
  • the mono- or di-C1-C4 alkylamino group substituted with a sulfo group in R 8 to R 10 is preferably the mono- or di-C1-C4 alkylamino group substituted with the sulfo group in R 5 to R 7 above. It may be the same including things.
  • the mono- or di-C1-C4 alkylamino group substituted with a carboxy group in R 8 to R 10 is preferably a mono- or di-C1-C4 alkylamino group substituted with a carboxy group in R 5 to R 7 above. It may be the same including things.
  • the unsubstituted C1-C4 alkylcarbonylamino group in R 8 to R 10 may be the same as the unsubstituted C1-C4 alkylcarbonylamino group in R 5 to R 7 including preferred ones.
  • Examples of the C1-C4 alkylcarbonylamino group substituted with a hydroxy group in R 8 to R 10 include the C1-C4 alkylcarbonylamino group substituted with a hydroxy group in R 5 to R 7 and preferable ones. Can be the same.
  • the C1-C4 alkylcarbonylamino group substituted with a carboxy group in R 8 to R 10 includes the C1-C4 alkylcarbonylamino group substituted with the carboxy group in R 5 to R 7 and preferred ones. Can be the same.
  • the unsubstituted N′-C1-C4 alkylureido group in R 8 to R 10 may be the same as the unsubstituted N′-C1-C4 alkylureido group in R 5 to R 7 including preferable ones.
  • the N′-C1-C4 alkylureido group substituted with a hydroxy group in R 8 to R 10 is preferably an N′-C1-C4 alkylureido group substituted with a hydroxy group in the above R 5 to R 7 It may be the same including things.
  • the N′-C1-C4 alkylureido group substituted with a sulfo group in R 8 to R 10 is preferably the N′-C1-C4 alkylureido group substituted with the sulfo group in R 5 to R 7 above. It may be the same including things.
  • the N′-C1-C4 alkylureido group substituted with a carboxy group in R 8 to R 10 is preferably an N′-C1-C4 alkylureido group substituted with a carboxy group in R 5 to R 7 above. It may be the same including things.
  • the phenylamino group in which the benzene ring in R 8 to R 10 is substituted with a chlorine atom is the same as the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom, including preferable ones. It's okay.
  • the phenylamino group in which the benzene ring in R 8 to R 10 is substituted with an unsubstituted C1-C4 alkyl group is the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group.
  • the group may be the same including preferable ones.
  • the phenylamino group in which the benzene ring in R 8 to R 10 is substituted with a nitro group is the same as the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a nitro group, including preferable ones. It's okay.
  • the phenylamino group in which the benzene ring in R 8 to R 10 is substituted with a sulfo group is the same as the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group, including preferable ones. It's okay.
  • the phenylamino group in which the benzene ring in R 8 to R 10 is substituted with a carboxy group is the same as the phenylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group, including preferable ones. It's okay.
  • the benzoylamino group in which the benzene ring in R 8 to R 10 is substituted with a chlorine atom is the same as the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom, including preferable ones. It's okay.
  • the benzoylamino group in which the benzene ring in R 8 to R 10 is substituted with an unsubstituted C1-C4 alkyl group is the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group.
  • the group may be the same including preferable ones.
  • the benzoylamino group in which the benzene ring in R 8 to R 10 is substituted with a nitro group is the same as the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a nitro group, including preferable ones. It's okay.
  • the benzoylamino group in which the benzene ring in R 8 to R 10 is substituted with a sulfo group is the same as the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group, including preferable ones. It's okay.
  • the benzoylamino group in which the benzene ring in R 8 to R 10 is substituted with a carboxy group is the same as the benzoylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group, including preferable ones. It's okay.
  • the phenylsulfonylamino group in which the benzene ring in R 8 to R 10 is substituted with a chlorine atom includes the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom, and preferable ones. Can be the same.
  • the phenylsulfonylamino group in which the benzene ring in R 8 to R 10 is substituted with an unsubstituted C1-C4 alkyl group is the phenyl sulfonyl ring in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group.
  • the sulfonylamino group may be the same including preferable ones.
  • the phenylsulfonylamino group in which the benzene ring in R 8 to R 10 is substituted with a nitro group includes the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a nitro group, and preferable ones. Can be the same.
  • the phenylsulfonylamino group in which the benzene ring in R 8 to R 10 is substituted with a sulfo group includes the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group, and preferable ones. Can be the same.
  • the phenylsulfonylamino group in which the benzene ring in R 8 to R 10 is substituted with a carboxy group includes the phenylsulfonylamino group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group, and preferable ones. Can be the same.
  • R 8 to R 10 are each independently a hydrogen atom, a C1-C4 alkylthio group substituted with a sulfo group, a chlorine atom, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, or It is an unsubstituted C1-C4 alkylcarbonylamino group, and at least two of R 8 to R 10 are preferably groups other than hydrogen atoms, R 9 is a hydrogen atom, and R 8 and R 10 are other than hydrogen atoms.
  • R 8 is a C1-C4 alkylthio group substituted with a sulfo group
  • R 9 is a hydrogen atom
  • R 10 is a chlorine atom, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group Or an unsubstituted C1-C4 alkylcarbonylamino group, wherein R 8 is a C1-C4 alkylthio group substituted with a sulfo group
  • R 9 is a hydrogen atom
  • 10 is an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, or an unsubstituted C1-C4 alkylcarbonylamino group.
  • the group A represents an unsubstituted 2-naphthothiazolyl group or a 2-naphthothiazolyl group having a substituent selected from the group consisting of the above specific groups.
  • the group A usually has 1 to 4, preferably 1 to 3, more preferably 2 or 3, and still more preferably 3 substituents.
  • the position of the substituent is not particularly limited, but when the sulfur atom is in the 1st position and the nitrogen atom is in the 2nd position and there are 4 substituents, the 3rd position, the 5th to 7th positions; 5-position and 7-position; when there are two substituents, 3-position, 5-position, 3-position and 6-position, 3-position and 7-position, 5-position and 7-position are preferred.
  • the unsubstituted C1-C4 alkyl group in the substituent of the group A may be the same as the unsubstituted C1-C4 alkyl group in R 5 to R 7 including preferable ones.
  • the unsubstituted C1-C4 alkoxy group in the substituent of the group A may be the same as the unsubstituted C1-C4 alkoxy group in R 5 to R 7 including preferable ones.
  • the C1-C4 alkoxy group substituted with a hydroxy group in the substituent of the group A may be the same as the C1-C4 alkoxy group substituted with the hydroxy group in R 5 to R 7 including preferable ones. .
  • the C1-C4 alkoxy group substituted with the unsubstituted C1-C4 alkoxy group in the substituent of the group A includes the C1-C4 alkoxy group substituted with the unsubstituted C1-C4 alkoxy group in the above R 5 to R 7 It may be the same including preferable ones.
  • the C1-C4 alkoxy group substituted with a sulfo group in the substituent of the group A may be the same as the C1-C4 alkoxy group substituted with the sulfo group in R 5 to R 7 including preferable ones. .
  • the C1-C4 alkoxy group substituted with a carboxy group in the substituent of the group A may be the same as the C1-C4 alkoxy group substituted with the carboxy group in R 5 to R 7 including preferable ones. .
  • the unsubstituted C1-C4 alkylsulfonyl group in the substituent of the group A may be the same as the unsubstituted C1-C4 alkylsulfonyl group in R 5 to R 7 including preferable ones.
  • the C1-C4 alkylsulfonyl group substituted with the sulfo group in the substituent of the group A is the same as the C1-C4 alkylsulfonyl group substituted with the sulfo group in the above R 5 to R 7 including preferable ones. It's okay.
  • the phenylsulfonyl group in which the benzene ring in the substituent of the group A is substituted with a chlorine atom is the same as the phenylsulfonyl group in which the benzene ring in R 5 to R 7 is substituted with a chlorine atom, including preferable ones. It's okay.
  • the phenylsulfonyl group in which the benzene ring in the substituent of the group A is substituted with an unsubstituted C1-C4 alkyl group the phenylsulfonyl in which the benzene ring in R 5 to R 7 is substituted with an unsubstituted C1-C4 alkyl group
  • the group may be the same including preferable ones.
  • the phenylsulfonyl group in which the benzene ring is substituted with a nitro group in the substituent of the group A is the same as the phenylsulfonyl group in which the benzene ring in R 5 to R 7 is substituted with a nitro group, including preferable ones. It's okay.
  • the phenylsulfonyl group in which the benzene ring in the substituent of the group A is substituted with a sulfo group is the same as the phenylsulfonyl group in which the benzene ring in R 5 to R 7 is substituted with a sulfo group, including preferable ones. It's okay.
  • the phenylsulfonyl group in which the benzene ring in the substituent of the group A is substituted with a carboxy group is the same as the phenylsulfonyl group in which the benzene ring in R 5 to R 7 is substituted with a carboxy group, including preferable ones. It's okay.
  • the group A is preferably a 2-naphthothiazolyl group having 2 or 3 sulfo groups; or two sulfo groups and one unsubstituted C1-C4 alkoxy group; A naphthothiazolyl group is more preferred.
  • dyes (II) represented by the above formula (3) preferred are the dyes represented by the above formula (6), and more preferred are the dyes represented by the above formula (7).
  • groups A, R 1 to R 3 , R 5 to R 7 , R 8 to R 10 , a to d, R 5 to R 7 or R 8 to R 10 are substituted.
  • the ring which includes the ring represented by the broken line has the same meaning as in the above formula (3), including preferred ones.
  • the group represented by the above formula (8) is preferable as the group A.
  • the unsubstituted C1-C4 alkoxy group for R 11 to R 14 may be the same as the unsubstituted C1-C4 alkoxy group for R 5 to R 7 , including preferred ones.
  • the C1-C4 alkoxy group substituted with a hydroxy group in R 11 to R 14 may be the same as the C1-C4 alkoxy group substituted with a hydroxy group in R 5 to R 7 including preferable ones. .
  • the C1-C4 alkoxy group substituted by the unsubstituted C1-C4 alkoxy group in R 11 to R 14 is preferably the above-mentioned unsubstituted C1-C4 alkoxy group in R 5 to R 7 Etc., including the same.
  • the C1-C4 alkoxy group substituted with a sulfo group in R 11 to R 14 may be the same as the C1-C4 alkoxy group substituted with the sulfo group in R 5 to R 7 including preferable ones. .
  • the C1-C4 alkoxy group substituted with a carboxy group in R 11 to R 14 may be the same as the C1-C4 alkoxy group substituted with a carboxy group in R 5 to R 7 including preferable ones. .
  • Examples of the unsubstituted C1-C4 alkylsulfonyl group for R 11 to R 14 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, isobutylsulfonyl, sec-butylsulfonyl, and t-butylsulfonyl; Is mentioned.
  • straight-chain compounds such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, and n-butylsulfonyl
  • branched chains such as isopropylsulfonyl, isobutylsulfonyl,
  • Examples of the C1-C4 alkylsulfonyl group substituted with a hydroxy group in R 11 to R 14 include linear or branched ones, and linear ones are preferred. Specific examples include 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl and the like.
  • Examples of the C1-C4 alkylsulfonyl group substituted with a sulfo group in R 11 to R 14 include linear or branched ones, and linear ones are preferred. Specific examples include 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl and the like.
  • Examples of the C1-C4 alkylsulfonyl group substituted with a carboxy group in R 11 to R 14 include linear or branched ones, and linear ones are preferred. Specific examples include carboxymethylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl and the like.
  • R 11 to R 14 are groups selected from the group consisting of a hydrogen atom, a sulfo group, and an unsubstituted C1-C4 alkoxy group, and any one of them is preferably a hydrogen atom. More preferably, any one is a hydrogen atom and the remaining three are sulfo groups; any two are hydrogen atoms and the remaining two are sulfo groups; or any one is a hydrogen atom, two are sulfo groups, and one is unsubstituted A C1-C4 alkoxy group; More preferably, any one is a hydrogen atom and the remaining three are sulfo groups.
  • the substitution position of R 11 to R 14 is not particularly limited.
  • R 21 , R 22 , R 23 , and R 24 are groups corresponding to R 11 , R 12 , R 13 , and R 14 in formula (8), respectively, and preferred ones. And the same meaning as R 11 to R 14 in formula (8). That is, the group represented by the formula (101) specifies the substitution positions of R 11 to R 14 in the group represented by the formula (8).
  • R 21 to R 24 is a sulfo group, any one of R 21 to R 23 is a sulfo group, the remaining is a hydrogen atom;
  • R 21 , R 23 , and R 24 are a sulfo group, R 22 Or a combination of any one of R 21 and R 24 is a sulfo group, R 22 is a hydrogen atom, and R 23 is an unsubstituted C1-C4 alkoxy group, and
  • R 21 , R 23 , and R 24 are A combination in which a sulfo group and R 22 is a hydrogen atom is more preferable.
  • the compound which combined the preferable thing described about the said Formula (1) and Formula (3) and those substituents is more preferable, and the compound which combined more preferable things is further more preferable.
  • the ring in which n, group A, R 1 to R 10 are substituted includes the ring represented by the broken line in formula (3). Means the same.
  • the same thing may be sufficient also in a preferable thing and the combination of things preferable.
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group
  • R 3 is a chlorine atom, an unsubstituted C1-C6 alkyl group, or an unsubstituted C1-C6 alkoxy group
  • a ring in which R 5 to R 7 are substituted is a benzene ring in which there is no ring represented by a broken line
  • a C1-C4 alkoxy group in which R 5 is substituted with a sulfo group, R 6 is a hydrogen atom
  • R 7 is an unsubstituted C1-C4 alkyl group
  • the ring in which R 8 to R 10 are substituted is a benzene ring in which no ring represented by a broken line exists, A C1-C4 alkylthio group in which R
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group or a carbamoyl group
  • R 3 is an unsubstituted C1-C6 alkyl group or an unsubstituted C1-C6 alkoxy group
  • a ring in which R 5 to R 7 are substituted is a benzene ring in which there is no ring represented by a broken line
  • a C1-C4 alkoxy group in which R 5 is substituted with a sulfo group, R 6 is a hydrogen atom
  • R 7 is an unsubstituted C1-C4 alkyl group
  • the ring in which R 8 to R 10 are substituted is a benzene ring in which no ring represented by a broken line exists, A C1-C4 alkylthio group in which R 8 is substituted with a sulf
  • R 1 is an unsubstituted C1-C4 alkyl group
  • R 2 is a cyano group or a carbamoyl group
  • R 3 is an unsubstituted C1-C6 alkyl group or an unsubstituted C1-C6 alkoxy group
  • R 6 is a hydrogen atom
  • R 7 is an unsubstituted C1-C4 alkyl group
  • R 9 is a hydrogen atom
  • R 10 is an unsubstituted C1-C4 alkyl group
  • a combination wherein the group A is a 2-naphthothiazolyl group having two or three
  • the salt of the dye (I) represented by the above formula (1) and / or the dye (II) represented by the formula (3) 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 salts, and ammonium salts.
  • organic cation salt include salts with quaternary ammonium represented by the following formula (13), but are not limited thereto.
  • the free acid, its tautomer, and various salts thereof may be a mixture.
  • any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt may be used.
  • the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate, or if it contains multiple salts, etc. Mixtures having suitable physical properties can also be obtained.
  • 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, and at least one of them One represents a group other than a hydrogen atom.
  • Specific examples of the alkyl group represented by Z 1 , Z 2 , Z 3 and Z 4 in the formula (13) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-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 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.
  • the dye (I) represented by the above formula (1) can be obtained according to the method described in Patent Document 2.
  • the dye (II) represented by the above formula (3) 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 3 , R 5 to R 10 , and R 5 to R 10 is a ring represented by a broken line.
  • a compound of the following formula (14) is diazotized by a conventional method, and this and a compound of the following formula (15) are coupled by a conventional method to obtain a compound of the following formula (16).
  • the compound of Formula (14) is compoundable according to the method as described in the German patent invention 223149 specification.
  • the obtained compound of the formula (16) is diazotized by a conventional method, and this is then coupled with a compound of the following formula (17) by a conventional method to obtain a compound of the following formula (18).
  • the obtained compound of the formula (18) is diazotized by a conventional method, and then this and a compound of the following formula (19) are subjected to a coupling reaction by a conventional method, whereby a dye represented by the above formula (3) ( II) can be obtained.
  • the compound of the said Formula (19) is compoundable according to the method as described in German patent invention 2000004488 specification.
  • the diazotization of the compound of the above formula (14) 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 of formula (14) with the compound of formula (15) 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 of formula (14) and the compound of formula (15) are used in approximately stoichiometric amounts.
  • the diazotization of the compound of formula (16) is also carried out by a method known per se.
  • nitrites such as alkali nitrites such as sodium nitrite in the presence of inorganic acids such as hydrochloric acid, sulfuric acid in water or aqueous organic media, for example at temperatures of -5 to 40 ° C., preferably 5 to 30 ° C. It is carried out using a metal salt.
  • Coupling of the diazotized compound of the compound of formula (16) with the compound of formula (17) 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 of formula (16) and the compound of formula (17) are used in approximately stoichiometric amounts.
  • the diazotization of the compound of formula (18) is also carried out by a method known per se.
  • an inorganic acid such as hydrochloric acid or sulfuric acid
  • it is sublimated at a temperature of, for example, ⁇ 5 to 40 ° C., preferably 10 to 30 ° C. in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent).
  • a nitrate for example an alkali metal nitrite such as sodium nitrite.
  • Coupling of the diazotized compound of the compound represented by the formula (18) and the compound of the formula (19) 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 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 of formula (18) and the compound of formula (19) are used in approximately stoichiometric amounts.
  • salting out is performed by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction, or hydrochloric acid or the like. It is isolated in the form of a free acid by adding a mineral acid, and this is washed with water, acidic water, an aqueous organic medium or the like as necessary to remove inorganic salts, and then the desired inorganic or By neutralizing with an organic base, a corresponding salt solution can be obtained.
  • 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.
  • aqueous organic medium examples include an organic substance miscible with water, or a so-called organic solvent miscible with water (specific examples include a water-soluble organic solvent described later) and water.
  • 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 ( 13) quaternary ammonium halogen salts and the like.
  • inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide (ammonia water), or alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate.
  • organic bases include organic amines such as quaternary ammoniums of the above formula (13) such as diethanolamine and triethanolamine, but are not limited thereto. is not.
  • the ink composition of the present invention will be described.
  • the ink composition of the present invention containing both the dye (I) and the dye (II) can color materials made of cellulose. Further, it is possible to color a material having a carbonamide bond, and it can be widely used for materials such as leather, woven fabric and paper.
  • each reaction solution after completion of the final step can be directly used for producing the ink composition of the present invention.
  • the reaction solution containing each dye is individually dried, for example, spray-dried; salted out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; hydrochloric acid, sulfuric acid, nitric acid
  • Each pigment is isolated by adding acid such as mineral acid such as acid salting out or acid salting out by combining salting out and aciding as described above, and then mixed to prepare an ink composition. You can also
  • the ink composition of the present invention contains both the dye (I) and the dye (II) as the dye.
  • Each of the dye (I) and the dye (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 ratio of the dye (I) in the total weight of the dye contained in the ink composition of the present invention is 2 to 30% by weight, preferably 5 to 30% by weight, more preferably 10 to 30% by weight, and the dye (II). Is 60 to 90% by mass, preferably 70 to 90% by mass.
  • the total content of the dye (I) and the dye (II) in the total mass of the ink composition of the present invention is usually 0.1 to 20% by mass, preferably 1 to 1%, based on the total mass of the ink composition.
  • the amount is 10% by mass, more preferably 2 to 8% by mass.
  • the ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent, for example, 0 to 20% by mass of an ink preparation agent, and the balance is water.
  • the pH of the ink composition of the present invention is preferably pH 5 to 11 and more preferably pH 7 to 10 for the purpose of improving storage stability.
  • the surface tension of the ink composition is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m.
  • the viscosity of the ink composition is preferably 30 mPa ⁇ s or less, and more preferably 20 mPa ⁇ s or less.
  • the pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.
  • the ink composition of the present invention is obtained by dissolving the dye (I) and the dye (II) in water or a water-soluble organic solvent (an organic solvent miscible with water) and adding an ink preparation agent as necessary. is there.
  • the metal cation chloride for example, sodium chloride
  • sulfate in the dye (I) and the dye (II) contained in the ink composition of the present invention
  • it is preferable to use a low content of inorganic impurities such as sodium sulfate.
  • the standard of the content of the inorganic impurities is about 1% by mass or less with respect to the total mass of the dye, and the lower limit may be less than the detection limit of the analytical instrument, that is, 0%.
  • a conventional method using a reverse osmosis membrane a dried pigment product or a wet cake is stirred in a mixed solvent of C1-C4 alcohol such as methanol and water, and the precipitate is separated by filtration. Then, it may be desalted by a method such as drying.
  • Examples of the ink preparation suitably used in the preparation of the ink composition of the present invention include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble UV absorbers, water-soluble polymer compounds, and dye dissolution. Agents, antioxidants, surfactants and the like. Hereinafter, these ink preparation agents will be described.
  • antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. .
  • preservative examples include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone , Benzyl bromacetate compounds, inorganic salt compounds and the like.
  • 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-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.
  • 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 in the range of, for example, 5 to 11 without adversely affecting the prepared ink.
  • specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Alkaline metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate;
  • chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.
  • rust inhibitor 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. .
  • surfactant examples include known surfactants such as anionic, cationic, and nonionic surfactants.
  • anionic surfactant examples 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, - dimethyl-1-hexyne-3-acetylene alcohol such as ol; for example, as other specific examples, Nissin Chemical Industry Co., Ltd., trade name Surfynol RTM 104,105,82,465, Olfine RTM STG and the like. These ink preparation agents are used alone or in combination. In this specification, “ RTM ” means a registered trademark.
  • the ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order.
  • the obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities.
  • the ink composition of the present invention includes the dye (I) and the dye (II In addition to), other pigments having various hues may be contained within a range that does not impair the effects obtained by the present invention.
  • black having a different hue or 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 (for example, CI Direct Red 89), red (for example, 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, etc.), magenta (for example C.I. Direct Red 227, etc.), can be violet, blue, navy, cyan, green, be used as a mixture of other colors of dye.
  • the ink composition of the present invention may further contain a dye represented by the following formula (2) or a salt thereof (hereinafter, for the same reason as above, Preferably, the term “pigment” including both “pigment or a salt thereof” is used.
  • R represents a hydrogen atom, an unsubstituted C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, or a sulfo group
  • n is 1 or 2
  • m is 1 to 3
  • q is 2 to 4
  • And y each represent an integer of 1 to 3
  • the ring substituted by — (SO 3 H) m is a benzene ring when there is no ring represented by a broken line; When present, it represents a naphthalene ring.
  • the dye represented by the formula (2) may be a single dye or a mixture of a plurality of dyes represented by the formula (2). Is preferred.
  • examples of the unsubstituted C1-C4 alkyl group for R include the same as the unsubstituted C1-C4 alkyl group for R a in the above formula (1), including preferable ones.
  • Examples of the unsubstituted C1-C4 alkoxy group for R include the same as the unsubstituted C1-C4 alkoxy group for R a in the above formula (1), including preferred ones.
  • R is preferably an unsubstituted C1-C4 alkoxy group among the above, and particularly preferably a methoxy group.
  • n is 1 or 2, preferably 1.
  • the substitution position on the benzene ring of “— (SO 3 H) n” whose substitution position is not specified is not particularly limited, but when n is 2 with the substitution position of the nitrogen atom on the benzene ring being the 1st position The 2nd and 4th positions are preferred. Similarly, when n is 1, the 4-position is preferred.
  • m is an integer of 1 to 3, preferably 1 or 2.
  • substitution position on the ring that is substituted by “— (SO 3 H) m” whose substitution position is not specified.
  • m is 1 and the substitution position of the nitrogen atom on the benzene ring is the 1st position, and “— (SO 3 H) m” Is more preferably substituted at the 3-position.
  • the ring has a ring represented by a broken line, that is, when it is a naphthalene ring, m is 2 and the substitution position of the nitrogen atom of the naphthalene ring is 2-position, so that “-(SO 3 H) m Are more preferably substituted at the 5th and 7th positions, the 6th and 8th positions, or the 4th and 8th positions.
  • q is an integer of 2 to 4, preferably 3.
  • Y is an integer of 1 to 3, preferably 2.
  • a preferable dye of the above formula (2) is a dye of the following formula (5).
  • R represents the same meaning as in formula (2), and L represents 1 or 2, preferably 1.
  • the most preferable one is the dye of the following formula (10).
  • the color of the pigment that the ink composition of the present invention may further contain is preferably yellow among the above.
  • the dye of the above formula (2) is also a yellow dye as described in Patent Document 3 disclosing this.
  • the dyes (I), (II), and C.I. I. It is also preferable to mix at least three kinds of the above yellow dyes including known ones having numbers.
  • the ratio of each pigment contained in the ink composition of the present invention is usually 2.0 to 30% for the pigment (I), 60 to 90% for the pigment (II), and yellow.
  • the color dye preferably 2.0 to 20% of the dye (I), 66 to 90% of the dye (II), 5 to 28% of the yellow dye; more preferably the dye (I) Is 5 to 15%, the dye (II) is 70 to 90%, and the yellow dye (particularly the dye of the formula (2)) is 5 to 15%.
  • the yellow dye in this case is not particularly limited, but the above C.I. I. Known dyes having numbers and dyes of the above formula (2) are preferred. C. I. Known dyes having numbers include C.I. I.
  • the dye of formula (2) is preferably the dye of formula (5).
  • the dye of the above formula (2) the dye of the above formula (10) is most preferable. Even when at least three kinds of pigments are blended in this way, the total content of the pigment (I), the pigment (II), and the yellow pigment in the total mass of the ink composition is the ink composition. In any case, the total mass is usually 0.1 to 20%, preferably 1 to 10%, more preferably 2 to 8% based on the mass.
  • the ink composition of the present invention can be used in various fields, but is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink for ink-jet recording. It is suitably used in the ink jet recording method of the invention.
  • the ink jet recording method of the present invention will be described.
  • recording is performed by using the ink composition of the present invention as an ink, ejecting ink droplets of the ink in accordance with a recording signal, and attaching the ink droplet to a recording material.
  • the ink nozzles used for recording are not particularly limited and can be appropriately selected according to the purpose.
  • the recording method is a known method, for example, a charge control method for ejecting ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element; An acoustic ink jet method in which the ink is irradiated and the ink is discharged using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Etc. can be adopted.
  • a method called a photo ink in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentrations in the ink differ with substantially the same hue.
  • a method of improving image quality using a plurality of inks; a method of using colorless and transparent inks, and the like are also included.
  • the colored body of the present invention is a substance colored with the ink composition of the present invention, and preferably a recording material colored with the ink composition of the present invention by an ink jet recording method using an ink jet printer.
  • the recording material that can be colored is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, and base materials for color filters.
  • a transmission sheet is preferred.
  • the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer.
  • the ink receiving layer is formed by, for example, impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing pigments in inks such as porous silica, alumina sol, and special ceramics are hydrophilic such as polyvinyl alcohol and polyvinyl pyrrolidone.
  • a sheet coated with a porous white inorganic material on the surface is particularly suitable for recording photographic images because of its high surface gloss and excellent water resistance.
  • the images recorded in these images are greatly discolored by ozone gas.
  • the ink composition of the present invention is excellent in ozone gas resistance, a great effect is exhibited even when ink jet recording is performed on such a recording material.
  • An example of a typical commercial product as a sheet coated on the surface with the porous white inorganic material as described above is manufactured by Canon Inc.
  • 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 ink such as green, blue (or violet) and red (or orange).
  • a composition can also be used in combination.
  • the ink composition of each color is poured into each container, and each container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the black ink composition of the present invention, and used for ink jet recording.
  • the coloring matter contained in the ink composition of the present invention is easy and inexpensive to synthesize. Further, since the solubility in a medium containing water as a main component is high and the solubility in water is excellent, the filterability by the membrane filter in the process of producing the ink composition is good.
  • the ink composition containing the coloring matter or the ink prepared from the ink composition is excellent in storage stability and ejection stability. That is, the ink composition of the present invention containing this pigment has good storage stability without solid precipitation, change in physical properties, change in hue, etc. after long-term storage.
  • the ink composition containing the coloring matter is suitably used for inkjet recording and writing instruments.
  • the ink composition of the present invention When used for recording on inkjet paper, it exhibits a neutral black to gray color with no hue in both dark and light color printing, and there is no change in hue for each medium.
  • the print density of the recorded image is very high, and even when a high concentration solution is printed, the image does not cause bronzing, and further, various fastnesses such as moisture resistance and water resistance, particularly light resistance and ozone gas resistance are excellent. ing.
  • full-color ink jet recording with excellent fastness and storage stability is possible, and of course can be used on plain paper. .
  • dye and ink composition of this invention are very useful as a black ink for inkjet recording.
  • the maximum absorption wavelength ( ⁇ max) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value of the measured compound was described in the examples.
  • combination showed all the solubility of 100 g / L or more with respect to water.
  • An aqueous solution was obtained by adding 30.3 parts of a wet cake containing the compound of the above formula (21), 2.0 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 liquid was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. over about 20 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, 800 parts of acetone was added, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (23).
  • an aqueous solution was obtained by adding 4.9 parts of a compound represented by the following formula (24) to 35 parts of water and then adding sodium hydroxide to adjust the pH to 5.0 to 5.5.
  • the diazo reaction liquid obtained by adding the sulfamic acid obtained as described above was added dropwise at a reaction temperature of 20 to 30 ° C. over 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 5.0 to 6.0. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, salted out by adding sodium chloride, and the precipitated solid was separated by filtration to obtain 23.4 parts of a wet cake containing a compound represented by the following formula (25). Obtained.
  • the compound represented by the following formula (24) was obtained by the method described in JP-A-2004-083492.
  • Step 6 After adding 13.0 parts of the compound represented by the formula (27) to 200 parts of the solution containing the compound represented by the above formula (26) and refluxing for 30 minutes with stirring, the reaction solution is concentrated under reduced pressure, and 100 parts of water is added. Then, sodium carbonate was added to adjust the pH to 7.0 to 7.5. The precipitated solid was separated by filtration and dried to obtain 8.3 parts of a compound represented by the following formula (28).
  • the compound represented by the following formula (27) was obtained by the method described in Japanese Patent No. 3383469.
  • Step 7 8.3 parts of the compound represented by the above formula (28), 12.0 parts of 28% sodium methoxide, and 7.2 parts of methyl acetoacetate were added to 100 parts of ethanol, and the mixture was refluxed for 30 minutes. 100 parts of water and then 35% hydrochloric acid were added to adjust the pH to 7.0 to 7.5, and the precipitated solid was separated by filtration and dried to obtain 11.1 parts of a compound represented by the following formula (29). It was.
  • the obtained compound represented by the following formula (29) was a mixture of compounds in which a methoxy group was substituted with b or c.
  • Step 8 After slowly adding 5.6 parts of the compound represented by the above formula (29) to 77 parts of 8% fuming sulfuric acid at 5 to 10 ° C., the mixture was reacted at the same temperature for 1.5 hours. The reaction solution was dropped into 150 parts of ice water over about 10 minutes, stirred at 65 to 70 ° C. for 30 minutes, and then the precipitated solid was separated by filtration to contain the compound represented by the following formula (30). 24.4 parts of wet cake were obtained.
  • the methoxy group is at the position b and the substitution position of the sulfo group is a, c, or d, or the methoxy group is at the position c, and the sulfo group was a mixture of compounds in which the substitution position was a, b, or d.
  • Step 9 18.7 parts of the wet cake containing the compound represented by the formula (25) obtained in the above (Step 4) is dissolved in 90 parts of water, 8.4 parts of 35% hydrochloric acid, and then at a reaction temperature of 20 to 25 ° C.
  • a diazo reaction liquid was obtained by adding 1.8 parts of a sodium nitrite aqueous solution dropwise over about 5 minutes and reacting for 30 minutes. To the obtained diazo reaction solution, 0.5 part of sulfamic acid was added and stirred for about 5 minutes.
  • 10.8 parts of a wet cake containing the compound represented by the above formula (30) was added to 55 parts of water, and the pH was adjusted to 7.5 to 8.0 with sodium hydroxide to obtain a liquid.
  • the diazo reaction liquid obtained by adding the sulfamic acid obtained as described above was added dropwise at a reaction temperature of 20 to 30 ° C. over 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 separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 100 parts of water, 200 parts of methanol was added, and the precipitated solid was separated by filtration to obtain a wet cake.
  • the obtained wet cake is dissolved again in 120 parts of water, and after adding 200 parts of methanol, the precipitated solid is separated by filtration and dried to correspond to the dye (II) represented by the following formula (31) 6.0 parts of the sodium salt were obtained.
  • the methoxy group in the following formula (31) is at the position b
  • the substitution position of the sulfo group is a, c, or d
  • the methoxy group is at the position c
  • the sulfo group was a mixed dye composed of 2 to 6 kinds of dyes having a, b, or d substitution positions.
  • ⁇ max 610.0 nm.
  • Example 1 [(A) Preparation of ink] After obtaining the ink composition of the present invention by mixing the components obtained in Synthesis Example 1 and Synthesis Example 2 with the components described in the following table, impurities are filtered off with a 0.45 ⁇ m membrane filter. Thus, a test ink was obtained.
  • the preparation of this ink is referred to as Example 1.
  • the obtained ink did not cause precipitation separation during storage, and no change in physical properties even after long-term storage.
  • the surfactant used for preparing the ink is trade name Surfinol RTM 104 manufactured by Nissin Chemical.
  • the water used for preparing the ink is ion-exchanged water. At the time of ink preparation, the pH of the ink was adjusted to pH 8 to 10 with sodium hydroxide, and ion exchange water was added to make the total amount 100 parts.
  • Example 2 The ink composition of the present invention was obtained by mixing each component described in the following table, and then a test ink was obtained by filtering out impurities with a 0.45 ⁇ m membrane filter. This ink preparation is referred to as Example 2.
  • the ink of Example 2 contains a total of three types of dyes of the above formula (10) for the purpose of finely adjusting the hue in addition to the dyes (I) and (II).
  • the obtained ink did not cause precipitation separation during storage, and no change in physical properties even after long-term storage.
  • Comparative Example 4 The ink disclosed in Example 3-2 (Table I-9) of Patent Document 1 was prepared by additional trial, and a comparative ink was obtained. This ink preparation is referred to as Comparative Example 4.
  • the ink composition of Comparative Example 4 is shown in Table 36 below.
  • This ink contains three kinds of dyes, and two kinds of dyes have the same composition as each example except that they are different from the dyes contained in the ink composition of the present invention.
  • dye used in the comparative example 4 is represented by following formula (32) and Formula (33).
  • the former is a compound of formula (36) in Patent Document 1, and the latter is a compound of formula (74).
  • the compound of the formula (80) is the same dye as the dye (I) represented by the formula (9) obtained in Synthesis Example 2 in this specification.
  • the glossy paper 1 (trade name, photographic paper crispia ⁇ high gloss, manufactured by Seiko Epson, Inc.) was manufactured by Canon inkjet printer, product name PIXUS RTM iP4100. >), Two types of information transmission sheets (inkjet paper) of glossy paper 2 (manufactured by Brother Kogyo Co., Ltd., photo glossy paper BP71GA4) were subjected to ink jet recording. At the time of recording, an image pattern was prepared so that the reflection density could be obtained in several gradations, and a dark black to light black gradation recorded matter was obtained. Using the obtained recorded matter as a test piece, the following evaluation test was performed.
  • Ozone gas resistance test manufactured by Suga Test Instruments Co., Ltd. A test piece was placed on an ozone weatherometer and left for 24 hours under conditions of an ozone concentration of 10 ppm, a humidity of 60% RH, and a temperature of 24 ° C.
  • CIE L * , a * , and b * were measured for the recorded images of each test piece before and after ozone exposure, and a color difference ⁇ E was calculated by the following equation.
  • L * , a * , and b * D65 was used as the light source, and the viewing angle was 2 degrees.
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the difference between L * , a * , and b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. ⁇ E represents a better result when it is smaller.
  • the evaluation results are shown in Table 37. ⁇ : ⁇ E is less than 10 ⁇ : ⁇ E is 10 or more and less than 15 ⁇ : ⁇ E is 15 or more
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the difference between L * , a * , and b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. ⁇ E represents a better result when it is smaller.
  • the evaluation results are shown in Table 38 below. ⁇ : ⁇ E is less than 10 ⁇ : ⁇ E is 10 or more and less than 25 ⁇ : ⁇ E is 25 or more
  • Comparative Example 1 containing only the dye (II) has a problem in the print density and saturation.
  • Example 2 containing the three of the prepared dye (I), dye (II), and dye of formula (10) has a higher print density and gives a recorded material close to achromatic black. I understood.
  • the comparative example 2 clearly showed a brown color and the comparative example 3 had a yellow color, so the hue was not evaluated, but these were either an ozone gas resistance test or a light resistance test, Or both were inferior to each Example.
  • the ink composition of the present invention containing two kinds of dyes of the dye (I) and the dye (II) has a high-quality black color even without containing three kinds of dyes as in Comparative Example 4. Even if it has a hue and further contains other pigments for the purpose of fine-tuning the black hue, it has various fastness properties required for inkjet recording images as compared with conventional black ink compositions. It was found that the ink was extremely excellent in properties, particularly ozone gas resistance and light resistance, and the printing density was sufficiently high.
  • the obtained solid is added to 200 parts of water, the pH of the solution is adjusted to 7.0 to 7.5 with 35% hydrochloric acid, sodium chloride is added for salting out, and the precipitated solid is separated by filtration to obtain the following formula ( 34) part of a wet cake containing the compound represented by 34) was obtained.
  • the total amount of the obtained wet cake containing the compound represented by the formula (34), 1.8 parts of activated carbon, and 0.4 part of anhydrous ferric chloride are added to 120 parts of water, and this liquid is heated to 70 to 80 ° C. Warm, 15 parts of 80% hydrazine monohydrate was added dropwise over about 30 minutes.
  • the reaction solution was heated to 85-95 ° C. and reacted for 3 hours, and then cooled to room temperature. After filtering off insoluble matter, the precipitated solid obtained by adding 50% sulfuric acid to the filtrate and acidifying it was separated by filtration, and 47.9 parts of a wet cake containing a compound represented by the following formula (35) was obtained
  • Step 6 5.0 parts of the compound represented by the above formula (40) were slowly added to 102 parts of 3% fuming sulfuric acid at 5 to 10 ° C., and then stirred at the same temperature for 1 hour.
  • the reaction solution was dropped into 240 parts of ice water over about 10 minutes, and the precipitated solid was separated by filtration to obtain 14.7 parts of a wet cake containing a compound represented by the following formula (41).
  • the compound represented by the following formula (41) was a compound in which the methyl group was at position a and the sulfo group was substituted at position c.
  • Step 7 17.4 parts of a wet cake containing the compound represented by the formula (36) obtained in the above (Step 2) is dissolved in 90 parts of water, 8.4 parts of 35% hydrochloric acid, and then at a reaction temperature of 20 to 25 ° C.
  • a diazo reaction liquid was obtained by dropping 1.8 parts of 40% aqueous sodium nitrite solution over about 5 minutes and reacting for 30 minutes.
  • 0.5 part of sulfamic acid was added and stirred for about 5 minutes.
  • 6.5 parts of a wet cake containing the compound represented by the above formula (41) was added to 55 parts of water, and the pH was adjusted to 7.5 to 8.0 with sodium hydroxide to obtain a liquid.
  • the diazo reaction solution obtained as described above was added dropwise at a reaction temperature of 20 to 30 ° C. over 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 separated by filtration to obtain a wet cake.
  • the obtained wet cake was dissolved in 100 parts of water, 200 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 120 parts of water and 200 parts of methanol was added.
  • the precipitated solid was separated by filtration and dried to obtain the dye (II) represented by the following formula (42). 6.5 parts of the corresponding sodium salt were obtained.
  • the methyl group in the following formula (42) was at the position a, and the substitution position of the sulfo group was at the position c. ⁇ max: 587.5 nm.
  • the methoxy group in the following formula (45) is at the position b
  • the substitution position of the sulfo group is a, c, or d
  • the methoxy group is at the position c
  • Examples 3 to 7 [(A) Preparation of ink]
  • the ink composition for comparison according to the present invention was obtained by mixing each component described in the following table, and then a test ink was obtained by filtering out impurities with a 0.45 ⁇ m membrane filter.
  • This ink was prepared as Examples 3 to 7 and Comparative Examples 5 to 8, respectively.
  • the obtained ink of the present invention did not cause precipitation separation during storage and did not change its physical properties even after long-term storage.
  • the water used for preparing the ink is ion-exchanged water.
  • the pH of each ink was adjusted to 8 to 10 using sodium hydroxide, and ion exchange water was added to make a total amount of 100 parts.
  • the ink of the comparative example 4 contains three kinds of pigments, there is no description in the following Table 41, but it was added to the evaluation test as a comparison target.
  • Ozone gas resistance test manufactured by Suga Test Instruments Co., Ltd., trade name: A test piece was placed on an ozone weatherometer and allowed to stand for 24 hours under conditions of an ozone concentration of 10 ppm, a humidity of 50% RH, and a temperature of 23 ° C.
  • CIE L * , a * , and b * were measured for the recorded images of each test piece before and after ozone exposure, and a color difference ⁇ E was calculated by the following equation.
  • L * , a * , and b * D65 was used as the light source, and the viewing angle was 2 degrees.
  • ⁇ L * , ⁇ a * , and ⁇ b * mean the difference between L * , a * , and b * before and after exposure, respectively.
  • ⁇ E ( ⁇ L * 2 + ⁇ a * 2 + ⁇ b * 2 ) 1/2
  • the test results were evaluated according to the following criteria. ⁇ E represents a better result when it is smaller.
  • the evaluation results are shown in Table 42 below. ⁇ : ⁇ E is less than 10 ⁇ : ⁇ E is 10 or more and less than 15 ⁇ : ⁇ E is 15 or more
  • the inks of the respective examples showed very excellent results in black quality without deteriorating the ozone gas resistance and the print density.
  • the ink of Comparative Example 4 contains three kinds of pigments and is excellent in printing density and black quality, but is extremely inferior to each example in ozone gas resistance.
  • the inks of Comparative Examples 5 and 6 both contain only the dye (II) as the dye, but have very high saturation and are inferior in black quality.
  • the inks of Comparative Examples 7 and 8 both both contain the compound represented by the formula (10) as the dye (II) and the yellow dye, but do not contain the dye (I). This ink has higher saturation than the respective examples, and the difference can be clearly confirmed visually, and is not practical black quality.
  • the ink composition of the present invention is suitably used as a black ink liquid for various recordings such as inkjet recording and writing instruments, particularly inkjet recording.

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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 une matière colorée pour encre noire qui est hautement soluble dans des milieux à base d'eau et sur des compositions d'encre la contenant. Une solution aqueuse et une encre de concentration élevée qui contiennent la matière colorante sont stables même lorsqu'elles ont été stockées pendant longtemps et permettent de produire des images imprimées ayant une densité extrêmement élevée. Même lorsque l'impression est effectuée à l'aide de la solution aqueuse de concentration élevée, il n'y a pas de bronzage dans les images imprimées ainsi obtenues. Les compositions d'encre permettent de produire des images imprimées noires qui présentent diverses excellentes solidités, en particulier d'excellentes solidités à la lumière et à du gaz contenant de l'ozone. Les compositions d'encre contiennent chacune : au moins une matière colorante représentée par la formule générale (1) ou un sel de celle-ci ; et au moins une matière colorante représentée par la formule générale (3), un tautomère de celle-ci ou un sel de la matière ou du tautomère. Dans la formule générale (1), Ra représente alkyle ou similaire ; et X représente amino aliphatique substitué ou similaire. Dans la formule générale (3), R1 représente alkyle ou similaire ; R2 représente cyano ou similaire ; R3 représente alcoxy substitué ou similaire ; R5 à R7 représentent chacun un atome d'hydrogène, alkyle, alcoxy substitué ou similaire ; R8 à R10 représentent chacun un atome d'hydrogène, alkyle, alkylthio substitué ou similaire ; A représente naphtothiazolyle substitué ; et a à d représentent les positions auxquelles le noyau est substitué par R3 et sulfo.
PCT/JP2010/059633 2009-06-12 2010-06-07 Compositions d'encre, procédé d'impression par jet d'encre et corps coloré Ceased WO2010143611A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006001274A1 (fr) * 2004-06-23 2006-01-05 Nippon Kayaku Kabushiki Kaisha Compose azo, composition d'encre et objet colore
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree
JP2009030023A (ja) * 2007-07-05 2009-02-12 Canon Inc インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
WO2009136577A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composition d'encre, procédé d'impression par jet d'encre et corps coloré
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006001274A1 (fr) * 2004-06-23 2006-01-05 Nippon Kayaku Kabushiki Kaisha Compose azo, composition d'encre et objet colore
WO2007077931A1 (fr) * 2006-01-06 2007-07-12 Nippon Kayaku Kabushiki Kaisha Compose triazoique, composition d’encre, procede d’impression et matiere coloree
JP2009030023A (ja) * 2007-07-05 2009-02-12 Canon Inc インク、インクジェット記録方法、インクカートリッジ、記録ユニット、及びインクジェット記録装置
WO2009136577A1 (fr) * 2008-05-07 2009-11-12 日本化薬株式会社 Composition d'encre, procédé d'impression par jet d'encre et corps coloré
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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