JP2009108219A - Aqueous black ink composition and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring matter compound for black ink giving a black recording image and an ink composition thereof high in solubility to an aqueous medium, stable even in case reserved in a high-concentration aqueous solution for a long period of time, giving a very high density of the image printed, free of bronzing on the image even in case the high-concentration solution is printed, and excellent in the robustness of the image printed, particularly in the light fastness and resistance against ozone gas. <P>SOLUTION: As coloring matter components, the black ink composition includes the dyes I, II, and III, wherein the dye I is one or more water-soluble dyes given by formula (1) or salt(s) thereof, while the dye II is one or more water-soluble dyes for black whose maximum absorbing wavelength lies in the range of 560-590 nm or a salt etc., thereof, and the dye III is one or more water-soluble dyes for black whose maximum absorbing wavelength lies in the range of 590-630 nm or a salt etc., thereof. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous black ink composition containing at least three kinds of dyes (D), Dye (II), and Dye (III) below, and a colored product colored with the ink composition.

The recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material do not contact each other and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used as inks such as fountain pens, felt-tip pens, and ink-jet recording inks. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. For this reason, these inks provide a recorded image with sufficient density, do not cause clogging of the pen tip or nozzle, have good drying properties on the recording material, have little bleeding, and have stable storage. It is required to have excellent properties and bronzing in printed images. Therefore, water-soluble dyes have particularly high solubility in water and high solubility in water-soluble organic solvents added to ink. Is required. Further, the formed image is required to have image fastness such as water resistance, light resistance, oxidation resistance gas resistance and moisture resistance.

Bronze is a bronzing phenomenon (also called a bronzing phenomenon) in which pigments form a piece of metal on the surface of glossy paper due to association of pigments or poor absorption of ink, resulting in a metallic luster. It is easy to happen. When the bronze phenomenon occurs, the gloss, print quality, and print density are all inferior to those without the bronze phenomenon.

Oxidation-resistant gas is usually called gas-resistance or ozone-resistance, but this is due to the fact that an oxidizing gas present in the air reacts with a dye in the recording paper, causing the printed image to fade and fade. It is the resistance to the phenomenon of making it happen. Examples of the oxidizing gas having this kind of action include ozone gas, NOx, SOx, etc. Of these oxidizing gases, ozone gas is considered as a causative substance that further promotes the discoloration phenomenon of the ink jet recording image. Ozone gas is used in the acceleration test to know the degree of these oxidation-resistant gas properties. Such a discoloration and fading phenomenon caused by an oxidizing gas is characteristic of an ink jet image, so that improvement of ozone gas resistance has become a more important issue. In particular, the ink receiving layer provided on the surface of photographic image quality inkjet paper uses a porous material such as a white inorganic pigment to speed up ink drying and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is noticeable on such recording paper.

Further, the moisture resistance is resistance to a phenomenon that the dye in the recording material bleeds when the colored recording material is stored in a high humidity atmosphere. If there is a blur of the dye, the image quality is remarkably deteriorated particularly in an image requiring a high-definition image quality such as a photographic tone. Therefore, it is important to reduce such a blur as much as possible. Therefore, moisture resistance is also an important issue required as an ink-jet pigment, as with the aforementioned ozone resistance.

In the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet recording and the colored bodies colored thereby will be further improved in water resistance, light resistance, moisture resistance and ozone gas resistance. There is a strong demand for improvement.

Ink of various hues is prepared from various dyes, and black ink among them is an important ink used not only for printing character information but also for color images. However, it is technically difficult to develop a dye that exhibits a neutral black hue and light color gamut, a high color density, and a good black color with low hue dependency on the light source. R & D has been carried out, but there are still few that have sufficient performance. Therefore, generally, a plurality of various dyes are mixed to form a black ink. However, when an ink is prepared by mixing a plurality of dyes, the hue differs depending on the medium (recording material) as compared to the case where the ink is prepared with a single dye. 2) The dye is decomposed by light or ozone gas. In particular, there is a problem that discoloration becomes large.

As a black dye for inkjet having various durability of printed matter, for example, the one of Patent Document 1 has been proposed. This dye is good as a black hue when printed at a high density, but when a low density printing is performed, for example, when expressing a slightly light black or gray color, the saturation becomes high, and an achromatic color generally preferred It cannot be said to be black or gray. In addition, as black ink in which yellow to orange dyes are blended with black dyes, for example, those disclosed in Patent Document 2 have been proposed. In particular, products that sufficiently satisfy market demands in terms of resistance to ozone gas are provided. It has not been done.

WO2007 / 032377A1 JP 2005-068416 A German published patent No. 2004488 Japanese Patent Application Laid-Open No. 2004-083492

The present invention is stable even when stored for a long period of time, exhibits a neutral black to gray color with no color even during dark color printing or light color printing, the density of the printed image is high, and An object of the present invention is to provide an aqueous black ink composition which gives a black recorded image which has no change in hue and has excellent image storability after printing, particularly ozone gas resistance and light resistance.

As a result of intensive studies to solve the problems as described above, the present inventors have reached the present invention. That is, the present invention
(1)
The dye (I) is one or more water-soluble dyes represented by the following formula (1) or a salt thereof,
The dye (II) is one or more water-soluble black dyes or salts thereof having absorption in water in the whole wavelength region of 380 to 720 nm and having a maximum absorption wavelength in the range of 560 to 590 nm,
Dye (III) is one or more water-soluble black dyes or salts thereof having absorption in the entire wavelength region of 380 to 720 nm in water and having a maximum absorption wavelength in the range of 590 to 630 nm,
A black ink composition comprising any of the dyes (I), (II) and (III) as a pigment component,

(In the formula (1),
Group A is a substituted phenyl group,
Y ₁ represents a methyl group, a carboxy group, a carboxymethyl group, an ethoxycarbonyl group or a phenyl group,
Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a carboxy group, a hydroxy group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C4 alkoxy group. ).
(2)
The black ink composition according to (1), wherein the dye (II) is one or more water-soluble black dyes represented by the following formula (2) or a salt thereof:

(In the formula (2),
Group B is a substituted phenyl group, a carboxy group; a sulfo group; a hydroxy group; an acetylamino group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; a C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with a group selected from: having a substituent selected from the group consisting of:
R ₂₁ represents an unsubstituted or carboxy-substituted C1-C4 alkyl group, an unsubstituted or sulfo-substituted phenyl group, or a carboxy group;
R ₂₂ represents a cyano group, a carbamoyl group or a carboxy group,
R ₂₃ and R ₂₄ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group,
R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₂₁₀ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group. ).
(3)
The black ink composition according to (1) or (2) above, wherein the dye (III) is one or more water-soluble black dyes represented by the following formula (3) or the following formula (6) or salts thereof: ,

(In formula (3),
m is 0 or 1,
R ³¹ represents a carboxy group; a C1-C8 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a C1-C8 alkoxycarbonyl-substituted or carboxy-substituted C1-C4 alkyl group; an unsubstituted phenyl group; or a hydroxy group, a sulfo group, and a carboxy group Represents a phenyl group substituted with a group selected from the group consisting of:
R ³² to R ³⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted mono- or di-C1-C4 alkylamino group; a hydroxy group A mono- or di-C1-C4 alkylamino group substituted with a group selected from the group consisting of a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylcarbonylamino group; a hydroxy- or carboxy-substituted C1-C4 alkylcarbonylamino group; Unsubstituted N′-C1-C4 alkylureido group; a hydroxy group, N'-C1-C4 alkylureido group substituted with a group selected from the group consisting of sulfo group and carboxy group; unsubstituted phenylamino group; benzene ring is chlorine atom, C1-C4 alkyl group, nitro group, sulfo group And a phenylamino group substituted with a group selected from the group consisting of a carboxy group; an unsubstituted benzoylamino group; a benzene ring selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group A substituted benzoylamino group; an unsubstituted phenylsulfonylamino group; or a benzene ring substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. Each represents a phenylsulfonylamino group;
The group C represents a substituted heterocyclic group represented by the following formula (4) or (5). )

(In formula (4),
R ³⁵ represents a mercapto group; an unsubstituted C1-C4 alkylthio group; or a C1-substituted by a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group. A C4 alkylthio group; )

(In Formula (5),
R ³⁶ to R ³⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a group, a C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with a group selected from the group; an unsubstituted phenylsulfonyl group; or a benzene ring selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. Each represents a phenylsulfonyl group substituted with a group
Group D is an unsubstituted or substituted phenyl group or naphthyl group,
When group D is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; an amino group; an unsubstituted mono- or diC1-C4 alkylamino group; An amino group; an unsubstituted benzoylamino group; a benzoylamino group in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group; Having a substituent
When group D is a substituted naphthyl group; a sulfo group; an unsubstituted C1-C4 alkoxy group; an unsubstituted phenylsulfonyloxy group; a phenylsulfonyloxy group in which the benzene ring is substituted with a methyl group, a nitro group or a chlorine atom; Having a substituent selected from the group consisting of: )

(In Formula (6),
R ₆₁ and R ₆₂ are each independently a hydrogen atom; halogen atom; cyano group; carboxy group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; unsubstituted or hydroxy-substituted C1-C4 Sulfonyl group; acyl group; ureido group; unsubstituted C1-C4 alkyl group; hydroxy or C1-C4 alkoxy substituted C1-C4 alkyl group C1-C4; unsubstituted C1-C4 alkoxy group; hydroxy group C1-C4 alkoxy group substituted with a group selected from the group consisting of C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group and carboxy group; acylamino group; alkylsulfonylamino group; unsubstituted phenylsulfonylamino A group; or phenyl is a halogen atom, Represents; phenyl sulfonylamino group substituted with a group selected from the group consisting of Le and nitro
R ₆₃ , R ₆₄ , R ₆₅ , R ₆₆ , R ₆₇ and R ₆₈ each independently represent a hydrogen atom; a halogen atom; a hydroxy group; a cyano group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group. N-phenylaminosulfonyl group; unsubstituted or hydroxy substituted C1-C4 alkylsulfonyl group; phosphono group; nitro group; acyl group; ureido group; unsubstituted C1-C4 alkyl group; hydroxy or C1-C4 alkoxy substituted C1-C4 An alkyl group; an unsubstituted C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; An acylamino group; an alkylsulfonylamino group; an unsubstituted phenylsulfonylamino group; Or a phenylsulfonylamino group in which phenyl is substituted with a group selected from the group consisting of a halogen atom, an alkyl group and a nitro group;
n represents 0 or 1, respectively. ).
(4)
The black ink composition according to any one of (1) to (3) above, wherein the dye (I) represented by the formula (1) is one or more water-soluble dyes represented by the following formula (7) or a salt thereof. ,

(In formula (7),
R ₇₁ represents a hydrogen atom, a C1-C3 alkyl group or a carboxy group,
R ₇₂ represents a hydrogen atom or a sulfo group,
Y ₁ to Y ₄ are the same as those described in (1) above. ).
(5)
In the total mass of the dyes (I), (II) and (III) contained in the ink composition as the pigment component, the ratio of the dye (I) is 5 to 30% by mass, and the ratio of the dye (II) is 20 to 80 The black ink composition as described in any one of (1) to (4) above, wherein the ratio of the mass% and the dye (III) is 15 to 60 mass%.
(6)
The above (1) to (5), wherein the total mass of the dyes (I), (II), and (III) contained in the ink composition as the pigment component is 2 to 8 mass% with respect to the total mass of the ink composition. ). The black ink composition according to any one of the above.
(7)
In the total mass of the dyes (I), (II) and (III) contained in the ink composition as a pigment component, the content of inorganic impurities in the total mass of the dyes (I), (II) and (III) is The black ink composition according to any one of (1) to (6), which is 1% by mass or less.
(8)
The black ink composition as described in any one of (1) to (7) above, which is used for inkjet recording.
(9)
In an ink jet recording method in which ink droplets are ejected according to a recording signal and recording is performed on a recording material, the black ink composition according to any one of (1) to (8) is used as ink. An inkjet recording method.
(10)
The inkjet recording method according to (9), wherein the recording material is an information transmission sheet.
(11)
The ink jet recording method according to (10), wherein the information transmission sheet has an ink image-receiving layer containing plain paper or a porous white inorganic substance.
(11)
A colored body colored with the black ink composition according to any one of (1) to (8) above.
(13)
The colored body according to (12), wherein coloring is performed by an ink jet printer.
(14)
Representing an inkjet printer filled with a container containing the black ink composition according to any one of (1) to (8) above,
About.

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. In addition, the ink composition of the present invention is used for inkjet recording and writing instruments, and the recorded image has a neutral hue when recorded on plain paper and inkjet dedicated paper, and even when the ink has a low density, the ink composition is black. A printed matter can be obtained, the printing density is high, ozone gas resistance, light resistance and moisture resistance are excellent, and the hue dependency on the light source is small. By using it together with magenta, cyan and yellow dyes, full-color ink jet recording excellent in light resistance and water resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail. Unless otherwise specified in the present invention, the sulfo group and the carboxy group are represented in the form of a free acid, and “dye or a salt thereof” is described as “dye” for the sake of convenience in order to avoid complicated description. And a dye or a salt thereof.

The dye (I) used in the present invention is one or more water-soluble dyes represented by the following formula (1) or salts thereof. 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). Dyes other than) are substantially not included. .

In the formula (1), the group A is a substituted phenyl group, Y ₁ represents a methyl group, a carboxy group, a carboxymethyl group, an ethoxycarbonyl group or a phenyl group, and Y ₂ , Y ₃ and Y ₄ are each independently Represents a hydrogen atom, a halogen atom, a sulfo group, a carboxy group, a hydroxy group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C4 alkoxy group.
The phenyl substituent of the group A includes amino group; carboxy group; sulfo group; hydroxy group; acetylamino group; 2-carboxyethylamino group: benzoylamino group; ureido group; methylsulfonylamino group; A group selected from the group consisting of a chlorine atom, a cyano group, a nitro group, a sulfamoyl group, a C1-C4 alkyl group, an unsubstituted C1-C4 alkoxy group, a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group A C1-C4 alkoxy group substituted with an unsubstituted benzothiazolyl group; and a benzothiazolyl group in which the benzene ring is substituted with a group selected from the group consisting of a C1-C4 alkyl group, a sulfo group and a carboxy group; Group to be used.

The unsubstituted C1-C4 alkyl group in formula (1) may be linear, branched or cyclic, but is preferably linear or branched. Specific examples 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 .; cyclic group such as cyclopropyl, cyclobutyl; Is mentioned.

The unsubstituted C1-C4 alkoxy group in formula (1) may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include a straight chain such as methoxy, ethoxy, n-propoxy, n-butoxy; a branched chain such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy;

The C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group in formula (1) is a carbon chain of the unsubstituted C1-C4 alkoxy group. A group selected from the above group is substituted at any position. Preferred specific examples include, for example, hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy Alkoxy substituted, such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxyalkoxy substituted such as 2-hydroxyethoxyethoxy; carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, etc. Carboxy-substituted ones; sulfo-substituted ones such as 3-sulfopropoxy and 4-sulfobutoxy;

Examples of the benzothiazolyl group in which the benzene ring in the formula (1) is substituted with a group selected from the group consisting of a C1-C4 alkyl group, a sulfo group and a carboxy group include 6-methylbenzothiazolyl and 6-ethylbenzothia Examples include zolyl, 6-methyl-7-sulfobenzothiazolyl, 6-carboxybenzothiazolyl, 6-carboxy-7-sulfobenzothiazolyl.

Preferred substituents in the group A of the formula (1) include sulfo, carboxy, nitro, chlorine atom, acetylamino, benzoylamino, toluenesulfonylamino, cyano, methyl, ethyl, methoxy, ethoxy, 3-sulfopropoxy, 2- Carboxyethylamino, ureido, methylsulfonylamino, methylthio, benzothiazolyl, 6-methylbenzothiazolyl, 6-methyl-7-sulfobenzothiazolyl, 6-carboxybenzothiazolyl, 6-carboxy-7-sulfobenzo Thiazolyl and the like, and more preferably, sulfo, carboxy, nitro, chlorine atom, acetylamino, 2-carboxyethylamino, methoxy, 6-methyl-7-sulfobenzothiazolyl, 6-carboxy-7- Sulfobenzothiazolyl, more preferred Ku is sulfo, 6-methyl-7-sulfo-benzothiazolyl, 6-carboxy-7-sulfo-benzothiazolyl. The group A can have 1 to 4, preferably 1 to 3 of these substituents.

Preferred Y ₁ in the formula (1) is carboxy, carboxymethyl or ethoxycarbonyl, more preferably carboxy.

Preferred Y _{2 to} Y ₄ in the formula (1) are a hydrogen atom, sulfo, carboxy, hydroxy, methoxy, and chlorine atom, and more preferably a hydrogen atom and sulfo.

More preferable examples of the dye represented by the formula (1) include dyes of the following formula (7).

In the formula (7), R ₇₁ represents a hydrogen atom, a C1-C3 alkyl group or a carboxy group, R ₇₂ represents a hydrogen atom or a sulfo group, and Y ₁ to Y ₄ represent those described in the above formula (1). It can be the same.
The represented C1-C3 alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. Specific examples include a straight chain such as methyl, ethyl and n-propyl; a branched chain such as isopropyl; and a cyclic group such as cyclopropyl; preferably a methyl group.
R ₇₂ represents a hydrogen atom or a sulfo group, preferably a hydrogen atom.
Preferred Y _{1 to} Y ₄ in Formula (7) are the same as those described in Formula (1) above.
A particularly preferred combination is that in formula (7), R ₇₁ is a methyl group, R ₇₂ is a hydrogen atom, Y ₁ is a carboxy group, Y ₂ is a sulfo group, and the substitution position on the benzene ring is a nitrogen atom of the pyrazole ring. 4-position when the bond to which position to the 1-position, Y ₃ and Y ₄ are both hydrogen atoms.

The dye represented by the formula (1) may have a tautomer. As this tautomer, the following formulas (8) and (9) are considered, and these isomers are also included in the scope of the present invention.

(In the formula (8), the groups A and Y _{1 to} Y ₄ have the same meaning as in the formula (1).)

(In formula (9), groups A and Y _{1 to} Y ₄ have the same meaning as in formula (1).)

“A water-soluble black dye or salt thereof having absorption in the entire wavelength region of 380 to 720 nm in water and having a maximum absorption wavelength in the range of 560 to 590 nm” means that the absorbance at the maximum absorption wavelength in water is 0. When the absorbance measurement solution concentration is adjusted to be in the range of 0.5 to 1.0, the maximum absorption wavelength in the range of 380 to 720 nm is in the range of 560 to 590 nm, and the range of 380 to 720 nm The dye has absorption in the entire wavelength region. The dye (II) is one or more water-soluble black dyes or salts thereof. That is, a single water-soluble black dye or a mixture of a plurality of water-soluble black dyes may be used, but substantially no dye other than the water-soluble black dye is included. . Preferable dye (II) includes a water-soluble black dye represented by the above formula (2).

The water-soluble dye for black represented by the formula (2) may have a tautomer. As the tautomers, the following formulas (10) and (11) are considered, and these isomers are also included in the present invention.

(In formula (10), groups B and R _{21 to} R ₂₁₀ have the same meaning as in formula (2).)

(In formula (11), groups B and R _{21 to} R ₂₁₀ have the same meaning as in formula (2).)

In groups B, R ₂₁ and R _{25 to} R ₂₁₀ in formula (2), the C1-C4 alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples 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 .; cyclic group such as cyclopropyl, cyclobutyl; Is mentioned.

In R ₂₁ in Formula (2), the carboxy-substituted C1-C4 alkyl group is a carboxy group substituted at any position of the C1-C4 alkyl group. Preferable specific examples include carboxymethyl, 2-carboxyethyl and the like.

In R ₂₁ in the formula (2), specific examples of the sulfo-substituted phenyl group include a sulfo group such as 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like. Examples include mono- or di-substituted phenyl groups.

In the group B and R _{25 to} R ₂₁₀ in the formula (2), the unsubstituted C1-C4 alkoxy group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include a straight chain such as methoxy, ethoxy, n-propoxy, n-butoxy; a branched chain such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy;

In the group B and R _{25 to} R ₂₁₀ in the formula (2), the C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group is A group selected from the above group is substituted at any position on the carbon chain of the substituted C1-C4 alkoxy group. Preferred specific examples include, for example, hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy Alkoxy substituted, such as ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxyalkoxy substituted such as 2-hydroxyethoxyethoxy; carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, etc. Carboxy-substituted ones; sulfo-substituted ones such as 3-sulfopropoxy and 4-sulfobutoxy;

In the substituent of the group B in the formula (2), the unsubstituted C1-C4 alkylsulfonyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include straight chain such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl; branched chain such as isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl; cyclopropylsulfonyl, cyclobutyl And a cyclic group such as sulfonyl.

In the substituent of the group B in the formula (2), the C1-C4 alkylsulfonyl group substituted with a hydroxy group, a sulfo group, and a carboxy group is located at any position on the carbon chain of the unsubstituted C1-C4 alkylsulfonyl group. And a group selected from the above group is substituted. As a preferable specific example,
Hydroxy-substituted ones such as hydroxyethylsulfonyl and 2-hydroxypropylsulfonyl; sulfo-substituted ones such as 2-sulfoethylsulfonyl and 3-sulfopropylsulfonyl; carboxy-substituted ones such as 2-carboxyethylsulfonyl and 3-carboxypropylsulfonyl Thing; etc. are mentioned.

Preferred substituents of group B in formula (2) include cyano, carboxy, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, acetylamino, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy and the like, more preferably cyano, carboxy, sulfo, sulfamoyl, methylsulfonyl, hydroxyethylsulfonyl, 3-sulfopropylsulfonyl and nitro, more preferably carboxy and sulfo.

In the formula (2), preferred substituents for R _{25 to} R ₂₁₀ include carboxy, sulfo, acetylamino, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfo Butoxy, carboxymethoxy, 2-carboxyethoxy, etc., more preferably sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, carboxymethoxy, and more preferably sulfo, methyl , Methoxy, 3-sulfopropoxy. As a preferable combination of R _{25 to} R ₂₁₀ , R ₂₅ is sulfo or 3-sulfopropoxy, R ₂₆ is a hydrogen atom or methyl, R ₂₇ and R ₂₉ are 3-sulfopropoxy, and R ₂₈ and R ₂₁₀ are methyl.

Preferred R ₂₁ in the formula (2) is methyl, ethyl, n-propyl, n-butyl, t-butyl, carboxymethyl, phenyl, 4-sulfophenyl, carboxy, more preferably methyl, n-propyl, Carboxymethyl and 4-sulfophenyl, and more preferably methyl.

In addition, in each of the above substituents, a dye in which preferable ones are combined is more preferable, and a dye in which more preferable ones are combined is more preferable. The same can be said throughout this specification, including dyes (II) and (III), which are sequentially described below. The same applies when a combination of substituents is described.

A preferred combination of R ₂₁ and R ₂₂ in the formula (2) is R ₂₁ is methyl and R ₂₂ is cyano, or R ₂₁ is methyl and R ₂₂ is carbamoyl.

Preferred R ₂₃ and R ₂₄ more in the formula (2) is a hydrogen atom, methyl, sulfo, preferably R ₂₃ and the combination of R ₂₄ is R ₂₃ is R ₂₄ is sulfo a hydrogen atom or R ₂₃ is sulfo, R ₂₄ is a hydrogen atom.

The dye (II) represented by the above formula (2) is more preferably a dye represented by the following formula (12).

In the above formula (12), R ²¹ to R ²¹⁰ represent the same meanings as in the above formula (2), combinations of the preferred groups and preferred groups are also the same as the above formula (2), the above R ²⁵ ~ More preferably, R ²¹⁰ is substituted at the position of formula (12).

The benzene ring substituted by R ^{211 to} R ²¹³ in the above formula (12) corresponds to the group B in the above formula (2). Accordingly, R ^{211 to} R ²¹³ have the same meaning as the substituent of the group B in the above formula (2), and preferred groups and preferred combinations of the groups are the same as those in the above formula (2).
In the formula (12), more preferable R ^{211 to} R ²¹³ can specify the substitution position.
That is, in the benzene ring substituted by R ^{211 to} R ^213, when the substitution position of the azo group is the 1st position, R ₂₁₁ is the 2nd or 3rd position, R ²¹² is the 4th position, and R ²¹³ is the 5th position Those substituted with are preferred.
Further, among the substituents of the group B, R ²¹¹ is a hydrogen atom, sulfo group or carboxy group substituted at the 2-position or 3-position, and R ²¹² is a hydrogen atom, sulfo group, acetylamino group substituted at the 4-position. or sulfo O propylsulfonyl group, the combination R ²¹³ is substituted with hydrogen atom or a sulfo group in the 5-position is particularly preferred.
Particularly preferred in formula (12) are those in which the substitution positions of R ^{25 to} R ²¹³ are specified as described above, and the types of substituents may be the same as those in formula (2).

“A dye for water-soluble black or a salt thereof having absorption in the entire wavelength region of 380 to 720 nm in water and having a maximum absorption wavelength in the range of 590 to 630 nm in water” refers to the maximum absorption in water. When the absorbance measurement liquid concentration is adjusted so that the absorbance at a wavelength is in the range of 0.5 to 1.0, the maximum absorption wavelength in the range of 380 to 720 nm is in the range of 590 to 630 nm, and It is a dye having absorption in the entire wavelength range of 380 to 720 nm. The dye (III) is one or more water-soluble black dyes or salts thereof. That is, a single water-soluble black dye or a mixture of a plurality of water-soluble black dyes may be used, but substantially no dye other than the water-soluble black dye is included. . Preferred dyes (III) include water-soluble black dyes represented by the above formula (3) or water-soluble black dyes represented by the above formula (6).

The water-soluble dye for black represented by the formula (3) may have a tautomer. Examples of the tautomer include the following formulas (13) to (15). These tautomers are also included in the present invention.

(In formula (13), group C, group D and R ^{31 to} R ³⁴ have the same meaning as in formula (3).)

(In formula (14), group C, group D and R ^{31 to} R ³⁴ have the same meaning as in formula (3).)

(In formula (15), group C, group D and R ^{31 to} R ³⁴ have the same meaning as in formula (3).)

In the above formula (3), R ³¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a C1-C8 alkoxycarbonyl-substituted or carboxy-substituted C1-C4 alkyl group; an unsubstituted phenyl group; Represents a phenyl group substituted with a group selected from the group consisting of a group, a sulfo group and a carboxy group.

When R ³¹ in formula (3) is a C1-C8 alkoxycarbonyl group, the alkoxycarbonyl group may be any of linear, branched and alkyl moieties having a cyclic structure, but linear and branched An alkoxycarbonyl group is preferred. Specific examples include, for example, straight chain such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl; A branched chain such as propoxycarbonyl, isobutyloxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, 2,2-dimethylpropoxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, 2-methylbutyloxycarbonyl; cyclopropylmethyl Alkyl moieties such as oxycarbonyl, cyclobutylmethyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl and the like have a cyclic structure. ; And the like.
A linear C1-C6 is more preferable, and a linear C1-C4 alkoxycarbonyl group is more preferable. Specific examples are the same as those described above.

When R ³¹ in Formula (3) is an unsubstituted C1-C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples of the C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.

When R ³¹ in Formula (3) is a C1-C8 alkoxycarbonyl-substituted C1-C4 alkyl group, the C1-C8 alkoxycarbonyl group is preferable when R ³¹ is a C1-C8 alkoxycarbonyl group. The same may be included.
Preferable specific examples include methoxycarbonylmethyl, ethoxycarbonylethyl, n-butoxycarbonylmethyl, n-octyloxycarbonylethyl and the like.
When R ³¹ is a C1-C4 alkyl group which may be substituted with a carboxy group, preferred specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and the like.

Specific examples in the case where R ³¹ in Formula (3) is a phenyl group substituted with a group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group include, for example, 2-hydroxyphenyl, 4-hydroxyphenyl, etc. Hydroxy-substituted phenyl of the above; sulfo-substituted phenyl such as 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl; 2-carboxyphenyl, 4-carboxyphenyl, 3,5- Carboxy-substituted phenyl such as dicarboxyphenyl; and phenyl substituted with a plurality of types of groups such as 2-hydroxy-5-sulfophenyl; and the like.

R ³¹ in the above formula (3) is more preferably a carboxy group; a C1-C4 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a carboxy-substituted C1-C4 alkyl group; or an unsubstituted phenyl group.
Specific examples of preferable R ³¹ in the formula (3) are methyl, ethyl, tert-butyl, carboxymethyl, 3-carboxypropyl, methoxycarbonylmethyl, carboxy, methoxycarboxy, ethoxycarboxy, n-octyloxycarboxy, phenyl, 2 -Hydroxyphenyl, more preferably methyl, carboxymethyl, carboxy and phenyl, still more preferably methyl and carboxy.

In the above formula (3), R ³² to R ³⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; an unsubstituted C1-C4 alkyl group; A C4 alkoxy group; a C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted mono- or di-C1- A mono- or di-C1-C4 alkylamino group substituted with a group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylcarbonylamino group; a hydroxy- or carboxy-substituted C1 -C4 alkylcarbonylamino group; unsubstituted N'-C1-C4 alkyluree Id group; N′-C1-C4 alkylureido group substituted with a group selected from the group consisting of hydroxy group, sulfo group and carboxy group; unsubstituted phenylamino group; benzene ring is chlorine atom, C1-C4 alkyl group Phenylamino group substituted with a group selected from the group consisting of nitro group, sulfo group and carboxy group; unsubstituted benzoylamino group; benzene ring is chlorine atom, C1-C4 alkyl group, nitro group, sulfo group and carboxy group A benzoylamino group substituted with a group selected from the group consisting of a group; an unsubstituted phenylsulfonylamino group; or a benzene ring selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group Each represents a phenylsulfonylamino group substituted with a group represented by

R ³² to R ³⁴ in Formula (3), when it is unsubstituted C1-C4 alkyl group, the alkyl group may be either linear or branched, linear is preferred. Specific examples of the C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.

R ³² to R ³⁴ in Formula (3), when an unsubstituted C1-C4 alkoxy group, the alkoxy group is preferably any of straight-chain or branched-chain. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
When the alkoxy group is substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, 2-hydroxyethoxy Hydroxy C1-C4 alkoxy groups such as 2-hydroxypropoxy and 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, C1-C4 alkoxy C1-C4 alkoxy groups such as isopropoxybutoxy and n-propoxybutoxy; hydroxy C1-C4 alkoxy C1-C4 alkoxy groups such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy , 4-sulfo C1-C4 alkoxy group such as sulfobutoxy; carboxymethoxy, 2-carboxyethoxy, carboxy C1-C4 alkoxy group such as a 3-carboxypropoxy; and the like.

When R ^{32 to} R ³⁴ in Formula (3) are an unsubstituted mono- or di-C1-C4 alkylamino group, the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chain such as butylamino, tert-butylamino, diisopropylamino, and the like.
When the mono- or di-C1-C4 alkylamino group is substituted with a group selected from the group consisting of a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxy Hydroxy-substituted mono- or di-C1-C4 alkylamino groups such as propylamino, 2,2′-dihydroxydiethylamino; 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3′-disulfodi Sulfo-substituted mono- or di-C1-C4 alkylamino groups such as propylamino; carboxy-substituted mono- or di-C1-C4 such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino Alkylamino group; and the like.

When R ^{32 to} R ³⁴ in Formula (3) are an unsubstituted C1-C4 alkylcarbonylamino group, the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
When the C1-C4 alkylcarbonylamino group is hydroxy- or carboxy-substituted, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, 4-hydroxybutano A hydroxy C1-C4 alkylcarbonylamino group such as noylamino; a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.

When R ^{32 to} R ³⁴ in Formula (3) are N′—C 1 -C 4 alkylureido groups, those having a substituent are preferable to being unsubstituted.
When the N′-C1-C4 alkylureido group is substituted with a group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group, specific examples thereof include, for example, N′-2-hydroxyethylureido, N′-hydroxy C1-C4 alkylureido groups such as N′-3-hydroxyethylureido; N′-sulfoC1-C4 alkylureido groups such as N′-2-sulfoethylureido and N′-3-sulfopropylureido N'-carboxy C1-C4 alkyl ureido groups such as N'-carboxymethylureido, N'-2-carboxyethylureido, N'-3-carboxypropylureido, N'-4-carboxybutylureido; It is done.

When R ^{32 to} R ³⁴ in Formula (3) are phenylamino groups in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group Specific examples thereof include, for example, a chlorine atom-substituted phenylamino group such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; 2-methylphenylamino, 4-methylphenylamino, 4-tert-butylphenyl C1-C4 alkyl-substituted phenylamino groups such as amino; nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenyl Sulfo-substituted phenylamino groups such as amino and 3,5-disulfophenylamino Carboxy-substituted phenylamino groups such as 2-carboxyphenylamino, 4-carboxyphenylamino, 2,5-dicarboxyphenylamino, 3,5-dicarboxyphenylamino; and the like.

R ^{32 to} R ³⁴ in Formula (3) are a phenylamino group, a benzoylamino group or a phenylsulfonylamino group having a substituent, and the substituent of the benzene ring contained in each group is a C1-C4 alkyl group. In this case, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ^{32 to} R ³⁴ in Formula (3) are benzoylamino groups in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group, Specific examples thereof include, for example, a chlorine atom-substituted benzoylamino group such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino C1-C4 alkyl-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino, nitro-substituted benzoylamino groups such as 3,5-dinitrobenzoylamino; 2-sulfobenzoylamino, 4-sulfobenzoylamino, etc. A sulfo-substituted benzoylamino group; 2-carboxy Carboxy-substituted benzoylamino groups such as benzoylamino, 4-carboxybenzoylamino, 3,5-dicarboxybenzoylamino; and the like.

When R ^{32 to} R ³⁴ in Formula (3) are phenylsulfonylamino groups in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group Specific examples thereof include, for example, a chlorine atom-substituted phenylsulfonylamino group such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-tert-butylphenylsulfonylamino C1-C4 alkyl-substituted phenylsulfonylamino group such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, nitro-substituted phenylsulfonylamino groups such as 4-nitrophenylsulfonylamino; 3-sulfophenylsulfonylamino And sulfo-substituted phenylsulfonylamino groups such as 4-sulfophenylsulfonylamino; carboxy-substituted phenylsulfonylamino groups such as 3-carboxyphenylsulfonylamino and 4-carboxyphenylsulfonylamino; and the like.

Specific examples of preferable R ³² to R ³⁴ in the formula (3) are a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy. Carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2′-dihydroxy Diethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N′-carboxymethylureido, N′-2 -Sulfoethylureido, 4- Ruphophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzoylamino, 3-sulfobenzoylamino, 2-carboxybenzoylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4- Nitrophenylsulfonylamino, 3-sulfophenylsulfonylamino, 4-carboxyphenylsulfonylamino and the like, more preferably hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, dimethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, N′-2-sulfoethylureido, 2,4-disulfophenylamino, benzoylamino It is 4-methyl-phenylsulfonylamino, more preferably a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy.

In a preferred combination of R ³² to R ³⁴ in the formula (3), R ³² is 3-sulfopropoxy or 4-sulfobutoxy, R ³³ is a hydrogen atom, and R ³⁴ is methyl.

In the above formula (4), R ³⁵ is selected from the group consisting of a mercapto group; an unsubstituted C1-C4 alkylthio group; or a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group. Represents a C1-C4 alkylthio group substituted with a group.

When R ³⁵ in formula (4) is unsubstituted C1-C4 alkylthio group, the C1-C4 alkyl moiety is preferably any of straight-chain or branched-chain, straight-chain is preferable. Specific examples thereof include linear ones such as methylthio, ethylthio, n-propylthio and n-butylthio; branched ones such as isopropylthio, isobutylthio, sec-butylthio and tert-butylthio;
When R ³⁵ is a C1-C4 alkylthio group having a substituent, the substituent is preferably a hydroxy group, a sulfo group or a carboxy group, more preferably a sulfo group or a carboxy group. Specific examples of the C1-C4 alkylthio group having a substituent include, for example, hydroxy C1-C4 alkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropoxy, 3-hydroxypropoxythio; methoxyethylthio, ethoxyethylthio, n -C1-C4 alkoxy C1-C4 alkylthio such as propoxyethylthio, isopropoxyethylthio, n-butoxyethylthio, methoxypropylthio, ethoxypropylthio, n-propoxypropylthio, isopropoxybutylthio, n-propoxypropylthio A hydroxy C1-C4 alkoxy C1-C4 alkylthio group such as 2-hydroxyethoxyethylthio; a sulfo C1-C4 alkylthio group such as 3-sulfopropylthio, 4-sulfobutylthio; carboxymethylthio, - carboxyethylthio, carboxy C1-C4 alkylthio group such as 3-carboxypropyl thio; and the like.

Specific examples of preferable R ³⁵ in the formula (4) are mercapto (—SH), methylthio, ethylthio, 2-hydroxyethylthio, methoxyethylthio, ethoxyethylthio, 2-sulfoethylthio-3-sulfopropylthio, 4-sulfo. Butylthio, carboxymethylthio, 2-carboxyethylthio, 3-carboxypropylthio and the like, more preferably methylthio, 2-sulfopropylthio, carboxymethylthio, 2-carboxyethylthio, and still more preferably 2-sulfo Propylthio, 2-carboxyethylthio.

In the formula (5), R ³⁶ to R ³⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; A C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; a hydroxy group; A C1-C4 alkylsulfonyl group substituted with a group selected from the group consisting of a sulfo group and a carboxy group; an unsubstituted phenylsulfonyl group; or the benzene ring is a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group Represents a phenylsulfonyl group substituted by a group selected from the group consisting of groups;

When R ³⁶ to R ³⁸ in formula (5) are an unsubstituted C1-C4 alkyl group, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. More preferred is a straight chain. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ³⁶ to R ³⁸ in Formula (5) are unsubstituted or a C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group, and a carboxy group The alkoxy group including the preferable one may be the same as the case where R ^{32 to} R ³⁴ in the above formula (3) are the corresponding C1-C4 alkoxy group.

In the case where R ³⁶ to R ³⁸ in the formula (5) are C1-C4 alkylsulfonyl groups substituted with a group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group, specific examples thereof include, for example, methylsulfonyl , Ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and the like linear or branched C1-C4 alkylsulfonyl groups; 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl Hydroxy C1-C4 alkylsulfonyl group such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl and the like; C1-C4 alkylsulfonyl group such as carboxymethylsulfonyl, 2-carboxyethyls Honiru, carboxy C1-C4 alkylsulfonyl group such as 3-carboxypropyl sulfonyl; and the like.

Specific examples of the phenylsulfonyl group in which R ³⁶ to R ³⁸ in formula (5) are substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group in the benzene ring Examples thereof include unsubstituted phenylsulfonyl; chlorine atom-substituted phenylsulfonyl groups such as 2-chlorophenylsulfonyl and 4-chlorophenylsulfonyl; 2-methylphenylsulfonyl, 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-tert A C1-C4 alkyl-substituted phenylsulfonyl group such as butylphenylsulfonyl; a nitro-substituted phenylsulfonyl group such as 2-nitrophenylsulfonyl and 4-nitrophenylsulfonyl; 3-sulfophenylsulfonyl, 4-sulfophenylsulfonyl, 3,5- Disulfo Sulfo-substituted phenylsulfonyl group such Enirusuruhoniru; 2-carboxyphenyl sulfonyl, 4-carboxyphenyl sulfonyl, 3,5-carboxyphenyl carboxy-substituted phenylsulfonyl group such as phenylsulfonyl; and the like.

Specific examples of preferred R ³⁶ to R ³⁸ in the formula (5) are hydrogen atom, chlorine atom, carboxy, sulfo, nitro, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy. 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-nitrophenylsulfonyl, 4-sulfophenylsulfonyl, 2-carboxyphenylsulfonyl, 4-carboxyphenylsulfonyl, etc. Ri, more preferably a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, methoxy, methylsulfonyl, 2-carboxyphenyl sulfonyl, more preferably a hydrogen atom, sulfo, methoxy. Among R ³⁶ to R ³⁸ , at least one is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

Preferred R ³⁶ to R ³⁸ combinations in formula (5) are a hydrogen atom, methoxy and sulfo, or one is sulfo and the other two are hydrogen atoms. When one is sulfo and the other two are hydrogen atoms, the substitution position of sulfo is more preferably the 6-position of the benzothiazole ring.

In the above formula (3), the group D is an unsubstituted or substituted phenyl group, or an unsubstituted or substituted naphthyl group.
When group D is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; an amino group; an unsubstituted mono- or diC1-C4 alkylamino group; An amino group; an unsubstituted benzoylamino group; a benzoylamino group in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group; Having a substituent.
When the group D is a substituted naphthyl group, a hydroxy group; a sulfo group; an unsubstituted C1-C4 alkoxy group; an unsubstituted phenylsulfonyloxy group; a phenylsulfonyloxy in which the benzene ring is substituted with a methyl group, a nitro group, or a chlorine atom A substituent having a substituent selected from the group consisting of:

In the case where the group D in the formula (3) is a phenyl group or naphthyl group having a substituent, and the substituent is a C1-C4 alkoxy group, the alkoxy group includes a preferable one in the above formula (3). ³² to R ³⁴ may the same as an unsubstituted C1-C4 alkoxy group.

When the group D in the formula (3) is a mono- or di-C1-C4 alkylamino group-substituted phenyl group, the mono- or di-C1-C4 alkylamino group includes R ^{32 to} R in the formula (3) including preferable ones. It may be the same as when ³⁴ is an unsubstituted mono- or di-C1-C4 alkylamino group.

When the group D in the formula (3) is a substituted naphthyl group, and the substituent is a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom, specific examples thereof include: Unsubstituted phenylsulfonyloxy; methyl-substituted phenylsulfonyloxy groups such as 4-methylphenylsulfonyloxy and 2,4-dimethylphenylsulfonyloxy; nitro-substituted phenylsulfonyloxy groups such as 2-nitrophenylsulfonyloxy and 4-nitrosulfonyloxy Chlorine atom substituted phenylsulfonyloxy groups such as 4-chlorophenylsulfonyloxy, 2,4-dichlorophenylsulfonyloxy, 3,5-dichlorophenylsulfonyloxy, and the like.

In the formula (3), m is preferably 1.

Specific examples of preferable substituents when the group D in the formula (3) is a substituted phenyl group include a hydrogen atom, hydroxy, sulfo, carboxy, methyl, ethyl, methoxy, ethoxy, dimethylamino, acetylamino, benzoylamino, 4 -Sulfobenzoylamino, 4-carboxybenzoylamino and the like, more preferably a hydrogen atom, hydroxy, sulfo, carboxy, methyl and acetylamino, and still more preferably a hydrogen atom, sulfo and carboxy.

Specific examples of preferable substituents when the group D in the formula (3) is a substituted naphthyl group include a hydrogen atom, hydroxy, sulfo, methoxy, ethoxy, phenylsulfonyloxy, 4-methylphenylsulfonyloxy, 2-nitrophenyl and the like. More preferably, they are a hydrogen atom, hydroxy, sulfo, and methoxy, and more preferably a hydrogen atom and sulfo.

Specific examples of preferable group D in the formula (3) include phenyl, 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 4-carboxyphenyl, 3,5- Carboxyphenyl, 4-methylphenyl, 3-methylphenyl, 3-hydroxy-4-carboxyphenyl, 5-sulfo-3-carboxy-2-hydroxyphenyl, 4-methoxyphenyl, 4-acetylaminophenyl, naphthyl, naphtho 2-yl, 6-sulfonaphthyl, 7-sulfonaphthyl, 4,7-disulfonaphthyl, 5,7-disulfonaphth-2-yl, 6,8-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl Yl, 4,6,8-trisulfonaphth-2-yl and the like, more preferably phenyl, 4-sulfophenyl, , 4-disulfophenyl, 4-carboxyphenyl, 3,5-carboxyphenyl, 5,7-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl, and more preferably phenyl, 4- Sulfophenyl, 4-carboxyphenyl and 3,5-carboxyphenyl.

The compound which combined the preferable thing described about the substituent of said Formula (3) to (5) and (13) to (15) is more preferable, and the compound which combined more preferable things is further more preferable. The same applies to preferable ones. As described above, in the formulas (13) to (15), the group C, the group D, and R ^{31 to} R ³⁴ have the same meaning as in the formula (3).

When R _{61 to} R ₆₈ in the formula (6) are N-alkylaminosulfonyl groups, specific examples thereof include N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-butyl) amino. N-C1-C4 alkylaminosulfonyl groups such as a sulfonyl group, N, N-dimethylaminosulfonyl group, N, N-di (n-propyl) aminosulfonyl group and the like can be mentioned. The C1-C4 alkyl is preferably unsubstituted and linear.

When R _{61 to} R ₆₈ in Formula (6) are an unsubstituted C1-C4 alkylsulfonyl group, the C1-C4 alkyl may be linear, branched or cyclic, but is preferably linear. Specific examples thereof include, for example, straight chain such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl; branched chain such as isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl; cyclopropylsulfonyl, cyclo And cyclic such as butylsulfonyl; and the like. Examples of the hydroxy-substituted C1-C4 alkylsulfonyl group include hydroxyethylsulfonyl, 2-hydroxypropylsulfonyl and the like.

When R _{61 to} R ₆₈ in the formula (6) are acyl groups, specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, benzoyl, naphthoyl and the like.

When R _{61 to} R ₆₈ in Formula (6) are an unsubstituted C1-C4 alkyl group, they may be linear, branched or cyclic, but are preferably linear or branched. Specific examples thereof include linear ones such as methyl, ethyl, n-propyl and n-butyl; branched ones such as isopropyl, isobutyl, sec-butyl and tert-butyl;
When R _{61 to} R ₆₈ in the formula (6) are hydroxy or a C1-C4 alkoxy-substituted C1-C4 alkyl group, specific examples thereof include hydroxy such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and the like. Substituted ones: C1-C4 such as methoxyethyl, 2-ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, n-propoxybutyl, etc. Alkoxy-substituted ones; and the like.

When R _{61 to} R ₆₈ in the formula (6) are unsubstituted C1-C4 alkoxy groups, they may be linear, branched or cyclic, but are preferably linear or branched. Specific examples thereof include linear ones such as methoxy, ethoxy, n-propoxy and n-butoxy; branched ones such as isopropoxy, isobutoxy, sec-butoxy and t-butoxy;
In the case where R _{61 to} R ₆₈ in formula (6) are C1-C4 alkoxy groups substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group, as specific examples thereof, Are, for example, hydroxy-substituted ones such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, C1-C4 alkoxy substituted groups such as n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy C1-C4 alkoxy substituted groups such as 2-hydroxyethoxyethoxy; carboxymethoxy, 2-carboxyethoxy, 3-carboxy Carboxy substituted ones such as ruboxypropoxy; sulfo substituted ones such as 3-sulfopropoxy and 4-sulfobutoxy; and the like.

When R _{61 to} R ₆₈ in formula (6) are acylamino groups, specific examples thereof include acetylamino, propionylamino, butyrylamino, isobutyrylamino, benzoylamino, naphthoylamino, and the like.

When R _{61 to} R ₆₈ in Formula (6) are alkylsulfonylamino groups, they may be linear, branched or cyclic, but are preferably linear. Specific examples thereof include methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino and the like.

When R _{61 to} R ₆₈ in formula (6) are phenylsulfonylamino groups in which phenyl is substituted with a group selected from the group consisting of a halogen atom, an alkyl group and a nitro group, specific examples thereof include, for example, chlorobenzenesulfonyl Halogen atom substituted such as amino; alkyl substituted such as toluenesulfonylamino; nitro substituted such as nitrobenzenesulfonylamino; and the like.

Preferred R ₆₁ and R ₆₂ in formula (6) are a hydrogen atom, a chlorine atom, a bromine atom, cyano, carboxy, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl, phosphono , Nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2 -Carboxyethoxy, acetylamino, benzoylamino, etc., more preferably hydrogen atom, chlorine atom, cyano, sulfamoyl, acetyl, methylsulfonyl, hydroxyethylsulfonyl, nitro, carboxy, sulfo Ri, more preferably a hydrogen atom, carboxy, sulfo. More preferred R ₆₁ is carboxy or sulfo, and sulfo is particularly preferred. R ₆₂ is particularly preferably a hydrogen atom. When the substitution position of R ₆₁ is ortho to the azo group, the substitution position of nitro is para to the azo group, and when the substitution position of R ₆₁ is para to the azo group, The substitution position is preferably ortho to the azo group.

Preferred R ₆₃ and R ₆₄ in the formula (6) are hydrogen atom, chlorine atom, hydroxy, cyano, carboxy, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl, nitro, Acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy , Acetylamino, benzoylamino and the like, more preferably a hydrogen atom, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 3-sulfopropoxy, carboxy, sulfo, more preferably Atom, methyl, 3-sulfopropoxy, carboxy, sulfo.

R _{65 to} R ₆₈ in formula (6) are preferably a hydrogen atom, a chlorine atom, a bromine atom, hydroxy, cyano, carboxy, sulfo, sulfamoyl, N-methylaminosulfonyl, N-phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl. , Phospho, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy 2-carboxyethoxy, acetylamino, benzoylamino, etc., more preferably a hydrogen atom, hydroxy, carboxy, sulfo, sulfamoyl, hydroxyethylsulfonyl, nitro, methyl, methoxy, ethyl, Ethoxy, more preferably hydrogen atom, hydroxy, carboxy, sulfo, sulfamoyl.
In a preferred combination of R _{65 to} R ₆₈ , R ₆₅ is a hydrogen atom, R ₆₆ and R ₆₇ are sulfo, R ₆₈ is hydroxy, and the substitution position of R ₆₈ is preferably peri with respect to the azo group.

In addition, when the specific group further has a configuration of “substituted with a group selected from the group consisting of” a plurality of groups, the selected group is usually 1 to 3 types, preferably 1 to 2 types. The number of substitutions for a specific group is usually 1 to 3, preferably 1 to 2.

The salt of each water-soluble dye represented by the formulas (1), (2), (3) and (6) is an inorganic or organic cation salt. Of these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts, and organic cation salts. Examples of the salt include, but are not limited to, quaternary ammonium ion salts represented by the following formula (16). The free acid, its tautomer, and various salts thereof may be a mixture. For example, 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. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, the type of salt can be selected as appropriate, or when multiple salts are included, the ratio can be changed to meet the purpose. A mixture having physical properties can also be obtained.

In the formula (16), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.
Specific examples of the alkyl group represented by Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (16) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Specific examples of the hydroxyalkyl group include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl and 2-hydroxybutyl. Examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl. Hydroxy C1-C4 alkoxy C1-C4 alkyl group, and hydroxyethoxy C1-C4 alkyl are preferred among these. Particularly preferred are hydrogen atoms; hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, hydroxy And hydroxyethoxy C1-C4 alkyl groups such as ethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. .

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 which} are preferable compounds as the formula (16) are shown in Table 1 below.

Preferred specific examples of the dye (I) represented by the above formula (1) are shown in Tables 2 and 3 below.

The dye (I) represented by the above formula (1) can be synthesized, for example, by the following method.
That is, it can be obtained by diazotizing a compound represented by the following formula (1-1) by a conventional method and subjecting a compound represented by the following formula (1-2) to a coupling reaction by a conventional method.

The diazotization of the compound of formula (1-1) is carried out in a manner known per se, for example a nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. It is carried out using an alkali metal nitrite such as Coupling of the diazotized compound of the compound of formula (1-1) with the compound of formula (1-2) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 5 to 30 ° C, and a weakly acidic to weakly alkaline pH value, for example pH 3-10. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia or organic amines, etc. Can be used. The compound of formula (1-1) and the compound of formula (1-2) are used in approximately stoichiometric amounts.

The dye (II) represented by the formula (2) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid. The groups B and R _{21 to} R ₂₁₀ used in the following formulas (2-1) to (2-8) have the same meanings as in the above formula (2).
A compound represented by the following formula (2-1) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (2-2) are subjected to a coupling reaction by a conventional method. The compound represented by 2-3) is obtained.

The obtained compound of the above formula (2-3) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (2-4) are subjected to a coupling reaction by a conventional method to obtain the following formula: The compound represented by (2-5) is obtained.

The obtained compound of the above formula (2-5) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (2-6) are subjected to a coupling reaction by a conventional method to obtain the following formula: The compound represented by (2-7) is obtained.

By diazotizing the obtained compound of the above formula (2-7) by a conventional method, the resulting diazo compound and a compound represented by the following formula (2-8) are subjected to a coupling reaction by a conventional method. The dye (II) of the present invention represented by the above formula (2) can be obtained. Moreover, the compound represented by the following formula (2-8) can be synthesized according to the method described in Patent Document 3.

The diazotization of the compound of formula (2-1) is carried out in a manner known per se, for example a nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 30 ° C, preferably 5 to 15 ° C. It is carried out using an alkali metal nitrite such as Coupling of the diazotized compound of the compound of formula (2-1) and the compound of formula (2-2) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C, and at an acidic to neutral pH value, for example pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia or organic amines, etc. Can be used. The compound of formula (2-1) and the compound of formula (2-2) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (2-3) is carried out in a manner known per se, for example a nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 40 ° C., preferably 5 to 30 ° C. It is carried out using an alkali metal nitrite such as Coupling of the diazotized compound of the compound of formula (2-3) and the compound of formula (2-4) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. As the base, the same ones as described above can be used. The compound of formula (2-3) and the compound of formula (2-4) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (2-5) is carried out in a manner known per se, for example a nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 50 ° C., preferably 5 to 40 ° C. It is carried out using an alkali metal nitrite such as Coupling of the diazotized compound of formula (2-5) with the compound of formula (2-6) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 [deg.] C, preferably 10 to 40 [deg.] C and an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. As the base, the same ones as described above can be used. The compound of formula (2-5) and the compound of formula (2-6) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (2-7) is also carried out in a manner known per se, for example of nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C. Such an alkali metal nitrite is used. Coupling of the diazotized compound of the compound of formula (2-7) and the compound of formula (2-8) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 5 to 10, and the pH value is adjusted by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia or organic amines Etc. can be used. The compounds of formulas (2-7) and (2-8) are used in approximately stoichiometric amounts.

Although it does not specifically limit as a suitable specific example of dye (II) of this invention shown to the said Formula (2), The compound of following Table 4 and 5 is mentioned. In each table, acidic functional groups such as sulfo and carboxy are expressed in the form of free acids.

The dye (III) represented by the above formula (3) can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each process shall be represented in the form of a free acid for convenience.
A compound represented by the following formula (3-1) is diazotized by a conventional method, and a compound represented by the following formula (3-2) is subjected to a coupling reaction by a conventional method to be represented by the following formula (3-3). To obtain the compound.

(In formula (3-1), group C has the same meaning as in formula (4) and formula (5).)

(In formula (3-2), R ³² to R ³⁴ have the same meaning as in formula (3).)

(In the formula (3-3), R ³² to R ³⁴ have the same meaning as in the formula (3).)

The obtained compound of the formula (3-3) is diazotized by a conventional method, and then this and a compound represented by the following formula (3-4) are subjected to a coupling reaction by a conventional method, and the following formula (3-5) The compound represented is obtained.

(In formula (3-4), m has the same meaning as in formula (3).)

(In formula (3-5), m and R ³² to R ³⁴ have the same meaning as in formula (3).)

The compound of the formula (3-5) thus obtained is diazotized by a conventional method, and then this and a compound represented by the following formula (3-6) are subjected to a coupling reaction by a conventional method, thereby being represented by the formula (3). The dye (III) of the present invention can be obtained.

(In formula (3-6), R ³¹ and group D have the same meaning as in formula (3).)

In addition, the compound represented by Formula (3-6) can purchase a commercial item as a product, or can be synthesize | combined by a well-known method.

Although it does not specifically limit as a suitable specific example of the dye 3 of this invention shown to the said Formula (3), The compound shown by the structural formula given to the following Tables 6-11 etc. is mentioned.
In each table, functional groups such as sulfo and carboxy are represented in the form of free acid for convenience.

The diazotization of the compound of the above formula (3-1) is carried out by a method known per se. For example, 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 formula (3-1) with the compound of formula (3-2) is also carried out under conditions known per se. It is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C. The compound of formula (3-1) and the compound of formula (3-2) are used in a substantially stoichiometric amount.

Diazotization of the compound of formula (3-3) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid 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 40 ° C, preferably 5 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound of the formula (3-3) and the compound of the formula (3-4) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 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 liquid 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 compounds of formulas (3-3) and (3-4) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (3-5) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid 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 40 ° C, preferably 10 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of a diazotized compound of the compound of formula (3-5) and a compound of formula (3-6) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 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. As the base, the same ones as described above can be used. The compounds of formulas (3-5) and (3-6) are used in approximately stoichiometric amounts.

A method for synthesizing the dye (III) represented by the formula (6) is disclosed in Patent Document 1, for example.
Although it does not specifically limit as a suitable specific example of dye (III) of this invention represented by the said Formula (6), The thing quoted in following Table 12 to 13 etc. are mentioned.
In each table, functional groups such as sulfo and carboxy are labeled in the form of free acid for convenience.

In order to make each dye compound represented by the formulas (1), (2), (3) and (6) into a desired salt, a desired inorganic salt or an organic cation salt is obtained after the coupling reaction. Is salted out by adding to the reaction solution, or is isolated in the form of free acid by adding a mineral acid such as hydrochloric acid, and this is washed with water, acidic water or an aqueous organic medium as necessary. After removing the inorganic salt, the solution can be made into a solution of the corresponding salt by neutralizing with a desired inorganic or organic base in an aqueous medium. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to water-miscible organic substances miscible with water and so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Organic substances that are not classified can be used as needed as long as they are miscible with water. Examples of organic substances not normally classified as solvents include urea and saccharides. Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride; ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above-mentioned formula (16). The halogen salt of the organic amine represented by these is mentioned. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of organic bases include, but are not limited to, organic amines such as quaternary ammoniums represented by formula (16) such as diethanolamine and triethanolamine.

The ink composition of the present invention will be described. The aqueous ink composition of the present invention containing all of the dyes (I), (II), and (III) can dye a material made of cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabrics and paper.

The reaction liquid containing the dyes (I), (II) and (III) can be used directly in the production of the ink composition of the present invention. That is, the ink composition of the present invention can also be produced by mixing three kinds of reaction liquids containing the dyes synthesized separately. However, first, each reaction solution containing each dye is individually dried, for example, spray-dried to isolate each dye; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, etc. Or by acidifying by adding a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; or by acidifying out a combination of salting out and aciding as described above; Ink compositions can also be prepared.

The ink composition of the present invention contains any of the three types of dyes (Dyes (I), (II) and (III)). Each of the dyes (I) to (III) may be a single water-soluble dye or a water-soluble black dye as long as the above specific conditions are satisfied, or each of the dyes may be a plurality of water-soluble dyes or water-soluble black dyes. It may be a mixture. Therefore, the ink composition of the present invention exhibits a black color by blending at least three kinds of dye compounds. The total mass of the above dyes (I), (II) and (III) contained in the ink composition as a pigment component is usually 0.1 to 20% by mass, preferably based on the total mass of the ink composition. The ratio is 1 to 10% by mass, more preferably 2 to 8% by mass, and the remainder in the other ink composition contains water as a main medium.
The ink composition of the present invention may further contain a water-soluble organic solvent, for example, 0 to 30% by mass, and an ink preparation agent, for example, 0 to 10% by mass. Further, if desired, other dyes may be included in the above range for the purpose of toning and the like. The pH of the ink composition is preferably 5 to 11 and more preferably 7 to 10 in terms of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less. The pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.

The ratio of each dye in the total mass of the dyes (I), (II), and (III) contained in the ink composition as a pigment component is 5 to 30% by mass of the dye (I) and the dye (II). 20 to 80% by mass and the dye (III) needs to fall within the range of 15 to 60% by mass, but 10 to 25% by mass is preferable for the dye (I), and 35 to 70 for the dye (II). The mass% is preferable, and the dye (III) is preferably 20 to 50 mass%.

The ink composition of the present invention comprises the dyes (I), (II), and (III), together with other coloring materials such as toning as necessary, water or a water-soluble organic solvent (organic miscible with water). Solvent) and an ink preparation agent is added as necessary. For the purpose of adjusting the black color of the ink composition to a neutral hue with no color, other toning pigments and the like may be appropriately added to the ink composition of the present invention. When this ink composition is used as an ink for an ink jet printer, the dyes (I), (II) and (III) should be used with a low content of inorganic impurities such as metal cation chlorides and sulfates. Is preferred. The standard of the inorganic impurity content is about 1% by mass or less with respect to the total mass of the dye. In order to produce the dye of the present invention with a small amount of inorganic impurities, for example, a conventional method using a reverse osmosis membrane or a dried product or wet cake of a dye is stirred in a mixed solvent of alcohol such as methanol and water, and the precipitate is separated by filtration. Then, it may be desalted by a method such as drying.

In the preparation of the ink composition, the water-soluble organic solvent adjusts the viscosity of the ink, adjusts the drying property of the ink, and has a permeability to the recording medium after printing and the ink receiving layer on the surface of the recording medium. Used for adjustment purposes. Specific examples of water-soluble organic solvents that can be used include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol; N, N-dimethylformamide or N, N A carboxylic acid amide such as dimethylacetamide; a lactam such as 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone or N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2- ON or cyclic ureas such as 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane, etc. Cyclic ether; Lene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, di Mono-, oligo- or poly-alkylene glycols or thioglycols having C2-C6 alkylene units such as propylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol; trimethylolpropane, glycerin or hexane-1,2,6 -Polyols such as triol (triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol C1-C4 alkyl ethers of polyhydric alcohols monobutyl ether (butyl carbitol) Triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; .gamma.-butyrolactone or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

The water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent in this specification for convenience.

Examples of ink preparations that are appropriately used in the preparation of the ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye-dissolving agents, and antioxidants. Agents and / or surfactants. These drugs are described below.

Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. . These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.

Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide, and 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 -Isothiazoline-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.

As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include 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); Alternatively, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; inorganic bases such as sodium silicate and disodium phosphate, and the like.

Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate or sodium uracil diacetate.

Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate or dicyclohexylammonium nitrite.

Examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Specific examples of the dye dissolving agent include ε-caprolactam, ethylene carbonate, urea, and the like.
As examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines or heterocyclic rings. .

Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates Salt 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, alkyl allyl sulfonate , Diethylsulfosuccinate, diethylhexylsylsulfosuccinate or dioctylsulfosuccinate.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, or Examples include imidazoline derivatives.
Specific examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Ether type, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, poly Esters such as oxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4 Acetylene glycols such as octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, and other specific examples include, for example, trade name Surfinol 104, 105, 82, manufactured by Nissin Chemical. 465, Olfin STG and the like.
These ink preparation agents are used alone or in combination.

The ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. In addition to the dyes (I), (II), and (III) described above, other pigments having various hues may be mixed in order to adjust the black color as the ink composition. In that case, black having other hues, yellow, orange, brown, scarlet, red, magenta, violet, blue, navy, cyan, green, and other color pigments can be mixed and used.

The ink composition of the present invention can be used in various fields, but is suitable for a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. It is suitably used in the inkjet printing method.

Next, the ink jet printing method of the present invention will be described. The ink jet printing method of the present invention is characterized in that recording is performed using the ink composition of the present invention. In the ink jet printing method of the present invention, recording is performed on an image receiving material using an ink jet ink containing the ink composition, but there are no particular restrictions on the ink nozzles used at that time, depending on the purpose. Can be selected as appropriate.
A known method, for example, a charge control method that ejects ink using electrostatic attraction; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; an electric signal is converted into an acoustic beam and the ink is irradiated And adopting an acoustic ink jet method that discharges ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, that is, a bubble jet (registered trademark) method; Can do.
In the inkjet printing method, a method called a photo ink, in which a large number of inks having a low pigment concentration (pigment content) are ejected in a small volume; the pigment concentrations in the ink differ substantially in the same hue. A system that improves image quality using a plurality of inks; a system that uses colorless and transparent ink, and the like are also included.

The colored body of the present invention is colored with an ink composition containing the dyes (I), (II) and (III), and more preferably by an ink jet printing method using an ink jet printer. It is colored by.
Although there is no restriction | limiting in particular as what can be colored, For example, sheets for information transmission, such as paper and a film, fiber, cloth (cellulose, nylon, wool, etc.), leather, a base material for color filters, etc. are mentioned.
Among them, the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer; or by using a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol or special ceramics, polyvinyl alcohol or polyvinyl Coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone;
The information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Specific examples include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photographic Paper (Glossy), PM Matt Paper, Crispia; Japan Hewlett-Packard Co., Ltd. Commercially available products such as advanced photo paper, premium plus photo paper, premium glossy film or photo paper are available. Of course, plain paper can also be used.

  Among the information transmission sheets described above, it is known that an image recorded on a sheet coated with a porous white inorganic material on the surface is particularly prone to discoloration by ozone gas. However, since the ink composition of the present invention is excellent in ozone gas resistance, it exhibits a particularly great effect when inkjet printing is performed on such a recording material.

In order to record on a recording material such as an information transmission sheet by the ink jet printing method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of an ink jet printer, and the recording material is processed by a normal method. Can be recorded.
The inkjet printing method of the present invention includes the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color ink such as green, blue (or violet), and red (or orange). A composition can also be used in combination.
The ink composition of each color is poured into each container, and each container is set in 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 printing.

The ink composition of the present invention has good storage stability because it does not cause crystal precipitation, change in physical properties, change in hue, etc. even when stored for a long period of time.
The ink composition containing the coloring matter of the present invention can be used for ink jet printing and writing instruments.
Furthermore, when printed on an information recording sheet, particularly ink jet dedicated paper, the print density of the printed image is high, and in addition, the durability of the printed image, in particular, ozone gas resistance and light resistance are excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples. In the text, “parts” and “%” are based on mass unless otherwise specified. In the following formulas, acidic functional groups such as sulfo are represented in the form of free acid for convenience.

Example 1 (Synthesis of Compound No. 16 in Table 3)
To 300 parts of water, 16.0 parts of dehydrothio-p-toluidinesulfonic acid and sodium hydroxide were added to obtain a solution having a pH of 7.0 to 8.0. After adding 23.5 parts of 35% hydrochloric acid, 9.9 parts of a 40% aqueous sodium nitrite solution were added dropwise at 15 to 25 ° C. over about 10 minutes. After dropping, the mixture was stirred at the same temperature for 1 hour to obtain a diazo reaction liquid.
On the other hand, 14.2 parts of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid was dissolved in 50 parts of water to a pH of 8-9 with sodium hydroxide. After adding 0.8 part of sulfamic acid to the diazo reaction liquid obtained previously and stirring for 5 minutes, the aqueous solution of 1-p-sulfophenyl-5-pyrazolone-3-carboxylic acid obtained above was added here. did. After the addition, the mixture was stirred for 2 hours at 20 to 25 ° C. while maintaining pH 8 to 9 by adding sodium carbonate. Acidified by addition of 35% hydrochloric acid and sodium chloride, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved in 350 parts of water to a pH of 7 to 8 by adding sodium hydroxide, crystallized by adding 300 parts of 2-propanol, and the precipitated solid was collected by filtration. Again, the obtained wet cake was dissolved in 300 parts of water, crystallized by adding 400 parts of 2-propanol, and the precipitated solid was collected by filtration and dried, whereby the compound 26. 0 parts were obtained. The maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution of this compound at pH 7 to 8 was 453 nm.

Example 2 (Synthesis of Compound No. 15 in Table 3) In Example 1, 20.0 parts of dehydrothio-p-toluidine disulfonic acid was used in place of 16.0 parts of dehydrothio-p-toluidine sulfonic acid. In the same manner as in Example 1, 29.0 parts of the compound represented by the formula (18) was obtained. The maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution with a pH of 7 to 8 was 434 nm.

Example 3 (Synthesis of Compound No. 17 in Table 3)
(Acts 3-1)
After adding 57.6 parts of dehydrothio-p-toluidine sulfonic acid and sodium hydroxide to 600 parts of water to adjust the pH to 7.0 to 7.5, the temperature was raised to 35 to 45 ° C. and dissolved. Acetic anhydride 23.0 parts was added. After the addition, the mixture was stirred at the same temperature for 20 minutes while maintaining pH 6.0 to 6.5 by adding sodium carbonate. Thereafter, the operation of stirring for 20 minutes at the above temperature was repeated 4 times while maintaining pH 6.0 to 6.5 by addition of 23.0 parts of acetic anhydride and addition of sodium carbonate. After cooling to room temperature and adjusting to pH 4.0-5.0 by adding 35% hydrochloric acid, the precipitate was collected by filtration to obtain a wet cake containing a compound of the following formula (41).

(Ex. 3-2)
A wet cake containing the compound of formula (41) obtained in (Ex. 3-1) was added to 1100 parts of water, heated to 60 to 65 ° C., and adjusted to pH 7.5 to 8.5 by adding sodium carbonate. . To this was added 23.0 parts of magnesium sulfate heptahydrate and 0.2 parts of sodium carbonate, and then 57.6 parts of potassium permanganate was added over 5 minutes. After stirring at 65-70 ° C. for 3 hours, 22.0 parts of potassium permanganate was further added. After stirring at the same temperature for 2 hours, 22.0 parts of potassium permanganate was further added and stirred at the same temperature for 2 hours. After insoluble matters were removed by filtration, the temperature was raised to 80 to 90 ° C., and the mixture was stirred at the same temperature for 4 hours while maintaining pH 10.5 to 11.5 by adding sodium hydroxide. After cooling to 60 to 65 ° C., sodium chloride was added, and the pH was adjusted to 6.0 to 7.0 by adding 35% hydrochloric acid. The precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (42).

(Ex. 3-3)
In Example 1, except that 2/5 amount of the wet cake containing the compound of the formula (42) obtained in place of 16.0 parts of dehydrothio-p-toluidinesulfonic acid (Ex. 3-2) was used. In the same manner as in Example 1, 27.0 parts of a compound represented by the following formula (19) was obtained. The maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution of pH 7 to 8 of this compound was 488 nm.

Example 4 (Synthesis of Compound No. 27 in Table 4)
(Actu 4-1)
5.4 parts of the compound of formula (20) (CI Acid Yellow 9) was suspended in 40 parts of water and dissolved by adding sodium hydroxide to a pH value of 4.0 to 5.0. After adding 6.0 parts of 35% hydrochloric acid to this solution, 2.9 parts of 40% aqueous sodium nitrite solution was added at 15 to 25 ° C. and stirred at the same temperature for 1 hour to obtain a diazo reaction liquid.

The obtained diazo reaction solution was dissolved in 30 parts of water obtained by the method described in Patent Document 4 in 30 parts of water and adjusted to pH 4.5 to 5.5 by adding sodium hydroxide. The solution was added dropwise at 15 to 25 ° C. over about 30 minutes. During the dropwise addition, the pH value of the solution was maintained at 4.0 to 5.0 by adding sodium carbonate. Thereafter, the mixture was stirred for 2 hours, acidified by addition of 35% hydrochloric acid, and the precipitate was separated by filtration to obtain a wet cake containing a disazo compound of the formula (22).

(Actu 4-2)
The wet cake containing the disazo compound of formula (22) obtained in (Ex. 4-1) is dissolved in 130 parts of water, and after adding 4.0 parts of 35% hydrochloric acid, 40% sodium nitrite at 20 to 35 ° C. 2.4 parts of an aqueous solution was added and stirred for 2 hours to obtain a diazo reaction solution. This diazo reaction solution was added to a solution obtained by dissolving 2.9 parts of the compound of the formula (21) in 25 parts of water and adjusting the pH to 4.5 to 5.5 by adding sodium hydroxide at 15 to 25 ° C. over about 30 minutes. It was dripped. During the dropwise addition, the pH value of the solution was maintained at 3.5 to 4.5 by adding sodium carbonate. Thereafter, the mixture was stirred for 2 hours, salted out by addition of sodium chloride, and the precipitate was separated by filtration to obtain a wet cake containing a trisazo compound of the formula (23).

(Act 4-3)
2- (Cyanomethyl) benzimidazole and ethyl acetoacetate are heated in ethanol in the presence of sodium methoxide and acidified by addition of dilute hydrochloric acid to yield 8.9 parts of the compound of the formula (24) that emits 6%. Slowly added to 64 parts of sulfuric acid at 15-25 ° C. After the addition, the mixture was stirred at the same temperature for 2 hours, and then dropped into 190 parts of ice water in about 10 minutes. The precipitated crystals were separated by filtration, washed with a hydrochloric acid acidic brine on a funnel, and dried to obtain 10.7 parts of a compound of the formula (25).

(Acts 4-4)
The wet cake containing the trisazo compound of the formula (23) obtained in (Ex. 4-2) was dissolved in 150 parts of water to a pH value of 6.0 to 7.0 by adding sodium hydroxide, and 40% was added thereto. After adding 2.1 parts of an aqueous sodium nitrite solution, this solution was dropped into a mixed solution of 4.7 parts of 35% hydrochloric acid and 40 parts of water at 20 to 35 ° C. and stirred for 1 hour to obtain a diazo reaction liquid. . This diazo reaction solution was dissolved in 3.0 parts of the compound of the formula (25) obtained in (Ex. 4-3) in 50 parts of water by adding sodium hydroxide to a pH value of 8.0 to 9.0. The solution was added dropwise at 20 to 35 ° C. During the dropwise addition, the pH value was maintained at 7.0 to 8.0 by adding sodium carbonate. After dropping, the mixture was stirred at the same temperature for 6 hours, salted out by adding sodium chloride, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 150 parts of water, crystallized by adding 120 parts of methanol, and the precipitate was separated by filtration. The obtained wet cake was further dissolved in 150 parts of water, and then crystallized by adding 180 parts of methanol. The precipitate was separated by filtration and dried to obtain 9.6 parts of an azo compound of the following formula (26) as a sodium salt. Obtained. This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was 580 nm, and was a black dye having absorption in all wavelength regions within the range. Moreover, the solubility was 100 g / L or more.

Example 5 (Synthesis of Compound No. 28 in Table 4)
(Acts 5-1)
6.0 parts of the compound of formula (25) was dissolved in 40 parts of 95% sulfuric acid, heated to 60 ° C. and stirred for 1.5 hours. After cooling to room temperature, the reaction solution was dropped into 120 parts of ice water, and after adding sodium chloride, the crystals were separated by filtration. The crystals were washed on a funnel with dilute hydrochloric acid in which sodium chloride was dissolved and then dried to obtain 5.1 parts of the compound of formula (27).

(Actu 5-2)
(Ex. 4-4) In the same manner as in Example 1 except that 3.0 parts of the compound of the formula (25) are replaced with 3.2 parts of the compound of the above formula (27), the following formula (28) 9.7 parts of the azo compound was obtained as a sodium salt. This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was a black dye having absorption in all wavelength regions in the range. Moreover, the solubility was 100 g / L or more.

Example 6 (Synthesis of Compound No. 32 in Table 4)
(Real 6-1)
Dissolve 3.9 parts of 2-aminobenzene-1,5-disulfonic acid in 30 parts of water, add 2.2 parts of 35% hydrochloric acid, adjust to 0-5 ° C., and 2.7 parts of 40% aqueous sodium nitrite solution Was added dropwise and stirred for 30 minutes to obtain a diazo reaction solution. To this diazo reaction solution, a solution prepared by dissolving 4.3 parts of the compound of the formula (21) in 50 parts of water and adding sodium hydroxide to a pH value of 4.5 to 5.5 was added dropwise over about 20 minutes. After dripping, it stirred at 10-20 degreeC for 4 hours, and obtained the solution containing the compound of following formula (29).

(Ex. 6-2)
(Ex. 4-1) In the same manner as in Example 1, except that 5.4 parts of the compound of the formula (20) are used and a solution containing the compound of the formula (29) is used, the formula (30) This gave 8.9 parts of the azo compound as a sodium salt. This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was a black dye having absorption in all wavelength regions in the range. Moreover, the solubility was 100 g / L or more.

Example 7 (Compound No. 61 in Table 9)
(Actu 7-1)
Suspend 3.5 parts of 2-aminobenzothiazole-6-sulfonic acid in 20 parts of 50% sulfuric acid, and drop 5.5 parts of 40% nitrosylsulfuric acid at 5-10 ° C. over about 10 minutes with stirring. By reacting, a diazo reaction liquid was obtained.
On the other hand, 3.7 parts of the compound of the formula (21), 0.6 part of sulfamic acid and then sodium hydroxide were added to 30 parts of water to obtain pH 5.0 to 5.5 to obtain an aqueous solution.
The above diazo reaction solution was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 10 minutes.
After completion of the dropwise addition, the mixture is stirred at the same temperature for 2 hours, sodium hydroxide is added to adjust the pH to 0.7 to 1.2, and the precipitated solid is collected by filtration to obtain a wet cake containing a compound of the following formula (31). It was.

(Real 7-2)
An aqueous solution was obtained by adding 4.8 parts of the compound of the following formula (32) to 50 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, by suspending the wet cake containing the compound of the formula (31) obtained in (Ex. 7-1) in 120 parts of water with stirring and adding sodium hydroxide to pH 6.0 to 6.5. An aqueous solution was obtained.
To the obtained aqueous solution, 5.4 parts of 35% hydrochloric acid and then 3.2 parts of 40% aqueous sodium nitrite solution at a reaction temperature of 15 to 20 ° C. were dropped over about 5 minutes, and reacted for 1 hour to obtain a diazo reaction liquid. Obtained.
The obtained diazo reaction liquid was dripped at the reaction temperature of 20-30 degreeC and 20 minutes to the aqueous solution containing the compound of the formula (32) obtained previously. 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 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 collected by filtration to obtain a wet cake containing a compound of the following formula (33).

(Acts 7-3)
An aqueous solution was obtained by adding 4.2 parts of the compound of the following formula (34) to 35 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, with stirring, the wet cake containing the compound of formula (33) obtained in (Ex. 7-2) was dissolved in 200 parts of water, 4.6 parts of 35% hydrochloric acid, and then at a reaction temperature of 20-25 ° C. A diazo reaction liquid was obtained by adding 2.8 parts of an aqueous sodium nitrite solution dropwise over about 5 minutes and reacting for 1 hour.
The obtained diazo reaction liquid was dripped at the reaction temperature of 20-30 degreeC and 30 minutes to the aqueous solution containing the compound of the formula (34) obtained previously. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 220 parts of water, 340 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 170 parts of water, 450 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration and dried to give a compound of the following formula (23) of the present invention. 3 parts were obtained as the sodium salt. This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was 604 nm, and was a black dye having absorption in all wavelength regions within the range. Moreover, the solubility was 100 g / L or more.

Example 8 (Synthesis of compound No. 51 in Table 8 and compound No. 22 in Table 9. Example 8 is a mixture of these two compounds.)
(Actu 8-1)
5.0 parts of 2-amino-6-methoxybenzothiazole was slowly added to 15 parts of 15% fuming sulfuric acid at 15-25 ° C. After the addition, the mixture was stirred at the same temperature for 2 hours, and then added dropwise to 60 parts of ice water in about 10 minutes. The precipitated crystals were collected by filtration and dried to obtain 6.4 parts of a compound of the following formula (36).

(Actu 8-2)
Suspend 3.2 parts of the compound of the formula (36) obtained in (Ex. 8-1) in 20 parts of 50% sulfuric acid, and 4.7 parts of 40% nitrosylsulfuric acid at 5-10 ° C. for about 10 minutes with stirring. Was added dropwise and reacted for 2 hours to obtain a diazo reaction liquid.
On the other hand, an aqueous solution was obtained by adding 2.9 parts of the compound of the formula (21), 0.4 part of sulfamic acid, and then sodium hydroxide to 30 parts of water to adjust the pH to 5.0 to 5.5.
The above diazo reaction solution was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 10 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium hydroxide was added to adjust the pH to 0.7 to 1.2, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (37). It was.

(Acts 8-3)
An aqueous solution was obtained by adding 4.0 parts of the compound of the formula (32) and then sodium hydroxide to 40 parts of water to adjust the pH to 7.5 to 8.0.
On the other hand, by suspending the wet cake containing the compound of the formula (37) obtained in (Actuation 8-2) in 130 parts of water with stirring and adding sodium hydroxide to pH 6.0 to 6.5. An aqueous solution was obtained.
To the resulting aqueous solution, 4.2 parts of 35% hydrochloric acid and then 2.6 parts of 40% aqueous sodium nitrite solution at a reaction temperature of 15 to 20 ° C. are added dropwise over about 5 minutes, and reacted for 1 hour to obtain a diazo reaction liquid. Obtained.
The obtained diazo reaction liquid was dripped at the reaction temperature of 20-30 degreeC and 20 minutes to the aqueous solution containing the compound of the formula (32) obtained previously. 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, salted out by addition of sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (38).

(Acts 8-4)
An aqueous solution was obtained by adding 3.6 parts of the compound of the formula (34) to 35 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, with stirring, the wet cake containing the compound of formula (38) obtained in (Act 8-3) was dissolved in 170 parts of water, 3.8 parts of 35% hydrochloric acid, and then at a reaction temperature of 20-25 ° C. A diazo reaction liquid was obtained by dropping 2.3 parts of a sodium nitrite aqueous solution in about 5 minutes and reacting for 1 hour.
The obtained diazo reaction liquid was dripped at the reaction temperature of 20-30 degreeC and 30 minutes to the aqueous solution containing the compound of the formula (34) obtained previously. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 200 parts of water, 300 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 160 parts of water, 420 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration and dried to obtain 12.7 parts of the compound of the following formula (39). Obtained as the sodium salt. This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was 605 nm, and was a black dye having absorption in all wavelength regions within the range. Moreover, the solubility was 100 g / L or more.

(A) Ink Preparation Example 9
An ink composition was prepared by mixing the components shown in Table 14 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. The obtained ink composition is hereinafter referred to as “ink”. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 14
Compound obtained in Example 1: Dye (I) 1.0 part Compound obtained in Example 4: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 10
An ink composition was prepared by mixing the components shown in Table 15 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. The structural formula of the compound obtained in Example 1 (No. 3 compound in Table 12) of Patent Document 1 used here is shown in the following formula (40). This compound had a maximum absorption wavelength (λmax) in the range of 380 to 720 nm in an aqueous solution having a pH of 7 to 8 and was 626 nm, and was a black dye having absorption in all wavelength regions in the range. Moreover, the solubility of this compound in water was 100 g / L or more. In addition, the ink did not undergo precipitation separation even during storage and after long-term storage, and physical properties did not change.

Table 15
Compound obtained in Example 1: Dye (I) 1.0 part Compound obtained in Example 4: Dye (II) 2.5 part Compound obtained in Example 1 of Patent Document 1: Dye (III 1.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (trade name Surfy Nord 104 manufactured by Nissin Chemical)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 11
An ink composition was prepared by mixing the components shown in Table 16 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 16
Compound obtained in Example 1: Dye (I) 1.0 part Compound obtained in Example 4: Dye (II) 2.5 part Compound obtained in Example 8: Dye (III) 1.5 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 12
An ink composition was prepared by mixing the components shown in Table 17 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 17
Compound obtained in Example 1: Dye (I) 1.0 part Compound obtained in Example 6: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 13
An ink composition was prepared by mixing the components shown in Table 18 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 18
Compound obtained in Example 1: Dye (I) 1.0 part Compound obtained in Example 5: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 14
An ink composition was prepared by mixing the components shown in Table 19 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 19
Compound obtained in Example 2: Dye (I) 1.0 part Compound obtained in Example 4: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Example 15
An ink composition was prepared by mixing the components shown in Table 20 below, and filtered through a 0.45 μm membrane filter to obtain an aqueous black ink composition of the present invention for inkjet. The water used was ion exchange water. The pH of the ink composition was adjusted with 2.8% sodium hydroxide so that the pH was 8-10. This ink did not undergo precipitation separation during storage or after long-term storage, and no change in physical properties occurred.

Table 20
Compound obtained in Example 3: Dye (I) 1.0 part Compound obtained in Example 4: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 Parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin (Chemical company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

Comparative Examples 1 to 5
Instead of blending the dyes corresponding to the above-mentioned dyes (I), (II) and (III), 5.0 parts of each compound obtained in Examples 4 to 8 was used alone as a comparative ink. A black ink was prepared with the same composition as the ink of Example 9 except that. Ink adjustment methods such as the use of a 0.45 μm membrane filter and pH adjustment are exactly the same as in each ink embodiment. The ink using the compound of Example 4 was used for Comparative Example 1, the ink using the compound of Example 5 was Comparative Example 2, the ink using the compound of Example 6 was used the compound of Comparative Example 3 and Example 7. The ink is Comparative Example 4 and the ink using the compound of Example 8 is Comparative Example 5. Comparative Examples 1 to 3 are inks using dye (II), and Comparative Examples 4 and 5 are inks using dye (III) alone.

Comparative Example 6
Instead of blending the dyes corresponding to the above dyes (I), (II) and (III), 5.0 parts of the compound obtained in Example 1 of Patent Document 1 is used alone as a comparative ink. A black ink was prepared with the same composition as the ink of Example 9 except for the above. Ink adjustment methods such as the use of a 0.45 μm membrane filter and pH adjustment are exactly the same as in each ink embodiment. Comparative Example 6 is an ink using dye (III) alone.

Comparative Example 7
As a comparison ink, an ink was prepared with the same composition as the ink of Example 9 except that 5.0 parts of the compound obtained in Example 1 was used as the pigment component. Ink adjustment methods such as the use of a 0.45 μm membrane filter and pH adjustment are exactly the same as in each ink embodiment. This ink composition had an orange color. Comparative Example 7 is an ink using dye (I) alone.

Comparative Example 8
As a comparative ink, a black ink composition described in Example 2 of Patent Document 2 was prepared. Ink adjustment methods such as the use of a 0.45 μm membrane filter and pH adjustment are exactly the same as in each ink embodiment. Comparative Example 8 is a black ink in which three kinds of dyes containing two kinds of dyes different from the dyes (I) and (III) and the dye (II) are blended.

Comparative Example 9
As described in Comparative Example 7 above, the ink using the dye compound of the formula (17) corresponding to the dye (I) obtained in Example 1 alone had an orange color. The ink composition shown in Table 21 below was prepared using the compound of Example 1 which is a dye exhibiting an orange color among the dye components used in the ink composition described in Example 2 of Patent Document 2 instead of did. Ink adjustment methods such as the use of a 0.45 μm membrane filter and pH adjustment are exactly the same as in each ink embodiment. Comparative Example 9 corresponds to an ink in which an orange dye different from the dye (I) and the dyes (II) and (III) are blended.

Table 21
Compound obtained in Example 2 of Patent Document 2 1.0 part Compound obtained in Example 4: Dye (II) 2.0 part Compound obtained in Example 7: Dye (III) 2.0 part Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Trade name Surfinol 104 Nissin Chemical (Made by company)
Water + sodium hydroxide 75.9 parts Total 100.0 parts

(B) Inkjet printing Using the ink obtained above, Canon ink jet printer, product name PIXUS iP4100, information recording sheet HP product name, product name Advanced photo paper (gloss) (inkjet dedicated paper) ink jet print Went.
At the time of printing, an image pattern was prepared so that the reflection density was obtained with several gradations, and a black printed matter was obtained.

(C) Evaluation of recorded image
Each print image obtained using the inks of Examples 9 to 16 and Comparative Examples 1 to 9 was evaluated for the density change of the image before and after the test with respect to light resistance and ozone gas resistance. Moreover, about the moisture resistance test, it printed with the check pattern which consists of a square whose minimum unit is 1.5 mm, and the presence or absence of the bleeding of the pigment | dye from a printing part to an unprinted part was observed.
Regarding the light resistance and ozone gas resistance, the density change of the print image was performed using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye, and the reflection density D value of the print image before the test was the highest at 1.0. It was measured by measuring the color of the near gradation part. The moisture resistance test was visually evaluated.
The test results are shown in Table 22.
The specific test method is as follows.
1) Ozone gas resistance test, trade name, manufactured by Suga Test Instruments Co., Ltd. Each print image was allowed to stand for 8 hours under the conditions of ozone concentration 40 ppm, humidity 60% RH, temperature 24 ° C. using an ozone weatherometer. After completion of the test, the colorimetry was performed using the above-described colorimeter, and the residual ratio of the dye in each print image was determined by the formula (reflection density after test / reflection density before test) × 100 (%). The test results were evaluated according to the following criteria.
○ Residual rate: 75% or more △ Residual rate: 50% or more and less than 75% × Residual rate: less than 50% 2) Light resistance test Using a low-temperature xenon weatherometer XL75 manufactured by Suga Test Instruments Co., Ltd. After irradiating each print image for 96 hours under the conditions of 100,000 Lux illuminance, humidity 60% RH, and temperature 24 ° C., the colorimetry is performed using the colorimeter described above, and the dye remaining in each image remains. The rate was determined by the formula of (reflection density after test / reflection density before test) × 100 (%). The test results were evaluated according to the following criteria.
○ Residual rate: 80% or more △ Residual rate: 70% or more and less than 80% × Residual rate: less than 70% 3) Moisture resistance test manufactured by Yamato Kagaku Co., Ltd., trade name: constant temperature and humidity machine IG400, humidity 80% RH, After storing each of the above printed materials at a temperature of 30 ° C., the degree of dye bleeding was judged by visual observation. The test results were evaluated according to the following criteria.
○ No blotting of the dye on the unprinted area is observed △ Slight blotting of the dye on the unprinted area is slightly observed × Blur of the dye on the unprinted area is clearly seen

Table 22
Ozone gas resistance Light resistance Moisture resistance Example 9 ○ ○ ○
Example 10 ○ ○ ○
Example 11 ○ ○ ○
Example 12 ○ ○ ○
Example 13
Example 14 ○ ○ ○
Example 15 ○ ○ ○
Comparative Example 1 ○ ○ ○
Comparative Example 2 ○ ○ ○
Comparative Example 3 ○ ○ ○
Comparative Example 4 ○ △ ○
Comparative Example 5 ○ △ ○
Comparative Example 6
Comparative Example 7 ○ × ○
Comparative Example 8 × △ ○
Comparative Example 9 △ △ ○

As an evaluation of the hue of the printed matter, the saturation C * was measured in both the high density portion and the low density portion. As described above, the printed material used for this evaluation uses an image pattern printed so that the reflection density can be obtained in several gradations, and distinguishes the high density portion and the low density portion according to the range of the lightness L *. did. That is, the high density portion is a lightness L * range of 4.0 to 10.0, and the low density portion is a portion of an image pattern having a lightness L * range of 40.0 to 50.0. Shown respectively. Since the lower the C * as achromatic black or gray, the better it was, the following criteria were used for evaluation.
In addition, since the ink of the comparative example 7 is orange, this evaluation was not performed.
The evaluation results are shown in Table 23.
○ C * is less than 15 △ C * is 15 or more and less than 20 × C * is 20 or more

Table 23
High concentration Low concentration Example 9 ○ ○
Example 10
Example 11
Example 12
Example 13
Example 14
Example 15
Comparative Example 1 ○ △
Comparative Example 2 ○ ×
Comparative Example 3 ○ ×
Comparative Example 4 ○ ×
Comparative Example 5 ○ △
Comparative Example 6
Comparative Example 8
Comparative Example 9

As is clear from the results in Tables 22 and 23, Comparative Examples 1 to 3 of the inks each using the above dye (II) alone have good ozone resistance and light resistance, but the hue at a low concentration is low. Somewhat bad. Further, Comparative Examples 4 and 5 of the ink using the dye (III) alone are slightly inferior in light resistance as compared with the respective examples, and since the saturation at a low density is high, an achromatic black or gray color. It cannot be said that the performance as a black ink for which color is desired is sufficiently satisfied. Comparative Example 6 of the ink using the compound of Example 1 of Patent Document 1, that is, the dye (III) of the present invention alone, is slightly inferior in ozone resistance and higher in saturation than the ink of each Example. Therefore, it is understood that it is not preferable to use this dye alone as a black ink dye for the same reason as described above.
Moreover, it turns out that the comparative example 7 of the ink which uses dye (I) independently is inferior in light resistance.
On the other hand, the images of Examples 9 to 15 containing the dyes (I), (II) and (III) have good ozone resistance, light resistance and moisture resistance, and change at high and low concentrations. It can be seen that it exhibits good black color and has higher performance than the black ink using each dye alone.
Moreover, although it turns out that the comparative example 8 is very favorable black about a color, ozone resistance is very bad. From this result, even when the dye (II) and three other dyes added with two other dyes are blended, no good ozone resistance effect is observed, and when the dyes (I) and (III) are blended For the first time, it has been found that the effect of the present invention in which ozone resistance is good can be obtained. Similarly, the ink of Comparative Example 9 also exhibits a good black color, but the results are inferior to those of the inks of Examples in terms of ozone resistance and light resistance, and dyes (II) and (III), and It is obvious that even when three types of dyes including one other type of dye are blended, the good fastness seen with the ink of the present invention cannot be obtained when the dye (I) is not contained. became.
From the above results, the fastness of the printed image obtained by the ink of the present invention is extremely excellent in ozone gas resistance and light resistance particularly required for the inkjet printed image, and good black color without changing at high density or low density. Or it turns out that a gray color is exhibited.

The ink composition of the present invention is suitably used as a black ink liquid for ink jet printing and writing instruments.

Claims (14)

The dye (I) is one or more water-soluble dyes represented by the following formula (1) or a salt thereof,
The dye (II) is one or more water-soluble black dyes or salts thereof having absorption in water in the whole wavelength region of 380 to 720 nm and having a maximum absorption wavelength in the range of 560 to 590 nm,
Dye (III) is one or more water-soluble black dyes or salts thereof having absorption in the entire wavelength region of 380 to 720 nm in water and having a maximum absorption wavelength in the range of 590 to 630 nm,
A black ink composition comprising any of the dyes (I), (II) and (III) as a pigment component,

(In the formula (1),
Group A is a substituted phenyl group,
Y ₁ represents a methyl group, a carboxy group, a carboxymethyl group, an ethoxycarbonyl group or a phenyl group,
Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a carboxy group, a hydroxy group, an unsubstituted C1-C4 alkyl group, or an unsubstituted C1-C4 alkoxy group. ). The black ink composition according to claim 1, wherein the dye (II) is one or more water-soluble black dyes represented by the following formula (2) or a salt thereof:

(In the formula (2),
Group B is a substituted phenyl group, a carboxy group; a sulfo group; a hydroxy group; an acetylamino group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; a C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with a group selected from: having a substituent selected from the group consisting of:
R ₂₁ represents an unsubstituted or carboxy-substituted C1-C4 alkyl group, an unsubstituted or sulfo-substituted phenyl group, or a carboxy group;
R ₂₂ represents a cyano group, a carbamoyl group or a carboxy group,
R ₂₃ and R ₂₄ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group,
R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₂₁₀ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a sulfo group and a carboxy group. ). The black ink composition according to claim 1 or 2, wherein the dye (III) is one or more water-soluble black dyes represented by the following formula (3) or the following formula (6) or a salt thereof.

(In formula (3),
m is 0 or 1,
R ³¹ represents a carboxy group; a C1-C8 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a C1-C8 alkoxycarbonyl-substituted or carboxy-substituted C1-C4 alkyl group; an unsubstituted phenyl group; or a hydroxy group, a sulfo group, and a carboxy group Represents a phenyl group substituted with a group selected from the group consisting of:
R ³² to R ³⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted mono- or di-C1-C4 alkylamino group; a hydroxy group A mono- or di-C1-C4 alkylamino group substituted with a group selected from the group consisting of a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylcarbonylamino group; a hydroxy- or carboxy-substituted C1-C4 alkylcarbonylamino group; Unsubstituted N′-C1-C4 alkylureido group; a hydroxy group, N'-C1-C4 alkylureido group substituted with a group selected from the group consisting of sulfo group and carboxy group; unsubstituted phenylamino group; benzene ring is chlorine atom, C1-C4 alkyl group, nitro group, sulfo group And a phenylamino group substituted with a group selected from the group consisting of a carboxy group; an unsubstituted benzoylamino group; a benzene ring selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group and a carboxy group A substituted benzoylamino group; an unsubstituted phenylsulfonylamino group; or a benzene ring substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. Each represents a phenylsulfonylamino group;
The group C represents a substituted heterocyclic group represented by the following formula (4) or (5). )

(In formula (4),
R ³⁵ represents a mercapto group; an unsubstituted C1-C4 alkylthio group; or a C1-substituted by a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group. A C4 alkylthio group; )

(In Formula (5),
R ³⁶ to R ³⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; A C1-C4 alkoxy group substituted with a group selected from the group consisting of a group, a C1-C4 alkoxy group, a sulfo group and a carboxy group; an unsubstituted C1-C4 alkylsulfonyl group; a hydroxy group, a sulfo group and a carboxy group A C1-C4 alkylsulfonyl group substituted with a group selected from the group; an unsubstituted phenylsulfonyl group; or a benzene ring selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group. Each represents a phenylsulfonyl group substituted with a group
Group D is an unsubstituted or substituted phenyl group or naphthyl group,
When group D is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; an unsubstituted C1-C4 alkyl group; an unsubstituted C1-C4 alkoxy group; an amino group; an unsubstituted mono- or diC1-C4 alkylamino group; An amino group; an unsubstituted benzoylamino group; a benzoylamino group in which the benzene ring is substituted with a group selected from the group consisting of a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, and a carboxy group; Having a substituent
When group D is a substituted naphthyl group; a sulfo group; an unsubstituted C1-C4 alkoxy group; an unsubstituted phenylsulfonyloxy group; a phenylsulfonyloxy group in which the benzene ring is substituted with a methyl group, a nitro group or a chlorine atom; Having a substituent selected from the group consisting of: )

(In Formula (6),
R ₆₁ and R ₆₂ are each independently a hydrogen atom; halogen atom; cyano group; carboxy group; sulfo group; sulfamoyl group; N-alkylaminosulfonyl group; N-phenylaminosulfonyl group; unsubstituted or hydroxy-substituted C1-C4 Sulfonyl group; acyl group; ureido group; unsubstituted C1-C4 alkyl group; hydroxy or C1-C4 alkoxy substituted C1-C4 alkyl group C1-C4; unsubstituted C1-C4 alkoxy group; hydroxy group C1-C4 alkoxy group substituted with a group selected from the group consisting of C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group, sulfo group and carboxy group; acylamino group; alkylsulfonylamino group; unsubstituted phenylsulfonylamino A group; or phenyl is a halogen atom, Represents; phenyl sulfonylamino group substituted with a group selected from the group consisting of Le and nitro
R ₆₃ , R ₆₄ , R ₆₅ , R ₆₆ , R ₆₇ and R ₆₈ each independently represent a hydrogen atom; a halogen atom; a hydroxy group; a cyano group; a carboxy group; a sulfo group; a sulfamoyl group; an N-alkylaminosulfonyl group. N-phenylaminosulfonyl group; unsubstituted or hydroxy substituted C1-C4 alkylsulfonyl group; phosphono group; nitro group; acyl group; ureido group; unsubstituted C1-C4 alkyl group; hydroxy or C1-C4 alkoxy substituted C1-C4 An alkyl group; an unsubstituted C1-C4 alkoxy group; a C1-C4 alkoxy group substituted with a group selected from the group consisting of a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group, and a carboxy group; An acylamino group; an alkylsulfonylamino group; an unsubstituted phenylsulfonylamino group; Or a phenylsulfonylamino group in which phenyl is substituted with a group selected from the group consisting of a halogen atom, an alkyl group and a nitro group;
n represents 0 or 1, respectively. ). The black ink composition according to any one of claims 1 to 3, wherein the dye (I) represented by the formula (1) is at least one water-soluble dye represented by the following formula (7) or a salt thereof.

(In formula (7),
R ₇₁ represents a hydrogen atom, a C1-C3 alkyl group or a carboxy group,
R ₇₂ represents a hydrogen atom or a sulfo group,
Y ₁ to Y ₄ are the same as described in claim 1. ). In the total mass of the dyes (I), (II) and (III) contained in the ink composition as the pigment component, the ratio of the dye (I) is 5 to 30% by mass, and the ratio of the dye (II) is 20 to 80 The black ink composition according to any one of claims 1 to 4, wherein the ratio of the mass% and the dye (III) is 15 to 60 mass%. The total mass of the dyes (I), (II) and (III) contained in the ink composition as a pigment component is 2 to 8 mass% with respect to the total mass of the ink composition. The black ink composition according to claim 1. In the total mass of the dyes (I), (II) and (III) contained in the ink composition as a pigment component, the content of inorganic impurities in the total mass of the dyes (I), (II) and (III) is It is 1 mass% or less, The black ink composition as described in any one of Claims 1 thru | or 6. The black ink composition according to claim 1, wherein the black ink composition is used for ink jet recording. An inkjet recording method for recording on a recording material by ejecting ink droplets according to a recording signal, wherein the black ink composition according to any one of claims 1 to 8 is used as an ink. Recording method. The inkjet recording method according to claim 9, wherein the recording material is an information transmission sheet. The ink jet recording method according to claim 10, wherein the information transmission sheet has an ink image-receiving layer containing plain paper or a porous white inorganic substance. The colored body colored with the black ink composition of any one of Claims 1 thru | or 8. The colored body according to claim 12, wherein the coloring is performed by an ink jet printer. The inkjet printer with which the container containing the black ink composition as described in any one of Claims 1 thru | or 8 was filled.