JPWO2008096697A1 - Trisazo compound, ink composition, printing method and colored body - Google Patents

Abstract

In the form of the free acid, the present invention is represented by the following formula (1) (wherein the group A is a substituted phenyl group or a substituted naphthyl group, R1 is a (C1-C4) alkyl group optionally substituted with a carboxy group, R2 Is a cyano group, R3 and R4 are each independently a hydrogen atom, a sulfo group, etc., and R5 to R10 are each independently a hydrogen atom, a sulfo group, a (C1-C4) alkyl group, etc., and R5 to R7 are substituted. And a ring substituted with R8 to R10 each represents a 1,4-phenylene ring, etc.). The trisazo compound has high solubility in a medium containing water as a main component, and a high-concentration aqueous solution and an ink composition containing the trisazo compound are stable even when stored for a long period of time. The density of an image printed using the trisazo compound is It is very high and does not cause bronzing even when a high-concentration solution is printed, and the printed image is excellent in fastness, particularly light resistance and ozone gas resistance, and is therefore useful as a coloring compound for black ink.

Description

  The present invention relates to a novel trisazo compound or a salt thereof, an ink composition containing these, and a colored product thereby.

  A recording method using an ink jet printer, which is one of the representative methods among various color recording methods (hereinafter also referred to as a printing method), generates ink droplets, which are used for various recording materials (paper, film, fabric, etc.). ) To be recorded. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact, so there is little noise and quietness, and it is easy to reduce the size and speed. Expected. Conventionally, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks for fountain pens and felt-tip pens, and inks for inkjet printing. In these water-based inks, a water-soluble organic solvent is generally added to prevent clogging of the ink at the pen tip or the ink discharge nozzle. In these inks, a recording image having a sufficient density (hereinafter also referred to as a print image) is provided, the clogging of the pen tip and the nozzle is not generated, the drying property on the recording material is good, and bleeding is caused. There are demands for a small amount and excellent storage stability. The water-soluble dye used is required to have a particularly high solubility in water and a high solubility in the water-soluble organic solvent added to the ink. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

  Among these, ozone gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action that exists in the air acts on the dye in the recording paper and causes the printed image to discolor. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx and SOx. However, among these oxidizing gases, ozone gas is a main causative substance that further promotes the discoloration and fading phenomenon of inkjet print images. Many ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper use a material such as a porous white inorganic material in order to speed up drying of ink and reduce bleeding at high image quality. Discoloration due to ozone gas is noticeable on such recording paper. Since this discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, the improvement of ozone gas resistance is one of the most important issues in the ink jet printing method.

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

  Various hue inks are prepared from various dyes, of which black ink is an important ink used for both monocolor and full color images. Many pigments for these black inks have been proposed to date, but they have not yet been able to provide products that fully satisfy market demands. Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as low image optical density, poor water resistance and moisture resistance, and insufficient light resistance and gas resistance. In general, polyazo dyes having a conjugated system have problems such as low water solubility and a tendency to cause a bronzing phenomenon in which a recorded image has a partially metallic luster, and insufficient light resistance and gas resistance. Similarly, many of the azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which is undesirable for safety and environmental issues to living organisms, and extremely resistant to ozone gas. There are problems such as weakness.

  As compounds for black ink for ink jet (black pigment) improved with respect to ozone gas resistance, which has become the most important issue in recent years, for example, compounds described in Patent Documents 1 and 2 can be mentioned. These compounds are not sufficient in terms of light resistance because ozone gas resistance does not sufficiently satisfy market requirements. Further, azo compounds having a benzimidazolopyridone skeleton are described in Patent Documents 3 to 6 and the like. Patent Document 3 specifically discloses a monoazo compound. Patent Documents 4 and 5 disclose trisazo compounds, but these trisazo compounds have a symmetric structure having two benzimidazolopyridone skeletons at both ends of a linking group containing a trisazo structure. As an example of the trisazo compound for black ink for ink jet which has no ozone gas resistance and does not have a benzimidazolopyridone skeleton, the compound described in Patent Document 7 is also included.

JP 2003-183545 A JP 2003-201412 A WO2004 / 050768 International Publication Pamphlet German Patent No. 2000004488 German Patent No. 2023295 JP 05-134435 A International Publication Pamphlet of WO2005 / 054374

  The present invention has high solubility in a medium containing water as a main component, is stable even when a high-concentration aqueous solution and ink are stored for a long period of time, and has a very high density of printed images. Even when a high concentration solution is printed, the image does not cause bronzing, gives a black recorded image with excellent fastness, especially light resistance and ozone gas resistance, and is easy to synthesize. Disclosed is a black ink coloring matter (compound) having characteristics such as being inexpensive, an ink composition containing the same, particularly a black ink composition for ink jetting, an ink jet printing method using the ink composition, and a colored body using the coloring matter. For the purpose.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the trisazo compound represented by the following formula (1) solves the above-mentioned problems, and completed the present invention. It is a thing. That is, the present invention
(1) Trisazo compound represented by the following formula (1) or a salt thereof

Formula (1)

(In the formula, the group A is a substituted phenyl group or a substituted naphthyl group, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom). Chloro group; cyano group; nitro group; sulfamoyl group; (C1-C4) alkyl group; (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, sulfo group or carboxy group; (C1-C4) alkylsulfonyl group (which may be substituted with a hydroxy group, sulfo group or carboxy group); (C1-C4) alkylcarbonylamino group which may be substituted with carboxy group; benzoyl An amino group (the benzene ring may be substituted with a sulfo group or a (C1-C4) alkyl group); and Benzenesulfonylamino group (benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom); has at least one substituent selected from the group consisting of,
R ¹ represents a (C1-C4) alkyl group which may be substituted with a carboxy group; a phenyl group which may be substituted with a sulfo group; or a carboxy group,
R ² represents a cyano group; a carbamoyl group; or a carboxy group,
R ³ and R ⁴ each independently represent a hydrogen atom; a methyl group; a chlorine atom; or a sulfo group,
R ⁵ to R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a (C1-C4) alkyl group; or a (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group; Which may be substituted with a sulfo group or a carboxy group)
The ring in which R ⁵ to R ⁷ are substituted and the ring in which R ⁸ to R ¹⁰ are substituted (a benzene ring having a dotted condensed ring) each independently represent a benzene ring or a naphthalene ring, and the group A is a substituted phenyl When the group is a group, at least one of the ring substituted with R ⁵ to R ⁷ and the ring substituted with R ⁸ to R ¹⁰ is a naphthalene ring, and when the group A is a substituted naphthyl group, ^The ring substituted with ⁵ to R ⁷ and the ring substituted with R ⁸ to R ¹⁰ may be either a benzene ring or a naphthalene ring.
For each)
(2) The trisazo compound or a salt thereof according to the above (1), which is represented by the following formula (2) and the group A is a substituted naphthyl group,

Formula (2)

(Wherein the group A has the same meaning as when the group A is a substituted naphthyl group in the formula (1), and R ¹ to R ¹⁰ have the same meaning as the formula (1)),
(3) The trisazo compound or a salt thereof according to the above (1) represented by the following formula (3)

Formula (3)

(Wherein R ¹ to R ¹⁰ have the same meaning as in formula (1),
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group and a chlorine atom); a chlorine atom; A cyano group; a nitro group; a sulfamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group); (C1-C4) alkylsulfonyl group (which may be substituted with a hydroxy group, sulfo group or carboxy group); (C1-C4) alkylcarbonylamino group which may be substituted with carboxy group; benzoylamino group (benzene The ring may be substituted with a sulfo group or a (C1-C4) alkyl group); or It represents sulfonylamino group (a benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom),
And at least one of R ¹¹ to R ¹³ represents a group other than a hydrogen atom),
(4) The trisazo compound or a salt thereof according to the above (1) represented by the following formula (4)

Formula (4)

(Wherein R ¹ to R ¹⁰ have the same meaning as in formula (1),
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group and a chlorine atom); a chlorine atom; A cyano group; a nitro group; a sulfamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group); (C1-C4) alkylsulfonyl group (which may be substituted with a hydroxy group, sulfo group or carboxy group); (C1-C4) alkylcarbonylamino group which may be substituted with carboxy group; benzoylamino group (benzene The ring may be substituted with a sulfo group or a (C1-C4) alkyl group); or It represents sulfonylamino group (a benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom),
And at least one of R ¹¹ to R ¹³ represents a group other than a hydrogen atom),
(5) The group A is a naphthyl group substituted with at least one sulfo group,
Any one of R ⁵ to R ⁷ is a sulfo (C1-C4) alkoxy group,
Any one of R ⁸ to R ¹⁰ is a sulfo (C1-C4) alkoxy group,
The trisazo compound or a salt thereof according to (2) above,
(6) any one of R ⁵ to R ⁷ is a sulfo (C1-C4) alkoxy group,
Any one of R ⁹ and R ¹⁰ is a sulfo group,
At least one of R ¹¹ to R ¹³ is a sulfo group,
The trisazo compound or a salt thereof according to (3) above,
(7) The trisazo compound or a salt thereof according to the above (1) represented by the following formula (5)

Formula (5)

(Wherein R ⁵ and R ⁸ each represent a sulfo (C1-C4) alkoxy group,
R ⁷ and R ¹⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group,
R ⁶ and R ⁹ represent a hydrogen atom,
R ¹⁴ to R ¹⁷ are each independently a hydrogen atom; a sulfo group; a nitro group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group, and a chlorine atom); ) Represents an alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group or a carboxy group); or a (C1-C4) alkylcarbonylamino group which may be substituted with a carboxy group. ,
And at least one of R ¹⁴ to R ¹⁷ represents a sulfo group),
(8) R ⁵ is a sulfopropoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrogen atom, and one of R ⁹ and R ¹⁰ is a sulfo group and the other is a hydrogen atom A trisazo compound or a salt thereof according to the above (3),
(9) R ⁵ is a hydrogen atom, one of R ⁶ and R ⁷ is a sulfo group, the other is a hydrogen atom or a methyl group, R ⁸ is a sulfopropoxy group or a sulfo group, R ⁹ is a hydrogen atom, and R ¹⁰ is a hydrogen atom or The trisazo compound or a salt thereof according to (4), which is a methyl group,
(10) ^{R 5} and ^{R 8} sulfopropoxy group, ^{R 7} and ^{R 10} are each independently a hydrogen atom or a methyl ^group, the ^{R 14} described in (7) at least is any two sulfo groups ^{R 17} A trisazo compound or a salt thereof,
(11) The trisazo compound or a salt thereof according to the above (1) to (10), wherein R ¹ is a methyl group, R ² is a cyano group or carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group,
(12) the group A is a mono, di or trisulfonaphthyl group, or a group selected from the group consisting of nitro, methoxy, 3-sulfopropoxy, hydroxy, 3-carboxypropionylamino and 4-toluenesulfonyloxy and disulfo A substituted naphthyl group, R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ and R ⁸ are a sulfopropoxy group or a sulfobutoxy group, R ⁶ and R A trisazo compound or a salt thereof according to (2), wherein ⁹ is a hydrogen atom, and R ⁷ and R ¹⁰ are methyl groups;
(13) R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁷ is a methyl group, and two of R ¹¹ to R ¹³ are sulfo groups and the remaining 1 The trisazo compound or a salt thereof according to the above (8), wherein one is a hydrogen atom or an acetylamino group,
(14) R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, one of R ⁶ and R ⁷ is a sulfo group, the other is a hydrogen atom, and R ¹¹ to R ¹³ Of the trisazo compound or a salt thereof according to the above (9), wherein one or two of them are a sulfo group and the remainder is a hydrogen atom,
(15) R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ and R ⁸ are sulfopropoxy groups, R ⁷ and R ¹⁰ are methyl groups, and R ¹⁴ 1 to 3 of R ¹⁷ to R ¹⁷ are sulfo groups and the rest are hydrogen atoms, or two of R ¹⁴ to R ¹⁷ are sulfo groups, one is a hydrogen atom, the other is nitro, 3-sulfopropoxy, 4- The trisazo compound or a salt thereof according to (7) above, which is a group selected from the group consisting of toluenesulfonyloxy and 3-carboxypropionylamino;
(16) R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfopropoxy group, R ⁷ is a methyl group, R ⁸ is a sulfopropoxy group, and R ¹⁰ is A trisazo compound or a salt thereof according to the above (7), wherein three of R ¹⁴ to R ¹⁷ are a sulfo group and the remaining one is a hydrogen atom,
(17) An ink composition comprising at least one trisazo compound or a salt thereof according to any one of (1) to (16) above,
(18) An ink jet printing method comprising attaching an ink composition containing at least one trisazo compound or a salt thereof according to (1) above to a recording material by ink jetting,
(19) The inkjet printing method according to (18), wherein the recording material in the inkjet printing method is an information transmission sheet,
(20) The ink jet printing method according to (19), wherein the information transmission sheet contains a porous white inorganic substance,
(21) An inkjet printer loaded with a container containing an ink composition containing at least one trisazo compound or a salt thereof according to any one of (1) to (16) above,
(22) A colored body colored with the trisazo compound according to any one of (1) to (16) above,
About.

  When the trisazo compound of the present invention is used alone for coloring or the like, an excellent black colored product can be obtained, so that the compound is useful as a black pigment. When the trisazo compound of the present invention is used as a black colorant, the black colorant is excellent in water solubility, so that the filterability by a membrane filter in the ink composition production process is good, and the stability during storage of the recording liquid Excellent discharge stability. Further, the ink composition of the present invention containing this trisazo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition containing the trisazo compound of the present invention is suitably used for inkjet printing and writing utensils, and when recorded on plain paper and inkjet dedicated paper, the print density of the recorded image is very high and high. Even when a concentrated solution is printed, bronzing does not occur in the image, and various fastness properties, particularly light resistance and ozone gas resistance are excellent. By using it together with an ink composition using magenta, cyan and yellow dyes, full-color ink jet printing having excellent fastness and storage stability is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet printing.

Hereinafter, the present invention will be described in detail.
In the description of the substituents and the like in the present specification, those that have no particular notice that they may have a substituent usually mean unsubstituted.
In this specification, the superscript RTM indicates a registered trademark.
Further, in the present specification, the trisazo compound of the present invention or a salt thereof is simply referred to as “trisazo compound” or “black dye”.
The trisazo compound represented by the formula (1) has a tautomer, and as the tautomer, the following formulas (6) and (7) can be considered in addition to the compound of the formula (1). These compounds are also included in the present invention.

Formula (6)

(Wherein the groups A and R ^{1 to} R ¹⁰ have the same meaning as in formula (1)).
In addition, the benzene ring which has a broken-line condensed ring in said Formula (6) of this specification, said Formula (1), etc. shall represent a benzene ring or a naphthalene ring.

Formula (7)

(Wherein the groups A and R ^{1 to} R ¹⁰ have the same meaning as in formula (1)).

  In the present invention, examples of the (C1 to C4) alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Of these alkyl groups, a linear alkyl group is preferred.

In the present invention, examples of the (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group or a carboxy group) include, for example, methoxy, ethoxy, n-propoxy, Isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, Methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, 3-sulfopropoxy, 4-sulfobutoxy And the like.
In the present invention, the (C1-C4) alkoxy group is preferably a sulfo (C1-C4) alkoxy group, more preferably 3-sulfopropoxy or 4-sulfobutoxy.

In the present invention, examples of the (C1 to C4) alkylsulfonyl group (which may be substituted with a hydroxy group, a sulfo group or a carboxy group) include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, hydroxyethylsulfonyl 2-hydroxypropylsulfonyl, 2-sulfoethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl and the like.
In the present invention, examples of the (C1-C4) alkylcarbonylamino group optionally substituted with a carboxy group include, for example, acetylamino, propionylamino, butyrylamino, isobutyrylamino, 3-carboxypropionylamino, 4-carboxy. And butyrylamino.

In the present invention, examples of the benzoylamino group (the benzene ring may be substituted with a sulfo group or a (C1-C4) alkyl group) include, for example, benzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino, 4-ethylbenzoylamino, 4-propylbenzoylamino, 2-sulfobenzoylamino and the like can be mentioned.
In the present invention, examples of the benzenesulfonylamino group (wherein the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom) include, for example, benzenesulfonylamino, 4-toluenesulfonylamino, 4-nitrobenzenesulfonylamino, 4-chlorobenzene sulfonylamino etc. are mentioned.
In the present invention, examples of the benzenesulfonyloxy group (wherein the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom) include, for example, benzenesulfonyloxy, 4-toluenesulfonyloxy, 4-nitrobenzenesulfonyloxy, 4-chlorobenzene sulfonyloxy etc. are mentioned.

Specific examples of the preferred substituent of the group A in the formula (1) include cyano, carboxy, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, hydroxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 4- And toluenesulfonyloxy, 4-toluenesulfonylamino, and more preferably, carboxy, sulfo, sulfamoyl, methylsulfonyl, hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, - sulfo propoxy. In some cases, methoxy, hydroxy, acetylamino, 3-carboxypropionylamino and 4-toluenesulfonyloxy may be added to more preferable substituents. More preferred are carboxyl and sulfo, and most preferred is sulfo.
The group A has 1 to 4, preferably 1 to 3, more preferably 2 or 3 of these substituents, with 3 being most preferred in some cases.

  Preferred group A in formula (1) includes substituted phenyl or substituted naphthyl having 1 to 3 substituents as described above, and more preferred is a phenyl group or naphthyl group having at least one sulfo as a substituent. Can be mentioned. The group A having at least one sulfo includes mono or disulfophenyl; phenyl having (C1-C4) alkylcarbonylamino (preferably acetylamino) and disulfo as substituents; mono, di or trisulfonaphthyl; or As substituents, hydroxy, (C1-C4) alkoxy (preferably methoxy), nitro, sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), 4-toluenesulfonyloxy and carboxy (C1-C4) alkylcarbonyl One group selected from the group consisting of amino (preferably 3-carboxypropionylamino) {preferably (C1-C4) alkoxy (preferably methoxy) and carboxy (C1-C4) alkylcarbonylamino (preferably 3-carboxy Professional Naphthyl having one group} and disulfo selected from the group consisting of Oniruamino). Among these, more preferred groups A include disulfophenyl, di or trisulfonaphthyl. The substituted naphthyl in these groups A is preferably bonded to the azo group at the 1-position or 2-position of the naphthyl, more preferably at the 2-position.

In R ¹ of the present invention, examples of the (C1-C4) alkyl group which may be substituted with a carboxy group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -Butyl, carboxymethyl, 2-carboxyethyl and the like.
Examples of the phenyl group which may be substituted with a sulfo group in R ¹ of the present invention include, for example, phenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, and 3,5-disulfo. And phenyl.
Preferred R ¹ in the present invention is unsubstituted linear (C1-C4) alkyl, t-butyl, carboxymethyl, phenyl, 4-sulfophenyl, carboxy, and more preferably unsubstituted linear (C1-C3). Alkyl, carboxymethyl and 4-sulfophenyl. More preferred is unsubstituted linear (C1-C3) alkyl, and most preferred is methyl.

A preferred combination of R ¹ and R ² in the present invention is a combination in which R ¹ is unsubstituted linear (C1-C3) alkyl, more preferably methyl, and R ² is cyano or carbamoyl, more preferably cyano. Especially preferred is a combination wherein R ¹ is methyl and R ² is cyano.
Preferable R ³ and R ⁴ in the present invention are each independently a hydrogen atom, methyl, or sulfo. A preferable combination of R ³ and R ⁴ is a case where one is a hydrogen atom and the other is sulfo, and for example, R ³ is a hydrogen atom and R ⁴ is sulfo.
In the preferred combination of R ^{1 to} R ⁴ in the present invention, R ¹ is unsubstituted linear (C1-C3) alkyl, more preferably methyl, R ² is cyano or carbamoyl, more preferably cyano, and R ³ Is a hydrogen atom and R ⁴ is sulfo.

In the present invention, preferred R ^{5 to} R ¹⁰ are each independently a hydrogen atom, carboxy, sulfo, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, Carboxymethoxy, 2-carboxyethoxy and the like, more preferably a hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy or carboxymethoxy, Preferred is a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy or 4-sulfobutoxy.

In the present invention, R ⁵ to R ⁷ and R ⁸ to R ¹⁰ are preferably at least one of R ⁵ to R ⁷ (preferably one or two, more preferably two) and R ^8. To at least one of R ¹⁰ (preferably one or two, more preferably two) represents the above group other than a hydrogen atom. Examples of the group other than a hydrogen atom include a carboxy group; a sulfo group; a hydroxy group; a (C1-C4) alkyl group; or a (C1-C4) alkoxy group (a hydroxy group as a substituent, a (C1-C4) alkoxy group, And a preferred group is a sulfo (C1-C4) alkoxy group (preferably a sulfo (C2-C4) alkoxy group, more preferably sulfopropoxy), (C1-C4) alkyl group (preferably methyl) or sulfo can be mentioned. In each group of R ⁵ to R ⁷ and R ⁸ to R ¹⁰ , if the two groups are groups other than hydrogen, the two groups in each group may be the same or different. A preferable group in the same case is a sulfo group, and it is preferable that a ring substituted by the group is a naphthyl ring. When the ring to be substituted in the group is a benzene ring, it is usually preferable that two groups other than hydrogen in the group are different, and in each group, one is a sulfo (C1-C4) alkoxy group (preferably a sulfo (preferably C2-C4) alkoxy group, more preferably sulfopropoxy), and the other is more preferably (C1-C4) alkyl group (preferably methyl).

Preferred groups of the phenylene group having R ⁵ to R ⁷ and a broken-line condensed ring have a sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl group (preferably methyl) as substituents. Examples include 1,4-phenylene, or sulfo 1,4-phenylene, sulfo 1,4-naphthylene or 1,4-naphthylene having sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and sulfo as a substituent. I can do it. Among these, more preferred groups are 1,4-phenylene or sulfo 1,4 having sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl groups (preferably methyl) as substituents. -Naphthylene, more preferred groups are 1,4-phenylene with sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl groups (preferably methyl) as substituents, most preferred Is 1,4-phenylene with sulfopropoxy and methyl as substituents.
Preferable groups of the phenylene group having R ⁸ to R ¹⁰ and a broken-line condensed ring have a sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl group (preferably methyl) as substituents. Mention may be made of 1,4-phenylene or sulfo 1,4-naphthylene. Of these, 1,4-phenylene having sulfopropoxy and methyl as substituents is more preferred.

  In the above, in the case of 1,4-phenylene having two substituents, the substitution positions are preferably substituted such that both are in the para position (for example, the 3rd and 6th positions when the left side of the phenylene group is the 1st position). ). In addition, when the phenylene group having a broken-line condensed ring is 1,4-naphthylene, the preferred substitution position in the case of one substituent is the 6th or 7th position, and in the case of two, the 6th and 8th positions.

A preferred combination of the above R ⁵ to R ⁷ and a phenylene group having a broken line condensed ring and a R ⁸ to R ¹⁰ and a phenylene group having a broken line condensed ring is any one of the above preferred phenylene groups or a more preferred phenylene group Is combined with the other phenylene group, and preferably one preferable phenylene group or a more preferable phenylene group is combined with the other preferable phenylene group or a more preferable phenylene group. As an example of a more preferable combination, the former (R ⁵ to R ⁷ and a phenylene group having a dotted condensed ring) is substituted with a sulfo (C 1 -C 4) alkoxy (preferably sulfopropoxy) and (C 1 -C 4) alkyl group. 1,4-phenylene having (preferably methyl), sulfo 1,4-phenylene or sulfo 1,4-naphthylene {among others, more preferably sulfo (C1-C4) alkoxy (preferably sulfopropoxy) 1,4 -Phenylene}, the latter (phenylene group having R ⁸ to R ¹⁰ and a broken-line condensed ring) as a substituent, sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl group (preferably Is methyl) -containing 1,4-phenylene or sulfo 1,4-naphthylene. Most preferred is the case of 1,4-phenylene, both having sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl groups (preferably methyl) as substituents.

As one of the preferable compounds of the above formula (1), there can be mentioned compounds having 4 to 7, more preferably 4 to 6 sulfo groups in the molecule of the formula (1), and compounds having 5 or more. Is most preferable from the viewpoint of water solubility. Further, the compound having the preferred group A is one of the preferred ones, and the compound having 4 to 7 sulfo groups in the molecule of the formula (1), more preferably 4 to 6 is more preferred. Compounds having ˜6 are more preferred. In the formula (1), a compound having a preferable combination of R ^{1 to} R ⁴ is also one of the preferable compounds, and the compound has 4 to 7 sulfo groups in the molecule of the formula (1), and more preferably. A compound having 4 to 6 is more preferred.
Further, as one of the more preferred compounds of the formula (1), a compound having the preferred group A and the preferred combination of R ^{1 to} R ⁴ can be exemplified. In this case, the molecule of the formula (1) A compound having 4 to 7, more preferably 4 to 6, more preferably 5 to 6 sulfo groups therein is more preferable.
In each of the preferred compounds of formula (1) above, in the preferred case of R ⁵ to R ⁷ and R ⁸ to R ¹⁰ (or the phenylene group having R ⁵ to R ⁷ and a broken-line condensed ring, and R ⁸ preferred combinations, or most preferred combination) combination of a compound of phenylene group having R ¹⁰ and the broken line fused ring is more preferred.

Specific preferred combinations include: group A is mono or disulfophenyl; phenyl having (C1-C4) alkylcarbonylamino (preferably acetylamino) and disulfo as substituents; mono, di or trisulfonaphthyl; or substitution As groups, hydroxy, (C1-C4) alkoxy (preferably methoxy), nitro, sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), 4-toluenesulfonyloxy and (C1-C4) alkylcarbonylamino ( Preferably one group selected from the group consisting of 3-carboxypropionylamino) (preferably (C1-C4) alkoxy (preferably methoxy) and carboxy (C1-C4) alkylcarbonylamino (preferably 3-carboxypropionylamino) Naphthyl having one group} and disulfo selected from the group consisting of a bond position to the azo group of naphthyl group 1 or 2 (more preferably 2), having R ⁷ and dashed fused from R ⁵ 1,4-phenylene, sulfo 1,4-phenylene or sulfo 1 in which the phenylene group has sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl groups (preferably methyl) as substituents , 4-naphthylene {more preferably sulfo (C1-C4) alkoxy (preferably sulfopropoxy) 1,4-phenylene}, and R ⁸ to R ¹⁰ and a phenylene group having a condensed ring with a broken line are substituted. Sulfo (C1-C4) alkoxy (preferably sulfopropoxy) and (C1-C4) alkyl groups (preferably as groups) 1,4-phenylene, or sulfo 1,4-naphthylene with methyl), ^{R 1} is methyl, ^{R 2} is cyano or carbamoyl, more preferably cyano, one is a hydrogen atom ^{R 3} and ^{R 4,} the other A combination that is sulfo.
Of the compounds represented by formula (1), one of the preferred compounds is a compound represented by the following formula (2).

Formula (2)

In the formula, the group A represents the same meaning as the substituted naphthyl group in the formula (1), and R ¹ to R ¹⁰ have the same meaning as the formula (1).
Examples of the substituent of the group A in the formula (2) include those exemplified as the substituent of the group A in the formula (1). Preferred substituents of the group A in the formula (2) include those of the formula (1). ), Those mentioned as preferred substituents for the group A.
For example, preferred substituents include sulfo, hydroxy, (C1-C4) alkoxy (preferably methoxy), nitro, sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), 4-toluenesulfonyloxy and carboxy (C1 To C4) at least one group selected from the group consisting of alkylcarbonylamino (preferably 3-carboxypropionylamino).
Preferable group A (substituted naphthyl) in formula (2) includes 1-naphthyl or 2-naphthyl having 1 to 3 substituents, and 2-naphthyl is more preferable. A naphthyl group having at least one sulfo as the substituent is more preferable. What is preferable as the naphthyl group is one having 1 to 3 (preferably 2 to 3) sulfo groups as substituents. When one or two sulfo groups are present, another substituent is further added. Examples of the substituent which may be present may include a group selected from those exemplified as preferred substituents on the naphthyl group other than sulfo. More preferably, it is a naphthyl group having 2 to 3 sulfo groups as a substituent, and when there are two sulfo groups, a substituent other than sulfo selected from those listed as preferred substituents on the naphthyl group ( Preferably, it may have one group selected from the group consisting of hydroxy, (C1-C4) alkoxy and carboxy (C1-C4) alkylcarbonylamino. Among these, a more preferred naphthyl group is a disulfonaphthyl group or trisulfonaphthyl, and trisulfonaphthyl is most preferred.

Specific examples of preferred group A (substituted naphthyl) include mono-, di- or trisulfonaphthyl groups or a group consisting of nitro, methoxy, 3-sulfopropoxy, hydroxy, 3-carboxypropionylamino and 4-toluenesulfonyloxy. One selected group and a naphthyl group substituted with disulfo.
In Formula (2), R ^{1 to} R ⁴ represent the same meaning as in Formula (1), and preferred groups, preferred combinations of groups, and the like are the same as in Formula (1).

In the formula (2), R ^{5 to} R ¹⁰ represent the same meaning as the formula (1), and preferred groups in each of the preferred groups of R ^{5 to} R ¹⁰ , R ^{5 to} R ⁷ and R ^{8 to} R ^10. The preferred combination of both groups is the same as in the case of the above formula (1).
In the formula (2), preferably, at least one of R ^{5 to} R ⁷ is sulfo (C1-C4) alkoxy. A preferred combination of R ⁵ to R ⁷ in formula (2) is such that R ⁵ is sulfo (C1-C4) alkoxy, more preferably 3-sulfopropoxy or 4-sulfobutoxy, more preferably 3-sulfopropoxy; R ⁶ is Hydrogen atom; a combination in which R ⁷ is a hydrogen atom, methyl or ethyl, more preferably a hydrogen atom or methyl, and even more preferably methyl. Incidentally, the substitution position of ^{R 5} in formula (2) is para to ^{R 7} are preferred.
In Formula (2), Preferably, at least any one of R < ⁸ > -R < ¹⁰ > is sulfo (C1-C4) alkoxy. The combination of ^{R 10} from the preferred ^{R 8} in the formula (2) is, ^{R 8} is sulfo (C1 -C4) alkoxy, more preferably 3-sulfopropoxy or 4 sulfobutoxy, more preferably 3-sulfopropoxy; is ^{R 9} Hydrogen atom; a combination in which R ¹⁰ is a hydrogen atom, methyl or ethyl, more preferably a hydrogen atom or methyl, and even more preferably methyl. Incidentally, the substitution position of ^{R 8} in the formula (2) ^are those which are para to ^{R 10} are more preferred.
A preferable combination of R ⁵ to R ^{10 is} a combination composed of the above-mentioned preferable combination of R ⁵ to R ⁷ and the above-mentioned preferable combination of R ⁸ to R ¹⁰ .

One preferred compound of the above formula (2) is a compound having 4 to 6, more preferably 5 or 6 sulfo groups in the molecule of the formula (2). Moreover, the compound which has the said preferable group A is also one of the preferable things, The compound in which this compound has 4-6 sulfo groups in the molecule | numerator of Formula (2), More preferably, 5 or 6 is more preferable. In addition, in the above formula (2), a compound having a preferable combination of R ^{1 to} R ⁴ is one of the preferable compounds, and the compound having 4 to 6 sulfo groups in the molecule of the formula (2) is More preferred.
As another preferred compound, a compound having the preferred group A and a preferred combination of R ^{1 to} R ⁴ can be mentioned. In this case as well, a sulfo group is present in the molecule of the formula (2). Compounds having 4-6, more preferably 5 or 6, are more preferred.
In each of the above preferred compounds, the compound having the above preferred combination of R ⁵ to R ⁷ or / and the above preferred combination of R ⁸ to R ¹⁰ is more preferred, and has the above preferred combination of R ⁵ to R ¹⁰ Compounds are particularly preferred.
As an example of a more preferable combination in the compound of the formula (2), the group A has at least one sulfo (preferably at least two) as a substituent, hydroxy as a substituent other than sulfo, (C1- 1-naphthyl or 2 which may have one group selected from the group consisting of C4) alkoxy and carboxy (C1-C4) alkylcarbonylamino, and which has 1 to 3 substituents including the sulfo A preferred substitution position of R ⁸ with -naphthyl (preferably 2-naphthyl), R ⁸ is sulfo (C1-C4) alkoxy; R ⁹ is a hydrogen atom; R ¹⁰ is (C1-C4) alkyl (preferably methyl) ^is para to ^{R 10, R 5} is sulfo (C1 -C4) alkoxy, (preferably 3-sulfopropoxy); ^{R 6} is a hydrogen atom; is ^{R 7} (C1 -C4) In alkyl (preferably methyl), preferably the substitution position of ^{R 5} is para to ^{R 7, R 1} is (C1 -C4) alkyl (preferably methyl), ^{R 2} is cyano, ^{R 3} and ^{R 4}
Can include compounds in which one is a hydrogen atom and the other is sulfo.

  Of the compounds represented by the formula (1), one of the preferred compounds other than the formula (2) is a compound represented by the following formula (3).

Formula (3)

In the formula, each symbol represents the same meaning as the formula (3). That is, R ^{5 to} R ¹⁰ represent the same meaning as in the formula (1), and preferred groups of R ^{5 to} R ¹⁰ are the same as those in the formula (1).
In the formula (3), preferably, at least one of R ^{5 to} R ⁷ is sulfo (C1-C4) alkoxy. A preferred combination of ^{R 5} from ^{R 7} in the formula (3) is, ^{R 5} is sulfo (C1 -C4) alkoxy, more preferably 3-sulfopropoxy or 4 sulfobutoxy, more preferably 3-sulfopropoxy; is ^{R 6} A hydrogen atom; a combination in which R ⁷ is a hydrogen atom or methyl, more preferably methyl. Incidentally, the substitution position of R ⁵ in the formula (3) are those which are para to R ⁷ are more preferred.
In the formula (3), preferably, R ⁸ is a hydrogen atom, and any one of R ⁹ and R ¹⁰ is sulfo. In Formula (3), a combination in which R ⁸ is a hydrogen atom, one of R ⁹ and R ¹⁰ is sulfo, and the other is a hydrogen atom is more preferable.
A preferable combination of R ⁵ to R ^{10 is} a combination composed of the above-mentioned preferable combination of R ⁵ to R ⁷ and the above-mentioned preferable combination of R ⁸ to R ¹⁰ .

In the formula (3), at least one of R ^{11 to} R ¹³ represents a group other than a hydrogen atom. Preferably, at least one of R ^{11 to} R ¹³ is sulfo (more preferably two are sulfo), and the remainder is a hydrogen atom or / and the groups listed as R ^{11 to} R ¹³ in the formula (3) ( Excluding hydrogen atoms). Among the groups (excluding a hydrogen atom) mentioned as R ^{11 to} R ¹³ in the formula (3), (C1 to C4) alkylcarbonylamino (preferably acetylamino) is preferable. Specific examples of preferable R ^{11 to} R ¹³ in the formula (3) include the same groups as the specific examples of the hydrogen atom and the substituent of the preferable group A in the formula (1). More preferable groups of R ^{11 to} R ¹³ include a hydrogen atom, sulfo, and (C 1 -C 4) alkylcarbonylamino (preferably acetylamino).
A preferred combination of the substitution position of R ^{11 to} R ^{13 and} the substituent is, when the substitution position of the azo group is the 1st position, two of R ^{11 to} R ¹³ are sulfo at the 2nd position and the 4th position, The other one is a hydrogen atom, or two of R ^{11 to} R ¹³ are sulfos at the 2-position and 5-position, and the other is a (C1-C4) alkylcarbonylamino (preferably at the 4-position) Acetylamino). In some cases, it is also preferred that one of R ^{11 to} R ¹³ is sulfo at the 2 or 4 position and the remaining two are hydrogen.

As one of the preferable compounds of the above formula (3), there can be mentioned compounds having 4 to 6, preferably 5 to 6 sulfo groups in the molecule of the formula (3), and preferred R ^{11 is} this. compounds that combine to R ¹³ are more preferred. In addition, in the above formula (3), a compound having a combination of preferable R ^{11 to} R ¹³ and preferable R ^{1 to} R ⁴ is also a preferable compound, and the compound is a sulfo group in the molecule of the formula (3). A compound having 4 to 6, preferably 5 to 6, is more preferable.
In each of the above preferred compounds, the compound having the above preferred combination of R ⁵ to R ⁷ or / and the above preferred combination of R ⁸ to R ¹⁰ is more preferred, and has the above preferred combination of R ⁵ to R ¹⁰ Compounds are particularly preferred.
Specifically, when a preferable combination is given, the phenyl group having R ^{11 to} R ¹³ is 2,4-disulfophenyl, or 4- (C1-C4) alkylcarbonylamino (preferably acetylamino) -2,5. -Disulfophenyl, the naphthylene group having R ^{8 to} R ¹⁰ is monosulfo-1,4-naphthylene, more preferably 6-sulfo-1,4-naphthylene, 1,4 having R ⁵ to R ⁷ -Phenylene is 3- {sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy)}-6-methyl-1,4-phenylene, R ¹ is methyl, R ² is cyano, R ³ and R ⁴ Is a compound in which either one is sulfo and the other is a hydrogen atom.

  Among the compounds represented by the formula (1), one of the other preferable compounds other than the formula (2) and the formula (3) is a compound represented by the following formula (4).

Formula (4)

Each symbol in the formula represents the same meaning as in the above (4).
In the formula (4), R ^{1 to} R ⁴ represent the same meaning as in the formula (1), and a preferable group and a preferable group combination are the same as those in the formula (1). Further, in the equation ^(4), R 5 ^{to R 10} is as defined in the formula ^(1), the same as if also preferred group R 5 ^{to R 10} of said formula (1).
A preferred combination of R ^{5 to} R ⁷ in formula (4) is as follows: R ⁵ is a hydrogen atom, one of R ⁶ and R ⁷ is sulfo, and the other is a hydrogen atom or methyl, more preferably a hydrogen atom. It is a certain combination. As the 1,4-naphthylene group having R ^{5 to} R ⁷ in the formula (4), 6-sulfo-1,4-naphthylene is preferable.
Preferred combinations of R ⁸ to R ¹⁰ in formula (4) are as follows: R ⁸ is sulfo or sulfo (C1-C4) alkoxy, more preferably sulfo or 3-sulfopropoxy; R ⁹ is a hydrogen atom; R ¹⁰ is a hydrogen atom, A combination that is methyl or ethyl, more preferably a hydrogen atom or methyl. Incidentally, the substitution position of ^{R 8} in the formula (4) ^are those which are para to ^{R 10} are more preferred.
A preferable combination of R ⁵ to R ^{10 is} a combination composed of the above-mentioned preferable combination of R ⁵ to R ⁷ and the above-mentioned preferable combination of R ⁸ to R ¹⁰ .

Preferable R ^{11 to} R ^{13 in the} above formula (4) can include the same groups and the same combinations as those mentioned in the above formula (3).
As one of the preferable compounds of the formula (4), there can be mentioned compounds having 4 to 6, preferably 5 to 6 sulfo groups in the molecule of the formula (4), and preferred R ^{11 is} this. to R ^13, and / or preferred compounds combined for ^R 1 to R ⁴ are more preferable.
In each of the above preferred compounds, the compound having the above preferred combination of R ⁵ to R ⁷ or / and the above preferred combination of R ⁸ to R ¹⁰ is more preferred, and has the above preferred combination of R ⁵ to R ¹⁰ Compounds are particularly preferred.

Specifically, when a preferable combination is mentioned, the phenyl group having R ^{11 to} R ¹³ is a sulfophenyl group (preferably the substitution position of sulfo is 4-position), 2,4-disulfophenyl, or 5-sulfo (C1 -C4) alkylcarbonylamino (preferably acetylamino) ^{-2,5-sulfophenyl,} naphthylene group monosulfonated 1,4-naphthylene with R 5 to R ^7, more preferably 6-sulfo -1, 4-naphthylene and 1,4-phenylene having R ⁸ to R ¹⁰ are 3- {sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy)}-6-methyl-1,4-phenylene or 3 - sulfo-1,4-phenylene, methyl ^{R 1, R 2} is cyano, one of ^{R 3} and ^{R 4} are sulfo, and the other is hydrogen atom compound It is.

  Among the compounds represented by the formula (2), one of the more preferable compounds is a compound represented by the following formula (5).

Formula (5)

In the formula (5), R ^{1 to} R ⁴ , R ^{5 to} R ⁷ and R ^{8 to} R ¹⁰ represent the same meaning as in the formula (2), and preferred groups, preferred combinations of groups, and the like are also represented by the formula (2). Same as the case.

Specific examples of preferable R ¹⁴ to R ¹⁷ in the formula (5) include a hydrogen atom, carboxy, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, nitro, methyl, methoxy, ethyl, ethoxy 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, hydroxy, acetylamino, 3-carboxypropionylamino, benzoylamino, 2-sulfobenzoylamino, 4 -Toluenesulfonyloxy and 4-toluenesulfonylamino are mentioned. In some cases, as preferred R ¹⁴ to R ¹⁷ in formula (5), each independently represents a hydrogen atom; a sulfo group; a nitro group; a hydroxy group; a benzene ring substituted with a methyl group, a nitro group, and a chlorine atom. A good benzenesulfonyloxy group; a hydroxy group, a (C1-C4) alkoxy group, a sulfo group or a carboxy group which may have a substituent (C1-C4) alkoxy group; or a carboxy group substituted Good (C1-C4) alkylcarbonylamino groups are mentioned. More preferable R ¹⁴ to R ¹⁷ include a hydrogen atom, sulfo, 4-toluenesulfonyloxy, nitro, 3-carboxypropionylamino and 3-sulfopropoxy, and more preferably a hydrogen atom, sulfo and 3-sulfopropoxy. Is mentioned. A compound in which at least one of R ¹⁴ to R ¹⁷ in formula (5) is sulfo (preferably at least two are sulfo) is more preferable.
As specific preferred combinations of R ¹⁴ to R ^17, a combination in which 1 to 3 (preferably 2 to 3) groups of R ¹⁴ to R ¹⁷ are sulfo, and the rest are hydrogen atoms, or R ¹⁴ To R ¹⁷ are one of 4-toluenesulfonyloxy, sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), nitro and carboxy (C1-C4) alkylcarbonylamino (preferably 3-carboxypropionylamino). A combination selected from the group consisting of: two being sulfo, and the other being a hydrogen atom. Among these, a compound having a combination in which two or three of R ¹⁴ to R ¹⁷ are sulfo and the rest is a hydrogen atom is more preferable, and a combination in which three of R ¹⁴ to R ¹⁷ are sulfo and the remaining is a hydrogen atom. Particularly preferred.
Examples of 2-naphthyl having R ¹⁴ to R ¹⁷ in formula (5) include 2-naphthyl groups having the combination of R ¹⁴ to R ¹⁷ described above, and specific more preferable 2-naphthyl includes disulfo-2. Mention may be made of -naphthyl or trisulfo-2-naphthyl. When there are two sulfo groups, the substitution positions of sulfo are preferably 1-position and 5-position, 4-position and 8-position, 6-position and 8-position, and 5-position and 7-position. When the sulfo has three substitution positions, one is at the 3rd or 4th position, and the other two are at the 6th and 8th positions, more preferably at the 4th, 6th and 8th positions. In some cases, tri-substituted-2-naphthyl having another substituent together with disulfo is also preferable, and the other substituent is 4-toluenesulfonyloxy, sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), nitro and carboxy (C1-C4) alkylcarbonylamino (preferably 3-carboxypropionylamino), and the position of the substituent in this case is the above three sulfo substitution It is the same as in the above case, and it is preferable that another substituent other than sulfo is at the 6-position or 8-position.
Also in the formula ^(5), Specific preferred examples of the naphthalene ring from ^{R 14} have the ^{R 17} below. When “2- (azo)” is described, it means that the bonding position of the azo group bonded to the naphthalene ring is the 2-position of the naphthalene ring, and other substituents have the same meaning. Preferred examples are 2- (azo) -6-sulfonaphthalene, 2- (azo) -4,8-disulfo-naphthalene, 2- (azo) -1,5-disulfonaphthalene, 2- (azo)- 6,8-disulfonaphthalene, 2- (azo) -5,7-disulfonaphthalene, 2- (azo) -1,7-disulfo-5-toluenesulfonyloxy-naphthalene, 2- (azo) -4, 6,8-trisulfo-naphthalene, 2- (azo) -3,6,8-trisulfo-naphthalene, 2- (azo) -3,6-disulfo-8- (3-sulfopropoxy) -naphthalene, 2- ( Azo) -4,8-disulfo-6-nitro-naphthalene, 2- (azo) -4,8-disulfo-6- (3-carboxypropionylamino) -naphthalene.

One preferred compound of the above formula (5) is a compound having 4 to 6 sulfo groups in the molecule of the formula (5). Moreover, (i) the compound which has the said specific preferable combination of R < ¹⁴ > -R < ¹⁷ >, and has 4-6 sulfo groups in the molecule | numerator of Formula (5) is more preferable. (Ii) In the above formula (5), a compound having a preferable combination of R ^{1 to} R ⁴ and 4 to 6 sulfo groups in the molecule of the formula (5) is more preferable.
Moreover, (iii) As one of the other preferable compounds, a compound having the preferable combination of R ^{14 to} R ¹⁷ and a preferable combination of R ^{1 to} R ⁴ can be exemplified. The compound having 4 to 6 sulfo groups in the molecule is more preferable.
In each of the above preferred compounds (i) to (iii), a compound having the preferred combination of R ⁵ to R ⁷ or a preferred combination of R ⁸ to R ¹⁰ is more preferred, and the preferred R ⁵ to Compounds having a combination of R ¹⁰ are particularly preferred.
Specifically, when a preferred combination is mentioned, 2-naphthyl having R ¹⁴ to R ¹⁷ is disulfo-2-naphthyl, trisulfo-2-naphthyl, or two sulfo groups and 4-toluenesulfonyloxy as a substituent. , A tri-substituted having one group selected from the group consisting of sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy), nitro and carboxy (C1-C4) alkylcarbonylamino (preferably 3-carboxypropionylamino) In the case of 2-naphthyl, the combination of R ¹ to R ¹⁰ may be the same as that described in the formula (2), specifically, R ⁸ is a sulfo (C1-C4) alkoxy. (Preferably 3-sulfopropoxy); R ⁹ is a hydrogen atom; R ¹⁰ is (C1-C4) alkyl (preferably Is methyl), preferably the substitution position of R ⁸ is para to R ¹⁰ ; R ⁵ is sulfo (C1-C4) alkoxy (preferably 3-sulfopropoxy); R ⁶ is a hydrogen atom; R ⁷ is (C1 -C4) alkyl (preferably methyl), preferably the substitution position of ^{R 5,} para to ^{R 7, R 1} is (C1 -C4) alkyl (preferably methyl), ^{R 2} is cyano, R ³ and R ⁴ may be a compound in which one is a hydrogen atom and the other is sulfo, and more preferable compounds include a combination of R ¹ to R ¹⁰ , R ⁸ is 3-sulfopropoxy; and R ⁹ is hydrogen. Atom: R ¹⁰ is methyl and R ⁸ is substituted at the para position relative to R ¹⁰ ; R ⁵ is 3-sulfopropoxy; R ⁶ is a hydrogen atom; R ⁷ is methyl, and R ⁵ is substituted at para position with respect to R ^7, R Methyl, R ² is cyano, R ³ and R ⁴ can be cited one of the other is sulfo hydrogen atom compounds.

  The salt of the trisazo compound represented by the formulas (1) to (5) is a salt of the compound and an inorganic or organic cation. Among them, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts and ammonium salts. Preferred inorganic salts are lithium salts, sodium salts, potassium salts and ammonium salts, and organic cations. Examples of the salt include, but are not limited to, a salt with an organic cation represented by the following formula (8). Moreover, the mixture of said various salt may be sufficient. Furthermore, these salts or a mixture of salts may contain a free acid and / or a tautomer thereof or a salt of the tautomer thereof. 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 is selected as appropriate, or when multiple salts are included, the physical properties suitable for the purpose can be changed by changing the ratio. It is also possible to obtain a mixture having. Usually, alkali metal salts such as sodium salt and lithium salt are preferred.

Formula (8)

In the formula, 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. Since equation (8) is the organic cation, any one of Z ¹ to Z ⁴ is a group other than a hydrogen atom.
Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (8) 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 such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, and 2-hydroxybutyl. Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2- Hydroxyeth Shibuchiru such hydroxy (C1 -C4) alkoxy - (C1 -C4) alkyl group. Among these hydroxyethoxy - (C1 -C4) alkyl is preferred. As particularly preferred Z ^{1 to} Z ⁴ , a hydrogen atom; methyl; a hydroxy- (C 1 -C 4) alkyl group (eg, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl) And hydroxyethoxy- (C1-C4) alkyl groups (hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3) -Hydroxyethoxybutyl, 2-hydroxyethoxybutyl, etc.).

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 which} are preferable compounds as the formula (8) are shown in Table 1.

  The black pigment represented by the formula (1) can be synthesized, for example, by the following method. In addition, the structural formula of the compound in each process shall be represented with the form of a free acid.

Formula (9)

In the formula, the group A represents the same meaning as in the formula (1).
The compound represented by the above formula (9) is diazotized by a conventional method, and this and the compound represented by the following formula (10) are coupled by a conventional method to obtain a compound represented by the following formula (11).

Formula (10)

In the formula, R ⁸ to R ¹⁰ represent the same meaning as in the formula (1).

Formula (11)

(In the formula, groups A and R ⁸ to R ¹⁰ have the same meaning as in formula (1)).
The obtained compound of formula (11) is diazotized by a conventional method, and then this and a compound represented by the following formula (12) are coupled by a conventional method to obtain a compound represented by the following formula (13). .

Formula (12)

(Wherein R ⁵ to R ⁷ represent the same meaning as in formula (1)).

Formula (13)

In the formula, groups A and R ⁵ to R ¹⁰ represent the same meaning as in formula (1).
The compound represented by the above formula (1) is obtained by diazotizing the obtained compound of the formula (13) by a conventional method and then subjecting it to a compound represented by the following formula (14) by a conventional method. The trisazo compound of the invention can be obtained.

Formula (14)

(In the formula, R ¹ to R ⁴ have the same meaning as in the formula (1).)
In addition, the compound represented by the said Formula (14) is compoundable according to the method of patent document 4.

Although it does not specifically limit as a suitable specific example of the compound of this invention represented by Formula (1), The compound represented by the structural formula given to the following Table 2 to 5 etc. is mentioned.
In each table, functional groups such as sulfo groups and carboxy groups are described in the form of free acids for convenience.

  The diazotization of the compound of the above formula (9) is carried out by a method known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. Coupling of the diazotized compound of the compound of formula (9) with the compound of formula (10) 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 solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compound of formula (9) and the compound of formula (10) are used in approximately stoichiometric amounts.

  The diazotization of the compound of formula (11) is carried out in a manner known per se. For example, it is carried out in an inorganic acid medium using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of, for example, -5 to 40 ° C, preferably 5 to 30 ° C. The coupling of the diazotized compound of the compound of formula (11) and the compound of formula (12) 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 solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. As the base, the same ones as described above can be used. The compound of formula (11) and the compound of formula (12) are used in approximately stoichiometric amounts.

  The diazotization of the compound of formula (13) is also carried out by a method known per se. For example, it is carried out using a nitrite, for example an alkali metal nitrite such as sodium nitrite, in an inorganic acid medium, for example at a temperature of −5 to 40 ° C., preferably 10 to 30 ° C. Coupling of the diazotized compound of the compound of formula (13) and the compound of formula (14) 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 (13) and (14) are used in approximately stoichiometric amounts.

The desired salt of the trisazo compound represented by the formula (1) of the present invention can be obtained in the form of a solid or a solution as follows.
For example, after salting out by adding an inorganic salt or an organic cation salt capable of forming a desired salt to the reaction solution after the final coupling reaction, the desired salt of the trisazo compound is converted into a solid form. Can be obtained. After the desired salt precipitated by salting out is separated as a solid by means of filtration separation or the like, purification and separation may be performed by means of washing, recrystallization, filtration separation or the like, if necessary. Further, by adding a mineral acid such as hydrochloric acid to the reaction solution, acid precipitation is performed, and the trisazo compound is separated in the form of a free acid, and this is separated into water, acidic water and / or aqueous organic as necessary. The corresponding salt can be obtained in the form of a solution by removing the inorganic salt, for example by washing with a medium, and then neutralizing it with the desired inorganic or organic base in an aqueous medium. Here, acidic water refers to an aqueous solution 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 means an organic substance miscible with water or / and a mixed solution of water and an organic solvent miscible with water. Specific examples of the organic solvent miscible with water include water-soluble organic solvents described later. Even if it is an organic substance which is not normally classified as a solvent, it can be dissolved in water and used as an aqueous organic medium as long as it is 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, and ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include those described above. And halogenated salts of organic amines represented by (8).
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 organic amines such as amines used for the formation of organic ammonium ions represented by the above formula (8) such as diethanolamine and triethanolamine. It is not limited to.

  The aqueous composition and ink composition of the present invention will be described. The aqueous composition containing the trisazo compound represented by the formula (1) of the present invention 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 compound of the present invention can be dissolved in a liquid medium and used as an ink composition.

  The reaction solution containing the trisazo compound of the present invention represented by the above formula (1), for example, the reaction solution containing the target compound in Example 1 (4) described later, can be used directly in the production of the ink composition. However, usually, this is first dried, for example, spray-dried to separate the trisazo compound, or salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate to the reaction solution. Then, the trisazo compound is precipitated by acid precipitation by addition of a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or acid precipitation, which is a combination of the salting-out and acid precipitation described above, and then taken out by filtration and the like. It is preferable to prepare an ink composition using the extracted trisazo compound of the present invention.

  The ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the trisazo compound of the present invention, with the balance being water as the main medium. Composition. The ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 15% by mass, preferably 0 to 10% by mass, of an ink preparation agent. Moreover, you may contain another pigment | dye for the purpose of toning etc. if desired. 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.

As described above, the ink composition of the present invention comprises the trisazo compound of the present invention, if necessary, together with other pigments for toning and the like, water or / and a water-soluble organic solvent (an organic solvent miscible with water). ) And the like are mixed and dissolved as appropriate, and an ink preparation agent is added as necessary. For the purpose of adjusting the color of the neutral black ink composition having no color, other toning pigments and the like may be appropriately added to the black pigment of the present invention.
When this ink composition is used as an ink for an ink jet printer, the trisazo compound of the present invention to be used preferably has a low content of inorganic substances such as metal cation chlorides and sulfates. The standard of the inorganic content is about 1% by mass or less with respect to the total mass of the trisazo compound (dye) of the present invention to be used. In order to produce the trisazo compound of the present invention with a small amount of inorganic substances, for example, a usual method using a reverse osmosis membrane, or a dried product or wet cake of the trisazo compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water, What is necessary is just to desalinate by a method of separating the precipitate by filtration and drying.

  Specific examples of the water-soluble organic solvent used for preparing the ink composition include (C1-C4) alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol; N Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide; Lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone or N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine- Cyclic ureas such as 2-one or 1,3-dimethylhexahydropyrimido-2-one; aliphatic ketones or aliphatic ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one A cyclic ester such as tetrahydrofuran or dioxane; Ter; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol Mono-, oligo- or polyalkylene glycols or alkylene thioglycols having (C2 to C6) alkylene units such as dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol; glycerin or hexane-1, Polyols such as 2,6-triol (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Mono- or di (C1-C4) alkyl ethers of polyhydric alcohols such as nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; γ-butyrolactone Or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

  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 surfactants. These drugs are described below.

  Specific examples of antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and its salts, and the like. It is done. 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, haloallyl sulfone, 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 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); Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; and alkali metal salts of organic acids such as potassium acetate; in addition to the above, inorganic bases such as sodium silicate and disodium phosphate Can be mentioned.

  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, and 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, or nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, 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 Ester systems such as oxyethylene stearate; or 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl Le 4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3-ol Acetylene glycol (alcohol) based, such as (e.g., Nissin Chemical Industry Co., Ltd., trade name Surfynol ^RTM 104 , 105, 82, 465, Olfine ^RTM STG, etc.).
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. Moreover, in order to adjust the black color as an ink composition, in addition to the trisazo compound of the present invention, other pigments having various hues may be mixed. 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 aqueous writing ink, aqueous printing ink, information recording ink, and the like. It is particularly suitable as an inkjet ink (composition), and is suitably used in the inkjet printing method of the present invention described below.

Next, the ink jet printing method of the present invention will be described. The inkjet 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 the recording material by ejecting the ink composition of the present invention as droplets by ink jetting and adhering to the recording material. There is no restriction | limiting in particular about the ink nozzle etc. which are used for an inkjet, According to the objective and the system of an inkjet, it can select suitably.
As an inkjet method, a known method, for example, a charge control method that ejects ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element; An acoustic ink jet method that irradiates ink using a radiation pressure instead of a beam and ejects the ink by using the radiation pressure; adopts a thermal ink jet (bubble jet ^RTM ) method that forms bubbles by heating the ink and uses the generated pressure can do.
In the ink jet 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 with substantially 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 includes any one that is colored with the trisazo compound of the present invention. Usually, the colored product of the present invention can be obtained by coloring various articles with the aqueous composition of the present invention containing the same, particularly the ink composition of the present invention. More preferably, it can be obtained by coloring various articles such as a recording material using the ink composition of the present invention by an inkjet printing method using an inkjet printer.
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, a fiber, cloth (cellulose, nylon, wool, etc.), leather, a base material for color filters, etc. are mentioned.
Among these, 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 base material with a cationic polymer, or a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol, or special ceramics. It is provided by a method of 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 thereof are trade names, professional photo paper, super photo paper or matte photo paper (manufactured by Canon Inc.); photo paper (glossy), PM matte paper or Crispier ^RTM (manufactured by Seiko Epson Corporation). ); Advance photo paper, premium plus photo paper, premium gloss film or photo paper (Nippon Hewlett-Packard Co., Ltd.); Photolike ^RTM QP (Konica Co., Ltd.), etc., are commercially 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 perform recording on a recording material such as an information transmission sheet by the ink jet printing method of the present invention, droplets of the ink composition of the present invention may be attached to the recording material by ink jetting. For example, a container containing the ink composition may be set at a predetermined position of an ink jet printer, ink may be ejected by a normal method, and recording may be performed on a recording material.
In the inkjet printing method of the present invention, the black ink composition of the present invention is mixed with, for example, known magenta, cyan, yellow, and, if necessary, each color such as green, blue (or violet), and red (or orange). These ink compositions can also be used in combination.
The ink composition of each color is poured into each container, and each container is set at 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 the black ink composition of the present invention. At the same time, it is used for inkjet printing.

The black pigment of the present invention is excellent in water solubility, and the ink composition of the present invention containing this pigment does not cause crystal precipitation, change in physical properties, change in hue, etc. even when stored for a long period of time. Good stability.
In addition, the ink composition containing the coloring matter of the present invention is suitable for inkjet printing and writing instruments.
When the ink composition is used for printing on an information transmission sheet, particularly ink jet paper, the printed image has a high print density, and in addition, durability, particularly 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 example.
In the text, “parts” and “%” are based on mass unless otherwise specified.
In the following formulas, functional groups such as sulfo and carboxy are described in the form of free acids.
Further, the pH value and reaction temperature described below are measured values in the reaction system.
Further, the maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value was described in the examples for the measured compound.
The synthesized trisazo compounds of the present invention all showed a solubility of 100 g / L or more at room temperature (20 ° C. to 30 ° C.).

Example 1
(1)
A solution was obtained by suspending 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid in 50 parts of water and adding sodium hydroxide to pH 7.0 to 8.0 with stirring. A diazo suspension was obtained by adding 10.3 parts of 35% hydrochloric acid to the obtained solution and then 5.3 parts of a 40% aqueous sodium nitrite solution at 3 to 8 ° C.
On the other hand, an aqueous solution was obtained by adding 7.2 parts of a compound of the following formula (15) to 70 parts of water and then adding sodium hydroxide to adjust the pH to 5.0 to 5.5.
To the above diazo suspension, 0.1 part of sulfamic acid was added and stirred for about 5 minutes. It was dripped in 10 minutes.
After completion of dropping, sodium carbonate was added and the reaction solution was kept at pH 2.0 to 3.0 and stirred for 2 hours to obtain a reaction solution containing a monoazo compound of the following formula (16).
In addition, the compound of following formula (15) was obtained by the method of Unexamined-Japanese-Patent No. 2004-083492.

Formula (15)

Formula (16)

(2)
Under stirring, 5.0 parts of the compound of the above formula (15) and sodium hydroxide were added to 50 parts of water to obtain an aqueous solution having a pH of 5.0 to 5.5.
On the other hand, it was obtained in Example 1 (1) to a solution obtained by adding 5.3 parts of 40% aqueous sodium nitrite solution to a mixed liquid of 50 parts of water and 8.0 parts of 35% hydrochloric acid under stirring. The diazo liquid was obtained by dripping the reaction liquid containing the compound of the said Formula (16) in reaction temperature 15-25 degreeC for 15 minutes.
To the obtained diazo liquid, 0.4 part of sulfamic acid was added and stirred for about 5 minutes, and this liquid was added to the aqueous solution containing the compound of the above formula (15) obtained previously at a reaction temperature of 15 to 25 ° C. Added dropwise over 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 3.0 to 4.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, salted out by adding sodium chloride, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (17).

Formula (17)

(3)
2- (Cyanomethyl) benzimidazole and ethyl acetoacetate are reacted by heating in ethanol in the presence of sodium methoxide, and then acidified by adding dilute hydrochloric acid to the reaction solution to obtain a compound of the following formula (18). It was. 8.9 parts of the obtained compound was slowly added to 64 parts of 6% fuming sulfuric acid at 15 to 25 ° C. After the addition, the resulting liquid 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 and dried to obtain 10.7 parts of a compound of the following formula (19).

Formula (18)

Formula (19)

(4)
Under stirring, 4.2 parts of the compound of the above formula (19) obtained in Example 1 (3) and sodium hydroxide were added to 80 parts of water to obtain an aqueous solution having a pH of 8.0 to 9.0.
On the other hand, with stirring, the wet cake containing the compound of the formula (17) obtained in Example 1 (2) was dissolved in 140 parts of water. To this aqueous solution was added 4.6 parts of 35% hydrochloric acid, and then 2.8 parts of 40% aqueous sodium nitrite solution was added dropwise at a reaction temperature of 15 to 25 ° C. over about 5 minutes to obtain a diazo liquid.
The obtained diazo liquid was added dropwise to the previously obtained aqueous solution containing the compound of the above formula (19) at a reaction temperature of 15 to 30 ° C. for 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of the dropping, the mixture was stirred at the same temperature for 3 hours to obtain a reaction solution containing the target compound represented by the following formula (20). Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 180 parts of water, 120 parts of methanol was added for crystallization, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was again dissolved in 150 parts of water, 200 parts of methanol was added to crystallize, and the precipitated solid was separated by filtration and dried to obtain a compound of the following formula (20) (Table) Compound No. 3 in No. 2) 12.2 parts was obtained as a sodium salt.
λmax: 551.5 nm.

Formula (20)

Example 2
Example 1 (1) was the same as Example 1 except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid was changed to 9.1 parts of 7-aminonaphthalene-1,3-disulfonic acid. Then, 13.2 parts of the compound of the following formula (21) (No. 4 compound in Table 2) of the present invention was obtained as a sodium salt.
[lambda] max: 569.5 nm.

Formula (21)

Example 3
Example 1 (1) is the same as Example 1 except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid is changed to 9.1 parts of 6-aminonaphthalene-1,3-disulfonic acid. 13.0 parts of the trisazo compound (No. 5 compound in Table 2) of the following formula (22) of the present invention was obtained as a sodium salt.
λmax: 563.5 nm.

Formula (22)

Example 4
In Example 1 (1), Example 1 and Example 1 were used except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid was changed to 11.5 parts of 7-aminonaphthalene-1,3,5-trisulfonic acid. In the same manner, 12.1 parts of a trisazo compound (No. 7 compound in Table 3) of the following formula (23) of the present invention was obtained as a sodium salt.
λmax: 559 nm.

Formula (23)

Example 5
Example 1 (1) is the same as Example 1 except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid is changed to 11.5 parts of 7-aminonaphthalene-1,3,6-trisulfonic acid. In the same manner, 12.1 parts of a trisazo compound (No. 8 compound in Table 3) of the following formula (24) of the present invention was obtained as a sodium salt.
[lambda] max: 558.5 nm.

Formula (24)

Example 6
Example 1 (1) is the same as Example 1 except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid is changed to 9.1 parts of 5-aminonaphthalene-1,3-disulfonic acid. 12.6 parts of the trisazo compound of the following formula (25) of the present invention (No. 9 compound in Table 3) was obtained as a sodium salt.
λmax: 570 nm.

Formula (25)

Example 7
Example 1 (1) except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid is 10.4 parts of 3-amino-7-nitronaphthalene-1,5-disulfonic acid. In the same manner as above, a trisazo compound (No. 12 compound in Table 3) of the following formula (26) of the present invention was obtained as a sodium salt.
The obtained crystals were dissolved in 450 parts of water, salted out by adding lithium chloride, and the precipitated solid was separated by filtration. The obtained wet cake was dissolved in 300 parts of water, 250 parts of methanol was added for crystallization, and the precipitated solid was separated by filtration. The obtained wet cake is dissolved again in 250 parts of water, and 300 parts of methanol is added for crystallization, and the precipitated solid is separated by filtration and dried to obtain a trisazo of the following formula (26) of the present invention. The compound was obtained as a mixed salt of sodium and lithium.
λmax: 567.5 nm.

Formula (26)

Example 8
(1)
In Example 1 (1), except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid was changed to 14.2 parts of 4-amino-5-toluenesulfonyloxynaphthalene-2,7-disulfonic acid In the same manner as in Examples 1 (1) and (2), a wet cake containing a disazo compound of the following formula (27) was obtained.
The 4-amino-5-toluenesulfonyloxynaphthalene-2,7-disulfonic acid is an alkaline aqueous solution of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid and 4-toluenesulfonyl chloride. It can obtain by reaction of.

Formula (27)

(2)
The wet cake containing the compound of the above formula (27) obtained in Example 8 (1) was dissolved in 150 parts of water with stirring, heated to 70 ° C., and then added with sodium hydroxide with stirring to pH 10.5-11. The mixture was stirred at 70 ° C. for 1.5 hours while maintaining 0.0. After cooling to room temperature, 35% hydrochloric acid was added to adjust the pH to 1.0 to 4.0, and sodium chloride was further added for acid precipitation. The precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (28).

Formula (28)

(3)
In Example 1 (4), the same procedure as in Example 1 (4) was conducted except that the wet cake containing the disazo compound of the formula (17) was replaced with the wet cake containing the disazo compound of the formula (28). 12.0 parts of the trisazo compound (No. 13 compound in Table 4) of the following formula (29) of the invention was obtained as a sodium salt.
[lambda] max: 577 nm.

Formula (29)

Example 9
(1)
Under stirring, 6.5 parts of 8-aminonaphthalene-2-sulfonic acid and sodium hydroxide were added to 100 parts of water to obtain an aqueous solution having a pH of 7.5 to 8.5.
On the other hand, under stirring, 7.6 parts of 4-aminobenzene-1,3-disulfonic acid and then 3.1 parts of 35% hydrochloric acid were added to 50 parts of water, and further 40% at a reaction temperature of 0 to 10 ° C. A diazo suspension was obtained by adding 5.3 parts of an aqueous sodium nitrite solution.
To this diazo suspension, 0.2 part of sulfamic acid was added and stirred for about 5 minutes, and then the aqueous solution containing 8-aminonaphthalene-2-sulfonic acid obtained above was reacted at a reaction temperature of 5 to 15 ° C., about Added dropwise over 15 minutes. The reaction liquid containing the compound of following formula (30) was obtained by stirring for 2 hours after completion | finish of dripping.

Formula (30)

(2)
In Example 1 (2), except that the reaction solution containing the compound of the formula (16) is replaced with the reaction solution containing the compound of the formula (30), the following formula (31) of the present invention is used. ) (13.3 parts of the compound No. 19 in Table 5) was obtained as a sodium salt.
λmax: 560 nm.

Formula (31)

Example 10
(1)
Under stirring, 5.4 parts of 8-aminonaphthalene-2-sulfonic acid and sodium hydroxide were added to 80 parts of water to obtain an aqueous solution having a pH of 7.5 to 8.5.
On the other hand, a solution having a pH of 4.0 to 5.0 was obtained by adding 8.9 parts of a compound (CI Acid Yellow 9) of the following formula (32) and sodium hydroxide to 70 parts of water under stirring. To this solution, 7.8 parts of 35% hydrochloric acid was added, and then 4.7 parts of 40% aqueous sodium nitrite solution was added at a reaction temperature of 10 to 20 ° C. to obtain a diazo suspension.

Formula (32)

After adding 0.3 part of sulfamic acid to the diazo suspension obtained above and stirring for about 5 minutes, the aqueous solution containing 8-aminonaphthalene-2-sulfonic acid obtained above was reacted. The solution was added dropwise at a temperature of 15 to 25 ° C. for about 15 minutes.
After completion of the dropwise addition, the reaction solution was stirred for 2 hours while maintaining the pH value at 2.5 to 3.0 by adding sodium carbonate. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (33).

Formula (33)

(2)
In Example 1 (4), the same as in Example 1 (4) except that the wet cake containing the compound of formula (17) was replaced with the wet cake containing the compound of formula (33). 11.6 parts of the compound of the formula (34) (the compound of No. 21 in Table 5) was obtained as a sodium salt.
λmax: 558 nm.

Formula (34)

Example 11
(1)
To 270 parts of water, 21.2 parts of 4-benzoylamino-5-naphthol-2,7-disulfonic acid and sodium hydroxide were added to obtain an aqueous solution having a pH of 8.0 to 9.0. To this solution, 18.2 parts of dimethyl sulfate was added, and then sodium carbonate was added, and the mixture was stirred overnight at a reaction temperature of 20 to 25 ° C. while maintaining the pH of the reaction solution at 8.0 to 9.0. did. The precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (35).
The obtained wet cake was added to 500 parts of water, heated to 85 ° C., and stirred for 7 hours while maintaining the pH at 11.0-11.5 with sodium hydroxide. After cooling to room temperature, 35% hydrochloric acid is added to the reaction solution to adjust the pH to 1.0 to 2.0. Further, sodium chloride is added to conduct acid precipitation, and the precipitated solid is separated by filtration to obtain the following formula (36) A wet cake containing the compound was obtained.

Formula (35)

Formula (36)

(2)
In Example 1 (1), except that 9.1 parts of 2-aminonaphthalene-1,5-disulfonic acid is a wet cake containing the compound of the above formula (36), the same procedure as in Example 1 is followed. 13.9 parts of the compound of the following formula (37) (No. 14 compound in Table 4) was obtained as a sodium salt.
λmax: 554.5 nm.

Formula (37)

Example 12
(1)
17.4 parts of 3-amino-7-nitronaphthalene-1,5-disulfonic acid was suspended in 180 parts of water, and sodium hydroxide was added to adjust the pH value to 6.5 to 7.5. To this, 0.3 parts of anhydrous iron (III) chloride and 1.3 parts of activated carbon were added, and then the temperature was raised to 70 ° C. with stirring. To this suspension, 9.3 parts of 80% hydrazine hydrate was added dropwise over 10 minutes, the temperature was raised to 80 to 90 ° C., and the mixture was stirred at the same temperature for 4 hours. After cooling to room temperature, insoluble matters were filtered off, and the filtrate was adjusted to pH 1.0 or less with a 50% aqueous sulfuric acid solution. Sodium chloride was added to the obtained acidic filtrate, and the precipitated crystals were separated by filtration to obtain a wet cake containing a compound of the following formula (38).

Formula (38)

(2)
An aqueous solution having a pH of 6.5 to 7.5 was obtained by adding a wet cake containing the compound of the above formula (38) obtained in Example 12 (1) and sodium hydroxide to 180 parts of water. 4.0 parts of succinic anhydride was added thereto at a reaction temperature of 15 to 30 ° C. over about 10 minutes, followed by stirring for 1 hour. Sodium carbonate was added to the reaction solution to adjust the pH to 5.0 to 6.0, then 4.0 parts of succinic anhydride was added over about 10 minutes, and the mixture was further stirred for 2 hours to obtain a compound of the following formula (39) A solution containing was obtained.

Formula (39)

(3)
Under stirring, 7.8 parts of the compound of formula (15) described in Example 1 (1) and sodium hydroxide were added to 70 parts of water to obtain an aqueous solution having a pH of 5.0 to 5.5.
On the other hand, with stirring, the solution containing the compound of the above formula (39) obtained in Example 12 (2) was added to 13.3 parts of 35% hydrochloric acid, and then 6.3 parts of 40% aqueous sodium nitrite solution at 3 to 8 ° C. Was added to obtain a diazo suspension.
After adding 0.4 part of sulfamic acid to the obtained diazo suspension and stirring for about 5 minutes, the aqueous solution containing the compound of the formula (15) obtained above is about 10 at a reaction temperature of 10 to 15 ° C. Dropped in minutes.
After completion of the dropping, sodium carbonate was added and stirred for 2 hours while maintaining the pH value at 2.0 to 3.0. Sodium chloride was added to the obtained reaction solution for salting out, and the precipitated solid was separated by filtration to obtain a wet cake containing a compound of the following formula (40).

Formula (40)

(4)
An aqueous solution having a pH of 5.0 to 6.0 was obtained by adding a wet cake containing the monoazo compound of the above formula (40) and sodium carbonate to 180 parts of water. The obtained aqueous solution containing the above formula (40) was used in Example 1 (2) in the same manner as in Example 1 except that it was used instead of the reaction solution containing the compound of the above formula (16). 12.9 parts of trisazo compounds of formula (41) (No. 16 compound in Table 4) were obtained as sodium salts.
λmax: 564 nm.

Formula (41)

Examples 13-20
(A) Preparation of ink A black ink composition of the present invention was obtained by uniformly mixing the following components. The obtained ink composition was filtered to remove impurities with a 0.45 μm membrane filter to obtain an ink composition that could be used for inkjet. For convenience, the obtained ink composition is hereinafter referred to as “ink”.
Water used was ion exchange water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion exchange water was added to make a total amount of 100 parts.

Table 6

  In Table 6, the following various tests performed using the ink containing each compound obtained in Examples 2 to 7, 9, and 11 are referred to as Examples 13 to 20, respectively. The aqueous black ink of the present invention did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

Comparative Example 1
As a comparative black pigment, the pigment of the following formula (42) disclosed in Example 1-2 of Patent Document 7 is used in place of the compound obtained in the example of the present invention, as in Table 6. A comparative ink was prepared in the same manner as in the preparation of the ink (A). The following various tests conducted using this ink are referred to as Comparative Example 1.

Formula (42)

(B) Inkjet printing Glossy paper 1 (manufactured by Canon Inc., trade name: Professional Photo Paper PR-101) using the ink obtained above and using an inkjet printer manufactured by Canon Inc. (trade name: PIXUS ^RTM iP4100). , Glossy paper 2 (manufactured by Seiko Epson Corporation, trade name: photographic paper Krispia ^RTM (high gloss)), glossy paper 3 (manufactured by Hewlett-Packard Japan, trade name: advanced photo paper (gloss)) Inkjet printing was performed on an information transmission sheet (inkjet paper).
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 print image
Each print image obtained using the inks of Examples 13 to 20 and Comparative Example 1 was evaluated for density change of the image before and after the test for each of light resistance and ozone gas resistance.
The density change of the print image is measured using a colorimeter (trade name: SpectroEye ^RTM ) manufactured by GRETAG-MACBETH, and the color of the gradation portion where the reflection density D value of the print image before the test is closest to 1.0 is measured. Was measured.
The test was performed for each of glossy papers 1, 2, and 3, and the test results are shown in Table 7.
The specific test method is as follows.
1) Light resistance test Using the low-temperature xenon weatherometer (trade name: XL75) manufactured by Suga Test Instruments Co., Ltd., for each of the above print images under the conditions of illuminance of 100,000 Lux, humidity of 60% RH, and temperature of 24 ° C. After irradiating for 96 hours, the colorimetry was performed using the above colorimeter, and the residual ratio of the dye of each image was determined by (reflected density after test / reflected 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% 2) Ozone gas resistance test Ozone concentration is 12 ppm, humidity using an ozone weatherometer manufactured by Suga Test Instruments Co., Ltd. Each printed image was left for 8 hours under the conditions of 60% RH and temperature of 24 ° C. After completion of the test, color measurement was performed using the above colorimeter, and the residual ratio of the dye in each print image was determined by (reflected density after test / reflected density before test) × 100 (%). The test results were evaluated according to the following criteria.
○ Residual rate: 90% or more △ Residual rate: 80% or more and less than 90% × Residual rate: less than 80%

Table 7
Light resistance Ozone gas resistance
Comparative Example 1 (Formula (42))
Glossy paper 1 △ ×
Glossy paper 2 △ △
Glossy paper 3 △ △
Example 13 (Formula (21))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 14 (Formula (22))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 15 (Formula (23))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 16 (Formula (24))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 17 (Formula (25))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 18 (Formula (26))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 19 (Formula (31))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 20 (Formula (37))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○

As is clear from the results in Table 7, the printed images of Examples 13 to 20 and the image of Comparative Example 1 are each better when the results of the ozone gas test are compared for each glossy paper. This is a better result than Comparative Example 1. That is, in Comparative Example 1, when glossy paper 1 is used, the dye residual ratio is less than 80%, and when glossy papers 2 and 3 are used, the dye residual ratio is 80% or more and less than 90%. In Examples 13 to 20 of the present invention, when glossy paper 1 is used, the dye residual ratio is 80% or more and less than 90%, and when glossy papers 2 and 3 are used, the dye residual ratio is 90% or more. Indicated.
Similarly, a difference was observed in light resistance. In Examples 13 to 20, when any glossy paper was used, the dye residual ratio was 80% or more, but Comparative Example 1 was similarly 70% or more and less than 80%. In each of the above tests, Examples 13 to 20 showed significantly better results than Comparative Example 1.
From the above results, the fastness of the printed image obtained with the ink containing the trisazo compound of the present invention is extremely excellent as compared with the image of the conventional trisazo compound used in Comparative Example 1, and particularly for the inkjet printed image. It can be seen that the required ozone gas resistance and light resistance are excellent.

  The trisazo compound of the present invention is useful as a black pigment for coloring materials and products, and the ink composition containing the compound is suitably used as a black ink liquid for ink jet printing and writing instruments.

Claims (22)

Trisazo compound represented by the following formula (1) or a salt thereof

(In the formula, the group A is a substituted phenyl group or a substituted naphthyl group, and as a substituent, a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring is substituted by a methyl group, a nitro group, or a chlorine atom) Chloro group; nitro group; sulfamoyl group; (C1-C4) alkyl group; (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, sulfo group or carboxy group) (C1-C4) alkylsulfonyl group (may be substituted with a hydroxy group, a sulfo group or a carboxy group); (C1-C4) alkylcarbonyl optionally substituted with a carboxy group Amino group; benzoylamino group (the benzene ring is substituted with a sulfo group or a (C1-C4) alkyl group) Good); and, benzenesulfonylamino group (benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom); has at least one group selected from the group consisting of,
R ¹ represents a (C1-C4) alkyl group which may be substituted with a carboxy group; a phenyl group which may be substituted with a sulfo group; or a carboxy group,
R ² represents a cyano group; a carbamoyl group; or a carboxy group,
R ³ and R ⁴ each independently represent a hydrogen atom; a methyl group; a chlorine atom; or a sulfo group,
R ⁵ to R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a (C1-C4) alkyl group; or a (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group; Which may be substituted with a sulfo group or a carboxy group)
The ring in which R ⁵ to R ⁷ are substituted and the ring in which R ⁸ to R ¹⁰ are substituted each independently represent a benzene ring or a naphthalene ring, and when the group A is a substituted phenyl group, R ⁵ to R ^When at least one of the ring substituted by ⁷ and the ring substituted by R ⁸ to R ¹⁰ is a naphthalene ring and the group A is a substituted naphthyl group, R ⁵ to R ⁷ are substituted The ring and the ring substituted by R ⁸ to R ¹⁰ may be either a benzene ring or a naphthalene ring.
Represents each). The trisazo compound or a salt thereof according to claim 1, which is represented by the following formula (2) and wherein the group A is a substituted naphthyl group:

(Wherein the group A has the same meaning as in the case where the group A is a substituted naphthyl group in the formula (1);
R ¹ to R ¹⁰ have the same meaning as in formula (1)). The trisazo compound or a salt thereof according to claim 1, which is represented by the following formula (3):

(Wherein R ¹ to R ¹⁰ have the same meaning as in formula (1),
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group and a chlorine atom); a chlorine atom; A cyano group; a nitro group; a sulfamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group); (C1-C4) alkylsulfonyl group (which may be substituted with a hydroxy group, sulfo group or carboxy group); (C1-C4) alkylcarbonylamino group which may be substituted with carboxy group; benzoylamino group (benzene The ring may be substituted with a sulfo group or a (C1-C4) alkyl group); or It represents sulfonylamino group (a benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom),
And at least one of R ¹¹ to R ¹³ represents a group other than a hydrogen atom). The trisazo compound or a salt thereof according to claim 1, which is represented by the following formula (4):

(Wherein R ¹ to R ¹⁰ have the same meaning as in formula (1),
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group and a chlorine atom); a chlorine atom; A cyano group; a nitro group; a sulfamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group); (C1-C4) alkylsulfonyl group (which may be substituted with a hydroxy group, sulfo group or carboxy group); (C1-C4) alkylcarbonylamino group which may be substituted with carboxy group; benzoylamino group (benzene The ring may be substituted with a sulfo group or a (C1-C4) alkyl group); or It represents sulfonylamino group (a benzene ring is a methyl group, may be substituted by nitro group or a chlorine atom),
And at least one of R ¹¹ to R ¹³ represents a group other than a hydrogen atom). The group A is a naphthyl group substituted with at least one sulfo group,
Any one of R ⁵ to R ⁷ is a sulfo (C1-C4) alkoxy group,
Any one of R ⁸ to R ¹⁰ is a sulfo (C1-C4) alkoxy group,
The trisazo compound or a salt thereof according to claim 2. Any one of R ⁵ to R ⁷ is a sulfo (C1-C4) alkoxy group,
Any one of R ⁹ and R ¹⁰ is a sulfo group,
At least one of R ¹¹ to R ¹³ is a sulfo group,
The trisazo compound or a salt thereof according to claim 3. The trisazo compound or a salt thereof according to claim 1, which is represented by the following formula (5):

(Wherein R ⁵ and R ⁸ each represent a sulfo (C1-C4) alkoxy group,
R ⁷ and R ¹⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group,
R ⁶ and R ⁹ represent a hydrogen atom,
R ¹⁴ to R ¹⁷ are each independently a hydrogen atom; a sulfo group; a nitro group; a hydroxy group; a benzenesulfonyloxy group (the benzene ring may be substituted with a methyl group, a nitro group, and a chlorine atom); ) Represents an alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group or a carboxy group); or a (C1-C4) alkylcarbonylamino group which may be substituted with a carboxy group. ,
And at least one of R ¹⁴ to R ¹⁷ represents a sulfo group). R ⁵ is a sulfopropoxy group, R ⁶ is a hydrogen atom, R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrogen atom, and one of R ⁹ and R ¹⁰ is a sulfo group and the other is a hydrogen atom. 3. The trisazo compound or a salt thereof according to 3. R ⁵ is a hydrogen atom, one of R ⁶ and R ⁷ is a sulfo group, the other is a hydrogen atom or a methyl group, R ⁸ is a sulfopropoxy group or a sulfo group, R ⁹ is a hydrogen atom, and R ¹⁰ is a hydrogen atom or a methyl group The trisazo compound or a salt thereof according to claim 4. The trisazo compound according to claim 7, wherein R ⁵ and R ⁸ are sulfopropoxy groups, R ⁷ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and at least any two of R ¹⁴ to R ¹⁷ are sulfo groups. salt. The trisazo compound or a salt thereof according to claim 1, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group. Group A is a mono, di or trisulfonaphthyl group or a group selected from the group consisting of nitro, methoxy, 3-sulfopropoxy, hydroxy, 3-carboxypropionylamino and 4-toluenesulfonyloxy as substituents And disulfo-containing naphthyl group, R ¹ is methyl group, R ² is cyano group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ and R ⁸ are sulfopropoxy group or sulfobutoxy group, R ⁶ and The trisazo compound or a salt thereof according to claim 2, wherein R ⁹ is a hydrogen atom, and R ⁷ and R ¹⁰ are methyl groups. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁷ is a methyl group, and two of R ¹¹ to R ¹³ are sulfo groups and the remaining one is a hydrogen atom Or the trisazo compound or its salt of Claim 8 which is an acetylamino group. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, one of R ⁶ and R ⁷ is a sulfo group, the other is a hydrogen atom, and 1 of R ¹¹ to R ¹³ The trisazo compound or a salt thereof according to claim 9, wherein one or two of them are a sulfo group and the remainder is a hydrogen atom. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ and R ⁸ are sulfopropoxy groups, R ⁷ and R ¹⁰ are methyl groups, and R ¹⁴ to R ¹⁷ 1 to 3 of them are sulfo groups and the rest are hydrogen atoms, or two of R ¹⁴ to R ¹⁷ are sulfo groups, one is a hydrogen atom, the other is nitro, 3-sulfopropoxy, 4-toluenesulfonyloxy And a trisazo compound or a salt thereof according to claim 7, which is a group selected from the group consisting of: 3-carboxypropionylamino. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfopropoxy group, R ⁷ is a methyl group, R ⁸ is a sulfopropoxy group, R ¹⁰ is a methyl group, The trisazo compound or a salt thereof according to claim 7, wherein three of R ¹⁴ to R ¹⁷ are a sulfo group and the remaining one is a hydrogen atom. An ink composition comprising at least one trisazo compound or a salt thereof according to any one of claims 1 to 4, 7, and 16. An ink-jet printing method comprising attaching an ink composition containing at least one trisazo compound or a salt thereof according to claim 1 to a recording material by ink-jetting. The inkjet printing method according to claim 18, wherein the recording material in the inkjet printing method is an information transmission sheet. The ink jet printing method according to claim 19, wherein the information transmission sheet contains a porous white inorganic substance. An inkjet printer loaded with a container containing an ink composition containing at least one trisazo compound or a salt thereof according to claim 1. The colored body colored with the trisazo compound as described in any one of Claim 1 to 4, 7, and 16.