JP5152966B2 - Trisazo compound, ink composition, recording method and colored body - Google Patents

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 representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) to perform recording. Is. 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, felt-tip pens and the like and inks for ink jet 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. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. In addition, the water-soluble dye used is required to have a particularly high solubility in water and a high solubility in a 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. A characteristic of the black pigment of the present invention is a trisazo compound having a heterocyclic group and a pyrazolyl group at the same time. Although there exist patent documents 3-7 as a trisazo compound which has a pyrazolyl group, the structure similar to this invention is not disclosed. In addition, the trisazo compounds disclosed in Patent Documents 3 to 7 also do not sufficiently satisfy market requirements for ozone gas resistance and light resistance. Examples of the trisazo compound for inkjet black ink having excellent ozone gas resistance include compounds described in Patent Document 8.

JP 2003-183545 A JP 2003-201412 A JP-A-10-195320 US Patent Application 2001/0027734 JP 2002-265809 WO2007 / 017631 Special table 2007-517082 International Publication Pamphlet of WO2005 / 054374

An object of the present invention is to provide a trisazo compound or a salt thereof used for a black ink particularly suitable for inkjet printing, and an ink composition containing the compound. Hereinafter, the trisazo compound of the present invention or a salt thereof is simply referred to as “trisazo compound” or “black dye”. The black pigment 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 on, the image does not cause bronzing, gives a printed black image with excellent fastness, especially light resistance and ozone gas resistance, and is easy to synthesize. In addition, it has features such as being inexpensive.

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

(In the formula (1), n is 0 or 1,
R ¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C8 alkylcarbonyl group optionally substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; or a hydroxyl group, a sulfo group or a carboxy group. Represents a good phenyl group,
R ² to R ⁴ are each independently hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; C1-C4 alkyl group; hydroxy group, C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group A C1-C4 alkoxy group optionally substituted with a group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; substituted with a hydroxy group or a carboxy group A C1-C4 alkylcarbonylamino group which may be substituted; an N′-C1-C4 alkylureido group which may be substituted with a hydroxy group, a sulfo group or a carboxy group; a benzene ring as a chlorine atom, a C1-C4 alkyl group, a nitro group A phenyl group which may be substituted with a sulfo group or a carboxy group A benzene ring in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring in a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group Each represents a phenylsulfonylamino group optionally substituted by a group or a carboxy group;
Group A is a substituted heterocyclic group represented by the following formula (2) or (3),

(In formula (2), R ⁵ represents a mercapto group; or a C1-C4 alkylthio group which may be substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group.)

(In formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; chlorine atom; carboxy group; sulfo group; nitro group; hydroxy group; carbamoyl group; sulfamoyl group; C1-C4 alkyl group; hydroxy group, C1 A C1-C4 alkoxy group optionally substituted with a C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; or a benzene ring is a chlorine atom, Each represents a C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonyl group which may be substituted with a carboxy group.)
Group B is an optionally substituted phenyl or naphthyl group,
When group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; a C1-C4 alkoxy group; an amino group; a mono- or di-C1-C4 alkylamino group; an acetylamino group; A benzoylamino group which may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; having a substituent selected from the group consisting of:
When group B is a substituted naphthyl group; selected from the group consisting of a hydroxy group; a sulfo group; a C1-C4 alkoxy group; a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom; Has a substituent. ),
(2)
The trisazo compound or a salt thereof according to the above (1), wherein the group B is a phenyl group which may be substituted, and the substituent is a hydroxy group, a sulfo group or a carboxy group;
(3)
The trisazo compound or a salt thereof according to the above (1), wherein the group B is an optionally substituted naphthyl group, and the substituent is a hydroxy group or a sulfo group,
(4)
The above (1) to (3) wherein R ¹ is an unsubstituted C1-C4 alkyl group or carboxy group, R ² is a sulfo C1-C4 alkoxy group, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, a methyl group or an ethyl group. ) A trisazo compound or a salt thereof according to any one of
(5)
Any one of the above (1) to (4), wherein the group A is represented by the formula (2), R ¹ is a methyl group or a carboxy group, and R ⁵ is a sulfo C1-C4 alkylthio group or a carboxy C1-C4 alkylthio group. Or a salt thereof,
(6)
The group A is represented by the formula (3), R ¹ is a methyl group or a carboxy group, R ⁶ to R ⁸ are each independently a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, The trisazo compound or a salt thereof according to any one of (1) to (4), which is a C1-C4 alkoxy group or a C1-C4 alkylsulfonyl group.
(7)
n is 1, R ¹ is a carboxy group, R ² is a sulfopropoxy group, R ³ is a hydrogen atom, R ⁴ is a methyl group, R ⁶ to R ⁸ are each independently a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, The trisazo as described in (1) to (4) or (6) above, which is a nitro group, a methyl group, a methoxy group, or a methylsulfonyl group, and the group B is a phenyl group that may be substituted with a sulfo group or a carboxy group A compound or a salt thereof,
(8)
An ink composition comprising at least one trisazo compound or salt thereof according to any one of (1) to (7) as a coloring matter;
(9)
An ink jet printing method comprising recording by ink jet printing using the ink composition according to (8) above,
(10)
The inkjet printing method according to (9), wherein the recording material in the inkjet printing method is an information transmission sheet,
(11)
The inkjet printing method according to (10), wherein the information transmission sheet contains a porous white inorganic substance,
(12)
An inkjet printer loaded with a container containing the ink composition according to (8) above,
(13)
A colored body colored with the trisazo compound or a salt thereof according to any one of (1) to (7),
About.

Since the black pigment of the present invention is excellent in water solubility, the filterability by the membrane filter in the process of producing the ink composition is good, and the storage stability and ejection stability of the ink composition or the ink containing the ink composition are good. Also excellent in properties. That is, 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.
The trisazo compound represented by the formula (1) has a tautomer, and examples of the tautomer include the following formulas (4) to (6) in addition to the compound of the formula (1). These tautomers are also included in the present invention.

(In formula (4), group A, group B and R ^{1 to} R ⁴ have the same meaning as in formula (1).)

(In formula (5), group A, group B and R ^{1 to} R ⁴ have the same meaning as in formula (1).)

(In the formula (6), the group A, the group B and R ^{1 to} R ⁴ have the same meaning as in the formula (1).)

In the above formula (1), R ¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C8 alkoxycarbonyl group or a C1-C4 alkyl group optionally substituted with a carboxy group; or a hydroxy group, a sulfo group or a carboxy group Represents a phenyl group which may be substituted with a group.

When R ¹ in Formula (1) is a C1-C8 alkoxycarbonyl group, the alkoxycarbonyl group may be any of linear, branched and alkyl moieties having a cyclic structure, but linear and branched An alkoxycarbonyl group is preferred. Specific examples include straight chain such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl and the like; A branched chain such as isopropoxycarbonyl, isobutyloxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, 2,2-dimethylpropoxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, 2-methylbutyloxycarbonyl; Alkyl moieties such as methyloxycarbonyl, cyclobutylmethyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl have a cyclic structure. Shall; and the like.
A linear C1-C6 is more preferable, and a linear C1-C4 alkoxycarbonyl group is more preferable. Specific examples are the same as those described above.

When R ¹ in Formula (1) is a C1-C4 alkyl group which may be substituted with a C1-C8 alkoxycarbonyl group or a carboxy group, and the C1-C4 alkyl group is an unsubstituted C1-C4 alkyl group, The alkyl group may be linear or branched, but is preferably linear. Specific examples of the C1-C4 alkyl group include linear chains such as methyl, ethyl, n-propyl and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl and tert-butyl.
When the C1-C4 alkyl group has a substituent, the alkyl group may be the same as described above including preferable ones. When the substituent is a C1-C8 alkoxycarbonyl group, the alkoxycarbonyl group may be the same as the case where R ¹ is a C1-C8 alkoxycarbonyl group, including preferable ones.
When R ¹ is a C1-C4 alkyl group substituted with a C1-C8 alkoxycarbonyl group, preferred specific examples include methoxycarbonylmethyl, ethoxycarbonylethyl, n-butoxycarbonylmethyl, n-octyloxycarboxyethyl and the like. It is done.
When R ¹ is a C1-C4 alkyl group which may be substituted with a carboxy group, preferred specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and the like.

Specific examples when R ¹ in formula (1) is a phenyl group which may be substituted with a hydroxy group, a sulfo group or a carboxy group include, for example, unsubstituted phenyl; 2-hydroxyphenyl, 4-hydroxyphenyl, etc. Hydroxy-substituted phenyl of the above; sulfo-substituted phenyl such as 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl; 2-carboxyphenyl, 4-carboxyphenyl, 3,5- Carboxy-substituted phenyl such as dicarboxyphenyl; and phenyl substituted with a plurality of types of groups such as 2-hydroxy-5-sulfophenyl; and the like.

R ¹ in the above formula (1) is more preferably a carboxy group; a C1-C4 alkoxycarbonyl group; an unsubstituted C1-C4 alkyl group; a carboxy group-substituted C1-C4 alkyl group; or an unsubstituted phenyl group.
Specific examples of preferable R ¹ in the formula (1) include methyl, ethyl, tert-butyl, carboxymethyl, 3-carboxypropyl, methoxycarbonylmethyl, carboxy, methoxycarboxy, ethoxycarboxy, n-octyloxycarboxy, phenyl, 2-hydroxyphenyl and 4-sulfophenylmethyl, more preferably methyl, carboxymethyl, carboxy and phenyl, and still more preferably methyl and carboxy.

In the formula (1), R ² to R ⁴ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a C1-C4 alkyl group; A C1-C4 alkoxy group optionally substituted with a group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; C1-C4 alkylcarbonylamino group which may be substituted with a hydroxy group or a carboxy group; N′-C1-C4 alkylureido group which may be substituted with a hydroxy group, a sulfo group or a carboxy group; the benzene ring is a chlorine atom, C1 -Substituted with C4 alkyl group, nitro group, sulfo group or carboxy group A phenylamino group which may be substituted; a benzene ring in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring which is a chlorine atom, a C1-C4 alkyl group Each represents a phenylsulfonylamino group which may be substituted with a nitro group, a sulfo group or a carboxy group.

When R ^{2 to} R ⁴ in Formula (1) are an unsubstituted C1-C4 alkoxy group, the alkoxy group is preferably either a straight chain or a branched chain. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
When the alkoxy group is substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group, specific examples thereof include 2-hydroxyethoxy, 2-hydroxypropoxy, 3 Hydroxy C1-C4 alkoxy groups such as hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxy C1-C4 alkoxy C1-C4 alkoxy group such as butoxy; Hydroxy C1-C4 alkoxy C1-C4 alkoxy group such as 2-hydroxyethoxyethoxy; 3-sulfopropoxy, 4-sulfobutoxy Sulfo C1-C4 alkoxy group and the like; carboxymethoxy, 2-carboxyethoxy, carboxy C1-C4 alkoxy group such as a 3-carboxypropoxy; and the like.

When R ^{2 to} R ⁴ in Formula (1) are an unsubstituted mono- or di-C1-C4 alkylamino group, the C1-C4 alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include linear chains such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino; sec- Branched chain such as butylamino, tert-butylamino, diisopropylamino, and the like.
When the mono- or di-C1-C4 alkylamino group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, 2-hydroxyethylamino, 2-hydroxypropylamino, 2,2 ′ -Hydroxy-substituted mono or di-C1-C4 alkylamino group such as dihydroxydiethylamino; sulfo-substituted mono such as 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3,3'-disulfodipropylamino Or a di-C1-C4 alkylamino group; a carboxy-substituted mono- or di-C1-C4 alkylamino group such as carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2′-dicarboxydiethylamino; It is done.

When R ^{2 to} R ⁴ in Formula (1) are an unsubstituted C1-C4 alkylcarbonylamino group, the C1-C4 alkyl moiety may be either a straight chain or a branched chain, preferable. Specific examples include acetylamino, propanoylamino, butanoylamino and the like.
When the C1-C4 alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the C1-C4 alkylcarbonylamino group include, for example, hydroxyethanoylamino, 2-hydroxypropanoylamino, A hydroxy C1-C4 alkylcarbonylamino group such as 4-hydroxybutanoylamino; a carboxy C1-C4 alkylcarbonylamino group such as 3-carboxypropanoylamino; and the like.

When R < ² > -R < ⁴ > in Formula (1) is a N'-C1-C4 alkylureido group, what has a substituent is preferable rather than unsubstituted.
When the N′-C1-C4 alkylureido group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include N′-2-hydroxyethylureido and N′-3-hydroxyethyl. N′-hydroxy C1-C4 alkylureido group such as ureido; N′-sulfoC1-C4 alkylureido group such as N′-2-sulfoethylureido, N′-3-sulfopropylureido; N′-carboxymethylureido N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-4-carboxybutylureido, and other N′-carboxyC1-C4 alkylureido groups;

Specific examples of the phenylamino group in which R ^{2 to} R ⁴ in Formula (1) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group are, for example, unsubstituted Phenylamino; chlorine atom-substituted phenylamino groups such as 2-chlorophenylamino, 4-chlorophenylamino, 2,4-dichlorophenylamino; C1 such as 2-methylphenylamino, 4-methylphenylamino, 4-tert-butylphenylamino -C4 alkyl-substituted phenylamino group; nitro-substituted phenylamino groups such as 2-nitrophenylamino and 4-nitrophenylamino; 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 3, Sulfo-substituted phenylamino groups such as 5-disulfophenylamino; 2 Carboxyphenyl amino, 4-carboxyphenyl amino, 2,5-carboxyphenyl amino, 3,5-dicarboxyphenyl carboxy-substituted phenylamino group phenylamino and the like; and the like.

R ^{2 to} R ⁴ in Formula (1) are a phenylamino group, a benzoylamino group, or a phenylsulfonylamino group having a substituent, and the substituent of the benzene ring contained in each group is a C1-C4 alkyl group. In this case, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

Specific examples of the benzoylamino group in which R ^{2 to} R ⁴ in Formula (1) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group are, for example, unsubstituted Benzoylamino; chlorine atom-substituted benzoylamino groups such as 2-chlorobenzoylamino, 4-chlorobenzoylamino, 2,4-dichlorophenylamino; C1 such as 2-methylbenzoylamino, 3-methylbenzoylamino, 4-methylbenzoylamino -C4 alkyl-substituted benzoylamino groups; nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino, 4-nitrobenzoylamino and 3,5-dinitrobenzoylamino; sulfo-substitutions such as 2-sulfobenzoylamino and 4-sulfobenzoylamino Benzoylamino group; 2-carboxy Benzoylamino, 4-carboxyphenyl benzoylamino, 3,5-carboxymethyl benzoyl carboxy-substituted benzoylamino group of the amino or the like; and the like.

Specific examples of the phenylsulfonylamino group in which R ^{2 to} R ⁴ in Formula (1) may be substituted with a benzene ring by a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group include: Substituted phenylsulfonylamino; chlorine atom-substituted phenylsulfonylamino groups such as 2-chlorophenylsulfonylamino, 4-chlorophenylsulfonylamino; 2-methylphenylsulfonylamino, 4-methylphenylsulfonylamino, 4-tert-butylphenylsulfonylamino, etc. C1-C4 alkyl-substituted phenylsulfonylamino group; nitro-substituted phenylsulfonylamino groups such as 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino; 3-sulfophenylsulfo Arylamino, 4-sulfophenyl sulfonyl sulfo-substituted phenylsulfonylamino group of the amino or the like; 3-carboxyphenyl sulfonylamino, 4-carboxyphenyl sulfonyl carboxy-substituted phenylsulfonylamino group of the amino or the like; and the like.

Specific examples of preferable R ² to R ⁴ in the formula (1) are a hydrogen atom, carboxy, sulfo, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy. Carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2′-dihydroxy Diethylamino, 2,2′-dicarboxydiethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, 4-hydroxybutanoylamino, N′-carboxymethylureido, N′-2 -Sulfoethylureido, 4-sul Phophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzoylamino, 3-sulfobenzoylamino, 2-carboxybenzoylamino, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4- Nitrophenylsulfonylamino, 3-sulfophenylsulfonylamino, 4-carboxyphenylsulfonylamino and the like, more preferably hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, dimethylamino, 3,3′-disulfodipropylamino, acetylamino, 3-carboxypropanoylamino, N′-2-sulfoethylureido, 2,4-disulfophenylamino, benzoylamino, 4-methylphenylsulfonylamino, more preferably a hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy.

In a preferred combination of R ² to R ⁴ in the formula (1), R ² is 3-sulfopropoxy or 4-sulfobutoxy, R ³ is a hydrogen atom, and R ⁴ is methyl.

In the above formula (2), R ⁵ represents a mercapto group; or a C1-C4 alkylthio group which may be substituted with a hydroxy group, a C1-C4 alkoxy group, a hydroxy C1-C4 alkoxy group, a sulfo group or a carboxy group.

When R ⁵ in Formula (2) is a C1-C4 alkylthio group, the C1-C4 alkyl moiety is preferably linear or branched, but more preferably linear. Specific examples thereof include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio and the like.
When R ⁵ is a C1-C4 alkylthio group having a substituent, the substituent is preferably a hydroxy group, a sulfo group or a carboxy group, more preferably a sulfo group or a carboxy group. Specific examples of the C1-C4 alkylthio group having a substituent include, for example, hydroxy C1-C4 alkylthio groups such as 2-hydroxyethylthio, 2-hydroxypropoxy, 3-hydroxypropoxythio; methoxyethylthio, ethoxyethylthio, n -C1-C4 alkoxy C1-C4 alkylthio such as propoxyethylthio, isopropoxyethylthio, n-butoxyethylthio, methoxypropylthio, ethoxypropylthio, n-propoxypropylthio, isopropoxybutylthio, n-propoxypropylthio A hydroxy C1-C4 alkoxy C1-C4 alkylthio group such as 2-hydroxyethoxyethylthio; a sulfo C1-C4 alkylthio group such as 3-sulfopropylthio, 4-sulfobutylthio; carboxymethylthio, - carboxyethylthio, carboxy C1-C4 alkylthio group such as 3-carboxypropyl thio; and the like.

Specific examples of preferable R ⁵ in the formula (2) are mercapto (—SH), methylthio, ethylthio, 2-hydroxyethylthio, methoxyethylthio, ethoxyethylthio, 2-sulfoethylthio-3-sulfopropylthio, 4-sulfo. Butylthio, carboxymethylthio, 2-carboxyethylthio, 3-carboxypropylthio and the like, more preferably methylthio, 2-sulfopropylthio, carboxymethylthio, 2-carboxyethylthio, and still more preferably 2-sulfo Propylthio, 2-carboxyethylthio.

In the formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; a chlorine atom; a carboxy group; a sulfo group; a nitro group; a hydroxy group; a carbamoyl group; a sulfamoyl group; a C1-C4 alkyl group; A C1-C4 alkoxy group optionally substituted with a C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; or a benzene ring is a chlorine atom, It represents a phenylsulfonyl group which may be substituted with a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group.

When R ⁶ to R ⁸ in Formula (3) are a C1-C4 alkyl group, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. More preferred are chains. Specific examples include, for example, linear chains such as methyl, ethyl, n-propyl, and n-butyl; branched chains such as isopropyl, isobutyl, sec-butyl, and tert-butyl.

When R ⁶ to R ⁸ in the formula (3) are C1-C4 alkoxy groups which may be substituted with a hydroxy group, a C1-C4 alkoxy group, a sulfo group or a carboxy group, the substituents include preferable ones. It may be the same as when R ^{2 to} R ⁴ in the above formula (1) are the corresponding C1-C4 alkoxy group.

Specific examples of the C1-C4 alkylsulfonyl group in which R ⁶ to R ⁸ in formula (3) may be substituted with a hydroxy group, a sulfo group or a carboxy group include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl , N-butylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and the like linear or branched C1-C4 alkylsulfonyl groups; 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl and the like hydroxy C1-C4 alkylsulfonyl groups A sulfo C1-C4 alkylsulfonyl group such as 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl; carboxymethylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropiyl; Carboxy C1-C4 alkylsulfonyl group such as rusulfonyl; and the like.

Specific examples of the phenylsulfonyl group in which R ⁶ to R ⁸ in the formula (3) may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group are, for example, unsubstituted Phenylsulfonyl; chlorine atom-substituted phenylsulfonyl groups such as 2-chlorophenylsulfonyl, 4-chlorophenylsulfonyl; 2-methylphenylsulfonyl, 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-tert-butylphenylsulfonyl, etc. C1-C4 alkyl-substituted phenylsulfonyl group; 2-nitrophenylsulfonyl, nitro-substituted phenylsulfonyl groups such as 4-nitrophenylsulfonyl; 3-sulfophenylsulfonyl, 4-sulfophenylsulfonyl, 3,5-disulfophenylsulfonyl, etc. A sulfo-substituted phenylsulfonyl group, such as 2-carboxyphenylsulfonyl, 4-carboxyphenylsulfonyl, and 3,5-dicarboxyphenylsulfonyl;

Specific examples of preferable R ⁶ to R ⁸ in the formula (3) include a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, and 3-sulfopropoxy. 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl 4-methylphenylsulfonyl, 2,4-dimethylphenylsulfonyl, 4-nitrophenylsulfonyl, 4-sulfophenylsulfonyl, 2-carboxyphenylsulfonyl, 4-carboxyphenylsulfonyl and the like. More preferably, they are a hydrogen atom, a chlorine atom, carboxy, sulfo, nitro, methyl, methoxy, methylsulfonyl, and 2-carboxyphenylsulfonyl, and more preferably a hydrogen atom, sulfo, and methoxy. Of R ⁶ to R ⁸ , at least one is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

Preferred R ⁶ to R ⁸ combinations in formula (3) are a hydrogen atom, methoxy and sulfo, or one is sulfo and the other two are hydrogen atoms. When one is sulfo and the other two are hydrogen atoms, the substitution position of sulfo is more preferably the 6-position of the benzothiazole ring.

In the above formula (1), the group B is an optionally substituted phenyl group or naphthyl group. When the group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a C1-C4 alkyl group; An alkoxy group; an amino group; a mono- or di-C1-C4 alkylamino group; an acetylamino group; a benzoylamino group in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group, or a carboxy group; A phenyl group having a substituent selected from the group consisting of a hydroxy group in the case of a substituted naphthyl group; a sulfo group; a C1-C4 alkoxy group; and a benzene ring which may be substituted with a methyl group, a nitro group or a chlorine atom Having a substituent selected from the group consisting of: an oxy group;

When the group B in the formula (1) is a phenyl group or a naphthyl group having a substituent, and the substituent is a C1-C4 alkoxy group, the alkoxy group includes a preferable one in the above formula (1). ^{2 to} R ⁴ may be the same as in the case of an unsubstituted C1-C4 alkoxy group.

When the group B in the formula (1) is a mono- or di-C1-C4 alkylamino group-substituted phenyl group, the mono- or di-C1-C4 alkylamino group includes R ^{2 to} R in the formula (1) including preferable ones. It may be the same as when ⁴ is an unsubstituted mono or di C1-C4 alkylamino group.

When the group B in the formula (1) is a substituted naphthyl group, and the substituent is a phenylsulfonyloxy group in which the benzene ring may be substituted with a methyl group, a nitro group or a chlorine atom, specific examples thereof include: Unsubstituted phenylsulfonyloxy; methyl-substituted phenylsulfonyloxy groups such as 4-methylphenylsulfonyloxy and 2,4-dimethylphenylsulfonyloxy; nitro-substituted phenylsulfonyloxy groups such as 2-nitrophenylsulfonyloxy and 4-nitrosulfonyloxy Chlorine atom substituted phenylsulfonyloxy groups such as 4-chlorophenylsulfonyloxy, 2,4-dichlorophenylsulfonyloxy, 3,5-dichlorophenylsulfonyloxy, and the like.

In the formula (1), n is preferably 1.

Specific examples of preferable substituents when the group B in the formula (1) is a substituted phenyl group include a hydrogen atom, hydroxy, sulfo, carboxy, methyl, ethyl, methoxy, ethoxy, dimethylamino, acetylamino, benzoylamino, 4 -Sulfobenzoylamino, 4-carboxybenzoylamino and the like, more preferably a hydrogen atom, hydroxy, sulfo, carboxy, methyl and acetylamino, and still more preferably a hydrogen atom, sulfo and carboxy.

Specific examples of preferred substituents when the group B in the formula (1) is a substituted naphthyl group include a hydrogen atom, hydroxy, sulfo, methoxy, ethoxy, phenylsulfonyloxy, 4-methylphenylsulfonyloxy, 2-nitrophenyl and the like. More preferably, they are a hydrogen atom, hydroxy, sulfo, or methoxy, and more preferably a hydrogen atom or sulfo.

Specific examples of preferable group B in the formula (1) are phenyl, 2-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 4-carboxyphenyl, 3,5- Carboxyphenyl, 4-methylphenyl, 3-methylphenyl, 3-hydroxy-4-carboxyphenyl, 5-sulfo-3-carboxy-2-hydroxyphenyl, 4-methoxyphenyl, 4-acetylaminophenyl, naphthyl, naphtho 2-yl, 6-sulfonaphthyl, 7-sulfonaphthyl, 4,7-disulfonaphthyl, 5,7-disulfonaphth-2-yl, 6,8-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl Yl, 4,6,8-trisulfonaphth-2-yl and the like, more preferably phenyl, 4-sulfophenyl, , 4-disulfophenyl, 4-carboxyphenyl, 3,5-carboxyphenyl, 5,7-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl, and more preferably phenyl, 4- Sulfophenyl, 4-carboxyphenyl and 3,5-carboxyphenyl.

The compound which combined the preferable thing described about the substituent of the said Formula (1) to (6) is more preferable, and the compound which combined more preferable things is further more preferable. The same applies to preferable ones. As described above, in formulas (4) to (6), group A, group B, and R ^{1 to} R ⁴ have the same meaning as in formula (1).

The salt of the trisazo compound represented by the formula (1) is an inorganic or organic cation salt. Of these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts, and organic cation salts. Examples of the salt include, but are not limited to, quaternary ammonium ions represented by the following formula (7). The free acid, its tautomer, and various salts thereof may be a mixture. For example, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt and ammonium salt may be used. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, the type of salt is selected as appropriate, or when multiple salts are included, the ratio can be changed to change the ratio to suit the purpose. It is also possible to obtain a mixture having.

In the formula (7), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.
Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (7) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Specific examples of the hydroxyalkyl group include hydroxy C1-C4 alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl and 2-hydroxybutyl. Examples of the hydroxyalkoxyalkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl. etc Dorokishi include C1-C4 alkoxy C1-C4 alkyl group, hydroxyethoxy C1-C4 alkyl are preferred among these. Particularly preferred are hydrogen atoms; hydroxy C1-C4 alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, hydroxy And hydroxyethoxy C1-C4 alkyl groups such as ethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. .

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ^{4 that} are preferable as the formula (7) are shown in Table 1 below.

The black pigment represented by the above 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 in the form of a free acid for convenience.
A compound represented by the following formula (8) is diazotized by a conventional method, and this and a compound represented by the following formula (9) are coupled by a conventional method to obtain a compound represented by the following formula (10).

(In formula (8), group A has the same meaning as in formula (2) and formula (3).)

(In formula (9), R ² to R ⁴ have the same meaning as in formula (1).)

(In formula (10), R ² to R ⁴ have the same meaning as in formula (1).)

The obtained compound of formula (10) is diazotized by a conventional method, and then this and a compound represented by the following formula (11) are coupled by a conventional method to obtain a compound represented by the following formula (12). .

(In formula (11), n has the same meaning as in formula (1).)

(In formula (12), n and R ² to R ⁴ have the same meaning as in formula (1).)

The present invention represented by the formula (1) is obtained by diazotizing the obtained compound of the formula (12) by a conventional method and then coupling it with a compound represented by the following formula (13) by a conventional method. The trisazo compound can be obtained.

(In formula (13), R ¹ and group B have the same meaning as in formula (1).)

In addition, the compound represented by Formula (13) can purchase a commercial item as a product, or can be synthesize | combined by a well-known method.

Although it does not specifically limit as a suitable specific example of the compound of this invention shown to the said Formula (1), The compound shown by the structural formula given to the following Table 2-7 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 (8) is carried out by a method known per se. For example, using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of -5 to 20 ° C, preferably 5 to 10 ° C. Coupling of the diazotized compound of the compound of formula (8) with the compound of formula (9) is also carried out under conditions known per se. It is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C. The compound of formula (8) and the compound of formula (9) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (10) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 5 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound of formula (10) and the compound of formula (11) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C., preferably 10 to 30 ° C. and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6-10. Since the diazotization reaction 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 compounds of formulas (10) and (11) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (12) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound of formula (12) and the compound of formula (13) 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 (12) and (13) are used in approximately stoichiometric amounts.

In order to obtain the desired salt of the trisazo compound represented by the formula (1) of the present invention, salting out is performed by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction, Alternatively, it is isolated in the form of a free acid by adding a mineral acid such as hydrochloric acid, and this is washed with water, acidic water or an aqueous organic medium as necessary to remove inorganic salts, and then desired in an aqueous medium. By neutralizing with an inorganic or organic base, a corresponding salt solution can be obtained. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to water-miscible organic substances miscible with water and so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Organic substances that are not classified can be used as needed as long as they are miscible with water. Examples of organic substances not normally classified as solvents include urea and saccharides. Examples of the inorganic salt 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 the above-described formula (10). The halogen salt of the organic amine represented by these, etc. are mentioned. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of organic bases include, but are not limited to, organic amines such as quaternary ammoniums represented by the above formula (7) such as diethanolamine and triethanolamine. .

The ink composition of the present invention will be described. The water-based ink 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. On the other hand, a typical use of the compound of the present invention is an ink composition dissolved in a liquid medium.

The reaction solution containing the trisazo compound of the present invention represented by the formula (1), for example, the reaction solution before salting out with sodium chloride in Example 1 (3) described later, is directly used for the production of the ink composition. I can do it. However, it is first isolated by drying, eg spray drying; salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; minerals such as hydrochloric acid, sulfuric acid, nitric acid The acid is precipitated by adding and printing; or the acid salting out of the salting-out and aciding-out described above is isolated; the trisazo compound of the present invention is isolated and the ink composition is prepared using the compound. You can also.

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 represented by the formula (1) of the present invention, and the balance. Is a composition with water as the main medium. The ink composition of the present invention may further contain a water-soluble organic solvent, for example, 0 to 30% by mass, and an ink preparation agent, for example, 0 to 10% by mass. 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.

In the ink composition of the present invention, water or a water-soluble organic solvent (an organic solvent miscible with water) is mixed with the trisazo compound represented by the above formula (1), if necessary, with other coloring materials such as toning. And an ink preparation agent is added if necessary. For the purpose of adjusting a neutral black ink composition having no tint, other toning dyes may be appropriately added to the black dye of the present invention. When this ink composition is used as an ink for an ink jet printer, it is preferable to use a trisazo compound of the present invention having a low content of inorganic impurities such as metal cation chlorides and sulfates. The standard of the inorganic impurity content is approximately 1% by mass or less with respect to the total mass of the pigment. In order to produce the azo compound of the present invention with less inorganic impurities, for example, a normal method using a reverse osmosis membrane or a dried product or wet cake of the azo 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 that can be used in the preparation of the ink composition include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol; N, N A carboxylic acid amide such as dimethylformamide or N, N-dimethylacetamide; a lactam such as 2-pyrrolidone, N-methyl-2-pyrrolidone or N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2- ON or cyclic ureas such as 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane, etc. Cyclic ether; Ethylene Glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene Mono-, oligo- or poly-alkylene glycols or thioglycols having C2-C6 alkylene units such as glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol; polyols such as glycerin or hexane-1,2,6-triol (Triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Chirueteru, diethylene glycol monobutyl ether (butyl carbitol) C1-C4 alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; .gamma.-butyrolactone or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

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

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

Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide, and isothiazoline compounds include, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4 -Isothiazoline-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate and the like.

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

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

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

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

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

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

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

The ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. Further, in order to adjust the black color as the ink composition, in addition to the trisazo compound represented by the formula (1) of the present invention, other dyes 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 a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. It is suitably used in the inkjet printing method.

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

The colored product of the present invention is colored by the compound of the present invention represented by the formula (1) or an ink composition containing the compound, and more preferably by an inkjet printing method using an inkjet printer. It is colored with an ink composition.
Although there is no restriction | limiting in particular as what can be colored, For example, sheets for information transmission, such as paper and a film, fiber, cloth (cellulose, nylon, wool, etc.), leather, a base material for color filters, etc. are mentioned.
Among them, the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer; or by using a porous white inorganic substance capable of absorbing a pigment in ink such as porous silica, alumina sol or special ceramics, polyvinyl alcohol or polyvinyl Coating the surface of the substrate together with a hydrophilic polymer such as pyrrolidone;
The information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Specific examples include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photographic Paper (Glossy), PM Matt Paper, Crispia; Japan Hewlett-Packard Co., Ltd. Commercially available products are available as company-made, product name Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper; Konica Corporation Product Name Photo-like QP; Of course, plain paper can also be used.

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

In order to record on a recording material such as an information transmission sheet by the ink jet printing method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of an ink jet printer, and the recording material is processed by a normal method. Can be recorded.
The inkjet printing method of the present invention includes the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and, if necessary, each color ink such as green, blue (or violet), and red (or orange). A composition can also be used in combination.
The ink composition of each color is poured into each container, and each container is set 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 used for ink jet 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.
The ink composition containing the coloring matter of the present invention can be used for ink jet printing and writing instruments.
Furthermore, when printed on an information recording sheet, particularly ink jet dedicated paper, the print density of the printed image is high, and in addition, the durability of the printed image, in particular, ozone gas resistance and light resistance are excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples.
In the text, “parts” and “%” are based on mass unless otherwise specified.
In the following formulas, functional groups such as sulfo and carboxy are expressed 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.
All of the synthesized trisazo compounds of the present invention showed a solubility of 100 g / L or more in water.

Example 1
(1)
By suspending 2.5 parts of 2-aminobenzothiazole-6-carboxylic acid in 25 parts of 85% phosphoric acid and adding dropwise 5.5 parts of 40% nitrosylsulfuric acid at 5-10 ° C. over about 10 minutes with stirring. A suspension was obtained.
On the other hand, an aqueous solution was obtained by adding 3.0 parts of the compound of the following formula (14), 0.6 part of sulfamic acid and then sodium hydroxide to 30 parts of water to adjust the pH to 5.0 to 5.5.
The above diazo suspension was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 10 minutes.
After completion of the dropwise addition, the mixture is stirred at the same temperature for 2 hours, sodium hydroxide is added to adjust the pH to 0.7 to 1.2, and the precipitated solid is collected by filtration to obtain a wet cake containing a compound of the following formula (15). It was.
In addition, the compound of following formula (14) was obtained by the method of Unexamined-Japanese-Patent No. 2004-083492.

(2)
An aqueous solution was obtained by adding 3.0 parts of the compound of the following formula (16) and then sodium hydroxide to 30 parts of water to adjust the pH to 7.5 to 8.0.
On the other hand, by stirring, a wet cake containing the compound of the formula (15) obtained in Example 1 (1) was suspended in 110 parts of water, and sodium hydroxide was added to adjust the pH to 6.0 to 6.5. An aqueous solution was obtained.
To the obtained aqueous solution, 3.6 parts of 35% hydrochloric acid and then 2.2 parts of 40% aqueous sodium nitrite solution were added dropwise at a reaction temperature of 15 to 20 ° C. over about 5 minutes to obtain a diazo suspension.
The obtained diazo suspension was added dropwise to the previously obtained aqueous solution containing the compound of formula (16) at a reaction temperature of 20 to 30 ° C. for 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, salted out by adding sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (17).

(3)
An aqueous solution was obtained by adding 3.3 parts of the compound of the following formula (18) to 30 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, with stirring, the wet cake containing the compound of formula (17) obtained in Example 1 (2) was dissolved in 150 parts of water, 3.3 parts of 35% hydrochloric acid, and then at a reaction temperature of 20-25 ° C. A diazo solution was obtained by dropwise addition of 2.0 parts of an aqueous sodium nitrite solution over about 5 minutes.
The obtained diazo liquid was added dropwise to the aqueous solution containing the compound of the formula (18) obtained previously at a reaction temperature of 20 to 30 ° C. for 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 180 parts of water, 250 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 150 parts of water, and 400 parts of methanol was added for crystallization. The precipitated solid was collected by filtration and dried to obtain a compound of the following formula (19) (Table No. 29 compound No. 6) 12.0 parts as a sodium salt.
λmax: 582.5 nm.

Example 2
(1)
5.0 parts of 2-amino-6-methoxybenzothiazole was slowly added to 15 parts of 15% fuming sulfuric acid at 15-25 ° C. After the addition, the mixture was stirred at the same temperature for 2 hours, and then added dropwise to 60 parts of ice water in about 10 minutes. The precipitated crystals were collected by filtration and dried to obtain 6.4 parts of a compound of the following formula (20).

(2)
Suspend 3.2 parts of the compound of the formula (20) obtained in Example 2 (1) in 20 parts of 50% sulfuric acid in 20 parts of 50% sulfuric acid, and 40% nitrosylsulfuric acid at 5-10 ° C. with stirring. A diazo suspension was obtained by dropping 7 parts in about 10 minutes.
On the other hand, an aqueous solution was obtained by adding 2.9 parts of the compound of the above formula (14), 0.4 part of sulfamic acid, and then sodium hydroxide to 30 parts of water to adjust the pH to 5.0 to 5.5.
The above diazo suspension was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 10 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium hydroxide was added to adjust the pH to 0.7 to 1.2, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (21). It was.

(3)
In Example 1 (2), except that the wet cake containing the compound of formula (15) is changed to a wet cake containing the compound of formula (21), the following formula (22) of the present invention is used. Of the compound as a sodium salt. In addition, this compound is No. in the said Table 4. 14 and No. 1 in Table 5. It is a mixture of 22 compounds.
λmax: 604.0 nm.

Example 3
In Example 2 (2), the following formula of the present invention was used in the same manner as in Example 2 except that 3.2 parts of the compound of formula (20) was 3.5 parts of 2-aminobenzothiazole-6-sulfonic acid. 12.9 parts of compound (23) (No. 24 compound in Table 5) was obtained as a sodium salt.
λmax: 604.5 nm.

Example 4
In Example 2 (2), 3.2 parts of the compound of formula (20) is 3.3 parts of 2-aminobenzothiazole-6-sulfonic acid, and 2.9 parts of the compound of formula (14) is 4-acetyl. Except for using 2.9 parts of amino-2-aminobenzenesulfonic acid, in the same manner as in Example 2, 11.3 parts of the compound of the following formula (24) of the present invention (the compound of No. 16 in Table 4) was added to sodium. Obtained as a salt.
λmax: 552.5 nm.

Example 5
(A) Preparation of ink After mixing the following components, a black ink composition of the present invention was obtained, and then impurities were separated by a 0.45 μm membrane filter. The obtained ink composition is hereinafter referred to as “ink”.
The 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 8
Each compound obtained in Examples 1 to 4 3.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Interface Activator 0.1 part (Brand name Surfynol 104 Nissin Chemical Co., Ltd.)
Water + sodium hydroxide 77.4 parts Total 100.0 parts

In Table 8, the following various tests conducted using the ink containing each compound obtained in Examples 1 to 4 are referred to as Examples 6 to 9, 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 same composition as in Table 8 was used except that the pigment of the following formula (25) disclosed in Example 1 of Patent Document 7 was used instead of the compound of each Example. Was prepared. The following various tests conducted using this ink are referred to as Comparative Example 1.

(B) Inkjet printing Using the ink obtained above, Canon paper, product name PIXUS iP4100, glossy paper 1 (Canon, product name Professional Photo Paper PR-101), glossy paper 2 (EPSON) Inkjet printing was carried out on three types of information recording sheets (inkjet paper), manufactured by the company, trade name: photographic paper Krispia (high gloss), and glossy paper 3 (manufactured by HP, trade name: Advanced Photo Paper (gloss)).
At the time of printing, an image pattern was prepared so that the reflection density was obtained with several gradations, and a black printed matter was obtained.

(C) Evaluation of recorded image
Each print image obtained using the inks of Examples 6 to 9 and Comparative Example 1 was evaluated for the density change of the image before and after the test with respect to light resistance and ozone gas resistance.
The change in density of the printed image is measured by measuring the gradation portion where the reflection density D value of the printed image before the test is closest to 1.0 using a colorimeter manufactured by GRETAG-MACBETH and the product name SpectroEye. did.
The test was performed for each of glossy papers 1, 2, and 3, and the test results are shown in Table 9.
The specific test method is as follows.
1) Ozone gas resistance test, trade name, manufactured by Suga Test Instruments Co., Ltd. Each print image was allowed to stand for 4 hours under the conditions of ozone concentration 40 ppm, humidity 60% RH, temperature 24 ° C. using an ozone weatherometer. After completion of the test, the colorimetry was performed using the above-described colorimeter, and the residual ratio of the dye in each print image was determined by the formula (reflection density after test / reflection density before test) × 100 (%). The test results were evaluated according to the following criteria.
○ Residual rate: 75% or more △ Residual rate: 65% or more and less than 75% × Residual rate: less than 65% 2) Light resistance test Suga Test Instruments Co., Ltd., trade name, low temperature xenon weatherometer XL75, After irradiating each print image for 96 hours under the conditions of 100,000 Lux illuminance, humidity 60% RH, and temperature 24 ° C., the colorimetry is performed using the colorimeter described above, and the dye remaining in each image remains. The rate was determined by the formula of (reflection density after test / reflection density before test) × 100 (%). The test results were evaluated according to the following criteria.
○ Residual rate: 80% or more △ Residual rate: 70% or more and less than 80% × Residual rate: less than 70%

Table 9
Ozone gas resistance Light resistance
Comparative Example 1 (Formula (25))
Glossy paper 1 × ×
Glossy paper 2 × △
Glossy paper 3 × △
Example 6 (Formula (19))
Glossy paper 1 ○ ×
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 7 (Formula (22))
Glossy paper 1 ○ △
Glossy paper 2 ○ ○
Glossy paper 3 ○ ○
Example 8 (Formula (23))
Glossy paper 1 △ ×
Glossy paper 2 ○ ○
Glossy paper 3 ○ △
Example 9 (Formula (24))
Glossy paper 1 ○ ×
Glossy paper 2 ○ △
Glossy paper 3 ○ △

As is clear from the results in Table 9, when the results of the ozone gas resistance test are compared for each glossy paper, the printed images of Examples 6 to 9 and the image of Comparative Example 1 are the same for each example. Is a better result than Comparative Example 1. That is, in Comparative Example 1, when any glossy paper is used, the dye residual ratio is less than 65%, whereas in Examples 6, 7, and 9 of the present invention, the dye remains in any glossy paper. The residual rate was 75% or more, and Example 8 showed a pigment residual rate of 65% or more and less than 75% only when glossy paper 1 was used, but 75% or more when glossy papers 2 and 3 were used. The dye residual ratio was shown. Thereby, it turned out that each Example is very excellent in ozone gas resistance with respect to a comparative example.
Similar differences were observed in the light resistance test. In Examples 6 and 7, when glossy papers 2 and 3 were used, the residual dye ratio was 80% or more. In Example 8, glossy paper 2 was used. In contrast, in Comparative Example 1, when the same glossy paper was used, the residual dye ratio was 70% or more and less than 80%. From this, the results of Examples 6 and 7 were better than those of Comparative Example 1, and the results of Examples 8 and 9 were also equal to or higher than those of 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 this is a well-balanced dye that is extremely excellent in required ozone gas resistance and at the same time excellent in light resistance.

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

Claims (11)

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

(In the formula (1), n is 0 or 1,
R ¹ is a carboxy group; a C1-C8 alkoxycarbonyl group; a C1-C8 alkylcarbonyl group optionally substituted with a C1-C8 alkoxycarbonyl group or a carboxy group; or a hydroxyl group, a sulfo group or a carboxy group. Represents a good phenyl group,
R ² to R ⁴ are each independently hydrogen atom; chlorine atom; hydroxy group; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; C1-C4 alkyl group; hydroxy group, C1-C4 alkoxy group, hydroxy C1-C4 alkoxy group A C1-C4 alkoxy group optionally substituted with a group, a sulfo group or a carboxy group; a mono- or di-C1-C4 alkylamino group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; substituted with a hydroxy group or a carboxy group A C1-C4 alkylcarbonylamino group which may be substituted; an N′-C1-C4 alkylureido group which may be substituted with a hydroxy group, a sulfo group or a carboxy group; a benzene ring as a chlorine atom, a C1-C4 alkyl group, a nitro group A phenyl group which may be substituted with a sulfo group or a carboxy group A benzene ring in which the benzene ring may be substituted with a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring in a chlorine atom, a C1-C4 alkyl group, a nitro group, a sulfo group Each represents a phenylsulfonylamino group optionally substituted by a group or a carboxy group;
Group A is a substituted heterocyclic group represented by the following formula (3) ,

(In formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; chlorine atom; carboxy group; sulfo group; nitro group; hydroxy group; carbamoyl group; sulfamoyl group; C1-C4 alkyl group; hydroxy group, C1 A C1-C4 alkoxy group optionally substituted with a C4 alkoxy group, a sulfo group or a carboxy group; a C1-C4 alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; or a benzene ring is a chlorine atom, Each represents a C1-C4 alkyl group, a nitro group, a sulfo group, or a phenylsulfonyl group which may be substituted with a carboxy group.)
Group B is an optionally substituted phenyl group ,
Substituents that group B may have are hydroxy group; sulfo group; carboxy group; C1-C4 alkyl group; C1-C4 alkoxy group; amino group; mono- or di-C1-C4 alkylamino group; acetylamino group; it is a substituent selected from the group consisting of; ring is a chlorine atom, C1-C4 alkyl group, a nitro group, a sulfo group or a benzoylamino group that may be substituted with a carboxy group. ) The trisazo compound or a salt thereof according to claim 1, wherein the group B is an optionally substituted phenyl group, and the substituent is a hydroxy group, a sulfo group or a carboxy group. R ¹ is unsubstituted C1-C4 alkyl group or a carboxy group, R ² is sulfo C1-C4 alkoxy group, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, according to claim 1 or 2 is a methyl group or an ethyl group Trisazo compounds or salts thereof. The group A is represented by the formula (3), R ¹ is a methyl group or a carboxy group, R ⁶ to R ⁸ are each independently a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a nitro group, a C1-C4 alkyl group, The trisazo compound or a salt thereof according to any one of claims 1 to 3 , which is a C1-C4 alkoxy group or a C1-C4 alkylsulfonyl group. The group A is represented by the formula (3), n is 1, R ¹ is a carboxy group, R ² is a sulfopropoxy group, R ³ is a hydrogen atom, R ⁴ is a methyl group, and R ⁶ to R ⁸ are independently hydrogen. 5. An atom, a chlorine atom, a carboxy group, a sulfo group, a nitro group, a methyl group, a methoxy group, and a methylsulfonyl group, and the group B is a phenyl group that may be substituted with a sulfo group or a carboxy group. The trisazo compound or a salt thereof according to any one of the above. An ink composition comprising at least one trisazo compound or a salt thereof according to any one of claims 1 to 5 as a coloring matter. An ink jet printing method comprising recording by ink jet printing using the ink composition according to claim 6 . The inkjet printing method according to claim 7 , wherein the recording material in the inkjet printing method is an information transmission sheet. The ink jet printing method according to claim 8 , wherein the information transmission sheet contains a porous white inorganic substance. An ink jet printer loaded with a container containing the ink composition according to claim 6 . A colored product colored with the trisazo compound or a salt thereof according to any one of claims 1 to 5 .