WO2007138925A1 - Azo compound, ink composition, recording method, and colored matter - Google Patents

Abstract

Disclosed is an azo compound represented by the formula (1) below or a salt thereof. Also disclosed is an ink composition containing such an azo compound or a salt thereof. (1) (In the formula, R1 and R2 independently represent a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group or the like; R3, R4, R5 and R6 independently represent a carboxyl group, a sulfo group or the like; R7, R8, R9 and R10 independently represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfonyl group or the like; and n represents 0 or 1.) The azo compound can be used as a dye for black, and has excellent solubility in a medium mainly containing water and good storage stability as a recoding liquid. When the azo compound or the ink composition is used for inkjet recording or a writing utensil, there can be obtained an excellent recorded matter having high light resistance and high ozone gas resistance, wherein a recorded image does not suffer from bronzing.

Description

 Specification

 Azo compound, ink composition, recording method and colored body

 Technical field

 [0001] The present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product colored by these.

 Background art

 [0002] A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.). It is for recording. 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 generation and quietness, and the size and high speed are easy. Is expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in water-based media have been used as inks used for applications such as fountain pens and felt-tip pens, and inks for inkjet recording. In general, water-soluble organic solvents are added to prevent clogging of ink at the pen tip and the ink discharge nozzle. These inks provide a sufficiently dense recorded image, do not cause clogging of the pen tip and nozzles, good drying properties on the recording material, low bleeding, and storage stability. It is required to be excellent. 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. Furthermore, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance.

[0003] Among these, the ozone gas resistance refers 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 discolors the printed image. It is resistance to do. In addition to ozone gas, NOx, SOx, etc. are examples of acidic gases that have this type of action. Among these acidic gases, ozone gas promotes the discoloration and fading phenomenon of inkjet recording images. It is said to be the main causative substance. The ink-receiving layer provided on the surface of the photographic image ink jet paper is made of a porous white inorganic material to accelerate ink drying and reduce image bleeding in high-quality recording. On many such recording papers, discoloration due to ozone gas is noticeable. This discoloration and fading phenomenon caused by acid-oxidizing gas is characteristic of inkjet images, so improving gas resistance, especially ozone gas resistance, is one of the most important issues in inkjet recording methods. Yes.

 [0004] In the future, the ink composition used for inkjet recording and the colored bodies colored thereby should be expanded in the field of use of printing methods using ink. Light resistance, ozone gas resistance, moisture resistance Further improvement in water resistance and water resistance is strongly demanded.

 [0005] While inks of various hues have been prepared with various dye strengths, of these black inks are important inks used for both monocolor and full color images. To date, many dyes have been proposed as dyes for black ink. We have been able to provide products that fully satisfy the demands of the factory! Many dyes are azo dyes. Among them, disazo dyes such as CI Food Black2 have low optical density, poor water and moisture resistance, and sufficient gas resistance. There are problems such as not. Polyazo dyes with extended conjugated systems generally have a low water solubility and are prone to bronzing, where the recorded image has a partially metallic luster! There are problems such as / ヽ and insufficient gas resistance. Similarly, many proposed azo-containing dyes contain metal ions, which are preferable for biological safety and environmental problems, but have problems such as extremely low ozone gas resistance.

[0006] As a compound (black pigment) used in an inkjet black ink which has been improved most recently in recent years and has become the most important issue in recent years, for example, a disazo compound described in Patent Document 1 can be used. Is mentioned. However, the ozone gas resistance of these compounds does not fully meet the market requirements. Patent Documents 2, 3 and 4 disclose trisazoy compounds, and Patent Documents 5, 6 and 7 disclose tetrakisazo compounds.

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-183545

 Patent Document 2: Japanese Patent Laid-Open No. 62-109872

 Patent Document 3: Japanese Unexamined Patent Publication No. 2003-201412

 Patent Document 4: WO2005Z054374

Patent Document 5: Japanese Unexamined Patent Publication No. 2005-68416 Patent Document 6: WO2005Z 097912

 Patent Document 7: WO2005Zl08502

 Disclosure of the invention

 Problems to be solved by the invention

 The present invention is stable even when a high-concentration aqueous solution or ink having high solubility in a medium containing water as a main component is stored for a long period of time, and a photograph in which the density of a printed image is very high. Even when a high-concentration solution is printed on inkjet paper, it does not cause bronzing, gives a printed black image with excellent fastness, especially ozone gas resistance, and is easy to synthesize. It is an object of the present invention to provide a black ink coloring matter and an ink composition thereof which are inexpensive.

 Means for solving the problem

 [0009] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific tetrakisazoy compound can solve the above-mentioned problems, and have reached the present invention. is there. That is, the present invention

 (1) an azo compound represented by the following formula (1) or a salt thereof,

(1)

[Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, an N-phenylaminosulfo group. -Group, (C1-C4) alkylsulfonyl group (the alkyl group may be substituted with a hydroxy group), phosphono group, nitro group, acyl group, ureido group, (C1-C4) alkyl group (hydroxy group) Group (which may be substituted with a group selected from the group consisting of (C1-C4) alkoxy groups), (C1-C4) alkoxy groups (hydroxy groups, (C1-C4) alkoxy groups, sulfo groups and carboxyl groups Substituted with a group selected from the group consisting of an acylamino group, an alkylsulfo-lumino group, or a phenylsulfo-lumino group (phenol). The-group may be substituted with a group selected from the group consisting of a halogen atom, an alkyl group and a -tro group).

R ⁹ and R ^1q are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, or an N-phenylaminosulfol group. , (C1-C4) alkylsulfonyl group (the alkyl group may be substituted with a hydroxy group), phosphono group, nitro group, acyl group, ureido group, (C1-C4) alkyl group (hydroxy group or (Cl-C4) may be substituted with an alkoxy group), (C1-C4) alkoxy group (substituted with a hydroxy group, (C1-C4) alkoxy group, a sulfo group or a carboxyl group! )), A acylamino group, an alkylsulfo-lumino group or a phenylsulfo-lumino group (the phenol group may be substituted with a halogen atom, an alkyl group or a -tro group), n is 0 or 1 , Respectively. ),

(2) At least one of R ^{3 to} R ⁶ is a group other than a hydrogen atom, at least two of R ^{7 to} R ^1Q are sulfo groups, and the total number of sulfo groups included in formula (1) is 8 to 10 The azo compound or salt thereof according to (1),

(3) R ³ ,

R ⁵ and R ⁶ are each independently a carboxyl group, a sulfo group, or a (C1-C4) alkyl group (substituted with a hydroxy group or a (C1-C4) alkoxy group !, may be!), (C 1 to C4) an alkoxy group (which may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group), or an acylamino group according to (1) or (2) Azo compounds or salts thereof,

(4) When R ¹ is a sulfo group or a carboxyl group, and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group, and the substitution of R ¹ When the position is para to the azo group, the substitution position of the nitro group is ortho to the azo group, and R ² is a hydrogen atom (1) to (3) Azo compound or its salt,

(5) R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, and n is 1 (1) to ( 4) the azo compound or salt thereof according to any one of

(6) The azo compound or a salt thereof according to any one of (1) to (5), wherein R ⁸ and R ⁹ are a sulfo group, (7) 1-3 of R ^{3 to} R ⁶ are sulfo-substituted or hydroxy-substituted (C1-C4) alkoxy groups, and at least one of them is a sulfo-substituted (C1-C4) alkoxy group, : Γ The remaining group is a hydrogen atom or a (C1 to C4) alkyl group (1) to (6)!

(8) The azoich compound or a salt thereof according to any one of (1) to (7), wherein R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, and R ^1Q is a hydroxy group,

(9) R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, R ⁷ is a hydrogen atom, R ⁸ and The azo compound or salt thereof according to any one of (1) to (8), wherein R ⁹ is a sulfo group, R ^1Q is a hydroxy group, the substitution position is peri to the azo group, and n is 1.

(10) When R ¹ is a sulfo group, a carboxy group or a cyano group, and the substitution position of R ¹ is ortho to the azo group, the force at which the substitution position of the nitro group is para to the azo group or When R ¹ is a sulfo group or a cyano group, and the substitution position of R ¹ is para to the azo group, the substitution position of the -together group is ortho to the azo group, and R ² is a hydrogen atom R ³ and R ^{5 are} sulfo- or hydroxy-substituted (C1-C4) alkoxy groups, and R ⁴ and R ⁶ are hydrogen atoms, (C1-C4) alkyl groups or hydroxy-substituted (C1-C4) alkoxy group, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, R ^1Q is a hydroxy group or a sulfo group, and the substitution position of R ^1Q is an azo group The azo compound or a salt thereof according to (1), which is in the peri position with respect to n and 1;

(11) R ¹ is a sulfo group, the substitution position is ortho to the azo group, the nitro substitution position is para to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are sulfo substitution (C1 -C4) alkoxy group, R ⁴ and R ⁶ are (C1 -C4) alkyl group, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ is a sulfo group, the substitution position R ^1Q is in hydrate proxy group to § zone group The peri-position, and n is 1. The azo compound or salt thereof according to (1),

(12) 1 ^ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are 3-sulfopropoxy R ⁴ and R ⁶ are methyl groups, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, R ^1Q is a hydroxy group, and the substitution position is peri-position to an azo group, and n is 1. The azo compound or salt thereof according to (1), (13) An ink composition comprising at least one of the azo compound or salt thereof according to any one of (1) to (12) above,

 (14) An inkjet print recording method comprising using the ink composition according to (13) above,

 (15) The inkjet recording method according to (14), wherein the recording material in the inkjet printing recording method is an information transmission sheet.

 (16) The ink jet recording method according to (15), wherein the information transmission sheet contains a porous white inorganic substance,

 (17) An inkjet printer loaded with a container containing the ink composition according to (13) above,

(18) A colored product colored with the azo compound or salt thereof according to any one of (1) to (12) above,

 About.

 The invention's effect

 [0012] The azo compound of the present invention or a salt thereof (hereinafter collectively referred to simply as azo compound) is excellent in water-solubility, and therefore has good filterability with a membrane filter in the process of producing an ink composition. Also, it has excellent stability during storage of recording liquid and ejection stability during ink jet recording. Further, the ink composition of the present invention containing this azo 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 azo compound of the present invention is suitably used for inkjet recording and writing instruments, and the recording density of recorded images when recorded on plain paper and ink jet paper is very high. Even when a high concentration solution is printed, the image does not cause bronzing, and it is also excellent in various fastness properties, particularly ozone gas resistance. When used with an ink composition using magenta, cyan and yellow dyes, full-color ink jet recording is possible with excellent fastness and storage stability. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

In the present invention, the description of the number of carbon atoms, “acyl”, “alkyl”, “alkoxy”, etc. The alkyl group in the group is not particularly limited unless otherwise specified, but is usually an alkyl group having about 1 to 20 carbon atoms, and a carbon having about 1 to about: LO is preferred. An alkyl group of about 1 to 4 is more preferable. For example, more preferable “alkyl” or “alkoxy” includes (C1-C4) alkyl or (C1-C4) alkoxy. Also, the term “halogen” is not particularly limited, but “chlorine atom” or “bromine atom” is usually preferable.

In ^ to 1 ^ ^{1 ()} in the above formula (1), examples of N-alkylaminosulfol groups include, for example, N-methylaminosulfol, N-ethylaminosulfol, N- (n —Propyl) aminosulfol, N— (n-butyl) aminosulfur, N, N-dimethylaminosulfurol, N, N-di (n-propyl) aminosulfol and the like N— (C1 ~ C4) an alkylaminosulfonyl group.

[0014] Examples of (C1-C4) alkylsulfol groups (wherein the alkyl group may be substituted with a hydroxy group ⁾ in ^ ^-1 ^ ^{1 ()} in the above formula (1) include, for example, methylsulfo- , Ethinolesnorehoninole, propinolesnorehoninole, butinolesnorehoninole, hydroxyethinolesnorephonyl, 2-hydroxypropylsulfol and 3-hydroxypropylsulfol. .

In R ¹ ! ^ In the above formula (1), examples of the acyl group include acetyl, piool, butyryl, isobutyryl, benzoyl and naphthoyl.

In R ¹ ! ^ In the above formula (1), examples of the (C1-C4) alkyl group which may be substituted with a hydroxy group or a (C1-C4) alkoxy group include, for example, methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyxetyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl, 2-ethoxyethyl, _n -propoxychetyl, isopropoxychetyl, Examples include _n -butoxetyl, methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, and n-propoxybutyl. Usually, unsubstituted (C1-C4) alkyl is preferred.

[0017] In ^ to 1 ^ ^{1 ()} in the above formula (1), it may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group, and (C1 to C4) of the alkoxy group As an example 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, npropoxypropoxy, isopropoxybutoxy, npropoxybutoxy, 2-hydroxyethoxyethoxy, carboxymethoxy, 2 carboxyethoxy, 3 carboxypropoxy, 3 sulfopropoxy and 4 sulfobutoxy Preferred substituents that are usually preferred to be substituted (C1-C4) alkoxy groups are hydroxy, sulfo or carboxyl, more preferably hydroxy or Luho.

[0018] In ^ to 1 ^ ^{1 ()} in the above formula (1), examples of the acylamino group include acetylamino, propionylamino-containing butyrylamino-containing isobutyrylamino-containing benzoylamino, naphthoylamino and the like.

In the above formula (1), ˜1 ^ ^{1 ()} ! /, Examples of the alkylsulfo-lumino group include, for example, methylsulfo-amidoethylsulfo-ramino and propylsulfo-ramino. .

[0020] In ^ to 1 ^ ^{1 ()} in the above formula (1), a halogen atom, an alkyl group or a -tro group may be substituted. Examples of the phenylsulfo-lumino group include benzenesulfo- Examples include benzene-sulfo-lumino, benzene-sulfo-lumino, and toluene-toluene-amido. Substituents on these ring rings can be substituted in the ortho, meta, or para positions on the ring ring relative to the sulforamino group! / It ’s okay.

Preferred R ¹ and R ² in the above formula (1) are each independently a hydrogen atom, a chlorine atom, a bromine atom, a carboxylated carboxyl, a sulfo, a sulfamoyl, an N-methylaminosulfonole, an N-phenenole. Aminosunorehonore, Methinoresnorehoninore, Hydroxyenolesnorehoninore, Phosphono, Nitro, Acetyl, Benzyl, Ureido, Methyl, Methoxy, Ethyl, Ethoxy, Propyl, Propoxy, 2-Hydroxyethoxy, 2-Methoxy Ethoxy, 2-ethoxyethoxy, 3 sulfopropoxy, 4 sulfobutoxy, carboxymethoxy, 2 carboxy ethoxy, acetylamino or benzoylamine, etc., one of which is a hydrogen atom, More preferably, the other is a group other than a hydrogen atom. More preferably, R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a sialamosulfuramoyl, acetyl, methylsulfur, hydroxyethylsulfol, nitro, carboxyl, or sulfo, Preferably, they are a hydrogen atom, carboxyl, sulfo, or cyan, and in these cases, one is a hydrogen atom and the other is more preferably a group other than a hydrogen atom. Further preferred R ¹ is carboxyl or sulfo, and sulfo is particularly preferred. R ² is particularly preferably a hydrogen atom. When R ² is a hydrogen atom and R ¹ is a group other than a hydrogen atom, the substitution position is R ^{1 when} the substitution position is ortho to the azo group, and the substitution position of the nitro group is the azo group. against a para position, when the substitution position of R ¹ is para-position to § zone group, the substitution position is substituted position § zone of preferred instrument R ¹ being ortho against the § zone group the nitro group It is more preferred that the position is ortho to the group, and the position of substitution of the -to-group is para to the azo group.

Preferred as the phenyl group substituted with NO, R ¹ and R ² in formula (1) is p

 2

-Toro 1-Snorehoefe-nore, p-Snorehoe 0--Trophe-Nole, p-Nitro 0-Chano-Fuel, p-Syano 0--Tro-Feol or p-Force Noreboxinore-0-Trophe-Nole etc. P-tro 0-sulfophenyl is most preferred, with the first two being more preferred. In the above formula (1), as one of the preferred cases of R ^{3 to} R ⁶ , there can be mentioned a case where at least one of these groups is a group other than a hydrogen atom, more preferably 2 to 2 of these groups. The case where four, more preferably 3 to 4, are groups other than hydrogen atoms can be mentioned. Preferred groups other than a hydrogen atom include carboxyl, sulfo, (C1-C4) alkyl (substituted with hydroxy or (C1-C4) alkoxy !, may be!), (C1-C4) alkoxy { Substitution with hydroxy, sulfo or carboxyl which may be substituted with hydroxy, (C1-C4) alkoxy, sulfo or carboxyl is preferred. More preferably, it is a case where it is substituted with hydroxy or sulfo}, or an acylamino group, and preferably a substituted (C1-C4) alkoxy (substituent is hydroxy, sulfo or carboxyl) or (C1-C4) alkyl group {which may be substituted with a hydroxy group or (C1-C4) alkoxy group, but is usually unsubstituted}. More specifically, when preferred, 1 to 3, preferably 2 to 3 of R ^{3 to} R ⁶ are sulfo- or hydroxy-substituted (C 1 to C 4) alkoxy groups, and At least one is sulfo-substituted (C 1 to C4) alkoxy group, preferably 2 are sulfo-substituted (C1 to C4) alkoxy groups, the rest are hydrogen atoms or (C1 to C4) alkyl groups, preferably all the rest are (C1 to C4) alkyl The case where it is a group can be mentioned. As the (C1-C4) alkoxy group in the above, an ethoxy group or a propoxy group is preferable.

As another preferred case, R ³ ,

R ⁵ and R ⁶ are each independently a carboxyl group, sulfo group, (C1-C4) alkyl group (which may be substituted with a hydroxy group or a (C1-C4) alkoxy group), (C1-C4) Examples include an alkoxy group (which may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group), or an acylamino group, and more preferably 1 to 2 (C 1 to C4) alkyl group, the remaining 2 to 3 are (C1 to C4) alkoxy groups (hydroxy groups, (C1 to C4) alkoxy groups, sulfo groups or carboxyl groups may be substituted, preferably hydroxy groups , A sulfo group or a carboxyl group, and more preferably a hydroxy group or a sulfo group.

Preferable R ³ and R ⁵ are each independently (C 1 -C 4) alkoxy substituted with sulfo, carboxyl or hydroxy, more preferably sulfo-substituted (C 1 -C 4) alkoxy. 3-sulfopropoxy is most preferred.

Preferable R ⁴ and R ⁶ are each independently a hydrogen atom, (C1-C4) alkyl or hydroxy-substituted (C1-C4) alkoxy, and (C1-C4) alkyl is more preferred methyl. Most preferred.

Specific examples of preferable R ^{3 to} R ⁶ in the above formula (1) are, independently of each other, a hydrogen atom, a chlorine atom, a hydroxy, a carboxy-containing carboxyl, a sulfo, a sulfamoyl, an N-methinoaminoaminorehoninole, an N— Phenylaminosulfonyl, methylsulfonyl, hydroxyethylsulfonyl, nitro, acetyl, benzoyl, ureido, methyl, methoxy, ethyl, ethoxy, propynole, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3 Sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino-containing benzoylamino, and the like, more preferably hydrogen atom, methyl, ethyl, methoxy, ethoxy, 2-hydroxyethoxy, 3-sulfopropoxy, carboxyxyl, or carbon More preferably hydrogen atom, methyl, 3-sulfopropoxy. Si, carboxyl or sulfo. Among these, as R ³ and R ⁵ , preferred are those independently contained in (C1-C4) alkoxy substituted with either sulfo, carboxyl or hydroxy, and more preferred. Is included in sulfo-substituted (C1-C4) alkoxy. Among these, preferable R ⁴ and R ⁶ are each independently a hydrogen atom or (C1-C4) alkyl or hydroxy-substituted (C1-C4) alkoxy, more preferably (C1-C4 ) It is included in alkyl.

Preferably of R ³ to R ^6, a combination, preferably the R ³ ~R ^6! /, A combination between ones are those more preferred one of preferred instrument R ³ to R ⁶ is the rest are preferable Combinations that are more preferable are combinations of R ^{3 to} R ^{6 that} are more preferable.

Preferable R ^{7 to} R ^1C> in the above formula (1) are a hydrogen atom, a chlorine atom, a bromine atom, a hydroxy, a carboxylated carboxyl, a sulfo, a sulfamoyl, an N-methylaminosulfol, and an N-phenol. Aminosunorehonore, Methinolesnorehoninore, Hydroxyenosenorehoninore, Phospho, Nitro, Acetyl, Benzyl, Ureido, Methyl, Methoxy, Ethyl, Ethoxy, Propyl, Propoxy, 2 Hydroxyethoxy, 2-Methoxy Toxyl, 2-ethoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, acetylamino-containing benzoylamino, and the like, more preferably a hydrogen atom, hydroxy, carboxinole, snorejo, snorefamoinole, hydroxye Chinores Nore Honinole, Nito , Mechinore a methoxyethanol, Echiru, ethoxy, more preferably a hydrogen atom, hydroxy, carboxyl, sulfo, sulfamoyl.

Preferably, R ⁷ includes a hydrogen atom. Preferably, R ⁸ and R ⁹ include sulfo. Preferred R ^1G includes sulfo or hydroxy, more preferably hydroxy. The substitution position of R ^1C) is preferably the peri-position (8-position) relative to the azo group.

The most preferred combination of R ^{7 to} R ^1G is when R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo, R ^1C) is hydroxy, and the substitution position of R ^1G is peri to the azo group It is.

 n is 0 or 1 !, it can be shifted! /, but 1 is preferred! /.

[0024] In the above formula (1), 1 ^ to 1 ^ substituents and n are preferably and , R ¹ and R ² , R ^{3 to} R ⁶ and R ^{7 to} R ^1G are preferably combined with each other, and more preferable combinations are (l) R ¹ and R ² , (2) R ^{3 to} R ^6. And (3) the case where at least one of the three of R ^{7 to} R ^1G is more preferable, the more preferable combination of (1) to (3) is more preferable (1) to More preferred in (3) is a combination of 1 to 2 and other more preferred. More preferred in (1) to (3), or more preferred U, most preferred, a combination of things. Is the most preferred.

More specifically, R ¹ is preferably sulfo, carboxy, or cyan as a combination of the substituents in the above formula (1), and the substitution position of R ^{1 is at} the ortho position with respect to the azo group. and - force the substitution position of Toro is para to § zone group or, R ¹ is sulfo or Shiano, para substitution position of R ¹ Whereas § zone group, and - substitution position Toro Is ortho to the azo group, R ² is a hydrogen atom, and R ³ and R ⁵ are (C1-C4) alkoxy substituted by either sulfo, carboxy or hydroxy, preferably sulfo Or (C1-C4) alkoxy substituted by either hydroxy, R ⁴ and R ⁶ are each a hydrogen atom, (C1-C4) alkyl, or hydroxy-substituted (Cl-C4) alkoxy, preferably one Is a hydrogen atom and the other is (C1-C4) alkyl Or hydrate proxy substituted (C 1~C4) alkoxy, or both are independently (C 1~C4) alkyl or hydrate proxy substituted (C1 -C4) alkoxy, more preferably both are (C1 -C4) alkyl, R ^A compound in which ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo, R ^1G is hydroxy or sulfo, R ^1C) is substituted at the peri position relative to the azo group, and n is 1 It is. More preferably, R ¹ is sulfo and the substitution position is ortho to the azo group, the nitro substitution position is para to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are sulfo substitution (C1 ~ C4) alkoxy, R ⁴ and R ⁶ are (C1-C4) alkyl, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo, R ^1G is hydroxy, and the substitution position is peri-position to the azo group, n Is a compound in which 1. Particularly preferably, R ^{1 is} sulfo, the substitution position is ortho to the azo group, the nitro substitution position is para to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are 3-sulfopropoxy, A compound in which R ⁴ and R ⁶ are methyl, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo, R ^1G is hydroxy, R ^1G is substituted at the peri position relative to the azo group, and n is 1. Is mentioned.

In the compound of the above formula (1), at least two of R ^{7 to} R ^1C) are sulfo groups, and the formula (1) The total number of sulfo groups possessed by the compound is preferably 8 to 10, more preferably 9 to 10, and most preferably 9.

 [0025] The salt of the azo compound represented by the formula (1) is an inorganic or organic cation salt. Among these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred salts are lithium, sodium, potassium, and ammonium salts, and Examples of organic cation salts include, but are not limited to, salts of compounds represented by the following formula (2).

 [0026]

[0027]

Z ² , Z ³ and Z ⁴ each independently represent a group selected from a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.

Formula (2)

Specific examples of the alkyl group of Z ³ or Z ⁴ include (C1-C4) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec butyl, tert butyl, etc. Specific examples include hydroxy- (C1-C4) alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxypropyl, 3-hydroxybutyl, 2-hydroxybutyl, and hydroxyalkoxyalkyl groups. Examples of hydroxymethyl, such as hydroxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl (C1-C4 ) Alkoxy— (C 1 -C 4 ) Alkyl groups, among which hydroxyethoxy (C1-C4) alkyl groups are preferred. Particularly preferred are a hydrogen atom; methyl; hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl. Hydroxy- (C1-C4) alkyl groups such as til and 2-hydroxybutyl; hydroxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3- And hydroxyethoxy- (C1-C4) alkyl groups such as hydroxyethoxybutyl and 2-hydroxyethoxybutyl.

As a preferable combination of these ZZ ² , Z ³ and Z ⁴ , either two are a hydrogen atom and Z or an alkyl group, and the other two are a hydroxy- (C1-C4) alkyl group, Alternatively, it is preferable that any one of them is a hydrogen atom or an alkyl group and the remaining three are hydroxy (C1-C4) alkyl groups! /.

[0028] Formula (2)

Specific examples of Z ³ and Z ⁴ are shown in Table 1.

 [0029] [Table 1]

 The azo compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method. Here, for convenience, the structural formula of the compound in each step is expressed in the form of a free acid.

Compound represented by the following formula (3)

(Wherein n has the same meaning as in formula (1).)

 Is reacted with p-toluenesulfuryl chloride in the presence of alkali to give the following formula (

[Wherein n has the same meaning as described above.]

 To obtain a compound represented by:

The obtained compound represented by the above formula (4) was diazotized by a conventional method, and the diazoi compound was subjected to a coupling reaction with 4 amino-5-naphthol-1,7-disulfonic acid under an acidic condition. The following formula (5)

 [0036]

[Wherein n has the same meaning as described above.] To obtain a compound represented by:

 Next, the following formula (6)

[Wherein R ¹ and R ² have the same meaning as in formula (1).]

 After the compound represented by the formula is diazotized by a conventional method, the diazotized compound and the compound represented by the above formula (5) are subjected to a coupling reaction to give the following formula (7)

[0042] (where

R ² and n have the same meaning as described above. )

 To obtain a compound represented by:

[0043] The obtained compound represented by the above formula (7) was hydrolyzed under alkaline conditions to obtain the following formula (8) [0044]

[0045] (where

R ² and n have the same meaning as described above. )

 To obtain a compound represented by:

On the other hand, the following formula (9) [0047]

(Wherein R ^{7 to} R ^1Q have the same meaning as in formula (1).)

 After the compound represented by formula (2) is diazotized by a conventional method, the diazo compound and the following formula (10)

(Wherein R ⁵ and R ⁶ have the same meaning as in formula (1).)

 And a compound represented by the following formula (11):

(Wherein R ^{5 to} R ^1Q have the same meaning as in formula (1).)

 To obtain a compound of

The obtained compound represented by the above formula (11) is diazotized by a conventional method, and then the diazo compound and the following formula (12) [0054]

(Wherein R ³ and R ⁴ have the same meaning as in formula (1).)

 And a compound represented by the following formula (13):

[0057] (wherein R ^{3 to} R ^1Q have the same meaning as described above)

 To obtain a compound represented by:

[0058] The obtained compound represented by the above formula (13) is diazotized by a conventional method, and then the above diazo compound and the compound represented by the above formula (8) are subjected to a coupling reaction. The azo compound of the present invention represented by the formula (1) or a salt thereof can be obtained.

[0059] Preferable specific examples of the compound of the present invention represented by the formula (1) include, but are not limited to, compounds described in Table 2 and Table 3 below. In each table, the sulfo group and carboxyl group are expressed in the form of free acid.

[0060] [Table 2] table

3] * 3.

The esterification reaction between the compound of formula (3) and p-toluenesulfuryl chloride is carried out by a method known per se. The esterification reaction may be carried out in water or an aqueous organic medium, for example at a temperature of 20-100 ° C, preferably 30-80 ° C, and a neutral force alkaline pH value, more preferably neutral to weakly alkaline, For example, the pH value is preferably 7 to 10. The pH value is adjusted by adding a base. As a base, for example, hydroxylated Alkali metal hydroxides such as lithium or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, and acetates such as sodium acetate can be used. The compound of formula (3) and p-toluenesulfuryl chloride are used in almost stoichiometric amounts.

 [0063] The diazotization of the compound of the formula (4) is 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 5-30 ° C., preferably 0-15 ° C.

 Coupling of the diazotized compound of formula (4) with 4-amino-5-naphthol 1,7-disulfonic acid is also carried out under conditions known per se. That is, the coupling reaction is carried out in water or an aqueous organic medium, for example, at a temperature of 5 to 30 ° C, preferably 5 to 25 ° C, and an acidic to neutral, preferably acidic to weakly acidic pH value such as ρΗ1. A pH value of ~ 4 is good. Since the inside of the coupling reaction system is usually acidic, it is preferable to keep the reaction system preferably from acidic to weakly acidic, for example, ρ 1 to 4, by adding a base. Examples of the base include lithium hydroxide or alkali metal hydroxide such as sodium hydroxide, alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, acetate such as sodium acetate, ammonia or Organic amines can be used. The compound of formula (4) and 4-amino-5-naphthol-1,7-disulfonic acid are used in an almost stoichiometric amount.

 [0064] Diazotization of the compound of formula (6) 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 5-30 ° C., preferably 0-15 ° C.

The coupling of the diazotized compound of formula (6) and the compound of formula (5) is also carried out under conditions known per se. The coupling reaction is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° C, and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, such as pH 5-10. Good to do. The pH value is adjusted by adding base. Examples of bases include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, or ammonia. Or organic amines can be used. The compounds of formula (5) and formula (6) are used in an almost stoichiometric amount. [0065] The production of the compound of the formula (8) by hydrolysis of the compound of the formula (7) is also carried out by a method known per se. For the hydrolysis, a method of heating in an aqueous alkaline medium is preferably used. For example, after adding sodium hydroxide or potassium hydroxide to a solution containing the compound of formula (7) and adjusting the pH to 9.5 or more, for example, It is carried out by heating to a temperature of 20 to 150 ° C, preferably 30 to 100 ° C. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to L1.5. The pH value is adjusted by adding a base. As the base, those described above can be used.

 [0066] Diazotization of the compound of the formula (9) is also carried out by a method known per se. The diazotid is used, for example, in a mineral acid medium using, for example, 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. To be implemented.

 The coupling of the diazotized compound of formula (9) and the compound of formula (10) is also carried out under conditions known per se. It may be carried out in water or an aqueous organic medium, for example at a temperature of 5-30 ° C., preferably 5-25 ° C. and an acidic to neutral pH value. The coupling reaction is carried out, for example, at ρΗ1 to 7, and the pH value is adjusted by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, or ammonia. Or an organic amine etc. can be used. The compounds of formulas (9) and (10) are used in almost stoichiometric amounts.

 [0067] Diazotization of the compound of formula (11) is also carried out by a method known per se. The diazotid is carried out in an inorganic acid medium, for example using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C. Is done.

The coupling of the diazotized compound of formula (11) and the compound of formula (12) is also carried out under conditions known per se. In water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, for example at a pH value of pH 6-10. It is advantageous to carry out a ring reaction. The pH value is adjusted by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or sodium carbonate, acetates such as sodium acetate, ammonia or Yes Machines can be used. The compounds of formulas (12) and (11) are used in approximately stoichiometric amounts.

[0068] Diazotization of the compound of the formula (13) is also carried out by a method known per se. The diazotium is carried out, for example, in a mineral acid medium, for example using a nitrite, for example an alkali metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° C, preferably 5 to 25 ° C.

 Coupling of the diazotized compound of formula (13) and the compound of formula (8) 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, and weak acidity is also alkaline, preferably weakly acidic to weakly alkaline, for example at a pH value of pH 6 to 10. good. The pH value is adjusted by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide or sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, ammonia or organic amines. Etc. can be used. The compounds of formulas (8) and (13) are used in almost stoichiometric amounts.

[0069] The compound represented by the formula (1) of the present invention is prepared by adjusting the pH of the reaction solution to neutral or acidic according to the purpose of acid precipitation after the coupling reaction, It can be obtained as a salt such as a sodium salt or a mixture of a salt and a free acid by salting out by adding a salt such as a salt. The obtained compound is dissolved in water as necessary, and crystallization with addition of an alcohol such as methanol or 2-propanol V is carried out about 1 to 3 times as appropriate, so that the metal cation salt can be obtained. Soil and inorganic salts such as Z or sulfate can be removed, and the target azo compound having a low content of the inorganic salt can be obtained. In addition, the compound represented by the formula (1) of the present invention can be isolated in the form of a free acid by adding a mineral acid to the reaction solution after the coupling reaction. Inorganic salts can be removed by washing the isolated compound with water or acidified water. Next, the acid type dye (compound) having a low inorganic salt content thus obtained is neutralized with a desired inorganic or organic base in an aqueous medium to form a corresponding salt solution. I can do it. Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide or potassium hydroxide, ammonium hydroxide, lithium carbonate, carbonate, and the like. Examples of organic bases include organic amines such as ethanolamine and triethanolamine, which are represented by the above formula (2). Force nor Examples include amines, but inorganic or organic bases are not limited to these.

[0070] Next, typical uses of the azo compound of the present invention will be described.

 The azo compound of the present invention can be used as a black pigment for dyeing various articles by a conventional method. A typical use is one in which the compound is dissolved in a liquid medium, preferably an aqueous medium, and used as an aqueous composition for dyeing. The aqueous composition containing the azo compound is capable of dyeing a material having a cellulose power. In addition, the aqueous composition can be used for dyeing leather, woven fabric, paper, and the like because it can dye a material having a carbonamide bond. A typical example of the aqueous composition is an ink composition.

 [0071] A reaction solution containing the azoich compound of the present invention represented by the above formula (1), for example, the reaction before preparing to pH 6.0 to 7.5 with 35% hydrochloric acid in Example 1 (3) described later The liquid can be used as it is in the production of the aqueous composition, particularly the ink composition. However, usually, the reaction solution is first dried, for example, spray-dried and isolated, and the pH is adjusted as necessary, as in the examples below. By salt praying with inorganic salts such as salt, sodium sulfate, sodium sulfate, etc., by acid praying with mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. It is preferable to isolate, then remove inorganic salts as necessary, and then use this to prepare the aqueous composition, particularly the ink composition.

 The content of the azo compound of the present invention in the aqueous composition can be variously changed according to the purpose, and is usually about 0.1 to 25% by mass with respect to the entire aqueous composition. The aqueous composition may contain about 0 to 30% by mass of other water-soluble organic solvents and about 0 to 20% by mass of other additives, with the balance being water.

 [0072] Hereinafter, the ink composition which is the most typical composition of the aqueous composition will be described in more detail.

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 azo compound represented by the formula (1) of the present invention. It is a composition with water as the main medium. The ink composition of the present invention further contains a water-soluble organic solvent, for example 0 to 30% by mass, preferably 2 to 25% by mass, more preferably 5 to 20% by mass of an ink preparation that may be contained, for example, 0 to 10% by mass, preferably 0 to 7% by mass. May be contained in an amount of 0 to 5% by mass. In addition, the pH of the ink composition is preferably pH 7 to 10 and more preferably pH 7 to 10 from the viewpoint of improving storage stability. The surface tension of the ink composition is preferably 25 to 70 mNZm, more preferably 25 to 60 mNZm. Further, the viscosity of the ink composition is preferably 30 mPa's or less, 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 described later.

[0073] The ink composition of the present invention dissolves the azo compound represented by the formula (1) in water or a water-soluble organic solvent (an organic solvent miscible with water), and the ink composition is used as necessary. A preparation is added. When this ink thread composite is used as an ink for an ink jet printer, the content of the inorganic compound such as a metal cation salt or an inorganic salt such as sulfate is low. The preferred content is, for example, about 1% by mass or less based on the chromogen. In order to produce the azo compound of the present invention with a small amount of inorganic substances, for example, the conventional method using a reverse osmosis membrane or a dried product or wet cake of the azo compound of the present invention is applied to the above-described method for removing inorganic salts. Alternatively, desalting may be performed by stirring in a mixed solvent of alcohol such as methanol and water, separating by filtration, and drying.

[0074] Specific examples of the water-soluble organic solvent that can be used for the preparation of the ink composition include C1-C4 such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, nibutanol or tert-butanol. Al-Nol; Carboxylic acid amides such as N, N dimethylformamide or N, N-dimethylacetamide; Ratatas such as 2-pyrrolidone or N-methylpyrrolidin 2one; 1,3 dimethylimidazolidin 2-one or 1, 3 Cyclic ureas such as dimethylhexahydropyrimido 2-one; ketones or keto alcohols such as acetonitrile, methyl ethyl ketone or 2-methyl-2-hydroxypentane-4-one; cyclic ethers such as tetrahydrofuran or dioxane; Ethylene glycol, 1, 2 propylene glycol, 1, 3 pro Glycol, 1, 2 butylene glycol, 1, 4-butylene glycol Honoré, 1, 6 hexylene glycol, diethylene glycidyl Mono-, oligo- or poly-alkylene glycols with (C2-C6) alkylene units such as cornole, triethylene glycol, tetraethylene dallicol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol or Thioglycol; polyol (triol) such as glycerin or hexane-1, 2, 6 triol; ethylene glycol monomethyl ether, ethylene glycol monoremonoethylenoatenore, diethyleneglycolenomonomethinoreatenore, diethyleneglycolmono (C1-C4) alkyl ethers of polyhydric alcohols such as ethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; γ-butyrolatatone; It can be mentioned dimethyl sulfoxide. These organic solvents can be used alone or in combination of two or more.

[0075] Ink preparations used for preparing the ink composition include, for example, antiseptic and antifungal agents, wrinkle adjusting agents, chelating reagents, antifungal agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dyes, and the like. Examples include solubilizers, antioxidants, and surfactants. These drugs are described below.

 [0076] Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ρ-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazoline 3-one and salts thereof. . These are preferably used in the ink composition in an amount of from 0.02 to 1.00% by mass.

[0077] Examples of the preservative include, for example, organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, halogenyl sulfone-based, odopropargyl-based, ハ ロ haloalkylthio-based, nitrile-based, pyridin-based, 8-oxyquinoline-based, Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brom Examples include compounds such as Hihidanone, benzyl bromoacetate and inorganic salts. Specific examples of organic halogen compounds include pentachlorophenol sodium, specific examples of pyridine oxide compounds include, for example, 2-pyridinethiol 1 oxide sodium, and specific examples of inorganic salt compounds. An example is sodium acetic anhydride. Examples of isothiazoline compounds include 1,2- 3-isone thiazoline 3-one, 2-n-octinole 4-isothiazoline 3-one, 5-methyl 2-methyl 4-isothiazoline 3-one, 5-black 2-methyl 4-isothiazoline 1 -On magnesium chloride, 5-methyl 2-isothiazoline 3-on calcium chloride or 2-methyl 4-isothiazoline 3-on calcium chloride. Specific examples of other antiseptic / antifungal agents include sodium sorbate and sodium benzoate.

The [0078] pH adjusting agent, without adversely affecting the ink to be prepared, the _P H of the ink for example 5: Any substance can be used as long as it can control the range of L 1. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine or N-methylethanolamine or organic bases such as potassium acetate; or lithium hydroxide, sodium hydroxide or potassium hydroxide Alkali metal hydroxides such as lithium carbonate, sodium carbonate, sodium bicarbonate or potassium carbonate, etc., hydroxyammonium (ammonia), sodium silicate or phosphoric acid Inorganic bases such as disodium; and the like.

 [0079] Specific examples of the chelating reagent include, for example, sodium ethylenediamine tetraacetate, sodium utrilotriacetate, sodium hydroxyethylethylenediamin triacetate, sodium diethylenetriaminepentaacetate, or sodium uracil diacetate.

[0080] Specific examples of the antifungal agent include, for example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate or dicyclohexyl ammonium. -Umnite light.

 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 polybulal alcohol, cellulose derivative, polyamine or polyimine.

[0081] Specific examples of the dye solubilizer include ε-force prolatatam, ethylene carbonate or urea.

Examples of antioxidants include, for example, various organic and metal complex anti-fading agents. Can be used. Examples of the organic anti-fading agent include rhino, idroquinones, alkoxyphenols, dialkoxyphenols, phenols, arrines, amines, indanes, chromans, alkoxylins or And heterocyclic rings. Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants. Examples of cation surfactants include alkyl sulfonates, alkyl carboxylates, a-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-amino acids and their salts, N-acylmethyl taurine. Salt, alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid sarcophagus, castor oil sulfate ester, lauryl alcohol sulfate ester, alkyl phenol phosphate ester, alkyl phosphate ester , Alkylaryl sulfonate, jetyl sulfonate, jetyl hexyl sulfonate, dioctyl sulfonate, and the like. Examples of the cationic surfactant include 2 vinyl pyridine derivatives and poly 4-vinyl pyridine derivatives. Specific examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkynole N canoleboxoxymethinole N hydroxyethyl imidazolium umbetaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, Octyl polyaminoethylglycine and other imidazoline derivatives. Specific examples of the non-ionic surfactant include polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether.

, Ethers such as polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether or polyoxyethylene alkyl ether; polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxy Esters such as ethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquilate, polyoxyethylene monooleate or polyoxyethylene stearate; 2, 4, 7, 9-tetramethyl- Acetylene glycols such as 5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6 diol, or 3,5 dimethyl-1-hexyne 3ol (eg, manufactured by Nissin Chemical Industry Co., Ltd.) ,Product : Such as Surfynol 104, 105, 82, 465 or Orufuin STG), and the like. These ink preparations are used alone Or it mixes and uses.

 [0083] 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 azo compound represented by the formula (1) of the present invention, other pigments having various hues may be mixed. In that case, black having other hues, yellow, magenta, cyan, and other colors can be mixed and used.

 [0084] The ink composition of the present invention can be used in various fields, but is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. It is suitably used in the ink jet recording method of the present invention described later.

 Next, the ink jet recording method of the present invention will be described. The ink jet recording method of the present invention is characterized by performing recording using the ink composition of the present invention. In the ink jet recording method of the present invention, the ink receiving ink containing the ink composition may be used for recording on the image receiving material by ink jet. There are no particular restrictions on the ink nozzles to be used at that time, and they can be appropriately selected according to the purpose. As a method for recording by ink jet, a known ink jet recording method can be used.For example, a charge control method for discharging ink using electrostatic attraction force, a drop-on-demand method (pressure pulse using the vibration pressure of a piezo element), or the like. System), an acoustic ink jet system that changes the electrical signal into an acoustic beam, irradiates the ink, and uses the radiation pressure to eject the ink, and forms a bubble by heating the ink to form a thermal ink jet that uses the generated pressure. (Bubble Jet (registered trademark)) method or the like can be adopted. The ink jet recording method uses a low density called photo ink, a method that ejects a large number of inks by volume, and a plurality of inks having substantially the same hue and different densities, thereby improving image quality. This includes a method that uses a transparent and colorless ink.

[0086] The colored product of the present invention is colored with the above-described compound of the present invention or an aqueous composition containing the compound, preferably an ink composition. More preferably, it is colored by an ink jet printer using the ink composition of the present invention. As what is colored, For example, information transmission sheet such as paper or film, fiber or Z and cloth (raw materials may be cellulose, nylon or Z and wool, etc.), leather, base material for color filter, and the like. Among them, the information transmission sheet is preferably a surface-treated sheet, and specifically, a sheet provided with an ink receiving layer on a substrate such as paper (including synthetic paper) or film. The ink-receiving layer is formed by impregnating or coating the above-mentioned base material with a cationic polymer, and a porous white inorganic substance capable of absorbing pigments in ink such as porous silica, alumina sol and special ceramics. It is provided by coating on the surface of the base material together with a hydrophilic polymer such as alcohol or polyvinylpyrrolidone. A paper provided with such an ink-receiving layer is usually called an inkjet paper (film) or a paper (film) or the like. For example, Pictorico (trade name, manufactured by Asahi Glass Co., Ltd.), professional photo paper, super photo Paper or matte photo paper (, slip is a trade name, manufactured by Canon Inc.), PM photo paper (gloss) or PM matte paper (, slip is a trade name, manufactured by Seiko Epson Corp.), premium plus photo paper, premium glossy paper Commercially available products such as film or photo paper (trade name, Nippon Hewlett Packard Co., Ltd.) or Photolike QP (trade name, Co-Camino Norta Photo Imaging Co., Ltd.) are available. Of course, plain paper can also be used.

 [0087] Of these, it is known that the discoloration caused by ozone gas in the image recorded on the information transmission sheet coated with a porous white inorganic substance on the surface is particularly large. However, since the ink composition of the present invention has excellent ozone gas resistance, it is particularly effective when recording on such a recording material.

[0088] In order to record on a recording material such as an information transmission sheet by the ink jet recording 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 a normal method is used. What is necessary is just to record on a recording material. In the ink jet recording method of the present invention, the black ink composition of the present invention is converted into a publicly known magenta ink composition, cyan ink composition, yellow ink composition, and, if necessary, a green ink composition, blue ink composition. (Or violet) ink composition and red (orange) ink composition, etc., can be used in combination with one or more appropriately selected. The ink composition of each color to be used together is injected into each container, and the container is used for the inkjet recording of the present invention. Similar to the container containing the aqueous black ink composition, it is used by being loaded into a predetermined position of the ink jet printer.

 [0089] The azo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this azo compound is stable in storage without crystal precipitation, physical property change, color change, etc. after long-term storage. Sex is good. Further, the black ink composition containing the azo compound of the present invention is used for ink jet recording or for writing instruments, and when recorded on plain paper and ink jet dedicated paper, the recorded image has a high print density black. In addition, its ozone gas resistance, light resistance and bronzing properties are excellent. For the sake of convenience in this specification, the phrase “excellent bronzing property! /,” Means that bronzing is not caused or difficult to occur.

 Example

 [0090] Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In the text, “parts” and “%” are based on mass unless otherwise specified. In the formulas in the examples, for the sake of convenience, acidic functional groups such as sulfo groups are expressed in the form of free acids.

 [0091] Example 1

(1) 2-amino-5-naphthol 1,7-disulfonic acid 6.4 parts and p-toluenesulfuric chloride 4.1 parts are reacted at pH 8.0-8.5 at 70 ° C for 1 hour. After that, she prayed for acid salt. The precipitate was separated by filtration to obtain a compound of the following formula (14). The compound (8.8 parts) was dissolved in water (90 parts) while adjusting the pH to 6.0 to 8.0 with sodium carbonate. After adding 6.8 parts of 35% hydrochloric acid, cool the resulting solution to 0-5 ° C, add 3.6 parts of 40% aqueous sodium nitrite solution, diazotize, and formula A suspension (diazo suspension) containing a diazo compound of the compound (14) was obtained. [0092]

After adding 5.8 parts of 4-amino-5-naphthol 1,7-disulfonic acid suspended in 60 parts of water to this diazo suspension, the pH of the resulting suspension was adjusted to 10 to 20 ° C. The mixture was stirred for 4 hours while being kept at 2.4 to 2.8 with sodium carbonate. Next, the pH value was adjusted to 7.0 to 8.5 with sodium carbonate, and the precipitate was dissolved to obtain a solution containing the compound of formula (15).

[0095] (2) Dissolve 5.2 parts of 4-troa-phosphoric acid 2-sodium sulfonate in 50 parts of water, 6.4 parts of 35% hydrochloric acid at 0-5 ° C, 40% sodium nitrite Add 4.0 parts of aqueous solution and diazotize. The obtained suspension was kept in a solution containing the compound of the formula (15) obtained in (1) above at 10 to 20 ° C., and the pH value was kept at 8.0 to 9.0 with sodium carbonate. While dripping. After completion of the dropwise addition, the obtained mixed solution was stirred at 15 to 30 ° C. for 2 hours at pH 8.0 to 9.0 to obtain a solution containing the compound of formula (16).

[0097] After the solution obtained above was heated to 70 ° C, the pH value was adjusted to 10.5 to 11 with sodium hydroxide. While stirring at 0, the mixture was stirred for 5 hours. The resulting solution was cooled to room temperature, and _P H7. 0 to 8. 0 by 35% hydrochloric acid, was Karoe Te salting the Shioi匕sodium therein. The resulting precipitate was separated by filtration to obtain a wet cake containing the compound of formula (17).

[0098]

(3) 15.3 parts of the compound of the following formula (18) obtained by the method described in JP-A-2005-068416 (from the reaction solution with 35% hydrochloric acid to a pH value of 0.5 or less) The product separated by filtration and dried) was added to 130 parts of water, and the pH was adjusted to 6.0 to 7.0 with sodium hydroxide, and the compound was dissolved. Thereto was added 7.7 parts of 35% hydrochloric acid and 4.0 parts of 40% sodium nitrite aqueous solution at 0 to 5 ° C., followed by diazosis (diazo reaction liquid).

[0100] Next, from 4-amino-5-naphthol-1,2,7-disulfonic acid and 2- (3-sulfopropoxy) -5-methyl-line (formula (19) below), JP-A-2004-083492 The compound of the following formula (19) obtained by the method described in the above is dissolved in 30 parts of water to 30 parts of water to pH 4.5 to 5.5 by adding sodium hydroxide, and this solution is dissolved in 15 to 25 parts. The mixture was added dropwise to the above diazo reaction solution for about 30 minutes at ° C. After completion of the dropwise addition, the pH value was adjusted to 3.5 to 4.5 with sodium carbonate additive, and the resulting solution was stirred for 2 hours, and sodium carbonate was further added thereto to adjust the pH value to 7.0 to 8. The coupling reaction was completed as 0. Salt was added to the reaction solution for salting out, and the precipitate was separated by filtration to obtain a wet cake containing a compound of the following formula (20).

(19)

[0103] (4) The wet cake containing the compound of the formula (20) obtained in the above (3) is placed in 80 parts of water, and the pH value is adjusted to 6.0 to 6.0 by adding sodium hydroxide. 7.0 The wet cake was dissolved as 0. To this, 8.3 parts of 35% hydrochloric acid and 3.0 parts of 40% sodium nitrite aqueous solution were added and diazed to obtain a diazo suspension. On the other hand, the wet cake containing the compound of the formula (17) obtained in the above (2) is added to 120 parts of water, and the pH value is adjusted to 8.0 to 9.0 by adding sodium hydroxide. The wet cake was dissolved. To the obtained solution, the above diazo suspension containing a diazo compound of the compound of formula (20) was added dropwise at 20-30 ° C. During the dropwise addition, the pH value was maintained at 8.0 to 9.0 by adding sodium carbonate. After the dropwise addition, the resulting solution was stirred at the same temperature for 2 hours to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of formula (21).

 [0104]

[0105] The obtained reaction solution was heated to 70 ° C, and reacted for 2 hours while maintaining ρΗΙΟ.8 ~: L1.0 with sodium hydroxide. After the reaction, 35% hydrochloric acid is added to the reaction solution to adjust the pH to 6.0 to 7.5. Then, the mixture was salted and added with sodium chloride salt, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 200 parts of water, crystallized with 250 parts of methanol, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 170 parts of water, 250 parts of methanol was added for crystallization, the precipitate was separated by filtration, and dried to obtain the compound of the formula (22) of the present invention (No. 2 in Table 2). 15.) 4 parts were obtained as a sodium salt. The maximum absorption wavelength (λ max) of this compound in an aqueous solution having a pH of 7 to 8 was 625 nm, and the solubility was lOOgZL or more.

 [0106]

 (twenty two)

[0107] Example 2

 (1) The compound of the following formula (181) obtained by using 4-amino-5-naphthol 1,7-disulfonic acid in place of 4-amino-5-naphthol 2,7-disulfonic acid in Example 1 (3) is represented by the formula (18 The compound of the following formula (23) of the present invention (No. 1 compound in Table 2) was obtained in the same manner as in Example 1 except that it was used in place of the compound of)) as a sodium salt. The maximum absorption wavelength (λ max) of this compound in an aqueous solution having a pH of 7 to 8 was 615 nm, and the solubility was lOOgZL or more.

 [0108]

[0109]

 (twenty three)

[0110] Example 3

 (1) In the same manner as in Example 1 except that 2-ditroaniline-4-sodium sulfonate is used in place of 4-nitrotrolin-2-sodium sulfonate in (2) of Example 1. Thus, 14.3 parts of an azo compound of the formula (24) of the present invention (No. 5 compound in Table 2) was obtained as a sodium salt. The maximum absorption wavelength (λ max) of this compound in an aqueous solution having a pH of 7 to 8 was 636 nm, and the solubility was 100 g / L or more.

 [0111]

 (twenty four)

[0112] Example 4

 Ink preparation

 By mixing the following components, a black ink composition of the present invention was obtained, and impurities were removed by filtration through a 0.45 m membrane filter.

 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-exchanged water was added to make the total amount 100 parts. The ink composition thus obtained did not undergo precipitation separation during storage and did not change its physical properties even after long-term storage.

 [0113] Table 4

 Compound of formula (22) obtained in Example 1 '· 5.0 parts

Glycerin 5.0 parts 5. O

 N-methyl 2-pyrrolidone 4. O

 Isopropyl alcohol 3.0 parts

 Butyl carbitol 2.0 parts

 Surfactant 0.1 part

 (Finole 104 manufactured by Nissin Chemical Industry Co., Ltd.)

 Water + sodium hydroxide 75.9

 100. 0

 [0114] Comparative Example 1

 As Example 4 except that the dye of Table 11 in Table 11 is used instead of the compound obtained in Example 1 as the water-soluble inkjet dye (Example (25)) in Example 4. A comparative ink composition was prepared with the following composition.

[0115]

[0116] Example 5 (Test Example)

 (1) Inkjet printing

 Using the ink composition obtained above, using an inkjet printer (trade name: PIXUS 1P4 100 manufactured by Canon Inc.), special glossy paper 1 (Professional Photo Paper PR-101 manufactured by Canon Inc.), special glossy paper 2 Inkjet recording (printing) was performed on three types of paper (Seiko Epson Co., Ltd., photographic paper Chrispia high gloss> KA420SCK) and special glossy paper 3 (Advanced Photo Paper made by Hewlett-Packard Japan). 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 (print sample) was obtained.

[0117] (2) Evaluation of recorded images

Based on the recorded image obtained in (1) above, a light resistance test and an ozone gas resistance test were conducted using a print sample, and the density change of the recorded image before and after the test was evaluated. . The test was performed on the above-mentioned exclusive glossy papers 1, 2 and 3 using the gradation portion where the reflection density D value of the printed matter before the test was closest to 1.0. In addition, a colorimeter (SpectroEye GRETAG—manufactured by MACBETH) was used for colorimetry for evaluation. The specific test method is as follows. The evaluation results are shown in Table 5.

[0118] i) Light resistance test

 Using a xenon weatherometer (Ci4000 ATLAS), a 2mm thick glass plate is installed so that an air layer is formed between the printed sample, and the humidity is 60% RH and the temperature is 24 ° C. The printed sample was irradiated with light at 0.336 WZ square meter illumination for 50 hours. After the test was completed, color measurement was performed using the above colorimeter. The dye residual ratio was determined by (reflection density after test Z reflection density before test) X 100 (%), and evaluated according to the following criteria.

 〇 Survival rate: 95% or more

 △ Residual rate: 85% or more and less than 95%

 X Residual rate: Less than 85%

[0119] ii) Ozone gas resistance test

 Using an ozone meter (Suga Test Instruments Co., Ltd.), the print sample was left for 4 hours at an ozone concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After completion of the test, the colorimetry was performed using the above-mentioned colorimeter, and the dye residual ratio was determined by (reflection density after test Z reflection density before test) X 1 00 (%) and evaluated according to the following criteria.

 〇 Survival rate: 70% or more

 △ Residual rate: 60% or more and less than 70%

 X Residual rate: Less than 60%

[0120] Table 5

 Light resistance Ozone gas resistance

 Example 4 (Formula (22))

 Exclusive glossy paper 1 〇 〇

 Exclusive glossy paper 2 ○ ○

 Exclusive glossy paper 3 ○ ○

Comparative Example 1 (Formula (25)) Exclusive glossy paper 1 XX

 Exclusive glossy paper 2 Δ 〇

 Exclusive glossy paper 3 Δ 〇

 [0121] As is apparent from the results in Table 5, the image recorded by the ink composition containing the azo compound of the present invention is superior in fastness compared to the image of the conventional black dye (comparative example). Good results were obtained even when using special glossy paper of V and misalignment.

 That is, when the exclusive glossy paper 1 is used in comparison with the dye residual rate of the ozone gas resistance test, Comparative Example 1 is less than 60% (X), whereas Example 4 of the present invention is 70% or more ( ○) and showed high robustness.

 Further, in the light resistance test, the difference appears more clearly. In the ink composition containing the azo compound of the present invention! Force with (○) In Comparative Example 1, 85% or more and less than 95% when using special glossy papers 2 and 3 (△), 85% when using special glossy paper 1 Less than (X), the fastness is remarkably inferior to that of Example 4 of the present invention.

 Industrial applicability

[0122] An image recorded with the azo compound of the present invention is extremely excellent in both light fastness and anti-ozone gas fastness, and the azo compound of the present invention has high solubility and stability, so that a high density ink. Therefore, the azo compound of the present invention is extremely useful as a coloring matter for inkjet ink.

Claims

The scope of the claims

 [1] An azo compound represented by the following formula (1) or a salt thereof,

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxy group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, or an N-phenylaminosulfol group. , (C1-C4) alkylsulfol groups (alkyl groups may be substituted with hydroxy groups), phosphono groups, nitro groups, acyl groups, ureido groups, (C1-C4) alkyl groups (hydroxy groups and ( C1-C4) Group power consisting of alkoxy groups (may be substituted with selected groups), (C1-C4) alkoxy groups (hydroxy groups, (C1-C4) alkoxy groups, sulfo groups and carboxyl groups) Substituted with a selected group), an acylamino group, an alkylsulfo-lumino group or a phenylsulfo-lumino group (the phenol group is composed of a halogen atom, an alkyl group and a -tro group) group The may) be substituted with a group selected,

R ⁹ and R ^1q are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a carboxyl group, a sulfo group, a sulfamoyl group, an N-alkylaminosulfol group, or an N-phenylaminosulfol group. , (C1-C4) alkylsulfonyl group (the alkyl group may be substituted with a hydroxy group), phosphono group, nitro group, acyl group, ureido group, (C1-C4) alkyl group (hydroxy group or (Cl-C4) may be substituted with an alkoxy group), (C1-C4) alkoxy group (substituted with a hydroxy group, (C1-C4) alkoxy group, a sulfo group or a carboxyl group! )), A acylamino group, an alkylsulfo-lumino group or a phenylsulfo-lumino group (the phenol group may be substituted with a halogen atom, an alkyl group or a -tro group), n is 0 or 1 , Represent each).

At least one of R ^{3 to} R ⁶ is a group other than a hydrogen atom, at least two of R ^{7 to} R ^1Q are sulfo groups, and the total number of sulfo groups contained in formula (1) is 8 to 10 Item 1 Zoi compound or its salt.

[3] R ⁵ and R ⁶ are each independently a carboxyl group, a sulfo group, a (C1 to C4) alkyl group (substituted with a hydroxy group or a (C1 to C4) alkoxy group !, may be!) 2. The azo compound according to claim 1, which is a (Cl to C4) alkoxy group (which may be substituted with a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group or a carboxyl group) or an acylamino group. Or a salt thereof.

[4] When R ¹ is a sulfo group or a carboxyl group, and the substitution position of R ¹ is ortho to the azo group, the substitution position of the nitro group is para to the azo group, and the substitution of R ¹ 2. The azo compound or a salt thereof according to claim 1, wherein when the position is para to the azo group, the substitution position of the nitro group is ortho to the azo group, and R ² is a hydrogen atom.

5. The method according to claim 1, wherein R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, and n is 1. An azo compound or a salt thereof.

[6] The azo compound or a salt thereof according to any one of claims 1, 3 and 4, wherein R ⁸ and R ⁹ are sulfo groups.

[7] ^{1-3 of} R ^{3 to} R ⁶ are sulfo- or hydroxy-substituted (C 1 -C 4) alkoxy groups, and at least one of them is a sulfo-substituted (C 1 -C 4) alkoxy group, 6. The azo compound or a salt thereof according to any one of claims 1 to 5, wherein the remaining L to 3 groups are a hydrogen atom or a (C1 to C4) alkyl group.

[8] R ⁷ is a hydrogen atom, R ⁸ and R ⁹ is a sulfo group, claim 1 R ^1Q is a hydroxy group, 3, 4 or

The azo compound or the salt thereof according to any one of 5 above.

[9] R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, R ⁷ is a hydrogen atom, R ⁸ and 2. The azo compound or a salt thereof according to claim 1, wherein R ⁹ is a sulfo group, R ^1Q is a hydroxy group, the substitution position thereof is peri to the azo group, and n is 1.

[10] When R ¹ is a sulfo group, a carboxy group, or a cyano group, and the substitution position of R ¹ is ortho to the azo group, the force that the substitution position of the nitro group is para to the azo group or When R ¹ is a sulfo group or a cyano group, and the substitution position of R ¹ is para to the azo group, the substitution position of the nitro group is ortho to the azo group, and R ² is a hydrogen atom Yes, R ³ and R ⁵ are sulfo Or a hydroxy substituted (C1-C4) alkoxy group, wherein R ⁴ and R ⁶ are a hydrogen atom, a (C1-C4) alkyl group or a hydroxy-substituted (C1-C4) alkoxy group, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, R ^1Q is a hydroxy group or a sulfo group, R ^1Q is substituted at the peri position relative to the azo group, and n is 1 The azo compound according to claim 1 or a salt thereof.

[11] R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is the para position to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are sulfo substitution (C1 To C4) alkoxy group, R ⁴ and are (C1 to C4) alkyl groups, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, R ^1Q is a hydroxy group, and the substitution position is relative to an azo group 2. The azo compound or a salt thereof according to claim 1, wherein n is 1.

[12] R ¹ is a sulfo group, the substitution position is ortho to the azo group, the substitution position of the nitro group is para to the azo group, R ² is a hydrogen atom, R ³ and R ⁵ are 3-sulfopropoxy R ⁴ and R ⁶ cate groups, R ⁷ is a hydrogen atom, R ⁸ and R ⁹ are sulfo groups, R ^1Q is a hydroxy group, and the substitution position is peri position relative to an azo group, n is 1 Item 2. The azo compound or salt thereof according to item 1.

 [13] An ink composition comprising at least one of the azo compound or salt thereof according to any one of claims 1 to 5 and 9 to 12.

 [14] An ink jet print recording method using the ink composition according to [13].

 15. The recording material in the ink jet print recording method is an information transmission sheet.

14. The inkjet print recording method according to 14

16. The ink-jet print recording method according to claim 15, wherein the information transmission sheet contains a porous white inorganic substance.

17. An ink jet printer loaded with a container containing the ink composition according to claim 13.

[18] A colored body colored with the azo compound or salt thereof according to any one of claims 1 to 5 and 9 to 12.