JP2626018B2 - Pyridone monoazo dye composition and method for dyeing or printing hydrophobic fiber material using the same - Google Patents

Description

The present invention relates to a pyridone-based monoazo dye composition and its application to dyeing or printing of a hydrophobic fiber material.

<Prior Art> A pyridone monoazo compound is generally useful as a dye capable of dyeing a hydrophobic fiber in a vivid greenish yellow to orange color. For example, the following compounds are known.

(Described in JP-B-47-18549) (Problems to be Solved by the Invention) However, these pyridone-based monoazo compounds are more stable under dyeing conditions than quinophthalone-based compounds often used as yellow dyes. Insufficiency (dye bath stability) and light fastness are inferior, so there is a limit in its use, and its improvement is strongly demanded.

Attempts to use a mixture of two or more dyes to improve the dye bath stability of such pyridone monoazo compounds have been made.
For example, JP-A-56-151765, 58-149957 and 58-1387
It is known in 56 publications. However, even with these, dyeing bath stability cannot be said to be sufficient, and further improvement is desired, and further improvement in dyeing properties, leveling properties, various fastnesses, and the like is also desired.

<Means for Solving the Problems> The present inventors have excellent dyeing properties, leveling properties, and various fastnesses,
As a result of intensive studies aimed at finding a dye having excellent dye bath stability, it was found that a dye mixture comprising a combination of specific pyridone-based monoazo compounds had the desired performance, and the present invention was completed. Reached.

The present invention relates to the following general formula (I) (Wherein X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group which may have a substituent; Represents a carbamoyl or sulfamoyl group optionally substituted with an alkyl group or a cyano group, and R ¹ represents an optionally substituted alkyl group, an alkenyl group or an optionally substituted cycloalkyl, phenyl or anilino group ), Or one or more selected from the group of pyridone-based monoazo compounds or tautomers thereof, and the following general formula (II) (Wherein X ³ and X ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group which may have a substituent, Represents a carbamoyl or sulfamoyl group which may be substituted with an alkyl group or a cyano group, and R ² represents an alkyl group which may be substituted, an alkenyl group or an optionally substituted cycloalkyl, phenyl or anilino group And a dye composition comprising a mixture of one or more selected from the group consisting of pyridone-based monoazo compounds or tautomers thereof, and dyeing or printing a hydrophobic fiber material using the same. Provide the law.

In the general formulas (I) and (II), X ¹ , X ² , X ³ and
The alkyl group in the carbamoyl or sulfamoyl group which may be substituted with an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylsulfonyl group and an alkyl group represented by X ⁴ means an alkyl group having 1 to 4 carbon atoms, The alkyl group in the alkyloxycarbonyl group which may have 1 to 4 carbon atoms means an alkyl group having 1 to 5 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms, a phenyl group or a phenoxy group.

Examples of these alkyl groups include a methyl group, an ethyl group, a propyl group, and a butyl group.Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and examples of the alkylcarbonyl group include an acetyl group and a propionyl group. Examples of the optionally substituted alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an ethoxyethoxycarbonyl group, a methoxybutoxycarbonyl group, a benzyloxycarbonyl group, and a phenylpropoxycarbonyl group. And a phenoxyethoxycarbonyl group. The alkylsulfonyl group is substituted with an alkyl group such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and the arylsulfonyl group is a phenylsulfonyl group, a toluenesulfonyl group, a chloro or bromophenylsulfonyl group. Examples of the carbamoyl or sulfamoyl group include a carbamoyl group, an ethylcarbamoyl group, a butylcarbamoyl group, a sulfamoyl group, an ethylsulfamoyl group, and a butylsulfamoyl group. Among them, X ¹ , X ² , X ³ and X ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonyl group, an arylsulfonyl group,
A cyano group and the like are preferable, and a hydrogen atom, a chlorine atom, a bromine atom, a methyl, ethyl, isopropyl group, a methylsulfonyl group, a phenylsulfonyl group, and a cyano group are particularly preferable.

The optionally substituted alkyl group represented by R ¹ and R ² has 1 to 8 carbon atoms, and is a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, (Wherein Z represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms), or a group represented by the following formula: -OR, -OCOR, -OCOOR, _{-COOR, -NHSO 2 R, -NHCOR,} -OCONHR wherein, R represents an alkyl group having 1 to 4 carbon atoms, 3 to 5 carbon atoms
An alkenyl group, an alkoxyalkyl group having 1 to 4 carbon atoms or a cycloalkyl group or group having 5 or 6 carbon atoms which may be substituted by alkyl having 1 to 4 carbon atoms (However, n represents an integer of 0 to 3 and Z represents the above-mentioned meaning).]

These alkyl groups represented by R ¹ and R ² include methyl, ethyl, n- or iso-propyl, n-,
Examples thereof include sec- or iso-butyl and 2-ethylhexyl. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a linear alkyl group is particularly preferable.

Further, as the alkyl group having a substituent, chloro or bromoethyl group, hydroxyethyl group, cyanoethyl group, benzyl, phenylalkyl group such as phenethyl,
Alkoxyalkyl groups such as methoxyethyl, ethoxypropyl and allyloxyethyl; alkoxyalkoxyalkyl groups such as methoxyethoxyethyl; acyloxyalkyl groups such as acetoxyethyl and propionyloxybutyl; alkoxy such as butoxycarbonyloxyethyl and cyclohexyloxycarbonyloxybutyl Carbonyloxyalkyl group, alkoxycarbonylalkyl group such as ethoxycarbonylethyl, sulfonylaminoalkyl group such as methylsulfonylaminopropyl, acylaminoalkyl group such as acetylaminoethyl, butyrylaminopropyl, propylaminocarbonyloxyethyl, cyclohexylaminocarbonyl Carbamoyloxyalkyl groups such as oxybutyl, phenoxyethyl, phenoxypropyl Phenyloxy alkyl group such, benzyloxy ethyl group, pheneticillin phenyl alkyloxyalkyl groups such as naphthyl oxyalkyl group, phenyl carbonyloxy group such as benzoyloxy ethyl group,
Phenyloxycarbonyloxyalkyl groups such as phenoxycarbonyloxyethyl groups, phenyloxycarbonylalkyl groups such as phenoxycarbonylethyl groups, phenylsulfonylaminoalkyl groups such as phenylsulfonylaminoethyl groups, and phenylcarbonylaminoalkyl groups such as benzoylaminoethyl groups And a phenylcarbamoyloxyalkyl group such as a phenylcarbamoyloxyethyl group. Examples of the substituent (Z) of the phenyl group include groups such as hydrogen, chloro, bromo, methyl, ethyl, methoxy, and ethoxy.

The alkenyl group represented by R ¹ and R ² is preferably one having 3 to 5 carbon atoms, and examples include allyl and crotyl. The cycloalkyl group has 1 to 4 carbon atoms.
Of these, those having 5 or 6 carbon atoms which may be substituted by alkyl are preferable, and examples thereof include cyclohexyl, methylcyclohexyl, and cyclopentyl. The substituents of the phenyl and anilino groups represented by R ¹ and R ² are alkyl and alkoxy groups having 1 to 4 carbon atoms at the o, m or p-position, and halogen, and have such substituents. Examples of phenyl and anilino groups include phenyl, tolyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, bromophenyl, anilino, methylanilino,
Examples thereof include methoxyanilino, chloroanilino, and bromoanilino.

Among them, R ¹ and R ² are each an unsubstituted carbon atom having 1 carbon atom.
To 8 alkyl groups, allyl groups, benzyl or phenethyl groups, or the following formulas: —OR ³ , —OCOR ³ , —CO ₂ R ³ (wherein R ³ is an alkyl group having 1 to 4 carbon atoms, an allyl group or phenyl) Or a C1-C4 alkyl group substituted with a cyano group.

In the pyridone monoazo compound represented by the general formula (I) used in the present invention, a preferred embodiment is that X ² is a hydrogen atom and X ¹ is an atom or group other than a hydrogen atom, or X ¹
Is a hydrogen atom and X ² is an atom or group other than a hydrogen atom, or X ¹ and X ² are both atoms or groups other than a hydrogen atom, and R ¹ is an unsubstituted C 1-8 An alkyl group of
Allyl group, benzene or phenethyl group, or a group represented by the following formula -OR ³ , -OCOR ³ , -CO ₂ R ³ (wherein R ³ has the above-mentioned meaning) or a cyano group It is a pyridone monoazo compound which is an alkyl group having 1 to 4 carbon atoms. Here, as atoms or groups other than hydrogen atoms,
Halogen atom, especially chlorine or bromine atom, carbon number 1
Preferred are an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, and a phenylsulfonyl group.

In particular, X ¹ is a halogen atom, particularly a chlorine or bromine atom or an alkyl group having 1 to 4 carbon atoms, X ² is a hydrogen atom or a chlorine atom, and R ¹ is an unsubstituted alkyl group having 1 to 4 carbon atoms. The pyridone monoazo compound represented by (I) is suitably used.

Among the pyridone-based monoazo compounds represented by the general formula (II), preferred embodiments are those in which X ⁴ is a hydrogen atom and X ³ is an atom or group other than a hydrogen atom, or X ³ is a hydrogen atom and ⁴ is an atom or group other than a hydrogen atom, or
X ³ and X ⁴ are the case where both are atoms or groups other than a hydrogen atom. Here, preferred embodiments as atoms or groups other than R ² and a hydrogen atom correspond to those described above for R ¹ and X ¹ and X ² , respectively.

In particular, X ³ is a halogen atom, especially a chlorine or bromine atom or an alkyl group having 1 to 4 carbon atoms, X ⁴ is a hydrogen atom or a chlorine atom, and R ² is an unsubstituted alkyl group having 1 to 4 carbon atoms. A pyridone monoazo compound represented by (II) is preferably used.

The pyridone monoazo compound represented by the general formula (I) can be prepared by a conventional method, for example, the following general formula (Ia) (Wherein X ¹ and X ² have the above-mentioned meanings). The diazo component represented by the following formula is diazotized by an ordinary method, and is represented by the following general formula (Ib) (Wherein, R ¹ has the above-described meaning.). Alternatively, the following general formula (Ic) (Wherein X ¹ and X ² have the above-mentioned meanings). A compound represented by the following formula (Id) R ¹ -L (Id) (wherein, R ¹ has the above-mentioned meanings) , L represents a leaving group.) Can also be produced by reacting with a compound such as an alkylating agent represented by

The compound represented by the general formula (II) is, for example, a diazo component represented by the following general formula (IIa) instead of (Ia) (Wherein X ³ and X ⁴ have the above-mentioned meanings).
In place of b), the following general formula (II b) (In the formula, R ² has the above-mentioned meaning.), And can be produced in the same manner as described above using each of the compounds.

Also, the following formula (IIc) (Wherein X ³ and X ⁴ have the above-mentioned meanings). The following formula (II d) R ² -L (II d) (wherein R ² and L have the above-mentioned meanings) And a compound such as an alkylating agent.

The mixture composition ratio of the pyridone monoazo compound of the present invention is:
The compound represented by the general formula (I) is preferably 1 to 99% by weight, and the compound represented by the general formula (II) is preferably 99 to 1% by weight, more preferably 15:85 to 95: 5 (weight ratio). Is within the range. By increasing the proportion of the compound represented by the general formula (I), it can be expected that the dye bath stability and light fastness are further improved, and the proportion of the compound represented by the general formula (II) It is expected that the dyeing property and the build-up property can be improved by increasing the ratio, so that the performance suitable for the purpose of use can be easily obtained by adjusting the composition ratio of the two.

The mixtures according to the invention are, for example, of the general formula (I) and (I
After the compounds of the formula (I) are separately produced, they can be separately obtained by dispersing them separately, or by mixing the dried powders or granules in the above proportions. Further, the respective compounds can be mixed in the above-mentioned ratio and then dispersed to obtain a dispersion dye solution comprising a mixture of the two.

In addition, after mixing both the diazo component and the coupling component, a diazotization-coupling reaction can be carried out to simultaneously produce a mixture of the compounds represented by the general formulas (I) and (II).

Dispersion of each of the compounds represented by the general formulas (I) and (II) or a mixture thereof is performed, for example, in a sand mill by dispersing an anionic dispersion of a formalin condensate of naphthalenesulfonic acid, ligninsulfonic acid, or cresol-shepheric acid. It can be carried out in an appropriate amount of an aqueous medium using a dispersant selected from various dispersants such as a dispersant or polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and other nonionic dispersants. The obtained disperse dye solution can be used as a powder or granules as it is or dried.

The dye composition of the present invention contains a mixture of the pyridone-based monoazo compounds represented by the general formulas (I) and (II), but may contain other disperse dyes for the purpose of adjusting the hue, and further include an extender and a pH adjuster. Agents, dispersion leveling agents, dyeing assistants and the like.

The dye composition of the present invention is a synthetic fiber material such as polyamit fiber, polyester fiber, semi-synthetic fiber such as di- or triacetate or a mixed fiber material thereof and natural fiber, particularly, polyester fiber and natural or regenerated cellulose fiber. Can be dyed in a vivid greenish yellow to orange color by an ordinary dip dyeing method, a continuous dyeing method, a carrier dyeing method or a printing method. Further, the dye composition of the present invention is also useful for transfer printing.

The dye composition of the present invention has excellent dyeing properties, in particular, high color yield, remarkably excellent dye bath stability and light fastness, and excellent wet fastness, sublimation fastness, and post-processing fastness. Can be given.

Furthermore, the dye composition of the present invention has good levelness,
Since uniform and uniform dyed matter can be easily obtained, it shows excellent suitability for dip dyeing in combination with its excellent dye bath stability.

The dye composition of the present invention can provide favorable results such as a change in color tone when used in combination with other dyes.

According to the present invention, the conventional pyridine-based monoazo compound is difficult, the dyeing bath stability and levelness are good, suitable for the dip dyeing method, further excellent dyeing properties and good fastness,
Provided is a pyridone-based monoazo dye composition which gives a dyed product having a clear hue.

 Hereinafter, the present invention will be described more clearly with reference to examples.

In Examples, "parts" means "parts by weight", and "color tone" means that on polyester fiber.

Example 1 a) Preparation of Disperse Dye Liquid Formula (1) 9 parts of a compound represented by the following formula (2) Was mixed with 70 parts of a naphthalenesulfonic acid formalin condensate and 150 parts of water, followed by treatment in a sand mill for 10 hours to obtain a dye composition in the form of a dispersion.

b) Dyeing 0.5 part of the dispersion obtained in a) is placed in a pot for dyeing together with 3000 parts of water, and the pH is adjusted to 5 with acetic acid. Next, 100 parts of a polyester fabric was charged and dyed at 130 ° C. for 60 minutes. After the dyeing was completed, washing and rinsing were carried out by a conventional method, and then dried. Excellent fastness including light fastness,
A clear, dense greenish-yellow dyed product was obtained.

In addition, the dye transfer ratio, which is an index of dye bath stability and leveling property, was excellent as shown in Table 1 below.

The dye bath stability and the transfer rate were determined by the following test methods.

(Dye bath stability test) 0.5 part of the dispersion obtained in a) was put together with 3000 parts of water in a dyeing pot, adjusted to pH 5, and then heated to 140 ° C and kept at the same temperature for 80 minutes. Thereafter, the mixture was cooled to 90 ° C., 100 parts of a polyester fabric was charged, and dyed at 130 ° C. for 60 minutes. After the dyeing was completed, washing and rinsing were carried out by a conventional method, and then dried.
The color value of the dyed material thus obtained is
Measured using COMUC-20 (Sumika Chemical Analysis Center)
The color value of the standard dyed product obtained by the method b) was compared with the color value, and the dye bath stability at pH 5 was determined using the following equation.

Further, in order to examine the influence of the pH change at the time of dyeing, the dye bath stability at pH 7 was determined using the same method as described above except that the pH was adjusted to 7.

(Transfer rate measurement method) The standard dyed product obtained by the methods of a) and b) above,
An undyed white cloth was closely adhered, kept at 130 ° C. for 60 minutes, washed with water, and dried. The amount of dye transferred to the white cloth was determined by colorimetry using the method described above, and was compared with the amount of dye remaining in the dyed product similarly determined, and the transfer rate was determined using the following equation.

Comparative Example 1 In place of the dye composition used in Example 1, the compound represented by the formula (2) was used alone, and the others were used in Example 1.
The dye bath stability and the dye transfer rate were determined in the same manner as described above.
The results are shown in Table 1 below.

Example 2 The following formula (3) 15 parts of the compound represented by the following formula (4) Example 1 using a composition comprising 15 parts of the compound represented by
The polyester fabric was dyed in the same manner as described above. A clear, high-density greenish-yellow dyed product having excellent fastnesses including light fastness was obtained.

When the dye bath stability and the dye transfer rate of this dye composition were determined by the above-mentioned test methods, excellent results were obtained as shown in Table 1 below.

Comparative Example 2 Instead of the dye composition used in Example 2, the compound represented by the above formula (4) was used alone, and the others were used in Example 2.
The dye bath stability and the dye transfer rate were determined in the same manner as described above.
The results are shown in Table 1 below.

Example 3 The following formula (5) And 19 parts of the compound represented by the formula (2)
The polyester fabric was dyed in the same manner as in Example 1 using 11 parts. A variety of fastnesses, particularly light fastness, were excellent, and a clear, high-density greenish-yellow dyed product was obtained.

Also, this dye composition showed extremely good dye bath stability.

The compound represented by the formula (5) was produced by the following method.

20.7 parts of 4,5-dichloro-2-nitroaniline are stirred vigorously with 180 parts of water and 36 parts of 30% hydrochloric acid at 0-5 ° C. in a solution of 7 parts of sodium nitrite in 50 parts of water. Perform diazotization. A clear diazo solution was prepared by dissolving 12.6 parts of 1,4-dimethyl-6-hydroxy-pyrid-2-one in 600 parts of water containing 25 parts of 28% sodium hydroxide and 33 parts of sodium acetate.
Add slowly at 5 ° C and stir at the same temperature for 30 minutes. The mixture was then acidified, washed, dried and yielded the compound of formula (5).

λmax 430nm (in DMF) Example 4 The following formula (6) Using 30 parts of the compound represented by the following formula, a disperse dye solution was prepared according to the method of Example 1a), and this was spray-dried to obtain a dye powder (A).

Next, the following equation (7) Using 30 parts of the compound represented by the formula (I), a dye powder (B) was obtained according to the above method.

Using a dye composition comprising 0.09 parts of the dye powder (A) and 0.08 parts of the dye powder, a dyed product obtained by dyeing a polyester fabric in the same manner as in Example 1 (b) is a clear, high-density yellow. And the robustness was excellent. In addition, this dye composition exhibited good dye bath stability.

The compound represented by the formula (6) was prepared by diazotizing 4,5-dimethyl-2-nitroaniline according to the same method as in the compound (5) of Example 3 to give 1-ethyl-6-hydroxy-4-methylpyrido. It was obtained by coupling with -2-one.

λmax 438 nm (in DMF) The compound represented by the formula (7) is similarly prepared by diazotizing 4-bromo-5-chloro-2-nitroaniline to give 1,4
-Dimethyl-3-cyano-6-hydroxypyrido-2-
Obtained by coupling with ON.

λmax 445 nm (in DMF) Example 5 The following formulas (8) and (9) And 10 parts of a compound represented by the following formula (10) The polyester fabric was dyed in the same manner as in Example 1 using a dye composition of 10 parts of the compound represented by the following formula: Excellent fastness, and a clear, high-density greenish-yellow dyed product was obtained.

 In addition, this dye composition exhibited good dye bath stability.

Compounds (8), (9) and (10) used in this example
According to the same method as in the compound (3) of Example 2, 22 parts of 4-bromo-2-nitroaniline was diazotized to give 1,4-dimethyl-6-hydroxypyrido-
A mixture comprising 3.5 parts of 2-one, 3.8 parts of 1-ethyl-6-hydroxy-4-methylpyrid-2-one and 8.2 parts of 3-cyano-1,4-dimethyl-6-hydroxypyrid-2-one and a cup. Manufactured by ring.

Examples 6 to 61 Compound (I) and Compound (II) shown in Table 2 below
Was dyed in the same manner as in Example 1 using 20 parts of a dye composition containing the same in the composition ratio shown in Table 2. All of them had excellent fastnesses, and were crisp and high in density to obtain dyeings having the hues shown in Table 2 below.

In addition, all dye compositions exhibited good dye bath stability.

Example 62 Using the dispersion obtained in a) of Example 1, a printing paste having the following composition was prepared.

(Printing paste composition) the dispersion liquid 3 Half emulsion stock paste ^{(Note 2)} 60 parts liquor stone acid 0.3 parts 0.2 parts Water remaining part Total 100 parts of sodium chlorate (Note 2) Half emulsion stock paste composition lamp oil 70 parts water 25 parts Bisukon KM-8 ^{(Note 3) 5} parts total 100 parts (Note 3) Shin-Nakamura chemical Co. product: 80 parts emulsion were mixed emulsifier above in a high speed mixer and Meipurogamu NP12% paste (Gurinau's products ) 70 parts were mixed to obtain a half emulsion base paste.

The polyester cloth is hand-printed using the printing paste thus obtained. Next, the cloth was dried and subjected to a superheated steam treatment at 175 ° C. for 7 minutes, followed by washing and drying by a conventional method.
A robust and clear greenish-yellow printed fabric was obtained.

Example 63 0.63 part of the disperse dye solution obtained in a) of Example 1 was mixed with Sumicaron Turquoise Blue S-GL (CI Disperse).
Blue 60, a disperse dye manufactured by Sumitomo Chemical Co., Ltd.) (2.2 parts) was used to dye the polyester fabric in the same manner as in Example 1 b). Excellent fastness to light, particularly light fastness, and a clear, high-density and uniform green dyed product were obtained.

Example 64 Same as b) of Example 1 except that 0.86 part of the disperse dye liquid obtained in a) of Example 1 and 0.15 part of Resorin Blue BBLS (CI Disperse Blue 165, disperse dye manufactured by Bayer AG) are used. The polyester fabric was dyed by the method. Excellent fastness to light, particularly light fastness, and a clear, high-density and uniform green dyed product were obtained.

Example 65 A method similar to that of Example 1b) was used, using 0.89 parts of the disperse dye liquid obtained in a) of Example 1 and 0.6 parts of disperse dye F3BS (CI Disperse Red 343, Bayer Co.). Dyed the polyester fabric. Excellent fastness to light, particularly light fastness, and a clear, high-density and uniform scarlet color dyed product were obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideo Hattori 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (56) References JP-A-2-185568 (JP, A JP-A-58-149957 (JP, A) JP-A-58-138756 (JP, A) JP-A-58-117258 (JP, A) JP-A-56-151765 (JP, A)

Claims (11)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group which may have a substituent; Represents a carbamoyl or sulfamoyl group which may be substituted with an alkyl group or a cyano group, and R ¹ represents an optionally substituted alkyl group, an alkenyl group or an optionally substituted cycloalkyl, phenyl or anilino group ), Or one or more selected from the group of pyridone-based monoazo compounds or tautomers thereof, and the following general formula (II) (Wherein X ³ and X ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group which may have a substituent, Represents a carbamoyl or sulfamoyl group which may be substituted with an alkyl group or a cyano group, and R ² represents an optionally substituted alkyl group, an alkenyl group or an optionally substituted cycloalkyl, phenyl or anilino group A dye composition comprising a mixture of one or more selected from the group consisting of a pyridone monoazo compound or a tautomer thereof represented by the following formula: 2. A pyridone monoazo compound represented by the general formula (I) or one or more selected from the group of tautomers thereof and a pyridone monoazo compound represented by the general formula (II): The dye composition according to claim 1, wherein the weight ratio to one or more selected from the group of the mutants is 1 to 99:99 to 1. 3. The method according to claim 1, wherein the mixture contains a pyridone monoazo compound represented by the general formula (I) wherein X ¹ and X ² are both atoms or groups other than a hydrogen atom, or a tautomer thereof. The dye composition as described in the above. 4. The mixture according to claim 1, wherein X ¹ and X ² each independently represent a chlorine or bromine atom, and have 1 carbon atom.
Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms or a phenylsulfonyl group, wherein R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, benzyl or phenethyl, or the following formula ^{-OR 3,, -OCOR 3, -CO} 2 R 3 ( wherein, R ³ represents. an alkyl group, an allyl group or a phenyl group having 1 to 4 carbon atoms) groups represented by 4. The dye composition according to claim 3, further comprising a pyridone-based monoazo compound, which is a C 1-4 alkyl group substituted with a cyano group, or a tautomer thereof. 5. 5. The dye composition according to claim 1, wherein the mixture contains a pyridone monoazo compound represented by the general formula (I) wherein X ¹ is a hydrogen atom, or a tautomer thereof. 6. The mixture according to claim 1, wherein X ² is a chlorine or bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkyl having 1 to 4 carbon atoms. Represents a sulfonyl group or a phenylsulfonyl group, wherein R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a benzyl or phenethyl group, or a group represented by the following formula: —OR ³ , —OCOR ³ , —CO ₂ R ³ (formula Wherein R ³ represents an alkyl group having 1 to 4 carbon atoms, an allyl group or a phenyl group.) Or a pyridone monoazo compound which is an alkyl group having 1 to 4 carbon atoms and substituted with a cyano group; The dye composition according to claim 5, which contains the tautomer. 7. The mixture according to claim 1, wherein X ² is a hydrogen atom, X ¹ is a chlorine or bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Numbers 1-4
Represents an alkylsulfonyl group or a phenylsulfonyl group, wherein R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a benzyl or phenethyl group, or the following formulas: —OR ³ , —OCOR ³ , and —CO ₂ R ³ (Wherein, R ³ represents an alkyl group having 1 to 4 carbon atoms, an allyl group or a phenyl group.) Or a pyridone monoazo compound having 1 to 4 carbon atoms substituted with a cyano group. The dye composition according to claim 1, which comprises the compound or a tautomer thereof. 8. The mixture according to claim 1, wherein X ⁴ is a hydrogen atom, X ³ is a chlorine or bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Numbers 1-4
Wherein R ² is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a benzyl or phenethyl group, or a group represented by the following formula: —OR ³ , —OCOR ³ , —CO ₂ R ³ (Wherein, R ³ represents an alkyl group having 1 to 4 carbon atoms, an allyl group or a phenyl group.) Or a pyridone monoazo compound having 1 to 4 carbon atoms substituted with a cyano group. The dye composition according to claim 1, which comprises the compound or a tautomer thereof. 9. The mixture represented by the general formula (II), wherein X ³ is a hydrogen atom, X ⁴ is a chlorine or bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Carbon number 1
4 represents an alkylsulfonyl group or a phenylsulfonyl group, wherein R ² is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a benzyl or phenethyl group, or the following formula: —OR ³ , —OCOR ³ , —CO ₂ R ³ (wherein, R ³ represents. an alkyl group, an allyl group or a phenyl group having 1 to 4 carbon atoms) pyridone is an alkyl group having 1 to 4 carbon atoms which is substituted with a group or cyano group represented by The dye composition according to claim 1, comprising a monoazo compound or a tautomer thereof. 10. The compound represented by the general formula (II), wherein X ³
And X ⁴ are each independently a chlorine or bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Represents an alkylsulfonyl group having 1 to 4 carbon atoms or a phenylsulfonyl group, wherein R ² is an unsubstituted alkyl group having 1 to 8 carbon atoms, an allyl group, a benzyl or phenethyl group, or the following formula: —OR ³ , —OCOR ³ , -CO ₂ R ³ (wherein, R ³ represents. an alkyl group, an allyl group or a phenyl group having 1 to 4 carbon atoms) alkyl group having 1 to 4 carbon atoms which is substituted with a group or cyano group represented by The dye composition according to claim 1, which comprises a pyridone monoazo compound or a tautomer thereof. 11. A method for dyeing or printing hydrophobic fibers, comprising using the dye composition according to claim 1.