JP2001207076A - Reactive dye composition and method for dyeing therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a blue reactive dye for a cellulose fiber material good in build-up property and little affected by variation of dyeing conditions. SOLUTION: This reactive dye composition comprises dyes represented by formula (I) and formula (VI). In formula (I), R1 and R2 are each a halogen and a pyridinio, R3-5 are each hydrogen, and U1 is phenylene, and Y1 represents a vinyl sulfone cellulose reactive group, and in formula (VI), X1 represents a halogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue reactive dye composition and a dyeing or printing method using the same.

[0002]

2. Description of the Prior Art As a reactive dye for a blue cellulose fiber material, a composition comprising an anthraquinone-based reactive dye and a copper formazan-based reactive dye (see JP-A-2-995) has been used.
No. 64, JP-A-1-103668 and the like, and a composition comprising a bisazo-based reactive dye (JP-A-1-1706).
No. 63, JP-A-8-209021) and the like.

[0003]

With respect to reactive dyes,
(i) good peel-off property, level dyeing property, good washability, small dependency on dyeing temperature, inorganic salt concentration dependency and bath ratio dependency,
(ii) It has excellent fastnesses such as light fastness, combined fastness with sweat and sunlight, washing fastness, chlorine fastness, NOx gas fastness, etc., and has the same level of fastness of dyes used. Is preferred. In particular, with regard to the performance of item (i), in recent years, with the automation of factories, the simplification of operations by shortening the dyeing time, and the diversification of types and forms of materials, more excellent levelness and cleaning properties have been achieved. There is a strong demand for a reactive dye composition having good dye reproducibility. And, regarding the performance of the item (ii), when the level of the fastness of the dye used for dyeing is not uniform, in some or all of the light fastness and sweat fastness, washing fastness and chlorine fastness. Problems such as conspicuous discoloration occur. In particular, there are few blue reactive dyes that are satisfactory in terms of fastness to sweat and sunlight, fastness to chlorine, and fastness to NOx gas, and it is difficult to obtain dyeings and prints having good fastnesses. On the other hand, in the case of dyeing using a reactive dye, particularly in the case of dyeing with a high dyeing concentration, a large amount of inorganic neutral salt is required, but the addition of a large amount of inorganic neutral salt requires a great deal of time and labor. In addition, the operability of the dyeing operation is significantly reduced. Further, addition of a large amount of inorganic neutral salt increases the content of inorganic neutral salt in dyeing wastewater, and is not preferable in view of environmental problems. Therefore, there is a demand for a reactive dye capable of obtaining a high-concentration dyeing product by adding a small amount of an inorganic neutral salt.
Furthermore, due to the recent increasing interest in environmental issues, the rules for the coloring load of the dyeing wastewater also tend to be stricter, and there is a strong demand for a reactive dye having a high fixation rate and a low degree of coloring of the dyeing wastewater.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems in dyeing and printing a blue-based reactive dye, and as a result, a specific blue-based reactive dye composition has been obtained. And accomplished the present invention.

That is, the present invention relates to a blue reactive dye represented by the following formula (I) and a blue reactive dye represented by the following formula (II) and / or (VI): A reactive dye composition comprising a dye and a method for dyeing or printing a cellulose fiber material using the reactive dye composition.

[0006]

Embedded image (I)

Wherein R1 and R2 are, independently of each other,
A halogen atom or an optionally substituted pyridinio group, R3, R4 and R5 each independently represent a hydrogen atom or an optionally substituted lower alkyl group;
Represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted C2-C6 alkylene, and Y1 represents -SO2CH = CH2 or -SO
Represents 2CH2CH2Z1, where Z1 represents a group which is eliminated by the action of an alkali. ]

[0008]

Embedded image (II)

Wherein R6 is sulfo, -SO2CH = C
Represents H ₂ or -SO ₂ CH ₂ CH ₂ Z2 group, Z2 represents a group capable of leaving by the action of an alkali. R7 has the following formula (II)
I)

[0010]

Embedded image (III)

[In the formula, R8 represents a hydrogen atom or a chlorine atom. Or a group represented by the following formula (IV).

[0012]

Embedded image (IV)

Wherein R9 and R10 are, independently of one another,
Halogen atom, lower alkylamino group which may be substituted, lower alkoxy group which may be substituted, phenylamino group which may be substituted or the following formula (V) -NH-U2-Y2 (V) {Formula Wherein U2 represents phenylene which may be substituted or C2-C6 alkylene which may be substituted;
2 represents -SO ₂ CH = CH ₂ or _{-SO 2 CH 2 CH 2 Z3,} Z3 represents a group capable of leaving by the action of an alkali. } Represents a group represented by ]

[0014]

Embedded image (VI) [wherein, X1 represents a halogen atom. Hereinafter, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The lower alkyl groups represented by R3, R4 and R5 in the above formula (I) include linear or branched C1-C4 such as methyl, ethyl, n-propyl and isobutyl. Can be mentioned. Examples of the substituent of these lower alkyl groups include hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl. As the above-mentioned substituted lower alkyl group, specifically, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl,
4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-
Cyanoethyl, 3-cyanopropyl, methoxyethyl,
Ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,
2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl,
-Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2- Methoxycarbonylethyl, 2-ethoxycarbonylethyl,
3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3- Ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl,
2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like.

The lower alkoxy groups represented by R9 and R10 in the formula (IV) include linear or branched alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy and iso-propoxy. it can. Examples of the substituent of these lower alkoxy groups include methoxy, cyano, chloro, hydroxy, and sulfo.

Further, the lower alkyl of the lower alkylamino group represented by R9 and R10 in the formula (IV) and the substituent of the alkyl include the above-mentioned R3, R4 and R4, respectively.
The same ones as exemplified in 5 can be mentioned.

The optionally substituted phenylene represented by U1 in the formula (I) is preferably C1-
Substituted by one or two substituents selected from the group consisting of C4 alkyl groups (methyl group, ethyl group, etc.), C1 -C4 alkoxy groups (methoxy, ethoxy, etc.), halogens (chlorine, bromine, etc.) and sulfo groups. May be phenylene, for example,

[0019]

Embedded image

(In the formula, an asterisk means a bond leading to -Y1.). The optionally substituted naphthylene represented by U1 in the formula (I) preferably includes naphthylene which may be substituted with one sulfo group. Specific examples of these include, for example,

[0021]

Embedded image

(In the formula, an asterisk means a bond leading to -Y1.).

The optionally substituted C2-C6 alkylene represented by U1 in the formula (I) is preferably-(CH2) 2-,-(CH2) 3- and -CH
(CH3) C2-C4 alkylene groups such as CH2- and the like.

Y1 in the formula (I) represents a vinyl sulfone-based fiber reactive group. Examples of Z1, which is a group capable of leaving under the action of an alkali, include, for example, halogen atoms such as fluoro, chloro, and bromo, sulfate, thiosulfate, phosphate, and acetyloxy. Particularly preferred is sulfate. .

R1 and R2 in the formula (I) each independently represent a halogen or an optionally substituted pyridinio, and examples of the halogen include fluoro, chloro and bromo. Is preferred.

The optionally substituted pyridinio represented by R1 and R2 is, for example, a group selected from the group consisting of carboxy, carbamoyl, sulfo, halogeno and optionally substituted alkyl having 1 to 4 carbon atoms. And pyridinio which may be substituted. Here, the alkyl having 1 to 4 carbon atoms which may be substituted includes 2-alkyl
Examples thereof include hydroxyethyl and 2-sulfoethyl.

Specific examples of the above pyridinio include pyridinio, 2-, 3- or 4-carboxypyridinio, 2
-, 3- or 4-carbamoylpyridinio, 3-sulfopyridinio, 4- (2-sulfoethyl) pyridinio, 3
-(2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio, 3,5-dicarboxypyridinio and the like can be mentioned. Preferably,
Pyridinio substituted with carboxy or carbamoyl, particularly preferred is 3- or 4-carboxypyridinio.

In the formula (II), R6 is a vinylsulfone-based fiber reactive group, and examples of Z2 which is a group capable of leaving by the action of an alkali include the same as those exemplified above for Z1.

In the formula (II), R7 is the same as the aforementioned formula (II)
Represents a group represented by the formula (I) or (IV), wherein R7 is a group represented by the formula (I)
Is a group represented by V), R6 fiber reactive group (-SO ₂ of vinylsulfone is CH = CH ₂ and -SO ₂ CH ₂ C
H ₂ Z2).

In the formula (IV), R9 and R10 each independently represent a halogen atom, an optionally substituted lower alkylamino group, an optionally substituted lower alkoxy group, an optionally substituted phenylamino group. Or a group represented by the formula (V), and examples of the halogen atom include fluoro, chloro, and bromo; and chloro or fluoro is preferable.

When R9 and R10 are an optionally substituted lower alkylamino group, examples of the optionally substituted lower alkyl in the group include the same as those exemplified above for R3. it can.

Examples of the optionally substituted lower alkylamino group include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 2-
Methoxyethylamino, 2-carboxyethylamino,
2-carbamoylethylamino, 2-sulfamoylethylamino and the like are preferred.

When R9 and R10 in the formula (IV) are an optionally substituted phenylamino group, examples of the optionally substituted phenyl in the group include alkyl having 1 to 4 carbon atoms, Alkoxy having 1 to 4 carbon atoms,
Sulfo, carboxy, halogeno, hydroxy, cyano,
Carbamoyl, sulfamoyl, carboxylate,
2-hydroxyethylsulfonyl, amino, acylamino (lower alkylcarbonylamino, phenylcarbonylamino and the like) and substituted by one or two substituents selected from the group of amino substituted by an alkyl group having 1 to 4 carbon atoms And the like.

The optionally substituted phenyl in the optionally substituted phenylamino group includes:
For example, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3-
Or 4-ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-carboxyphenyl, 2
-Sulfo-4-methoxyphenyl, 2-, 3- or 4-
Examples include hydroxyphenyl, 2-, 3- or 4-chlorophenyl and 3-chloro-4-methylphenyl.

U2 in the formula (V) represents an optionally substituted phenylene or an optionally substituted C2-6 alkylene, and specific examples thereof include the aforementioned U1
And the same as those exemplified above.

In the formula (V), Y2 is a vinylsulfone-based fiber reactive group, and Z3, which is a group capable of leaving by the action of an alkali, includes the same groups as those exemplified for Z1. .

X1 in the formula (VI) represents a halogen, and examples of the halogen include fluoro, chloro and bromo, and chloro or fluoro is preferable.

Although the method for producing the reactive dye represented by the formula (I) is not particularly limited, it can be produced, for example, as follows.

When both R1 and R2 in the formula (I) are halogeno, for example, the following method can be exemplified.

A compound represented by the formula H2NCN (VII) and a compound represented by the following formula (VIII)

[0041]

Embedded image (VIII) wherein R3 has the meaning described above. Is condensed with 2,4,6-trihalogeno-s-triazine according to a known method to obtain the following formula (IX)

[0042]

Embedded image (IX)

[Wherein, R3 represents the above-mentioned meaning, and W1 represents halogeno. ] Can be obtained.

On the other hand, the formula R5NH-U1-Y1
(X) wherein R5, U1 and Y1 have the above-mentioned meanings. And a compound represented by the following formula (XI):

[0045]

Embedded image (XI)

[Wherein, R 4 has the meaning described above. ] 2,4,6-trihalogeno-
By condensation with s-triazine according to a known method, the following formula (XII)

[0047]

Embedded image (XII)

[Wherein R4, R5, U1 and Y1 represent the above-mentioned meanings, and W2 represents halogeno. ] Can be obtained.

The amine compounds represented by the formulas (IX) and (XII) are each diazotized according to a conventional method, and the resulting diazotized product is converted into a free acid by the following formula (X)

[0050]

Embedded image (XIII)

Is coupled with the 1-amino-8-naphthol compound at a temperature of -10 ° C. to 30 ° C. while adjusting the pH to 0 to 4. Then, the former diazotized product is added to the coupling reaction product with 0% By coupling while adjusting the pH to 2 to 8 at 40 ° C to 40 ° C, the following formula (XI)
The compound represented by V) can be obtained.

[0052]

Embedded image (XIV)

[Wherein R3, R4, R5, U1 and Y1
Represents the above-mentioned meaning, and W1 and W2 represent halogeno. ] Can be obtained.

Among the reactive dyes of the formula (I), those in which R1 and R2 are optionally substituted pyridinio are:
For example, a compound of formula (XIV) whose free acid form is synthesized in the same manner as described above and a pyridine compound corresponding to an optionally substituted pyridinio at a temperature of 10 ° C. to 100 ° C.
By reacting under the conditions of H2 to H9, the following formula (X
The compound of V) can be obtained.

[0055]

Embedded image (XV)

Wherein R3, R4, R5, U1 and Y1
Represents the same meaning as described above, and W3 and W4 represent optionally substituted pyridinio. ]

In the above-mentioned production method, in the condensation reaction with 2,4,6-trihalogeno-s-triazine, the order and reaction conditions are not particularly limited. For example, the first condensation reaction is carried out at a temperature of -10 ° C. The reaction was carried out under the conditions of 40 ° C. and pH 1 to 10, and the second condensation reaction was carried out at a temperature of 0 ° C. to 70 ° C.
C. and pH 2 to 10 can be carried out.

The reactive dye represented by the formula (II) is produced according to the methods described in JP-A-56-00983, JP-A-56-128380, JP-A-6-287463, and the like. Can be.

The reactive dye composition of the present invention comprises a composition containing the dyes of the formulas (I) and (II),
Compositions containing the dyes of the formula (I) and formulas (I), (I)
It is a composition containing the dyes of I) and (VI), and each of the dyes in the formulas (I), (II) and (VI) may be one kind or plural kinds. Further, each of the reactive dyes described above is present in the form of a free acid or a salt thereof, and alkali metal and alkaline earth metal salts are preferable.
Sodium, potassium and lithium salts are particularly preferred. The reactive dye used in the present invention may be mixed in a solid state or in a liquid state.

The mixing ratio of each reactive dye in the reactive dye composition of the present invention is not particularly limited, but the total amount of the reactive dyes of the formulas (I), (II) and (VI) is 1000 parts by weight. Preferably, the amount of the reactive dye (I) is 50 to 950 parts by weight.

The reactive dye composition of the present invention may optionally contain
Inorganic salts such as sodium sulfate and sodium salt, β-sodium naphthalene sulfonate / formalin condensate, methyl naphthalene sulfonate / formalin condensate, dispersants such as acetylaminonaphthol compounds, and dust dispersion such as di-2-ethylhexyl terephthalate It may contain known dyeing assistants such as inhibitors, pH buffering agents such as sodium acetate and sodium phosphate, hard water softeners such as polyphosphate, and other dyes. The form of the reactive dye composition of the present invention is not particularly limited, and may be, for example, a powder form, a granular form, or a liquid form.

The reactive dye composition of the present invention is useful for dyeing or printing fiber materials, especially cellulosic fiber materials and polyamide fiber materials, and fiber materials containing the same. The cellulosic fiber material is not particularly limited, and examples thereof include natural or regenerated cellulosic fibers such as cotton, linen, hemp, jude, ramie fiber, viscose human silk, and Bemberg, and polyamide fiber material is particularly limited. Although not limited, wool, silk and the like are exemplified.
Examples of the fiber material containing these include cotton / polyester, cotton / nylon, cotton / acryl, cotton / wool, and mixed wool / polyester.

As a method for dyeing and printing in the present invention, any known method may be used. In the exhaust dyeing method,
Examples of the method include dyeing using a known inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, and a known acid binder such as sodium carbonate, sodium bicarbonate, caustic soda, and sodium tertiary phosphate, alone or in combination. The amount of the inorganic neutral salt or acid binder used at this time is not limited, but is preferably at least 1 g / L or more, and may be 100 g / L or more.
Further, these inorganic neutral salts and acid binders may be charged into the dyeing bath at one time, or may be dividedly charged by a conventional method. In addition, other dyeing assistants such as leveling agents, dyeing agents, bath softeners and the like may be used in combination with known methods, but the dyeing assistants are not particularly limited to these. The dyeing temperature is usually 40 to 90 ° C, preferably 50 to 90 ° C.
It is. In the cold batch-up dyeing method, after padding using a known inorganic neutral salt such as anhydrous sodium sulfate and sodium chloride, and a known acid binder such as caustic soda or sodium silicate, the temperature is preferably 0 to 90 ° C. in a closed packaging material. Is exemplified by a method of dyeing by leaving it at a temperature of 10 to 40 ° C. In the continuous dyeing method, a known acid binding agent such as sodium carbonate, sodium bicarbonate, and caustic soda is mixed with the dye padding solution, and padding is performed by a known method, followed by a one-bath padding method of dyeing by dry heat or steaming. A two-bath padding method in which a known inorganic neutral salt such as sodium sulfate and salt and a known acid binder such as caustic soda and sodium silicate are padded and dyed by dry heat or steaming by a known method, dyeing is exemplified. The method is not limited to these. The printing method is a one-phase printing method in which a printing paste containing a known acid binder such as sodium carbonate and sodium bicarbonate is printed, dried and then steamed for printing. A known method for printing by a two-phase printing method or the like in which a known inorganic neutral salt and a known acid binder solution such as caustic soda and sodium silicate are put into a high temperature of 80 ° C. or more to perform printing is used. In dyeing or printing, a known leveling agent, a slow dyeing agent and a bath softener may be used in combination by a known method.

Suitable acid binders for fixing the reactive dye composition of the present invention on cellulose fibers include, for example, an alkali metal or an alkaline earth metal and an inorganic salt or an organic acid or a compound which releases an alkali under heating. Is a water-soluble basic salt of In particular, mention may be made of hydroxides of alkali metals and alkali metals of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Examples of such an acid binder include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

[0065]

The reactive dye composition of the present invention is excellent in various dye properties such as leveling property, dye reproducibility and build-up property in dyeing and printing of a fiber material, and has an effect on the combined action of sweat and sunlight. Dyeings and prints having good fastnesses such as fastness, chlorine fastness and fastness to oxidizing gas are provided. In particular, in exhaustion dyeing, the dependency on the dyeing temperature and bath ratio is small, the dyeing reproducibility is excellent, and even at a high dyeing concentration, sufficient color yield can be obtained by adding a small amount of neutral inorganic salt, and the fixation rate is high. Therefore, the coloring load of the dyeing wastewater is small.

[0066]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% and parts are% by weight unless otherwise specified.
And parts by weight.

Example 1 The form of the free acid is represented by the formula (1)

[0068]

Embedded image (1)

400 parts of the dye represented by the formula
Equation (2)

[0070]

Embedded image (2)

By mixing 600 parts of the dye represented by the formula (1), a blue reactive dye composition is obtained. A dyeing apparatus (bath ratio: 1: 1) was prepared by setting 0.3 g of the composition thus obtained and 3.0 g of anhydrous sodium sulfate in 10 g of a knitted fabric made of cotton fiber.
0, the bath temperature is 60 ° C.) by a known method.
The knit is treated at 0 ° C. for about 20 minutes, then 2.0 g of sodium carbonate is poured into the bath, and the knit is dyed and washed at this temperature for 60 minutes, resulting in good light fastness, chlorine and wash fastness. A uniform blue dyeing without spots is obtained.
Also, the reproducibility of the above dyeing is good.

Example 2 The form of the free acid is represented by the following formula (3)

[0073]

Embedded image (3)

The dye represented by the following formula (4) is represented by the following formula (4):

[0075]

Embedded image (4)

By mixing 300 parts of the dye represented by the formula (1), a dark blue composition is obtained. As in Example 1, 0.8 g of this composition and 5.0 g of anhydrous sodium sulfate were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 g of a knitted fabric made of cotton fiber was set. The knitted fabric was treated at 60 ° C. for about 20 minutes after the addition, and then 0.3 ml of 38 ° C. caustic soda was poured into the bath.
Dyeing and washing the knitted fabric for 0 minutes gives a uniform, dark blue dyeing with good lightfastness, perspiration, chlorine and washing fastness. Also, the reproducibility of the above dyeing is good.

Example 3 The form of the free acid is represented by the following formula (5)

[0078]

Embedded image (5)

In the form of the free acid, 700 parts of the dye represented by
The following formula (6)

[0080]

Embedded image By mixing 300 parts of the dye represented by (6), a dark blue composition is obtained. 50 g of this composition and 500 g of common salt were charged by a known method into a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 70 ° C.) in which 1,000 g of cotton fiber yarn was set.
After treatment at 70 ° C. for 20 minutes, 200 g of sodium carbonate was put into the bath, and then dyed and washed at this temperature for 60 minutes. The concentration between the inner and outer layers of the cheese, which was good in light fastness, sweat sunlight, chlorine and washing fastness, was improved. A uniform dark blue dyed yarn with no difference is obtained. Also, the reproducibility of this cheese dyeing is good.

Example 4 The form of the free acid is represented by the following formula (7)

[0082]

Embedded image (7)

400 parts of the dye represented by the following formula,
The following formula (8)

[0084]

Embedded image (8)

By mixing 600 parts of the dye represented by the formula (1), a blue reactive dye composition is obtained. 0.2 g of the above composition and anhydrous sodium sulfate were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 g of rayon knit was set.
0 g, knitted at 60 ° C. for 20 minutes, 2.0 g of sodium carbonate, dyed and washed at this temperature for 60 minutes. A dyed product having good fastness is obtained. Even if the above dyeing is repeated, the reproducibility is good.

Example 5 10 g of a rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 60 ° C. The form of the free acid is
The following equation (9)

[0087]

Embedded image (9)

150 parts of the dye represented by the formula
The following formula (10)

[0089]

Embedded image (10)

0.6 g of a composition obtained by mixing 700 parts of the dye represented by the following formula, 150 parts of the dye represented by the above formula (5), and 5.0 g of anhydrous sodium sulfate are put into a bath by a known method. After that, the knitted fabric was treated at this temperature for 20 minutes, and 2.0 g of sodium carbonate was put into the bath by a known method. Subsequently, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform and dark blue with no spots. The obtained dyed product had good light fastness, sweat and sunlight, chlorine, and washing fastness. In addition, the above-mentioned dyeing was repeatedly carried out, and in each case, the reproducibility of the dyeing was good.

Example 6 The form of the free acid is represented by the following formula (11)

[0092]

Embedded image (11)

In the form of the free acid, 700 parts of the dye represented by
When 300 parts of the dye represented by the formula (5) is sufficiently mixed, a dark blue dye composition is obtained. This dye composition 20
After dissolving 0 parts with hot water, the mixture was cooled to 25 ° C., 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate,
Then, 20 parts of sodium bicarbonate was added, and water was further added to make the total amount 1000 parts by volume at 25 ° C. Using this solution as a padding solution, padding a cotton fabric,
After drying at 0 ° C. for 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dye, a dyed product having a uniform dark blue color and having good light fastness, perspiration, chlorine and washing fastness is obtained. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 10 g of a rayon knit was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 60 ° C. The form of the free acid is
The following formula (12)

[0095]

Embedded image (12)

In a bath, 800 g of the dye represented by the following formula, 0.7 g of a composition obtained by sufficiently mixing 200 parts of the dye represented by the formula (1), and 5.0 g of anhydrous sodium sulfate are added in a bath by a known method. After that, the knitted fabric was treated at this temperature for 20 minutes, and 2.0 g of sodium carbonate was poured into the bath by a known method. Subsequently, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform and dark blue with no spots. The obtained dyed product had good light fastness, sweat and sunlight, chlorine, and washing fastness. In addition, the above-mentioned dyeing was repeatedly carried out, and in each case, the reproducibility of the dyeing was good.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 62/513 C09B 62/513 D06P 1/38 D06P 1/38 Z

Claims (7)

[Claims] 1. A blue reactive dye having a free acid form represented by the following formula (I) and a blue reactive dye having a free acid form represented by the following formula (II) and / or (VI): A reactive dye composition comprising: Embedded image (I) wherein R1 and R2 independently represent a halogen atom or an optionally substituted pyridinio group;
R4 and R5 each independently represent a hydrogen atom or an optionally substituted lower alkyl group; U1 represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted C2; ~ C6 alkylene, Y1 represents -SO2CH = CH2 or -SO2CH2CH
Represents 2Z1, wherein Z1 represents a group capable of leaving by the action of an alkali. ] (II) [wherein, R6 is sulfo, -SO2CH = CH ₂ or -SO
₂ CH ₂ CH ₂ Z2 represents a group which is eliminated by the action of an alkali. R7 is represented by the following formula (III): (III) wherein R8 represents a hydrogen atom or a chlorine atom. Or a group represented by the following formula (IV). Embedded image (IV) wherein R 9 and R 10 are, independently of each other, a halogen atom, a lower alkylamino group which may be substituted, a lower alkoxy group which may be substituted, a phenylamino group which may be substituted or Formula (V) -NH-U2-Y2 (V) {wherein, U2 represents phenylene which may be substituted or C2-C6 alkylene which may be substituted;
2 represents -SO ₂ CH = CH ₂ or _{-SO 2 CH 2 CH 2 Z3,} Z3 represents a group capable of leaving by the action of an alkali. } Represents a group represented by ] (VI) [wherein, X1 represents a halogen atom. ] Y1 is at wherein formula _{(I), -SO 2 CH 2} C
The composition of claim 1 which is H ₂ OSO ₃ H. 3. The composition according to claim 1, wherein R6 in the formula (II) is a sulfo group, and R7 is a group represented by the formula (III). 4. A compound of the formula (II) wherein R6 is --SO ₂ CH
= CH ₂ or _{-SO 2 CH 2 CH 2 OSO 3} H, R7
Is a group represented by the formula (III). 5. R5 in the formula (II) is --SO ₂ CH
= CH ₂ or _{-SO 2 CH 2 CH 2 OSO 3} H, R7
Is a group represented by the formula (IV). 6. R6 in the formula (II) is --SO ₂ CH
= CH ₂ or _{-SO 2 CH 2 CH 2 OSO 3} H, R7
Is a group represented by the formula (IV), and one of R9 and R10 is halogeno. 7. A method for dyeing or printing a fiber material, comprising using the composition according to claim 1.