JP2001200176A - Reactive dye composition and method for dyeing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a blue reactive dye for cellulose fiber having a slight influence of fluctuation of build-up and dyeing condition. SOLUTION: This reactive dye composition comprises reactive dyes of formula (I) [R1 and R2 are each a halogen or a substitutable pyridinio; R3 to R5 are each hydrogen or an alkyl; U1 is a substitutable phenylene or a substitutable alkylene; Y1 is a vinyl sulfone-based fiber reactive group] and formula II [X1 is a halogen or a substitutable pyridinio; D1 is a substitutable alkyl or a substitutable phenyl; R6 is a group of the formula: -NHCOC(Br)=CH2 or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a blue reactive dye composition and a method for dyeing or printing a fiber material using the same.

[0002]

2. Description of the Related Art Reactive dyes have been widely used for dyeing and printing of fiber materials. Blue reactive dye compositions for dyeing and printing cellulosic fiber materials include, for example, anthraquinone type reactive dyes and copper dyes. Mixtures comprising formazan-based reactive dyes (JP-A-2-99564, JP-A-1-103668, etc.) and compositions comprising bisazo-based reactive dyes (JP-A-1-170663, JP-A-8-209012) Gazettes) are known.

[0003]

With respect to reactive dyes,
(i) Good build-up properties, level dyeing properties, and detergency, low dependence on dyeing temperature, inorganic salt concentration, bath ratio, etc., (ii) Light fastness and combined fastness with sweat and sunlight It is preferable that various fastnesses such as fastness, washing fastness, chlorine fastness, and NOx gas fastness are excellent, and that the dyes used have the same level of fastness. In particular, with regard to the performance of the item (i), in recent years, with the automation of factories, the simplification of operations by shortening the dyeing time, and the diversification of the types and forms of materials, more excellent leveling and washing properties have been achieved. There is a strong demand for a reactive dye having good reproducibility of dyeing. 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 having satisfactory fastness to sweat and sunlight, fastness to chlorine and fastness to NOx gas, and it is difficult to obtain dyeings or 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 of reactive dyes, and as a result, a specific blue reactive dye composition has achieved this object. And completed the present invention.

That is, the present invention relates to 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 a method of dyeing or printing a fiber material using the 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 -S
O2CH2CH2Z1 represents a group capable of leaving by the action of an alkali. ]

[0008]

Embedded image (II)

[In the formula, X1 represents a halogen atom or an optionally substituted pyridinio group, D1 represents an optionally substituted lower alkyl group or an optionally substituted phenyl group, and R6 represents -NHCOC. (Br) = CH
₂ group, -NHCOCH (Br) CH ₂ Br group or the following formula (III)

[0010]

Embedded image (III)

In the formula, X2 represents a halogen atom or an optionally substituted pyridinio group, and D2 represents an optionally substituted lower alkyl group or an optionally substituted phenyl group. } Represents a group represented by Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The above formulas (I), (II) and (II)
The lower alkyl groups represented by R3, R4, R5, D1 and D2 in I) include methyl, ethyl, n-propyl,
Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as isobutyl. Examples of the substituent of the lower alkyl group include hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl. Specific examples of these substituted lower alkyl groups include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, , 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, 2-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-sulfo Famoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like.

The optionally substituted phenylene represented by U1 in the above formula (I) is preferably
1-C4 alkyl group (methyl group, ethyl group, etc.), C1-C4
Phenylene which may be substituted by one or two substituents selected from the group consisting of an alkoxy group (e.g., methoxy, ethoxy), a halogen (e.g., chlorine, bromine) and a sulfo group;

[0014]

Embedded image

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

[0016]

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.

In the formula (I), Y1 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 halogen or optionally substituted pyridinio. Examples of the halogen include fluoro, chloro, and bromo, and chloro or fluoro is preferable.

Examples of the optionally substituted pyridinio include, for example, those substituted with a group selected from the group consisting of carboxy, carbamoyl, sulfo, halogeno and optionally substituted alkyl having 1 to 4 carbon atoms. And good pyridinio. Examples of the optionally substituted alkyl having 1 to 4 carbon atoms which is a substituent of pyridinio include 2-hydroxyethyl and 2-sulfoethyl.

Specific examples of the pyridinio include pyridinio, 2-, 3- or 4-carboxypyridinio,
-, 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, 3- or 4-carboxypyridinio is particularly preferred.

X in the above formulas (II) and (III)
1 and X2 represent halogen or optionally substituted pyridinio. Examples of the halogen represented by X1 and X2 include fluoro, chloro, and bromo, and chloro or fluoro is preferable.

The optionally substituted pyridinio represented by X1 and X2 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. Examples of the optionally substituted alkyl having 1 to 4 carbon atoms which is a substituent of pyridinio include 2-hydroxyethyl and 2-sulfoethyl. Specific examples of the optionally substituted pyridinio represented by X1 and X2 include:
The same groups as those exemplified for R1 and R2 can be exemplified.

D in the above formulas (II) and (III)
1 and D2 represent an optionally substituted lower alkyl group or an optionally substituted phenyl group. Examples of the above-mentioned optionally substituted phenyl group include unsubstituted phenyl, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, carboxy, sulfo, halogeno, nitro and nitro. Q (Q is -SO ₂ CH = CH ₂ or -SO
Phenyl substituted by one, two or three substituents selected from the group consisting of ₂ CH ₂ CH ₂ Z2 groups, wherein Z2 represents a group which is eliminated by the action of an alkali.

Examples of the optionally substituted phenyl represented by D1 and D2 include the following.

[0027]

Embedded image

[0028]

Embedded image

[Wherein Q represents the above meaning. ]

R6 in the above formula (II) is --NHC
_{OC (Br) = CH 2,} -NHCOCH (Br) CH 2 B
r or a group represented by the above formula (III), wherein R6 is-
NHCOC (Br) = CH ₂ or -NHCOCH (B
r) When it is a group represented by CH ₂ Br, preferred D1
_The, -SO ₂ CH = CH 2 or -SO ₂ CH ₂ CH ₂
Examples include phenylene substituted with an OSO ₃ H group.

On the other hand, when R6 is a group represented by the formula (III), D1 and D2 are preferably phenyl substituted with a group selected from alkyl, carboxy, sulfo and halogen, and X1 and X2 are Preferably independently of one another chloro, fluoro or pyridinio.

The method for producing the compound represented by the above formula (I) is not particularly limited, but it can be produced, for example, as follows.

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

A compound represented by H2NCN (IV) and the following formula (V)

[0035]

Embedded image (V)

[Wherein, R 3 has the meaning described above. ] 2,4,6-trihalogeno-
By condensation with s-triazine according to a known method, the following formula (VI)

[0037]

Embedded image (VI)

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

On the other hand, the following formula (VII)

R5NH-U1-Y1 (VII) wherein R5, U1 and Y1 have the above-mentioned meanings. And a compound represented by the following formula (VIII):

[0041]

Embedded image (VIII)

[Wherein, R4 has the above-mentioned meaning. ] 2,4,6-trihalogeno-
By condensation with s-triazine according to a known method, the following formula (IX)

[0043]

Embedded image (IX)

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

Each of the amine compounds represented by the above formulas (VI) and (IX) is diazotized according to a conventional method, and the resulting diazotized product is converted into a free acid by the following formula (X)

[0046]

Embedded image (X)

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, and then the coupling reaction product is treated with the former diazotized product and By coupling while adjusting the pH to 2 to 8 at 40 ° C to 40 ° C, the following formula (X)
The compound represented by I) can be obtained.

[0048]

Embedded image (XI)

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

Among the reactive dyes of the above formula (I), those in which R1 and R2 are optionally substituted pyridinio are, for example, those in which the free acid form is the above-mentioned compound of the formula (XI) A pyridine compound produced by the same method and corresponding to an optionally substituted pyridinio is prepared at a temperature of 10 ° C to 100 ° C.
The compound of the following formula (XII) can be obtained by reacting at pH 2 to 9 under the conditions of pH 2 to 9.

[0051]

Embedded image (XII)

[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.degree. 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 compound represented by the above formula (II) can be produced by a known method, for example, according to the method described in JP-A-10-06297.

The reactive dyes of the formulas (I) and (II) are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the sodium, potassium and Lithium salts are preferred.

In the reactive dye composition of the present invention, the reactive dyes of formulas (I) and (II) may be mixed in a solid state or in a dye solution.

The reactive dye composition of the present invention comprises one or more blue dyes selected from the reactive dyes of formula (I) and one or more blue dyes of formula (II)
And one or more blue dyes selected from the reactive dyes. The mixing ratio of each reactive dye is not particularly limited, but the total amount of the reactive dyes of the formulas (I) and (II) is 1000. It is preferred that the reactive dye of the formula (I) is 50 to 950 parts by weight per part 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 reactive dye composition of the present invention is not particularly limited in its form, and may be, for example, a powder, a granule, or a liquid. .

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 them. 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 the dyeing and printing method 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.

The acid binder suitable for fixing the reactive dye composition of the present invention on cellulose fibers is, 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.

[0063]

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 exhaust dyeing, the dye temperature dependency and bath ratio dependency are small, the dye reproducibility is excellent, and even at a high dye concentration, sufficient color yield can be obtained by adding a small amount of neutral inorganic salt, and the fixation rate is low. Since it is high, the coloring load of dyeing wastewater is small.

[0064]

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)

[0066]

Embedded image (1)

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

[0068]

Embedded image (2)

By mixing 500 parts of the dye represented by the above formula, a dark blue reactive dye composition is obtained. A dyeing apparatus (bath ratio: 1: 1) was prepared by setting 0.6 g of the composition thus obtained and 5.0 g of anhydrous sodium sulfate in 10 g of a knitted fabric made of cotton fiber.
0, the bath temperature is 70 ° 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 dark 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)

[0071]

Embedded image (3)

750 parts of the dye represented by the following formula (4)

[0073]

Embedded image (4)

By mixing 250 parts of the dye represented by the formula (1), a dark blue composition is obtained. Similar to Example 1, 0.8 g of this composition and 6.0 g of anhydrous sodium sulfate were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 10 g of a knitted fabric made of cotton fiber was set. The knitted fabric was treated at 80 ° C. for about 20 minutes, and then 0.3 ml of caustic soda of 38 ° Baume 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)

[0076]

Embedded image (5)

The dye represented by the following formula (600 parts) is in the form of a free acid.
The following formula (6)

[0078]

Embedded image When 400 parts of the dye represented by (6) is mixed, a dark blue composition is obtained. 60 g of this composition and 500 g of common salt,
A cheese dyeing device (bath ratio: 1:10, bath temperature: 80 ° C.) is set by a known method and 1000 g of cotton fiber yarn is set. After treatment at 80 ° C. for 20 minutes, 200 g of sodium carbonate is charged into the bath. Then, dyeing and washing at this temperature for 60 minutes gives a uniform dark blue dyed yarn with good light fastness, sweat, chlorine and washing fastness, with no difference in concentration between the inner and outer layers of the cheese. Also, the reproducibility of this cheese dyeing is good.

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

[0080]

Embedded image (7)

The dye represented by the following formula (500 parts) has the form of a free acid,
The following formula (8)

[0082]

Embedded image (8)

By mixing 500 parts of the dye represented by the above formula, 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: 80 ° C.) in which 10 g of rayon knit was set.
0 g, knitted at 80 ° C. for 20 minutes, treated with 2.0 g of sodium carbonate, dyed and washed at this temperature for 60 minutes. A dyed product having good fastness is obtained. Also, the reproducibility is good even if the above dyeing is repeated.

Example 5 10 g of rayon knitted fabric was set in a dyeing apparatus,
The bath ratio was 1:10 and the water temperature was 70 ° C. The form of the free acid is
The following equation (9)

[0085]

Embedded image (9)

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

[0087]

Embedded image (10)

In a bath, 720 parts of the dye represented by the following formula, 0.3 g of a composition obtained by sufficiently mixing 100 parts of the dye represented by the formula (5), and 4.0 g of anhydrous sodium sulfate are added in a bath by a known method. After the introduction, the knitted fabric was treated at this temperature for 20 minutes, and 2.0 g of sodium carbonate was introduced 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 obtained dyed product was a uniform blue color with no spots. The obtained dyed product had good light fastness, sweat and sunlight, chlorine, and washing fastness. Also, the above dyeing was repeated,
In each case, the reproducibility of the staining was good.

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

[0090]

Embedded image (11)

400 parts of the dye represented by the formula
When 600 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 hydrogencarbonate was added, and water was further added to make the total amount 1000 parts at 25 ° C. Using this solution as a padding solution, padding a cotton fabric, and heating the fabric at 120 ° C.
For 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dyestuff, yielding a dyed product having a uniform dark blue color and having good light fastness, sweat, chlorine and washing fastness. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 10 g of a rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 70 ° C. The form of the free acid is
The following formula (12)

[0093]

Embedded image (12)

In a bath, 700 g of the dye represented by the following formula, 0.2 g of a composition obtained by sufficiently mixing 300 parts of the dye represented by the formula (1), and 3.0 g of anhydrous sodium sulfate are added in a known manner. 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 obtained dyed product was a uniform blue color with no spots. The obtained dyed product had good light fastness, sweat and sunlight, chlorine, and washing fastness. Also, the above dyeing was repeated,
In each case, the reproducibility of the staining was good.

Claims (6)

[Claims] 1. A reactive dye composition comprising 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): object. 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 -SO2CH2C
H2Z1 represents a group capable of leaving by the action of an alkali. ] (II) [wherein, X1 represents a halogen atom or an optionally substituted pyridinio group, D1 represents an optionally substituted lower alkyl group or an optionally substituted phenyl group, and R6 represents -NHCOC (Br) = CH ₂ group, —NHC
OCH (Br) CH ₂ Br group or the following formula (III): (III) In the formula, X2 represents a halogen atom or an optionally substituted pyridinio group, and D2 represents an optionally substituted lower alkyl group or an optionally substituted phenyl group. } Represents a group represented by ] (2) Y1 in the formula (I) is -SO ₂ C
The composition of claim 1 which is H ₂ CH ₂ OSO ₃ H. 3. The compound of the formula (II) wherein R6 is -NHC
The composition according to claim 1, wherein (Br) = CH ₂ or a group represented by the formula (III). (4) R6 in the formula (II) is -NHC
(Br) = CH ₂ or _{-NHCH (Br) CH 2 Br,} D1 is -SO ₂ CH = CH ₂ or -SO ₂ C ₂ H ₄ OS
O ₃ composition according to any one of claims 1 to 3 H is a phenyl group substituted with. 5. A compound of the formula (II) wherein R6 is
The composition according to any one of claims 1 to 3, which is a group represented by I), and wherein X1 and X2 are both halogen atoms. 6. A method for dyeing or printing a fiber material, comprising using the composition according to claim 1.