JP2001200175A - 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 material having excellent build-up and a slight influence of fluctuation of a dyeing condition. SOLUTION: This reactive dye composition comprises dyes of formula (I) [R1 and R2 are each a halogen or a substitutable pyridinio; R3 to R5 are each hydrogen or the like; U1 is a substitutable phenylene or a substitutable alkylene; Y1 is a vinyl sulfone-based reactive group] and formula (II) [R6 and R7 are each hydrogen, an alkoxy, sulfo or the like; Y2 is a vinyl sulfone-based reactive group; Y3 is a vinyl sulfone-based reactive group or a group of formula (III): -NHCO(CH2)m-Y4].

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 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, for blue reactive dyes,
Few are satisfactory in the fastness to sweat and sunlight, the fastness to chlorine and the fastness to NOx gas, and it is difficult to obtain a dyed product or a printed material having good fastness. 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 growing interest in environmental issues in recent years,
The rules for the coloring load of the dyeing wastewater also tend to be strict, and a reactive dye having a high fixation rate and a low coloring degree of the dyeing wastewater is strongly desired.

[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)

Wherein R6 and R7 are, independently of one another,
Hydrogen atom, an optionally substituted lower alkyl group, optionally substituted represents an lower alkoxy group or a sulfo group, Y2 is, -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH
₂ represents Z2, and Z2 represents a group which is eliminated by the action of an alkali. Y3 is, -SO ₂ CH = CH ₂ group, -SO ₂ CH ₂ CH
₂ Z3 (Z3 is a group which desorbs under the action of an alkali) group, or the following formula _{(III) -NHCO (CH 2)} m-Y4 (III) { wherein, m represents an integer or 0 to 3 Where m is 1
3 Y4 when an integer represents -SO ₂ CH = CH ₂ groups, and Y4 when m is 0 -C (Br) = CH
_Two groups, —CH (Br) CH ₂ Br group or the following formula (IV)

[0010]

Embedded image (IV)

(Where Y5 is -SO_TwoCH = CH_TwoOr
-SO_TwoCH_TwoCH_TwoZ4 represents the action of alkali
Represents a leaving group. ). Indicated by｝
Represents a group. ]  Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The lower alkyl group represented by R3, R4, R5, R6 and R7 in the above formulas (I) and (II) may be a straight chain such as methyl, ethyl, n-propyl, isobutyl or the like. Examples thereof include a branched alkyl group having 1 to 4 carbon atoms. Examples of the lower alkoxy groups represented by R6 and R7 include straight-chain or branched alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy and iso-propoxy. R3, R4, R5, R6 and R
As the substituent of the lower alkyl group represented by 7, hydroxy, cyano, alkoxy, halogen, carbamoyl,
Examples thereof include 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-methoxy Propyl, 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-carbamoylethyl
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 and 4-sulfamoylbutyl.
Examples of the substituent of the lower alkoxy group represented by R6 and R7 include methoxy, cyano, chloro, hydroxy, sulfo 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 such as CH2- is exemplified.

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.

R6 and R7 in the above formula (II) are
Each independently represents a hydrogen atom, a lower alkyl group which may be substituted, a lower alkoxy group which may be substituted or a sulfo group; As the lower alkyl group which may be substituted, a methyl group and an ethyl group are preferable, and as the lower alkoxy group which may be substituted, a methoxy group and an ethoxy group are preferable. As R6 and R7, hydrogen, methoxy and sulfo are particularly preferred.

In the formula (II), Y2 and Y3 are
Represents a vinyl sulfone-based fiber reactive group. Examples of the groups Z2 and Z3 which are eliminated by the action of an alkali include, for example, halogen atoms such as fluoro, chloro and bromo, sulfate, thiosulfate, phosphate and acetyloxy. Sulfate is preferred.

In the above formula (III), when m is 0, Y4 is —C (Br) ＝ CH ₂ group, and —CH (Br) C
Represents an H ₂ Br group or a group represented by the above formula (IV),
If There is a 1 to 3, Y4 represents -SO ₂ CH = CH _2. If Y4 is -SO ₂ CH = CH _2, preferably,
m is 2 or 3.

Y5 in the formula (IV) represents a vinyl sulfone-based fiber reactive group. Examples of Z4 which is a group which is eliminated by the action of an alkali include the same as those exemplified above for Z1 and Z2.

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

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

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

[0030]

Embedded image (VI)

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

[0032]

Embedded image (VII)

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

On the other hand, the formula R5NH-U1-Y1 (VI
II) wherein R5, U1 and Y1 have the meaning given above. And a compound represented by the following formula (IX):

[0035]

Embedded image (IX)

Wherein R4 has the meaning described above. ] 2,4,6-trihalogeno-
By condensing with s-triazine according to a known method, the following formula (X)

[0037]

Embedded image (X)

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

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

[0040]

Embedded image (XI)

Is coupled to 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 coupling product is combined with the former diazotized product and By performing the coupling while adjusting the pH to 2 to 8 at a temperature of from 40 to 40 ° C, a compound having a free acid form represented by the following formula (XII) can be obtained.

[0042]

Embedded image (XII)

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

Among the blue dyes of the formula (I), those in which R1 and R2 are optionally substituted pyridinio are:
For example, when the free acid form is obtained by synthesizing the compound of the above formula (XII) in the same manner as described above, the pyridine compound corresponding to the optionally substituted pyridinio is converted at a temperature of 10 ° C. to 100 ° C.
By reacting under the conditions of H2 to H9, the following formula (XI)
The compound of II) can be obtained.

[0045]

Embedded image (XIII)

[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 formula (II) can be produced by a known method, for example, according to the methods described in JP-A-8-120188 and JP-A-59-120656. it can.

The reactive dyes of the formulas (I) and (II)
It is present in the form of the free acid or in the form of a salt thereof, and particularly preferred are alkali metal and alkaline earth metal salts, and particularly preferred are sodium salt, potassium salt and lithium salt.

In the reactive dye composition of the present invention, the reactive dyes of the 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 the formula (I) and one or more blue dyes of the 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 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 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.

Acid binders suitable for immobilizing the reactive dye composition of the present invention on cellulose fibers include, for example, an alkali metal or 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.

[0056]

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.

[0057]

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)

[0059]

Embedded image (1)

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

[0061]

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 0.4 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)

[0064]

Embedded image (3)

625 parts of the dye represented by the following formula and the form of the free acid are represented by the following formula (4)

[0066]

Embedded image (4)

By mixing 375 parts of the dye represented by the formula (1), a dark blue composition is obtained. In the same manner as in Example 1, 0.6 g of this composition and 5.0 g of anhydrous sodium sulfate were used 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 knit 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)

[0069]

Embedded image (5)

670 parts of the dye represented by the formula
The following equation (6)

[0071]

Embedded image (6)

When 330 parts of the dye represented by the formula is mixed, a dark blue composition is obtained. 70 g of this composition and 500 salt
g in a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 1,000 g of a cotton fiber yarn is set, and treated at 60 ° C. for 20 minutes.
0 g is poured into the bath, then dyed at this temperature for 60 minutes, and then washed to give a uniform dark blue dyeing with good lightfastness, perspiration, chlorine and washing fastness, with no difference in concentration between the inner and outer layers of cheese. Yarn 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)

[0074]

Embedded image (7)

In the form of 500 parts of the dye represented by
The following formula (8)

[0076]

Embedded image (8)

By mixing 500 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 bath temperature was 60 ° C. The form of the free acid is
The following equation (9)

[0079]

Embedded image (9)

The form of the free acid dissolved in 190 parts of the dye represented by the following formula is represented by the following formula (10)

[0081]

Embedded image (10)

750 parts of the dye represented by the following formula, 0.5 g of a composition obtained by sufficiently mixing 60 parts of the dye represented by the formula (5), and 5.0 g of anhydrous sodium sulfate are added to 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 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)

[0084]

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 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.
After drying 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 can be obtained.
Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 10 g of 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 formula (12)

[0087]

Embedded image (12)

710 parts of the dye represented by the following formula, 0.8 g of a composition obtained by mixing 290 parts of the dye represented by the formula (1), and 6.0 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.

Claims (8)

[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, R6 and R7 each independently represent a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group or a sulfo group, and Y2 represents-
Represents SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z2,
Z2 represents a group which is eliminated by the action of an alkali. Y3 is-
SO ₂ CH = CH ₂ group, (group Z3 removable by the action of an alkali) -SO ₂ CH ₂ CH ₂ Z3 group, or the following formula (I
_{II) -NHCO (CH 2) m} -Y4 (III) { wherein, m represents an integer or 0 to 1 to 3, m is 1
3 Y4 when an integer represents -SO ₂ CH = CH ₂ groups, and Y4 when m is 0 -C (Br) = CH
_Two groups, —CH (Br) CH ₂ Br group or the following formula (IV): (IV) (wherein, Y5 is, -SO ₂ CH = CH ₂ or -SO ₂ CH ₂
Represents CH ₂ Z4, wherein Z4 represents a group which is eliminated by the action of an alkali. ). Represents a group represented by｝. ] 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 and R7 in the formula (II) are a hydrogen atom, an optionally substituted lower alkoxy group or a sulfo group. 4. The composition according to claim 1, wherein Y 2 and Y 3 in the formula (II) are both —SO ₂ CH ₂ CH ₂ OSO ₃ H. 5. The compound of the formula (II) wherein Y2 is —SO ₂ CH ₂ C
A H ₂ Z2 group, Y3 is a group represented by the formula (III), m is 0, a group Y4 is represented by the formula (IV), and, Y5 is -SO ₂ CH ₂ CH ₂ The composition according to any one of claims 1 to 3, which is a Z4 group. 6. A compound of the formula (II) wherein Y2 is -SO ₂ CH =
A CH ₂ group, wherein Y 3 is a group represented by the formula (III);
m is 2 or 3, and, Y4 is -SO ₂ CH = CH ₂
The composition according to any one of claims 1 to 3, which is a group. 7. The compound of the formula (II) wherein Y2 is -SO ₂ CH =
A CH ₂ group, m is 0, Y4 is -C (Br) =
A CH ₂ group or —CH (Br) CH ₂ Br group.
A composition according to any one of claims 1 to 3. 8. A method for dyeing or printing a fiber material, comprising using the composition according to claim 1.