JP2001214087A - Reactive dye composition and dyeing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive dye useful for dyeing cellulosic fiber brown or the like. SOLUTION: A reactive dye composition comprises respective dyes represented by formulas (I) (wherein R1 and R2 are each a halogen or the like; R3 to R5 are each H or the like; U1 is phenylene allowed to be substituted, or the like; and Y1 is a vinyl sulfone-based group capable of reacting with fiber) and (II).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 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 are frequently used for dyeing fiber materials, especially cellulosic fibers, because of their excellent dye properties. In dyeing fiber materials using reactive dyes, it is known to use yellow, red, and blue reactive dyes as three primary colors, and to dye or print by appropriately combining the three primary color dyes or dyes of each color.

[0003]

With respect to reactive dyes,
(i) good build-up property and level dyeing property of each dye, small dependency on dyeing temperature, inorganic salt concentration and bath ratio, etc .; (ii) build-up property of three primary colors, dye dyeing speed. , Dyeing temperature dependency, inorganic salt concentration dependency, bath ratio dependency, etc. are uniform, so-called compatibility is good, (iii) light fastness, combined fastness with sweat and sunlight, washing fastness It is preferred that various fastnesses such as degree and fastness of chlorine 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 fiber materials, the dyeing of dyes is more excellent. There is a strong need for a reproducible reactive dye composition. Regarding the compatibility of the item (ii), the dyeing properties are the same when the build-up properties of the three primary color dyes are different from each other, or when the dyes are dyed by using the respective dyes alone and appropriately combined with each other. If not, there is a problem that it is difficult to perform color matching using a computer color matching system that is frequently used in recent years. Further, when the dyeing speed of each dye of the three primary colors and the dependence on the dyeing temperature and the like are different from each other,
Problems such as uneven dyeing, in which spotting occurs during dyeing, and problems in poor reproducibility of dyeing, such as color differences between dyeing lots, occur. Furthermore, when the fastness levels of the dyes used in the item (iii) are not uniform, discoloration is conspicuous in some or all of light fastness, sweat fastness, washing fastness and chlorine fastness, and good dyeing is performed. Problems such as difficulty in obtaining a product arise. On the other hand, in the case of dyeing using a reactive dye for each color or for the three primary colors, especially in the case of high dyeing dyeing,
Although a large amount of the inorganic neutral salt is required, the addition of a large amount of the inorganic neutral salt requires a great deal of time and labor, so that the operability of the dyeing operation is significantly reduced. Also, 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 strong demand for a reactive dye composition that can obtain 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 strict, and there is a strong demand for a reactive dye composition having a high fixation rate and a low coloring degree of the dyeing wastewater.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems in dyeing and printing of a reactive dye composition for each color or using three primary color dyes. The inventors have found that this object is achieved and completed the present invention.

That is, the present invention provides a reactive dye composition containing the following reactive dyes a) and b) and a method for dyeing or printing a fiber material using the same.

A) The free acid form is one or more blue reactive dyes represented by the following formula (I): b) CI No., CAS No. or the free acid form is the following formula (I)
I)-(IX), CAS No. 85765-41-9, CAS No. 183185-
50-4, CAS No.156291-01-9, CAS No.183205-49-4, C
AS No.189574-45-6, CAS No.12226-52-7, CAS No.12226
-54-9, CAS No.154603-22-2, CIReactive Yellow 1
61, CIReactive Yellow 175, CAS No. 104256-92-
0, CIReactive Yellow 143, CAS No. 143804-55-1,
CAS No.107231-52-7, CAS No.74388-34-4, CAS No.1
09736-54-1, CAS No.88159-08-4, CAS No.83400-21-
9, CAS No. 72509-99-0, CAS No. 63817-39-0, CIReact
ive Yellow 163, CAS No. 140876-14-8, CIReactive
Yellow 165, CAS No.146548-74-5, CAS No.146632-1
1-3, CIReactive Yellow 136, CIReactive Yellow
137, CAS No.77907-38-1, CAS No.178198-11-3, CAS N
o.104981-57-9, CAS No.195739-93-6, CAS No.195876
-25-6, CAS No.183185-19-5, CAS No.149850-32-8, C
AS No.61951-85-7, CAS No.96726-28-2, CAS No.14905
7-74-9, CAS No. 118578-13-5, CAS No. 130711-86-3,
CAS No.71720-86-0, CAS No.68806-24-6, CAS No.14
6177-84-6, CAS No.143683-22-1, CAS No.80162-04-
5, CAS No.121591-05-7, CAS No.148159-34-6, CAS
No.114764-54-4, CAS No.70776-19-1, CAS No.101200-
49-1, CAS No. 173995-81-8, CAS No. 181188-59-0, C
AS No.116912-36-8, CAS No.106359-92-6, CAS No.1498
50-34-0, CAS No.183185-18-4, CAS No.149850-33-
9, CAS No. 152397-21-2, CAS No. 157707-94-3, CAS N
o.68959-17-1, CAS No.70833-38-4, CAS No.99441-48-
2, CAS No. 64104-00-3, CAS No. 68413-52-5, CAS No.
107231-93-6, CAS No. 74077-24-0, CAS No. 70817-81-
1, CAS No. 83763-62-6, CAS No. 146303-09-5, CAS N
o.146632-12-4, CAS No.70929-83-8, CAS No.73139-3
6-9, CAS No.94158-79-9, CAS No.118578-11-3, CAS
No.190914-22-8, CAS No.68214-04-0, CAS No.120265-1
4-7, CAS No. 61931-52-0, CAS No. 101698-02-6, CAS N
o.86422-60-8, CAS No.101453-62-7, CIReactive Red
229, CAS No.85605-32-9, CAS No.12226-33-4 and CA
S 1 selected from the reactive dye group represented by No.12226-32-3
More than species:

[0007]

Embedded image (I)

Wherein R1 and R2 are independently of each other:
Represents a halogen or optionally substituted pyridinio,
R3, R4 and R5 each independently represent hydrogen or an optionally substituted lower alkyl group, and U1 may be an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted Represents a C2-C6 alkylene, and Y1 represents -SO2CH = CH2 or -SO2CH2
CH2Z1 represents a group capable of leaving by the action of an alkali. ]

[0009]

Embedded image (II)

[0010]

Embedded image (III)

[0011]

Embedded image (IV)

[0012]

Embedded image (V)

[0013]

Embedded image (VI)

[0014]

Embedded image (VII)

[0015]

Embedded image (VIII)

[0016]

Embedded image (IX) Hereinafter, the present invention will be described in detail.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The lower alkyl groups represented by R3, R4 and R5 in the above formula (I) include, for example, straight-chain or branched ones having 1 carbon atom such as methyl, ethyl, n-propyl and isobutyl. To 4 alkyl groups. As the substituent of the lower alkyl group, for example, hydroxy, cyano, alkoxy, halogen, carbamoyl,
Examples thereof include carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo, and sulfamoyl. As the substituted lower alkyl group, for example,
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, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonyl Methyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxy Methyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, Le carbonyloxy-butyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4
-Sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like.

The optionally substituted phenylene represented by U1 in the above formula (I) is preferably
C1-C4 alkyl group (methyl, ethyl, etc.), C1-C4 alkoxy group (methoxy, ethoxy, etc.), halogen (chlorine,
Phenylene which may be substituted by one or two substituents selected from the group of bromine and the like and a sulfo group, 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 above formula (I) is preferably 1
And naphthylene which may be substituted with a plurality of sulfo groups. Specific examples of these include, for example,

[0022]

Embedded image

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

The optionally substituted C2-C6 alkylene represented by U1 in the above formula (I) is preferably, for example,-(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 above formula (I) each independently represent a halogen or an 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 pyridinio which may be 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 the like. Here, examples of the substituted alkyl having 1 to 4 carbon atoms include 2-hydroxyethyl and 2
-Sulfoethyl and the like.

Specific examples of such 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.

The method for producing the compound represented by the formula (I) is not particularly limited, but 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.

[0031]

A compound represented by H2NCN (IX) and the following formula (X)

[0032]

Embedded image (X)

[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 (XI)

[0034]

Embedded image (XI)

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

On the other hand, the formula R5NH-U1-Y1 (XII) wherein R5, U1 and Y1 have the above-mentioned meaning. ]
And a compound represented by the following formula (XIII):

[0037]

Embedded image (XIII)

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

[0039]

Embedded image (XIV)

[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 (XI) and (XIV) are each diazotized according to a conventional method, and the resulting diazotized product is converted into a free acid by the following formula (X)
V)

[0042]

Embedded image (XV)

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 product is combined 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 (XV
The compound represented by I) or a salt thereof can be obtained.

[0044]

Embedded image (XVI)

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

Among the bisazo compounds (I) of the present invention, those in which R1 and R2 are optionally substituted pyridinio may be, for example, the compounds of the above formula (XIV) whose free acid form is the same as described above. A pyridine compound corresponding to optionally substituted pyridinio at a temperature of 10 ° C.
The compound of the following formula (XVII) can be obtained by reacting at 〜100 ° C. under conditions of pH 2-9.

[0047]

Embedded image (XVII)

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.
C. and pH 2 to 10 can be carried out.

The reactive dye used in the present invention is present in the form of a free acid or a salt thereof, particularly preferably an alkali metal and alkaline earth metal salt, particularly preferably a sodium salt, a potassium salt and a lithium salt. .

The method of mixing the reactive dyes used in the present invention is not particularly limited, but they may be mixed in a solid state or in a liquid state.

The present invention is a reactive dye composition containing the reactive dyes of the above a) and b), and the number of reactive dyes of the formula (I) may be one or more. . Similarly, the reactive dyes of b) are each C.I. I. No. And one or more dyes of each CAS No. And one or more dyes of the formulas (II), (III) and (I
One or more dyes selected from the reactive dyes of V), (V), (VI), (VII), (VIII) and (IX) may be used, and may be selected from the reactive dyes of the respective formulas. It may be a mixed dye of two or more of one kind. Further, the reactive dye of the above b) comprises one or more dyes selected from the reactive dyes of the above formula and each of the C.I. I. No. Or a mixture of one or more dyes selected from the reactive dyes of the above formulas with each CAS No. And a mixture with one or more dyes selected from reactive dyes. I. No. And at least one CAS No. May be a mixture with one or more dyes selected from the reactive dyes, and one or more dyes selected from the reactive dyes of the above formulas and each C.I. I. No. And one or more dyes selected from the reactive dyes
o. And a mixture with one or more dyes selected from the reactive dyes. The mixing ratio of the reactive dyes is not particularly limited, but preferably, the reactive dye of the formula (I) is used in an amount of 50 to 950 with respect to the total amount of the reactive dyes used of 1,000 parts by weight.
It is in the range of 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 a known dyeing aid such as an inhibitor, a pH buffer such as sodium acetate and sodium phosphate, a water softener such as polyphosphate, and other dyes.

The reactive dye composition of the present invention is not particularly limited in its form. For example, the reactive dye composition may be in the form of powder, granules, or 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 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 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 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.

[0058]

Industrial Applicability The reactive dye composition of the present invention is excellent in various dye properties such as excellent leveling property and reproducibility and good build-up property in dyeing and printing of fiber material, and It provides dyeings and prints with good fastness, including fastness to combined sweat-sunlight action, fastness to chlorine and fastness to oxidizing gas. In particular, in exhaust dyeing, the dyeing temperature dependency and bath ratio dependency are small and excellent in reproducibility, and even at high dyeing concentration, sufficient color yield can be obtained by addition of a small amount of neutral inorganic salt, and the fixation rate is high, The coloring load of dyeing wastewater is small.

[0059]

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 following formula (1)

[0061]

Embedded image (1)

400 parts of a dye represented by the formula
The following formula (2)

[0063]

Embedded image

(2)

A green reactive dye composition is obtained by mixing 600 parts of the dye represented by the formula (1). 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 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 green stain 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)

[0067]

Embedded image (3)

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

[0069]

Embedded image (4)

By mixing 300 parts of the dye represented by the formula (1), a green composition is obtained. Similarly to 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 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 green dyeing with good lightfastness, perspiration, chlorine and wash 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)

[0072]

Embedded image (5)

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

[0074]

Embedded image By mixing 300 parts of the dye represented by (6), a purple composition is obtained. 50 g of this composition and 500 g of salt,
A cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 70 ° C.) is set by a known method and set at 1000 g of cotton fiber yarn, treated at 70 ° C. for 20 minutes, and then charged with 200 g of sodium carbonate in the bath. Then, when dyeing and washing at this temperature for 60 minutes, a uniform purple dyed yarn having good light fastness, sweat and sunlight, chlorine and washing fastness and having no difference in concentration between the inner and outer layers of the cheese is obtained. Also, the reproducibility of this cheese dyeing is good.

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

[0076]

Embedded image (7)

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

[0078]

Embedded image (8)

By mixing 600 parts of the dye represented by the above formula, a purple 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: 70 ° C.) in which 10 g of rayon knit was set.
0 g, knitted at 70 ° C. for 20 minutes, treated with 2.0 g of sodium carbonate, dyed and washed at this temperature for 60 minutes to give a uniform, purple, light, sweat, sunlight, chlorine and wash 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 a rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the bath temperature was 80 ° C. The form of the free acid is
The following equation (9)

[0081]

Embedded image (9)

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

[0083]

Embedded image (10)

In the form of 400 parts of the dye represented by
The following formula (11)

[0085]

Embedded image (11)

A dye obtained by mixing 450 parts of the dye represented by the formula (5), 50 parts of the dye represented by the formula (5), and 0.6 g of a composition obtained by mixing the anhydrous sodium sulfate with 5.0 g of the anhydrous sodium sulfate were put into a bath by a known method. After that, the knitting is treated for 20 minutes at this temperature,
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 brown 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 10 g of rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the bath temperature was 80 ° C. 300 parts of the dye represented by the above formula (9), 400 parts of the dye represented by the above formula (10), and 300 parts of the dye represented by the above formula (6) Is added to a bath by a known method, and the knitted fabric is treated at this temperature for 20 minutes, and sodium carbonate 2. 0 g was put into the bath. The knit is then treated at this temperature for 60 minutes,
Staining was terminated. The obtained dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform and dark brown 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 7 10 g of a rayon knit was set in a dyeing apparatus.
The bath ratio was 1:10 and the bath temperature was 80 ° C. The form of the free acid is
200 parts of the dye represented by the above formula (3) and the form of the free acid are represented by the following formula (12)

[0089]

Embedded image (12)

In the form of 500 parts of the dye represented by
The following formula (13)

[0091]

Embedded image (13)

0.6 g of a composition obtained by mixing 300 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 brown 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 8 10 g of a rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 80 ° C. The form of the free acid is 300 parts of the dye represented by the above formula (5), the form of the free acid is 400 parts of the dye represented by the above formula (2), and the form of the free acid is the following formula (1)
4)

[0094]

Embedded image (14)

0.6 g of a composition obtained by mixing 400 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 brown 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 9 The form of the free acid is represented by the following formula (15)

[0097]

Embedded image (15)

300 parts of the dye represented by the formula
Equation (16)

[0099]

Embedded image (16)

300 parts of the dye represented by the formula
When 400 parts of the dye represented by the formula (1) is sufficiently mixed, a brown dye composition is obtained. After dissolving 200 parts of this dye composition in hot water, it is cooled to 25 ° C., and sodium alginate 1
, 10 parts of sodium metanitrobenzenesulfonate, and 20 parts of sodium hydrogen carbonate, and further, water was added to make a total volume of 1000 parts by volume at 25 ° C. Using this solution as a padding solution, padding a cotton fabric, 120 fabrics
After drying for 2 minutes at 100 ° C. and then steaming at 100 ° C. for 5 minutes to fix the dye, a uniform brown color was obtained,
Dyeings with good sweat, chlorine and washing fastness are obtained. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 10 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 250 parts of the dye represented by the formula (1), and the form of the free acid is the following formula (1)
7)

[0102]

Embedded image 450 parts of the dye represented by (17) and the form of the free acid are represented by the following formula (18)

[0103]

Embedded image (18)

0.6 g of a composition obtained by mixing 300 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 brown 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 11 10 g of knitted fabric made of rayon 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 250 parts of the dye represented by the formula (3), and the form of the free acid is the formula (1)
9)

[0106]

Embedded image (19)

400 parts of the dye represented by the following formula,
The following formula (20)

[0108]

Embedded image (20)

0.6 g of a composition obtained by mixing 350 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 obtained dyed product was uniform brown 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 12 10 g of rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 80 ° C. The form of the free acid is 150 parts of the dye represented by the above formula (3), the form of the free acid is 400 parts of the dye represented by the above formula (4), and the form of the free acid is the following formula (2)
1)

[0111]

Embedded image (21)

0.8 g of a composition obtained by mixing 450 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 brown 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 13 10 g of a rayon knitted fabric was set in a dyeing apparatus.
The bath ratio was 1:10 and the water temperature was 80 ° C. The form of the free acid is 300 parts of the dye represented by the formula (1), and the form of the free acid is the following formula (2)
2)

[0114]

Embedded image (22)

A dye represented by the following formula (23)

[0116]

Embedded image (23)

0.7 g of a composition obtained by mixing 200 parts of the dye represented by the following formula, and 5.0 g of anhydrous sodium sulfate
Was put into the bath by a known method, and then 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 obtained dyed product was a uniform dark brown 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 F term (reference) 4H056 FA01 JA06 JB02 JB03 JD11 JD21 JD22 JD23 JE03 4H057 AA01 AA02 BA07 BA24 DA01 DA21 DA24 GA04 GA07 GA08

Claims (7)

[Claims] 1. A reactive dye composition comprising the following reactive dyes a) and b). a) the form of the free acid is one or more of the blue reactive dyes represented by the following formula (I); b) the CI No., CAS No. or the form of the free acid is the following formula (I)
I)-(IX), CAS No. 85765-41-9, CAS No. 183185-
50-4, CAS No.156291-01-9, CAS No.183205-49-4, C
AS No.189574-45-6, CAS No.12226-52-7, CAS No.12226
-54-9, CAS No.154603-22-2, CIReactive Yellow 1
61, CIReactive Yellow 175, CAS No. 104256-92-
0, CIReactive Yellow 143, CAS No. 143804-55-1,
CAS No.107231-52-7, CAS No.74388-34-4, CAS No.1
09736-54-1, CAS No.88159-08-4, CAS No.83400-21-
9, CAS No. 72509-99-0, CAS No. 63817-39-0, CIReact
ive Yellow 163, CAS No. 140876-14-8, CIReactive
Yellow 165, CAS No.146548-74-5, CAS No.146632-1
1-3, CIReactive Yellow 136, CIReactive Yellow
137, CAS No.77907-38-1, CAS No.178198-11-3, CAS N
o.104981-57-9, CAS No.195739-93-6, CAS No.195876
-25-6, CAS No.183185-19-5, CAS No.149850-32-8, C
AS No.61951-85-7, CAS No.96726-28-2, CAS No.14905
7-74-9, CAS No. 118578-13-5, CAS No. 130711-86-3,
CAS No.71720-86-0, CAS No.68806-24-6, CAS No.14
6177-84-6, CAS No.143683-22-1, CAS No.80162-04-
5, CAS No.121591-05-7, CAS No.148159-34-6, CAS
No.114764-54-4, CAS No.70776-19-1, CAS No.101200-
49-1, CAS No. 173995-81-8, CAS No. 181188-59-0, C
AS No.116912-36-8, CAS No.106359-92-6, CAS No.1498
50-34-0, CAS No.183185-18-4, CAS No.149850-33-
9, CAS No. 152397-21-2, CAS No. 157707-94-3, CAS N
o.68959-17-1, CAS No.70833-38-4, CAS No.99441-48-
2, CAS No. 64104-00-3, CAS No. 68413-52-5, CAS No.
107231-93-6, CAS No. 74077-24-0, CAS No. 70817-81-
1, CAS No. 83763-62-6, CAS No. 146303-09-5, CAS N
o.146632-12-4, CAS No.70929-83-8, CAS No.73139-3
6-9, CAS No.94158-79-9, CAS No.118578-11-3, CAS
No.190914-22-8, CAS No.68214-04-0, CAS No.120265-1
4-7, CAS No. 61931-52-0, CAS No. 101698-02-6, CAS N
o.86422-60-8, CAS No.101453-62-7, CIReactive Red
229, CAS No.85605-32-9, CAS No.12226-33-4 and
One or more selected from the group of reactive dyes represented by CAS No. 12226-32-3: (I) wherein R 1 and R 2 independently represent a halogen or an optionally substituted pyridinio;
R4 and R5 independently represent hydrogen or optionally substituted lower alkyl, and U1 represents optionally substituted phenylene, optionally substituted naphthylene or optionally substituted C2-C6. Represents alkylene, Y
1 is -SO2CH = CH2 or -SO2CH2CH2Z
And Z1 represents a group capable of leaving by the action of an alkali. ] (II) (III) (IV) (V) (VI) (VII) (VIII) (IX) Y1 is at wherein formula _{(I), -SO 2 CH 2} C
A H ₂ Z1, and A composition according to claim 1 Z1 is -OSO ₃ H. (3) R3, R4 and R5 in the formula (I) are
2. A hydrogen atom, methyl or ethyl, independently of one another.
Or the composition according to 2. 4. The composition according to claim 1, wherein R1 and R2 in the formula (I) are each independently halogen. 5. The composition according to claim 1, wherein U1 in the formula (I) is an optionally substituted ferrene. 6. The composition according to claim 1, wherein U1 in the formula (I) is an optionally substituted C2 to C6 alkylene. 7. A method for dyeing or printing a fiber material, comprising using the composition according to claim 1.