JP2001214086A - Reactive dye composition and method of dyeing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive dye of blue color that is useful for dyeing cellulosic fiber. SOLUTION: The objective reactive dye composition comprises a dye represented by formula (I) (wherein R1 and R2 are each a halogen and the like; R3-R5 are each H and the like; U1 is phenylene which may be substituted and the like and Y1 is a fiber-reactive vinyl sulfone group) and a dye represented by formula (X VI) (wherein Y3 represents a fiber-reactive vinyl sulfone group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As a blue-based reactive dye for dyeing and printing cellulosic fiber materials, for example, a mixture of an anthraquinone-based reactive dye and a copper formazan-based reactive dye (JP-A-2-99564, JP 1
JP-A-103668, etc.), and mixtures comprising bisazo-based reactive dyes (JP-A-1-170663, JP-A-8-16863)
JP-A-209021), and a mixture comprising a copper formazan-based reactive dye and a bisazo-based reactive dye (JP-A-5-7070).
No. 7) is 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 the fastness, washing fastness, chlorine fastness, and NOx gas fastness are excellent, and that the dyes used have the same level of fastness. In particular, regarding the performance of the term (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, there is a strong demand for reactive dyes with excellent leveling properties, dye reproducibility and washability. It is rare. Further, regarding the performance of the item (ii), when the level of the fastness of the dye used for dyeing is not uniform, the light fastness, the sweat fastness, the washing fastness and the chlorine fastness are partially or entirely. Problems such as conspicuous discoloration occur. There are few blue reactive dyes that are particularly satisfactory in terms of sweat and sunlight fastness, chlorine fastness and NOx gas fastness,
This causes problems such as difficulty in obtaining a dyed product having various fastnesses. On the other hand, in the case of dyeing using a reactive dye, particularly in the case of dyeing with a high dye 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, It significantly reduces the operability of the dyeing operation. Also, addition of a large amount of inorganic neutral salt increases the content of inorganic neutral salt in the 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 growing interest in environmental issues in recent years, the rules for the coloring load of dyeing wastewater also tend to be strict,
There is a strong demand for a blue-based reactive dye having a high fixation rate and a low coloring degree of dyeing wastewater.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems in dyeing and printing a blue-based reactive dye, and as a result, a specific blue reactive dye composition has achieved this object. 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.

[0006] a) the free acid form is a blue reactive dye represented by the following formula (I); b) the free acid form is the following formulas (II), (X) and (XV)
One or more dye groups selected from the group of blue reactive dyes represented by I):

[0007]

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. D-A1 (II) wherein A1 is a group represented by the following formula (III) or (IV)

[0009]

Embedded image (III)

{Wherein, X1 represents a hydrogen atom, a chlorine atom or a fluorine atom, and X2 and X3 independently represent a fluorine atom or a chlorine atom. }

[0011]

Embedded image (IV)

{Wherein, X4 represents a halogen atom or an optionally substituted pyridinio group, and R6 represents a group represented by the following formula (V).

[0013]

Embedded image (V)

(Wherein R7 represents a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl group, R8 represents a hydrogen atom, an optionally substituted lower alkyl group, Represents an optionally substituted phenyl group or a group represented by the following formula (VI) -U2-Y2 (VI), wherein U2 represents an optionally substituted phenylene group, an optionally substituted naphthylene group, An optionally substituted C2-C6 alkylene group of the formula-(CH
2) represents a group represented by 2O (CH2) 2- (VII) or a group represented by the formula -CONH (CH2) 2- * (VIII), and an asterisk denotes a bond leading to Y2;
2 is -SO2CH = CH2 or -SO2CH2CH2Z
And Z2 represents a group capable of leaving by the action of an alkali. )} Represents a group represented by the following formula (IX)

[0015]

Embedded image (IX)

{Wherein R is a hydrogen atom, —SO 2 CHＣＨC
H2 or -SO2CH2CH2Z3, wherein Z3 represents a group which is eliminated by the action of an alkali. } Represents a group represented by ]

[0017]

Embedded image (X)

Wherein D represents the above-mentioned meaning, X5 and X6 each independently represent a halogen atom, m represents 0 or 1, and when m is 0, A2 represents -NH- A 2 represents a group represented by the following formula (XII)
Represents any of the groups represented by (XV). ]

[0019]

Embedded image (XII)

[0020]

Embedded image (XIII)

[0021]

Embedded image (XIV)

[0022]

Embedded image (XV)

[0023]

Embedded image (XVI)

[In the formula, Y3 represents -SO2CH = CH2 or -SO2CH2CH2Z4, and Z4 represents a group which is eliminated by the action of an alkali. Hereinafter, the present invention will be described in detail.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The optionally substituted lower alkyl groups represented by R3, R4, R5, R7 and R8 in the above formulas (I) and (V) include, for example, methyl, ethyl, n- Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as propyl and 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 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, 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;

[0027]

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,

[0029]

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-(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.

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

Specific examples of the optionally substituted pyridinio represented by R1 and R2 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. Preference is given to pyridinio substituted with carboxy or carbamoyl, especially 3- or 4-carboxypyridinio.

A1 in the formula (II) is the same as the formula (II)
When the groups represented by I), it in D of the formula (IX), the substitution position of -SO ₃ H are, -NH- is para to the carbon atom of the benzene ring which is substituted are preferred, whereas, when the groups of the A1 is represented by formula (IV), in D of the formula (IX), the substitution position of -SO ₃ H is, -C (O) -O- group is substituted It is preferably para to the carbon atom of the benzene ring being used.

X1 in the above formula (III) represents hydrogen, chlorine or fluorine, and X2 and X3 independently of each other,
Represents chlorine or fluorine, especially X1, X2 and X3 are all chlorine, X1 is chlorine, and X2 and X3 are fluorine, or X1 is hydrogen;
It is preferred that X2 and X3 are fluorine.

X4 in the above formula (IV) represents 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 represented by X4 include carboxy, carbamoyl,
Sulfo, halogeno and optionally substituted carbon number 1
And the like. Pyridinio which may be substituted with a group selected from the group consisting of 4 alkyl groups, and the like, and the substituted alkyl having 1 to 4 carbon atoms include, for example, 2-hydroxyethyl and 2
-Sulfoethyl and the like.

Specific examples of the optionally substituted pyridinio represented by X4 include pyridinio, 2-, 3- or 4-carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, -Sulfopyridinio, 4- (2-
Sulfoethyl) pyridinio, 3- (2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio, 3,5-dicarboxypyridinio and the like can be mentioned. Preference is given to pyridinio substituted with carboxy or carbamoyl, and particularly preferred is 3- or 4-carboxypyridinio.

R6 in the formula (IV) represents a group represented by the formula (V). Examples of the optionally substituted phenyl group represented by R8 in the formula (V) include alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, carboxy, halogeno, hydroxy,
1 selected from the group consisting of cyano, carbamoyl, sulfamoyl, carboxylic acid ester, 2-hydroxyethylsulfonyl, amino, acylamino (such as alkylcarbonylamino and phenylcarbonylamino), and amino substituted with an alkyl group having 1 to 4 carbon atoms Or phenyl which may be substituted by two substituents.

As such phenyl, for example, phenyl, 2-, 3- or 4-methylphenyl, 2
-, 3- or 4-methoxyphenyl, 2-, 3- or 4
-Ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-carboxyphenyl, 2-sulfo-4-methoxyphenyl, 2-, 3- or 4-hydroxyphenyl, 2-3 -Or 4-chlorophenyl, 3
-Chloro-4-methylphenyl, 2-sulfo-4-chlorophenyl, 2-sulfo-5-chlorophenyl and 3-
Sulfo-6-chlorophenyl and the like.

U2 in the above formula (VI) represents phenylene which may be substituted, naphthylene which may be substituted, C2-C6 alkylene which may be substituted,-
_{(CH 2) 2 O (CH} 2) 2 - or -CONH (CH2) 2
-* [Where * represents a bond leading to Y2,
Represents a vinyl sulfone-based fiber reactive group, and the group which is eliminated by the action of an alkali represented by Z2 is the same as that exemplified for Z1. ]. Optionally substituted phenylene, optionally substituted naphthylene and optionally substituted C2-C6 represented by U2
As the alkylene, those similar to the ones exemplified for U1 can be exemplified.

R in the group D represented by the formula (IX) represents hydrogen or a vinylsulfone-based fiber reactive group.
Examples of Z3 which is a group capable of leaving under the action of an alkali include halogen atoms such as fluoro, chloro and bromo, sulfate, thiosulfate, phosphate and acetyloxy.

X5 and X6 in the above formula (X) are
Each independently represents halogen, and as halogen,
For example, fluoro, chloro and bromo can be mentioned, and chloro and fluoro are preferred.

Y3 in the formula (XVI) represents a vinyl sulfone-based fiber reactive group. Examples of Z4, which is a group capable of leaving by the action of an alkali, are the same as those exemplified above for Z1.

The method for producing the blue reactive dye 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 halogen, for example, the following method can be exemplified. A compound represented by the formula H2NCN (XVII) and a compound represented by the following formula (XVIII)

[0049]

Embedded image (XVIII)

[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 (XIX)

[0051]

Embedded image (XIX)

[Wherein, R 3 represents the above-mentioned meaning, and W 1 represents halogen. ] Can be obtained.

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

[0054]

Embedded image (XXI)

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

[0056]

Embedded image (XXII)

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

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

[0059]

Embedded image (XXIII)

And coupling 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 adding the former diazotized product to the obtained coupling reaction product. At pH 0 to 40 ° C.
By coupling while adjusting to 8, a compound represented by the following formula (XXIV) or a salt thereof can be obtained.

[0061]

Embedded image (XXIV)

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

Further, among the blue reactive dyes (I), those in which R1 and R2 are optionally substituted pyridinio are:
For example, a compound of the formula (XIV) whose free acid form is synthesized by the same method as described above, and a pyridine compound corresponding to an optionally substituted pyridinio at a temperature of 10 ° C. to 100 ° C. and a pH of 2 to 9 By reacting with the following formula (X
XV) can be obtained.

[0064]

Embedded image (XXV)

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

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

The blue reactive dyes represented by the formulas (II), (X) and (XVI) can be prepared by known methods, for example,
No. 10669, based on the method described in JP-A-4-258674 or JP-A-6-49381,
Can be manufactured.

The blue reactive dyes a) and b) are present in the form of the free acid or in the form of a salt thereof, and are preferably alkali metal and alkaline earth metal salts, especially sodium salt, potassium salt and lithium salt. Salts are preferred. The method of mixing the reactive dyes used in the present invention is not particularly limited, and may be mixed in a solid state or in a liquid state.

The reactive dye composition of the present invention comprises the reactive dye of the above a) and the reactive dye of the above b), and comprises the blue reactive dye of the formula (I) and the blue reactive dye of the formula (II). A mixture of a blue reactive dye of the formula (I) and a blue reactive dye of the formula (X), a mixture of a blue reactive dye of the formula (I) and a blue reactive dye of the formula (XVI), A mixture of the blue reactive dye of the formula (I), the blue reactive dye of the formula (II) and the blue reactive dye of the formula (X) may be used, and the blue reactive dye of the formula (I), the blue reactive dye of the formula (II) and the formula (XVI) )
Or a mixture of a blue reactive dye of formula (I), a blue reactive dye of formula (X) and a blue reactive dye of formula (XVI), or a blue reactive dye of formula (I) A mixture of the blue reactive dye of the formula (II), the blue reactive dye of the formula (X) and the blue reactive dye of the formula (XVI) may be used.

The reactive dye composition of the present invention has the formula (I)
A mixture of at least one blue reactive dye of formula (II), one or more dyes of one or more dyes selected from the group of reactive dyes of formulas (II), (X) and (XVI) Good.

In the reactive dye composition of the present invention, the mixing ratio of each blue reactive dye is not particularly limited.
In a total of 1000 parts by weight of the reactive dyes of the formulas (I), (II), (X) and (XVI), the blue reactive dye of the formula (I) is 50-95.
It is preferably 0 parts by weight.

The reactive dye composition of the present invention may optionally contain
Inorganic salts such as sodium sulfate and sodium salt, β-sodium naphthalene sulfonate / formalin condensate, methyl naphthalene sulfonate / formalin condensate, dispersants such as acetylaminonaphthol compounds, and dust dispersion such as di-2-ethylhexyl terephthalate It may contain known dyeing assistants such as inhibitors, pH buffering agents such as sodium acetate and sodium phosphate, hard water softeners such as polyphosphate, and other dyes.

The 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.

The dyeing and printing methods in the present invention may be any of the known methods. 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.

[0077]

When the reactive dye composition of the present invention is used for dyeing or printing a cellulose fiber material or the like, various dye properties such as leveling property, build-up property and dye reproducibility are excellent, and sweat- A dyed or printed material having good fastnesses such as fastness to combined action of sunlight, fastness to chlorine, fastness to oxidizing gas and the like can be obtained. In particular, in exhaustion dyeing, the dependence on the dyeing temperature and bath ratio is small, the dyeing reproducibility is excellent, and the fixation rate is high, so even with high dyeing concentration, sufficient color yield can be obtained by adding a small amount of neutral inorganic salt. And the coloring load of the dyeing wastewater is small.

[0078]

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)

[0080]

Embedded image (1)

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

[0082]

Embedded image (2)

By mixing 600 parts of the dye represented by the above formula, a blue reactive dye composition is obtained. A dyeing apparatus (bath ratio 1: 1) was prepared by setting 0.3 g of the composition thus obtained and 3.0 g of anhydrous sodium sulfate in 10 g of a knitted fabric made of cotton fiber.
0, the bath temperature is 80 ° C) by a known method.
The knit is treated at 0 ° C. for about 20 minutes, then 2.0 g of sodium carbonate is poured into the bath, and the knit is dyed and washed at this temperature for 60 minutes, resulting in good light fastness, chlorine and wash fastness. A uniform blue dyeing without spots is obtained.
Also, the reproducibility of the above dyeing is good.

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

[0085]

Embedded image (3)

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

[0087]

Embedded image (4)

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

[0090]

Embedded image (5)

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

[0092]

Embedded image By mixing 300 parts of the dye represented by (6), a dark blue composition is obtained. 50 g of this composition and 500 g of salt,
A cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) is set by a known method and 1000 g of cotton fiber yarn is set. After treatment at 60 ° 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)

[0094]

Embedded image (7)

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

[0096]

Embedded image (8)

By mixing 600 parts of the dye represented by the formula (1), a blue reactive dye composition is obtained. 0.2 g of the above composition and anhydrous sodium sulfate 3.0 were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 g of rayon knit was set.
g, knitted at 60 ° 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, uniform blue, lightfast, sweaty, chlorinated and washed A dyed product having good fastness is obtained. Even if the above dyeing is repeated, the reproducibility is good.

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

[0099]

Embedded image (9)

In the form of the free acid, 150 parts of the dye represented by
The following formula (10)

[0101]

Embedded image (10)

Into a bath were introduced 0.6 g of a composition obtained by mixing 700 parts of the dye represented by the following formula, 150 parts of the dye represented by the above formula (5), and 5.0 g of anhydrous sodium sulfate. 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 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. 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)

[0104]

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 above formula (5) is sufficiently mixed,
A dark blue 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 at 2 ° C. for 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dye, a uniform dark blue 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 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 60 ° C. The form of the free acid is
The following formula (12)

[0107]

Embedded image (12)

In a bath, 800 g of the dye represented by the following formula, 0.7 g of a composition obtained by sufficiently mixing 200 parts of the dye represented by the above formula (1), and 5.0 g of anhydrous sodium sulfate are added in a bath by a known method. After that, the knitted fabric was treated at this temperature for 20 minutes, and 2.0 g of sodium carbonate was poured into the bath by a known method. Subsequently, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The 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 8 10 g of knitted fabric made of rayon 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
600 parts of the dye represented by the above formula (9) and the form of the free acid are represented by the formula (13)

[0110]

Embedded image (13)

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 obtained dyed product was uniform dark blue without 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 was represented by the following formula (14)

[0113]

Embedded image (14)

140 parts of the dye represented by the following formula,
Equation (15)

[0115]

Embedded image (15)

140 parts of the dye represented by the following formula,
When 720 parts of the dye represented by the above formula (3) are sufficiently mixed,
A dark blue 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 at 2 ° C. for 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dye, a uniform dark blue 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 knitted fabric made of rayon 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 formula (16)

[0118]

Embedded image (16)

In a bath, 800 g of the dye represented by the following formula, 0.7 g of a composition obtained by thoroughly mixing 200 parts of the dye represented by the above formula (1), and 5.0 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. Example 11 The form of the free acid was 400 parts of the dye represented by the formula (1), and the form of the free acid was the formula (17)

[0120]

Embedded image (17)

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

Example 12 The form of the free acid was 450 parts of the dye represented by the formula (3) and the form of the free acid was the formula (18)

[0123]

Embedded image (18)

By mixing 550 parts of the dye represented by the formula (1), a blue composition is obtained. As in Example 1, 0.8 g of this composition and 5.0 g of anhydrous sodium sulfate were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 60 ° C.) in which 10 g of a knitted fabric made of cotton fiber was set. The knitted fabric was treated at 60 ° C. for about 20 minutes after the addition, and then 0.3 ml of 38 ° C. caustic soda was poured into the bath.
Dyeing and washing the knitted fabric for 0 minutes gives a uniform, uniform blue dyeing with good lightfastness, sweat, chlorine and wash fastness. Also, the reproducibility of the above dyeing is good.

Example 13 The free acid form was 700 parts of the dye represented by the formula (5), and the free acid form was the following formula (19)

[0126]

Embedded image (19)

By mixing 300 parts of the dye represented by the formula (1), a dark blue composition is obtained. 50 g of this composition and 500 salt
g in a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) set with 1000 g of a cotton fiber yarn, and treated at 80 ° C. for 20 minutes.
0 g was put into the bath, and then dyed and washed at this temperature for 60 minutes to obtain a uniform dark blue dyed yarn having good light fastness, sweat, chlorine and washing fastness and no difference in concentration between the inner and outer layers of the cheese. can get. Also, the reproducibility of this cheese dyeing is good.

Example 14 The form of the free acid was 800 parts of the dye represented by the formula (7), and the form of the free acid was the following formula (20)

[0129]

Embedded image (20)

By mixing 200 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 3.0 were placed in a dyeing apparatus (bath ratio 1:10, bath temperature 80 ° C.) in which 10 g of rayon knitting was set.
g, knit the fabric at 80 ° C. for 20 minutes, add 2.0 g of sodium carbonate, dye and wash 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 15 10 g of rayon knitted fabric was set in a dyeing apparatus,
The bath ratio was 1:10 and the bath temperature was 70 ° C. The form of the free acid is
600 parts of the dye represented by the formula (9) and the form of the free acid are represented by the following formula (21)

[0132]

Embedded image (21)

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 obtained dyed product was uniform dark blue without 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 (12)

[Claims] 1. A reactive dye composition comprising the following reactive dyes a) and b). a) the form of the free acid is a blue reactive dye represented by the following formula (I); b) the form of the free acid is the following formulas (II), (X) and (XV)
One or more dye groups selected from the group of blue reactive dyes represented by I): (I) wherein R1 and R2 independently represent a halogen atom or an optionally substituted pyridinio group;
R3, R4 and R5 independently represent a hydrogen atom or an optionally substituted lower alkyl group, and U1 represents an optionally substituted phenylene, an optionally substituted naphthylene or an optionally substituted Represents a good C2-C6 alkylene, wherein Y1 is -SO2CH = CH2 or -SO2C
Represents H2CH2Z1, where Z1 represents a group which leaves under the action of an alkali. D-A1 (II) wherein A1 is a group represented by the following formula (III) or (IV): (III) {wherein, X1 represents a hydrogen atom, a chlorine atom or a fluorine atom, and X2 and X3 independently represent a fluorine atom or a chlorine atom. } (IV) {wherein, X4 represents a halogen atom or an optionally substituted pyridinio group, and R6 represents the following formula (V)
Represents a group represented by Embedded image (V) (wherein, R7 represents a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl group, R8 represents a hydrogen atom, an optionally substituted lower alkyl group, Represents an optionally substituted phenyl group or a group represented by the following formula (VI) -U2-Y2 (VI), wherein U2 represents an optionally substituted phenylene group, an optionally substituted naphthylene group, An optionally substituted C2-C6 alkylene group of the formula-(CH
2) represents a group represented by 2O (CH2) 2- (VII) or a group represented by the formula -CONH (CH2) 2- * (VIII), and an asterisk denotes a bond leading to Y2;
2 is -SO2CH = CH2 or -SO2CH2CH2Z
And Z2 represents a group capable of leaving by the action of an alkali. ) Represents a group represented by D, and D represents the following formula (IX): (IX) {wherein, R is a hydrogen atom, -SO2CH = CH2
Or -SO2CH2CH2Z3, wherein Z3 represents a group which is eliminated by the action of an alkali. } Represents a group represented by ] (X) wherein D represents the above-mentioned meaning, and X5 and X6
Each independently represents a halogen atom, and m represents 0 or 1
When m is 0, A2 represents a -NH- group, and when m is 1, A2 is represented by the following formula (XII)
Represents any of the groups represented by (XV). ] (XII) (XIII) (XIV) (XV) (XVI) wherein Y3 is -SO2CH = CH2 or-
SO2CH2CH2Z4, wherein Z4 represents a group which is eliminated by the action of an alkali. ] 2. A method according to claim 1, wherein Y1 in the formula (I) is --SO ₂ CH ₂ CH
A ₂ Z1, and, according to claim 1 Z1 is -OSO ₃ H
A composition according to claim 1. 3. The reactive dye of the above b) includes a dye represented by the formula (II), wherein A1 in the formula (II) is
The composition according to claim 1 or 2, which is a group represented by I), wherein X1 in the formula (III) is a chlorine atom, and both X2 and X3 are fluorine atoms. 4. A dye represented by the formula (II) as the reactive dye of b), wherein A1 in the formula (II) is
V) wherein X4 in the formula (IV) is
3. The composition according to claim 1, which is a halogen atom. 5. The composition according to claim 4, wherein R6 is a group represented by the formula (V), and R8 in the formula (V) is a phenyl group which may be substituted. 6. The composition according to claim 4, wherein R6 is a group represented by the formula (V), and R8 in the formula (V) is a group represented by the formula (VI). 7. The reactive dye of b) contains a dye of the formula (II), and the substitution position of -SO ₃ H in D of the formula (IX) is such that -NH- is substituted. 4. The carbon atom of the benzene ring in the para position.
A composition according to claim 1. 8. The reactive dye of the above b) contains a dye represented by the formula (II), and the substitution position of -SO ₃ H in D represented by the formula (IX) is -C (O) -O 7. The composition according to claim 1, 2, 4, 5 or 6, wherein the group is para to the carbon atom of the substituted benzene ring. 9. The reactive dye of b) includes a dye represented by the formula (X), wherein m in the formula (X) is 1 and -SO ₃ H in D represented by the formula (IX) The composition according to claim 1 or 2, wherein the substitution position is para to the carbon atom of the benzene ring in which the -C (O) -O- group is substituted. 10. The reactive dye of the above b) includes a dye represented by the formula (X), wherein X5 and X6 in the formula (X) are fluoro, and A2 is a group represented by the formula (XV). A composition according to claim 1, 2 or 9. 11. The reactive dye of the above b) includes a dye represented by the formula (X), wherein X5 and X6 in the formula (X) are chloro, and A2 is a compound represented by the formula (XII) or (XIII)
The composition according to claim 1, 2 or 9, which is any group selected from the groups represented by (XIV) and (XIV). 12. A method for dyeing or printing a fiber material, comprising using the composition according to any one of claims 1 to 11.