JP2001354870A - Reactive dyestuff composition and its application for fibrous material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive dyestuff useful for dyeing a cellulosic fiber in scarlet color. SOLUTION: This reactive dyestuff composition is obtained by incorporating reactive dyestuffs shown by formulae (I) and (IV) [wherein, (m) is 0 or 1; R1 is H or methyl; Z1 is a heterocycic fiber-reacting group; B1, B2 are each an optional fiber-reacting group; D1, D2 are each a substitutable phenylene or a substitutable naphthylene; X5 is fluoro, chloro, a substitutable pyrydinio or NR8R9; and R8, R9 are each H, a substitutable alkyl or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reactive dye composition,
And their application to fiber materials.

[0002]

2. Description of the Related Art When dyeing cotton fibers in scarlet red, a scarlet-color reactive dye and a red reactive dye composition have been conventionally used.

[0003]

However, even if the above-mentioned conventional reactive dye composition is dyed in scarlet red, the dyeing performance (exhaustion / fixing property, build-up property, reproducibility of dyeing, unfixed dye Ease of washing / removal from fiber material, etc.), storage stability in dry, wet and solution state, solubility in dye bath, etc., compatibility with other reactive dyes, degree of dyeing in compound dyeing, Suitability for more economical dyeing formulations, and various fastnesses (chlorine resistance, light resistance, sweat resistance, sweat and sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance, peroxide washing resistance) Etc.), in particular, there is no reactive dye composition having a good balance of washing fastness, leveling property and build-up property.
There is a demand for a reactive dye composition having excellent performances.

[0004]

DISCLOSURE OF THE INVENTION As compared with the conventional reactive dye composition, the present inventors have a better balance of washing fastness, leveling property and build-up property and can dye at a low salt concentration. As a result of intensive research to develop a composition that gives scarlet red dyeings and prints excellent in various fastnesses, the present inventors have found that a specific reactive dye composition achieves the above object, and have developed the present invention. It was completed.

That is, the present invention relates to a reactive dye having a free acid form represented by the following formula (I) and a reactive dye having a free acid form represented by the following formula (IV)
A reactive dye composition comprising a reactive dye represented by
Another object of the present invention is to provide a method for dyeing or printing a fiber material using the composition.

[0006]

Embedded image (I)

Wherein m is 0 or 1, R ¹ represents hydrogen or methyl, and Z ¹ represents a fiber-reactive group represented by the following formula (IIa) or (IIb).

[0008]

Embedded image (IIa)

[0009]

Embedded image (IIb)

(Wherein X ¹ and X ² both represent chloro, or X ¹ is fluoro, chloro, optionally substituted pyridinio or the following formula (IIIa)

[0011]

Embedded image (IIIa)

X ² represents a fiber-reactive group represented by the following formula (IIIb):

[0013]

Embedded image (IIIb)

A fiber-reactive group represented by the following formula (III)
c), (IIId) or (IIIe)

[0015]

Embedded image (IIIc)

[0016]

Embedded image (IIId)

[0017]

Embedded image (IIIe)

Wherein A ¹ and A ² are each independently alkylene optionally substituted with a non-fiber-reactive group, phenylene optionally substituted with a non-fiber-reactive group, or non-fiber-reactive Represents naphthylene which may be substituted with a group,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another, hydrogen,
Represents an alkyl that may be substituted with a non-fiber-reactive group or a phenyl that may be substituted with a non-fiber-reactive group,
Q is _{-CH 2 -, - O -,} - S -, - SO 2 - or -NR
It represents ^7, R ⁷ represents hydrogen, alkyl which may be substituted with a non-fiber-reactive phenyl optionally substituted with one or non-fiber-reactive group, n is 1, 2 or 3, Y ¹ and Y ² are independently of each other —CH ＝ CH ₂ or —CH ₂ C
Represents H ₂ L, where L is a group which is eliminated by the action of an alkali. }, X ³ represents fluoro or chloro, and X ⁴ represents chloro, hydrogen, methyl or cyano. )]

[0019]

Embedded image (IV)

[In the formula, B ¹ and B ² independently represent a fiber-reactive group, and D ¹ and D ² independently represent a phenylene or a phenylene which may be substituted with a non-fiber-reactive group. Represents naphthylene which may be substituted with a non-fiber-reactive group,
X ⁵ represents fluoro, chloro, optionally substituted pyridinio or —NR ⁸ R ⁹ , wherein R ⁸ and R ⁹ independently of one another, hydrogen, alkyl optionally substituted by a non-fiber-reactive group, or Represents phenyl optionally substituted with a non-fiber-reactive group. Hereinafter, the present invention will be described in detail.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the reactive dye (I) used in the composition of the present invention, m represents 0 or 1, but is preferably 0. R ¹ in formula (I) represents hydrogen or methyl, but is preferably hydrogen.

Z ¹ in the above formula (I) represents a fiber-reactive group represented by the above formula (IIa) or (IIb).

X ¹ and X ² in the formula (IIa) both represent chloro, or X ¹ is fluoro, chloro, optionally substituted pyridinio or a fiber-reactive group represented by the above formula (IIIa) X ² represents a fiber-reactive group represented by the above formula (IIIb) or a compound represented by the formula (IIIc), (IIId) or (II
Represents a non-fiber-reactive group represented by Ie).

Formulas (IIIa), (IIIb), (IIIc) and (II
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in Ie) may be, independently of one another, hydrogen, alkyl optionally substituted with a non-fiber-reactive group or substituted with a non-fiber-reactive group. Represents a good phenyl. A ¹ and A ² in the formulas (IIIa) and (IIIb) each independently represent an alkylene which may be substituted with a non-fiber-reactive group, a phenylene or a non-fiber which may be substituted with a non-fiber-reactive group. Represents naphthylene which may be substituted with a reactive group. The alkylene which may be substituted with the non-fiber-reactive group in A ¹ and A ² is preferably, for example, an unsubstituted alkylene such as-(CH2) 2-,-(CH2) 3- and -CH (CH3) CH2- C ₂ -C ₄ alkylene.

In formulas (IIIa) and (IIIb), Y ¹ and Y ² are independently of each other —CH ＝ CH 2 or —CH 2 CH 2
L represents a group capable of leaving by the action of an alkali. As the above L, for example, sulfate, thiosulfate, phosphate, acetate, halogeno, or
1 selected from the group consisting of carboxy and carbamoyl
And pyridinio which may be substituted with 2 to 2 groups.

Q in the formula (IIId) is -CH2-,-
O -, - S -, - SO2- or -NR ⁷ - represents, R ⁷ is hydrogen, a non-fiber-reactive may be substituted with a group phenyl or a non-fiber-reactive alkyl which may be substituted with a group Represents Further, n in the formula (IIId) represents 1, 2 or 3, and is preferably 2. X ³ in the formula (IIb) represents fluoro or chloro, and X ⁴ represents chloro, hydrogen, methyl or cyano.

D ¹ and D ² in the reactive dye (IV) independently represent phenylene which may be substituted with a non-fiber-reactive group or naphthylene which may be substituted with a non-fiber-reactive group.

X ⁵ in the formula (IV) represents fluoro, chloro, optionally substituted pyridinio or —NR ⁸ R ⁹ . R ⁸ and R ⁹ each independently represent hydrogen, alkyl optionally substituted with a non-fiber-reactive group, or phenyl optionally substituted with a non-fiber-reactive group.

B ¹ and B ² in the formula (IV) each independently represent a fiber-reactive group. Examples of the fiber-reactive group include, under dyeing conditions, in the presence of an acid binder described below. Ester groups of mineral or organic acids of 2-hydroxyethylsulfonyl, 1,3,5-triazine, quinoxaline, phthalazine and pyrimidine which yield vinylsulfonyl. Examples of other fiber-reactive groups include halogen-substituted pyridazone groups and 2-alkylsulfonylbenzthiazole groups. Further, examples of the fiber reactive group include vinylsulfonyl and 2-chloroethylsulfonyl. Specific examples of the fiber reactive group include the following groups.

[0030]

Embedded image

In the above specific examples, Hal represents fluorine or chlorine, and R ¹⁰ is alkyl having 1 to 6 carbons or 1 carbon.
Represents alkoxy, R ¹¹ represents hydrogen or nitro, and ring C may be substituted by a group selected from the group consisting of hydrocyclsulfonyl, carboxysulfonyl, chlorine, nitro, methoxy and methyl.

In formulas (IIIa), (IIIb), (IIIc) and (IIIe), -NR ^7- represented by Q in formula (IIId) and X ⁵ in formula (IV) Specific examples of alkyl which may be substituted with a non-fiber-reactive group represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ in —NR ⁸ R ⁹ As, for example, methyl, ethyl, n-propyl, is
o-propyl, n-butyl, iso-butyl, sec-
Butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl,
3-hydroxybutyl, 4-hydroxybutyl, 2,3
-Dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-
Methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, carboxymethyl, 2-
Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxy Carbonylethyl, 2-ethoxycarbonylethyl, 3
-Methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methyl Carbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-
Sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl,
Examples thereof include 3-bromopropyl, 4-chlorobutyl, and 4-bromobutyl.

Formulas (IIIa), (IIIb), (IIIc) and (II
Ie), -NR represented by Q in the formula (IIId) ⁷ -, and, R ^2, R ³ in the -NR ⁸ R ⁹ represented by X ⁵ in the formula ^{(IV), R 4, R} 5 Specific examples of phenyl optionally substituted with a non-fiber-reactive group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ include, 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-isopropylphenyl, 2-, 3- or 4-carboxyphenyl, 2
-, 3- or 4-carbamoylphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-sulfophenyl, 2-, 3- or 4-hydroxyphenyl, 2-sulfo-4-methoxyphenyl , 2-sulfo-4-acetylaminophenyl, 2-carboxy-4-acetylaminophenyl, 2-methoxy-5-methylphenyl, 2,
Preferred are 4-dimethoxyphenyl and 2,5-dimethoxyphenyl.

The phenylene which may be substituted by the non-fiber-reactive group represented by A ¹ , A ² , D ¹ and D ² in the formulas (IIIa), (IIIb) and (IV) includes, for example, carbon Phenylene which may be substituted by one or two non-fiber-reactive groups selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, and halogeno (chloro, bromo, etc.) Is preferred. Among them, phenylene which may be substituted by one or two non-fiber-reactive groups selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo is particularly preferred. As such phenylene, for example,

[0035]

Embedded image

[In the formula, *** indicates -NR ^2- , -NR
³ -, - B ¹ or ^{-B 2 (R 2, R 3} , B 1 and B ² is a is defined above) refers to a bond that leads to. And the like. Particularly, phenylene which may be substituted with one or two groups selected from the group consisting of methyl and methoxy is preferable.

In the formulas (IIIa), (IIIb) and (IV), the naphthylene which may be substituted by the non-fiber-reactive group represented by A ¹ , A ² , D ¹ and D ² is 1 or 2 Naphthylene which may be substituted by two sulfo is preferred. As such naphthylene, for example,

[0038]

Embedded image

[In the formula, *** indicates -NR ^2- , -NR
³ -, - B ¹ or ^{-B 2 (R 2, R 3} , B 1 and B ² is a is defined above) refers to a bond that leads to. And the like.

X ¹ and X ⁵ in the formulas (IIa) and (IV)
As the optionally substituted pyridinio represented by
For example, pyridinio, 2-, 3- or 4-carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, 3-sulfopyridinio, 4- (2-sulfoethyl)
Examples thereof include pyridinio, 3- (2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio, and 3,5-dicarboxypyridinio. Among them, 3- or 4-carboxypyridinio is preferable.

The reactive dyes (I) and (IV) may be, for example, in the form of a mixture of the free acid form and a salt thereof, but are preferably alkali metal salts, alkaline earth metal salts, And a mixture containing them, and among them, a soda salt, a potassium salt, a lithium salt and a mixture containing them are particularly preferable.

The reactive dye composition of the present invention comprises the reactive dye (I)
And (IV), and the preparation method is not particularly limited. That is, the reactive dyes (I) and (IV) may be obtained by mixing them before dyeing, or may be obtained by mixing them in a dyeing bath at the time of dyeing.

The reactive dye composition of the present invention is selected from one of the reactive dyes represented by the formula (I) or a mixture of two or more of the reactive dyes represented by the formula (IV). It is composed of one type of dye or a mixture of two or more types. Preferably, 99 to 1% by weight of the reactive dye represented by the formula (I) and 1 to 99% by weight of the reaction represented by the formula (IV) It contains a dye. More preferably, 80
-20% by weight of the reactive dye of formula (I)
It contains 80% by weight of a reactive dye represented by the formula (IV).

The reactive dye (I) used in the composition of the present invention can be produced, for example, by the method described in JP-A-63-101458. The reactive dye (IV) can be produced, for example, by the method described in JP-A-11-043623.

The reactive dye composition of the present invention can be used as a dye for dyeing and printing fiber materials. The fiber material is not particularly limited as long as it contains a hydroxy group and / or an amide group. For example, natural or regenerated cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber, leather, and a blend containing these are used. Materials and the like can be mentioned. Specific examples of the natural cellulose fiber include cotton, linen, hemp, jute, and ramie fiber. Preferably, it is cotton. Specific examples of the regenerated cellulose fiber include rayon, polynosic, cupra fiber, and trade names “Tencel”, “Toughcell”, “Modal”, “Certima”, and the like. Specific examples of the natural or synthetic polyamide fiber include wool, silk, polyamide-6,6, polyamide-6, polyamide-11, polyamide-4, and the like. Examples of the blended material containing these include a blended material of these fiber materials and a blended material of these fiber materials and synthetic fibers such as polyester, nylon, and acrylic.

The composition of the present invention can be applied to the above-mentioned materials, especially the above-mentioned fibrous materials, in a manner depending on the physical and chemical properties,
It can be dyed or printed. Specifically, for example, a method of dyeing or printing on the above-mentioned fiber by an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, a printing method, or the like can be mentioned. For example, in the case of dyeing cellulose fibers by an exhaustion dyeing method, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, in the presence of an acid binder such as caustic soda, if necessary, neutral salt such as sodium sulfate and sodium chloride. In addition, if necessary, a dissolution aid, a penetrant or a leveling agent is used in combination,
A method of dyeing at a temperature of about 30 to 100 ° C. is exemplified. Here, the addition of the acid binder, the neutral salt, and the like may be performed at once, or may be performed in a divided manner by a conventional method. When dyeing on cellulose fiber by the cold batch-up method, after padding using neutral salts such as sodium sulfate and sodium chloride, and an acid binder such as caustic soda and sodium silicate, it is fixed in a hermetically sealed packaging material. For example, a method in which the treatment is carried out by leaving at a temperature is exemplified. In the case of dyeing on a cellulose fiber by a continuous dyeing method, padding is carried out at room temperature or at an elevated temperature by a known method in the presence of an acid binder such as sodium carbonate and sodium bicarbonate, followed by steaming or dry heat treatment. After the fiber is immersed in a phase padding method or a padding solution in which the compound of the present invention is dissolved, padding is performed with a neutral salt such as sodium sulfate or sodium chloride and an acid binder such as caustic soda or sodium silicate. Examples include a two-phase padding method in which the treatment is performed by teaming or drying. In the case of printing on cellulose fiber, in one phase, printing with a printing paste containing an acid binder such as baking soda, and then steaming at a high temperature of 80 ℃ or more, or in two phases, for example, neutral or A method of printing with a weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or overpadging with an alkaline electrolyte-containing padding solution, followed by steaming or dry heat treatment is exemplified. . Here, the printing paste may contain a sizing agent such as sodium alginate and starch ether and / or an emulsifier, and if necessary, a printing aid and / or a dispersant such as urea. May be. When dyeing or printing the compound of the present invention on cellulose fibers, the acid binder used is not particularly limited, for example, hydroxides of alkali metals, aqueous solutions of alkali metals or alkaline earth metals and inorganic or organic acids. Examples thereof include a basic salt, and a compound that releases an alkali under heating. In particular, mention may be made of alkali metal hydroxides and alkali metal salts of inorganic acids or organic acids of weak to moderate strength, of which sodium or potassium hydroxides, sodium salts and potassium salts are preferred. Specific examples of such an acid binder include the above-mentioned sodium carbonate, sodium bicarbonate, sodium tertiary phosphate, sodium hydroxide, sodium silicate, potassium hydroxide, sodium formate, potassium carbonate, primary or secondary sodium phosphate, trichloroacetic acid. Soda or the like can also be used. In the case of exhaustion dyeing on a synthetic or natural polyamide fiber or polyurethane fiber, the compound of the present invention is exhausted in an acidic to weakly acidic dyeing bath under control of pH and then at 60 to 120 ° C. For example, a method of changing the pH to neutral to alkaline at a moderate temperature is exemplified. Here, if necessary, a leveling agent or the like, for example, a condensation product of cyanuric chloride and aminobenzenesulfonic acid, a condensation product of cyanuric chloride and aminonaphthalenesulfonic acid, an addition product of stearylamine and ethylene oxide, etc. A leveling agent may be used.

The composition of the present invention can be used by mixing with other dyes, if necessary, in order to obtain a desired hue, as long as the characteristics of the present invention are not impaired. The dye used in combination is not particularly limited as long as it is a reactive dye.For example, as a reactive group, a sulfatoethyl sulfone group, a vinyl sulfone group, a monochlorotriazine group, a monofluorotriazine group, a triazine mononicotinate group,
At least one of a dichlorotriazine group, a difluoromonochloropyrimidine group, and a trichloropyrimidine group
Dyes having at least one species, or Sumifix, S
umifix HF, Sumifix Supra, Remazol, Levafix
, Procion, Cibacron, Basilen, Drimarene, K
ayacion, dyes commercially available under the titles such as Kayacelon React, and further, JP-A-50-178, JP-A-56-948
3, JP-A-56-15481, JP-A-56-118976, JP-A
56-128380, JP-A-57-2365, JP-A-57-89679
No., JP-A-57-143360, JP-A-59-15451, JP-A-Showa
58-191755, JP-A-59-96174, JP-A-59-161463
No., JP-A-60-6754, JP-A-60-123559, JP-A-60-123559
No. 60-229957, JP-A-60-260654, JP-A-61-126
No. 175, JP-A-61-155469, JP-A-61-225256,
JP-A-63-77974, JP-A-63-225664, JP-A-1-185
No. 370, JP-A-3-770, JP-A-5-32907, JP-A-5
-117538, JP-A-5-247366, dyes described in JP-A-6-287463, and CIReactiveBlue 1
9, dyes represented by CIReactive Black 5, and the like.

[0048]

The reactive dye composition of the present invention is characterized in that it exhibits excellent performance in dyeing and printing fiber materials. The composition is particularly suitable for dyeing and printing cellulosic fibrous materials in scarlet red, and this composition has an excellent balance of wet fastness such as washing resistance and sweat-sun resistance, leveling property and build-up property. In addition, the reactive dye composition of the present invention has good solubility and excellent dyeing power (leveling property, wash-off property, exhaustion / fixing property), Excellent staining power at low salt concentration.
And it is hardly affected by fluctuations in the dyeing temperature, the amount of dyeing assistants such as salts and alkaline agents, and bath ratios, and a dyed product of stable quality can be obtained. Furthermore, there is little discoloration at the time of fix processing or resin processing of the obtained dyed matter,
It is also excellent in that there is little change due to contact with a basic substance during storage.

[0049]

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)

[0051]

Embedded image (1)

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

[0053]

Embedded image (2)

By mixing 500 parts of the dye represented by the formula, a scarlet red reactive dye composition is obtained. 0.6 g of the composition thus obtained and 5.0 g of anhydrous sodium sulfate were dyed with a dyeing apparatus (bath ratio: 1:
10, the bath temperature is 70 ° C.), the knitted fabric is treated at 70 ° C. for about 20 minutes, and then 2.0 g of sodium carbonate is poured into the bath. Dyeing and washing the knitted fabric for a minute gives a uniform, dark scarlet red dyeing with good washing and perspiration fastness. Also, the reproducibility of the above dyeing is good.

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

[0056]

Embedded image (3)

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

[0058]

Embedded image (4)

By mixing 250 parts of the dye represented by the formula, a scarlet red composition is obtained. Similar to Example 1, 0.8 g of this composition and 6.0 g of anhydrous sodium sulfate were placed in a dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 10 g of a knitted fabric made of cotton fiber was set. The knitted fabric is treated at 80 ° C. for about 20 minutes, and then 0.3 ml of 38 ° C. soda is poured into the bath, and the knitted fabric is dyed and washed at this temperature for 50 minutes. And a uniform dark scarlet red dyeing having good spotlight fastness and no spots is obtained. Also, the reproducibility of the above dyeing is good.

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

[0061]

Embedded image (5)

400 parts of the dye represented by the following formula (6)

[0063]

Embedded image (6)

By mixing 600 parts of the dye represented by the formula, a scarlet red composition is obtained. 60 g of this composition and salt 50
0 g was charged by a known method into a cheese dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 1,000 g of cotton fiber yarn was set, and treated at 80 ° C. for 20 minutes.
When 100 g are poured into the bath and then dyed and washed at this temperature for 60 minutes, a uniform scarlet red dyeing yarn having good washing and sweat 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 following formula (7)

[0066]

Embedded image (7)

500 parts of a dye represented by the following formula (8):

[0068]

Embedded image (8)

By mixing 500 parts of the dye represented by the formula, a scarlet red reactive dye composition is obtained. 0.2 g of the above composition and 3.0 g of anhydrous sodium sulfate are put into a dyeing apparatus (bath ratio: 1:10, bath temperature: 80 ° C.) in which 10 g of rayon knit is set, and knitting is performed at 80 ° C. for 20 minutes. Process,
When 2.0 g of sodium carbonate is added and dyed and washed at this temperature for 60 minutes, a uniform scarlet red dyeing free of spots and having good fastness to washing and sweat and sunlight is obtained. Also, the reproducibility is good even if the above dyeing is repeated.

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

[0071]

Embedded image (9)

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

[0073]

Embedded image (10)

In a bath, 720 parts of the dye represented by the following formula, 0.3 g of a composition obtained by sufficiently mixing 100 parts of the dye represented by the above formula (5), and 4.0 g of anhydrous sodium sulfate are added in a bath by a known method. After the introduction, the knitted fabric was treated at this temperature for 20 minutes, and 2.0 g of sodium carbonate was introduced into the bath by a known method. Subsequently, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The resulting dyed product was uniform scarlet red with no spots.
Washing and perspiration fastness of the obtained dyed product were both good. 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)

[0076] (11)

When 400 parts of the dye represented by the following formula and 600 parts of the dye represented by the above formula (5) in the form of the free acid are sufficiently mixed, a scarlet red 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 hydrogencarbonate, and further, water was added to make the total amount 1000 parts at 25 ° C. Using this solution as a padding liquid, padding a cotton fabric, After drying at 120 ° C. for 2 minutes and then steaming at 100 ° C. for 5 minutes to fix the dyestuff, a dyestuff is obtained which is homogeneous dark scarlet red and has good washing and sweat fastness. Even if the above dyeing is repeated, the reproducibility of the dyeing is good.

Example 7 0.5 part of the reactive dye composition obtained in Example 3 was added to 20 parts each.
Dissolve in 0 parts of water, add 20 parts of Glauber's salt, and further add 10% of cotton
Then, the temperature is raised to 70 ° C. After reaching 70 ° C, 3
After a lapse of 0 minutes, 4 parts of sodium carbonate was added, and the mixture was dyed at the same temperature for 1 hour. Next, washing and soaping are performed. The amount of coloring of the dyeing wastewater at the time of washing and soaping is small, and a dyed product excellent in various fastnesses such as a uniform and deep scarlet red washing fastness can be obtained.

Example 8 Reactive dye composition 1.
2 g and a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde (degree of sulfonation 110%,
Dyeing is carried out in the same manner as in Example 1, except that a mixture of average polymerization degree 1.8) 0.06 g is used. The dyeings obtained have the same quality as the dyeings obtained in Example 1.

Example 9 Dyeing was carried out in the same manner as in Example 1 except that 1.2 g of the reactive dye composition was used instead of 0.6 g of the reactive dye composition obtained in Example 1. The dyed product obtained using 1.2 g of the reactive dye composition was sufficiently darker than that of Example 1 using 0.6 g, and the build-up property of the used composition was good.

Example 10 Using the reactive dye composition obtained in Example 1, a color paste having the following composition is prepared.

[0082] color paste composition reactive dye composition 5 parts of urea 5 parts Sodium alginate (5%) stock paste 50 parts Hot water 25 parts sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts

This color paste is printed on a mercerized cotton broad, intermediately dried, steamed at 100 ° C. for 5 minutes, washed with hot water, soaped, washed with hot water, and dried.
Finish. The resulting prints are all uniform dark scarlet red. The prints obtained have good fastnesses.

Example 11 30 g of the reactive dye composition obtained in Example 1 was dissolved in hot water and cooled to 25 ° C. To this dye solution,
15 g of a 2.5% aqueous solution of caustic soda and 150 g of 50 ° water glass are added, and water is further added at 25 ° C. to make the total amount 1000 g. The padded cotton fabric is rolled up, closed with a polyethylene film, left at room temperature of 25 ° C. for 20 hours, washed by a conventional method, and dried to finish. All of the dyeings obtained are uniform and deep scarlet red. The obtained dyeings have good fastnesses.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Minoru Uchiyama 3-1-198 Kasuganaka, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. F-term (reference) 4H056 FA01 JA02 JB02 JB03 JC05 JD08 JD20 JE03 4H057 AA02 BA07 BA24 DA01 DA20 DA24 EA01 GA04 GA07

Claims (4)

[Claims] 1. A reactive dye composition comprising a reactive dye having a free acid form represented by the following formula (I) and a reactive dye having a free acid form represented by the following formula (IV). Embedded image (I) wherein m is 0 or 1, R ¹ represents hydrogen or methyl, and Z ¹ represents a fiber-reactive group represented by the following formula (IIa) or (IIb). Embedded image (IIa) (IIb) wherein X ¹ and X ² both represent chloro, or X
¹ is fluoro, chloro, optionally substituted pyridinio, or the following formula (IIIa): Represents a fiber-reactive group represented by (IIIa), X ² is the following formula (IIIb) embedded image (IIIb) a fiber-reactive group represented by the following formula (IIIc), (IIId) or (IIIe): (IIIc) (IIId) (IIIe) {wherein, A ¹ and A ² are each independently an alkylene optionally substituted with a non-fiber-reactive group, a phenylene optionally substituted with a non-fiber-reactive group, or a non-fiber-reactive Represents naphthylene which may be substituted with a group, R ² , R ³ , R
⁴ , R ⁵ and R ⁶ independently of one another represent hydrogen, alkyl optionally substituted with a non-fiber-reactive group or phenyl optionally substituted with a non-fiber-reactive group, and Q represents -CH ₂
-, - O -, - S -, - SO 2 - represents or -NR ^7, R
⁷ represents hydrogen, phenyl optionally substituted with a non-fiber-reactive group or alkyl optionally substituted with a non-fiber-reactive group, n is 1, 2 or 3, and Y ¹ and Y ² are , independently of one another, denote -CH = CH ₂ or -CH ₂ CH ₂ L, L is a group capable of leaving by the action of an alkali. }, X ³ represents fluoro or chloro, and X ⁴ represents chloro, hydrogen, methyl or cyano. )] (IV) [wherein B ¹ and B ² independently represent a fiber-reactive group, and D ¹ and D ² independently represent a phenylene or a phenylene which may be substituted with a non-fiber-reactive group. X ⁵ represents naphthylene which may be substituted by a non-fiber-reactive group, and X ⁵ represents fluoro, chloro, optionally substituted pyridinio or -N
R ⁸ represents R ⁹ , and R ⁸ and R ⁹ independently of one another represent hydrogen, alkyl optionally substituted with a non-fiber-reactive group or phenyl optionally substituted with a non-fiber-reactive group. ] 2. A reaction dye of the formula (I) of from 99 to 1% by weight and a reaction dye of the formula (IV) of from 1 to 99% by weight.
The composition according to claim 1, comprising: 3. A reactive dye group represented by the formula (I):
0% by weight and 20 to 80 of the reactive dye represented by the formula (IV).
2. The composition according to claim 1, comprising% by weight. 4. A method for dyeing or printing a fiber material, comprising using the reactive dye composition according to claim 1.