JPH11323168A - Reactive dye mixture and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a mixture which can give a dyeing having good dyeing performances and various fastnesses by mixing a plurality of free-acid-form reactive dyes comprising triazine derivatives with each other. SOLUTION: There is provided a dye mixture containing 100 pts.wt. at least one free-acid-form reactive dye represented by formula I and 1-80 pts.wt. at least one free-acid-form reactive dye represented by formula II. Exhaustion dyeing on a cellulosic fiber can be performed at a relatively low temperature by using a dye bath prepared by adding a neutral inorganic salt such as Glauber's salt to the dye mixture in the presence of an acid binder such as sodium carbonate or sodium tertiary phosphate and further adding a penetrant, a level dyeing agent, etc. To print a cellulosic fiber, the fiber is printed with a printing paste containing acid binder such as sodium bicarbonate and steamed at 95-160 deg.C. In the formulae, R1 is a halogen, a 1-4C alkyl, or the like; R2 is H or the like; R3 is H, a 1-4C alkyl, or the like; R4 to R6 are each H or an alkyl; B1 to B3 are each phenylene or naphthylene; Y1 to Y3 are each -CH2 CH2 L (wherein L is a leaving group) or vinyl; m is 1 or 2; n is 0 or 1; and m+n=2 or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a yellow reactive dye mixture and its application.

[0002]

2. Description of the Related Art Various reactive dyes and mixtures thereof have hitherto been known, and are widely used in the field of dyeing or printing cellulosic fiber materials. However, even when dyeing or printing fiber materials using these reactive dyes and their mixtures, the dyeing performance (exhaust properties, solubility, leveling properties, fixation rate, build-up, Properties, alkali bath stability, and ease of washing and removal of unfixed dyes from the fiber material, etc.), in particular, exhaustion properties, solubility, leveling properties, alkali bath stability, etc., are not sufficiently satisfied. There is a problem.
In addition, various fastnesses (for example, light fastness, sweat fastness, sweat sunlight fastness, chlorine fastness, acid hydrolysis fastness, alkali fastness, washing fastness, washing fastness over peroxide , And the stability of fiber-dye bonds).

[0003]

Under these circumstances, the present inventors have developed a dyeing performance, particularly, an exhaustion property, a solubility, a leveling property, and an alkaline bath in dyeing or printing of a cellulosic fiber material. As a result of intensive studies to develop a reactive dye mixture having excellent stability and capable of giving dyeings or prints having good various fastnesses, a reactive dye mixture containing a specific heterogeneous dye has been obtained for the above purpose. And accomplished the present invention.

That is, the present invention provides a compound represented by the following general formula (I)

[0005]

Embedded image (I)

Wherein R ₁ is a halogen atom, a C _1-4 alkyl group, ureido, C _1-4 alkylcarbonylamino,
_2-4 represents alkenylcarbonyl amino or optionally substituted phenyl carbonylamino, R ₂ is either a hydrogen atom, or may form a benzene ring together with R _l, and Dowa is It may be substituted with a sulfo group. R ₃ represents a hydrogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group or a sulfo group; R ₄ and R ₅ independently represent a hydrogen atom or an optionally substituted alkyl group; B ₁ and B ₂ independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and Y ₁ and Y ₂ each independently represent -CH ₂ C
H ₂ L (L is a group capable of leaving by the action of an alkali) or a vinyl group; m represents 1 or 2; n represents 0 or 1;
2 or 3. At least one of the reactive dyes represented by
In the form of a species and a free acid, the following general formula (II)

[0007]

Embedded image (II)

[Wherein, R ₁ , R ₂ , R ₃ , m and n have the same meanings as above, R ₆ represents a hydrogen atom or an optionally substituted alkyl group, and B ₃ represents a substituent. Represents a phenylene group which may be possessed or a naphthylene group which may have a substituent, and Y ₃ represents -CH ₂ CH ₂ L (L is a group which is eliminated by the action of an alkali) or a vinyl group . A reactive dye mixture comprising at least one reactive dye represented by the formula:
And a method for dyeing or printing a fiber material using the same. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive dye mixture of the present invention comprises at least one of the reactive dye represented by the formula (I) or a salt thereof and the reactive dye represented by the formula (II) or a salt thereof.
And seeds.

In the general formulas (I) and (II), R
_{When 1} represents C _1-4 alkylcarbonylamino or C _2-4 alkenylcarbonylamino, these alkyl and alkenyl may be substituted by a substituent such as a sulfo, carboxy or halogen atom. When R ₁ represents phenylcarbonylamino, the phenyl may be substituted with a substituent such as a sulfo, carboxy, methyl or halogen atom. Preferred R ₁ is methyl,
Ureido, acetylamino, propionylamino, Murray sulfonyl amino, or a succinylamino or benzoylamino, or, R _l together with R ₂ to form a benzene ring, and one sulfo in the ring is replaced Is what it is. When R ₃ is C _1-4 alkyl or C _1-4 alkoxy, the carbon chain may be linear or branched, and may have a substituent such as chloro or hydroxy, Preferably they have a small number of carbon atoms, especially methyl and methoxy. The best combination of R ₁ , R ₂ and R ₃ is that R ₂ is a hydrogen atom, R ₁ is ureido or acetylamino and R ₃ is a hydrogen atom, or R ₂ is a hydrogen atom And R ₁ is methyl, R ₃
Is methoxy.

In the formulas (I) and (II), R ₄ and R ₅
Or, when R ₆ is alkyl, the alkyl group includes, for example, methyl, ethyl, n-propyl, iso-
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, methoxymethyl, 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, methoxycarbonyl Methyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxy Methyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxy Butyl, 4-ethylcarbonyloxy-butyl, sulfomethyl, 2-sulfoethyl, can be mentioned 3-sulfopropyl and 4-sulfobutyl and the like.

As R ₄ , R ₅ and R ₆ , a hydrogen atom, methyl or ethyl is particularly preferred. Formulas (I) and (I)
In I), B ₁ , B ₂ and B ₃ represent a phenylene group which may be substituted or a naphthylene group which may be substituted, and the substituent includes an alkyl group having 1 to 4 carbon atoms, Examples thereof include an alkyloxy group having 1 to 4 groups, a hydroxyalkyl group, an alkoxyalkyl group having 2 to 8 carbon atoms, a sulfo group, and the like. Specifically, methyl, ethyl, n-propyl, iso-propyl, n- Butyl,
iso-butyl, sec-butyl, methoxy, ethoxy, iso-propoxy, 2-hydroxyethyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl,
-Ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl.

As B ₁ , B ₂ and B ₃ , unsubstituted phenylene and phenylene substituted with methyl or methoxy are preferred.

In the formulas (I) and (II), Y ₁ , Y ₂
Alternatively, when Y ₃ is —CH ₂ CH ₂ L, L is a group known as a group capable of leaving by the action of an alkali, such as sulfate, thiosulfate,
Acetoxy and chloro. Formulas (I) and (I)
Among the reactive dyes of I), preferred is a case where Y ₁ , Y ₂ and Y ₃ are both β-sulfatoethyl, and in the reactive dye, Y ₁ , Y ₂ or Y ₃ is vinyl. Certain reactive dyes may be present. The dyes of the general formulas (I) and (II) used in the present invention are preferably alkali metal or alkaline earth metal salts,
Particularly, sodium or potassium salts are preferable.

The method for producing the dyes of the general formulas (I) and (II) used in the present invention is described in
-210170, can be synthesized by a known method described in JP-A-63-225664, but they may be mixed at the time of synthesis by being synthesized at the same time, or may be mixed after being separately synthesized. You may. Furthermore, they may be mixed at the time of dyeing. The mixed form may be a solid such as a powder or a granule, an aqueous solution, or a combination thereof. The mixing amount of the dye of the formula (II) is preferably 1 to 80 parts by weight based on 100 parts by weight of the dye of the formula (I).

The reactive dye mixture of the present invention has fiber reactivity and can be used for dyeing and printing fiber materials containing hydroxy groups and / or amide groups. The fibrous material may be used in the form of a fibrous base material, in the form of a yarn, or in the form of a blended base material. Examples of the hydroxy group-containing fiber material include natural or synthetic hydroxy group-containing materials such as cellulose fiber materials, regenerated products thereof, and polyvinyl alcohol. Cellulose fiber materials include cotton and other vegetable fibers such as linen, hemp, jute and ramie fibers. As the regenerated cellulose fiber, for example, viscose staple,
Filament viscose can be mentioned. Examples of carbonamide-based fiber materials include, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers such as wool, other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11, polyamide
-4.

The reactive dye mixture of the present invention can be dyed or printed on the above-mentioned fiber material by a method depending on physical and chemical properties.

For example, when exhaustion dyeing is carried out on cellulose fibers, a neutral inorganic salt such as sodium sulfate or sodium chloride is optionally added in the presence of an acid binder such as sodium carbonate, sodium tertiary phosphate, caustic soda and the like. Can be dyed at a relatively low temperature by using a dissolution aid, a penetrant or a leveling agent in combination. The neutral inorganic salt which promotes the exhaustion of the dye may be added only after the original dyeing temperature has been reached or before that, and may optionally be added in portions.

When dyeing cellulose fibers according to the padding method, they can be padded at room temperature or at an elevated temperature, dried, and then fixed by steaming or dry heat.

When printing on cellulosic fibers, printing is carried out in one phase, for example with a printing paste containing baking soda or another acid binder, followed by steaming at 95 to 160 ° C., or by two-phase printing. For example, by printing with a neutral or weakly acidic printing paste and passing it through a hot electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether can be used, if desired, in combination with a usual printing aid and / or dispersant such as urea. .

The acid binder suitable for fixing the reactive dye mixture of the present invention on cellulose fibers is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary and secondary carbonates Alternatively, sodium tertiary phosphate, sodium silicate, sodium trichloroacetate and the like can be mentioned. When dyeing a synthetic or natural polyamide or polyurethane fiber using the reactive dye mixture of the present invention, for example, the dye is exhausted under control of the pH value in an acidic to weakly acidic dye bath, And, if necessary, changing the pH value of the dyeing bath to an alkaline pH value. Dyeing can be carried out at a temperature of 60 to 120 ° C., and at the time of dyeing, a leveling agent, for example, a condensation product of cyanuric chloride with 3 times moles of aminobenzenesulfonic acid and aminonaphthalenesulfonic acid, and stearylamine Addition products with ethylene oxide can also be used.

The reactive dye mixture 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, β-sulfatoethyl sulfone group, vinyl sulfone group, monochlorotriazine group, monofluorotriazine group, triazine mononicotinate A dye having at least one of a group, a dichlorotriazine group, a difluoromonochloropyrimidine group, and a trichloropyrimidine group, or Sumi
fix, SumifixSupra, Remazol, Levafix, Proci
on, Cibacron, Basilen, Drimarene, Kayacion,
Dyes which are commercially available under the titles such as Kayacelon React, and further, JP-A-50-178, JP-A-56-9483, JP-A-56-15481, JP-A-56-118976, Showa 56-12
No. 8380, JP 57-2365, JP 57-89679, JP 57-143360, JP 59-15451, JP 58-191755
No., JP-A-59-96174, JP-A-59-161463, JP-A-59-161463
No. 60-6754, JP-A-60-123559, JP-A-60-22995
7, JP-A-60-260654, JP-A-61-126175, JP-A-61-155469, JP-A-61-225256, JP-A-63-7
No. 7974, JP-A-63-225664, JP-A-1-185370, JP-A-3-770, JP-A-5-117538, JP-A-5-247366
No., dyes described in JP-A-6-287463,
Dyes represented by CIReactive Blue 19, CIReactive Black 5, and the like.

[0024]

The reactive dye mixture of the present invention has excellent exhaustion properties, solubility and leveling properties in dyeing or printing processing, has a high fixation rate, and particularly has excellent build-up properties in a dark color region. is there.

The reactive dye mixture of the present invention is hardly affected by changes in temperature during dyeing, fluctuations in the amount of neutral inorganic salt / acid binder, fluctuations in the dye bath ratio, and the like. The dyed and printed materials have stable quality and good fastness properties.

[0026]

The present invention will be described in more detail with reference to the following examples. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 The form of the free acid is represented by the following structural formula (1)

[0028]

Embedded image (1)

The compound represented by the following structural formula (2)

[0030]

Embedded image (2)

Is sufficiently mixed with 15 parts of the compound represented by the following formula:
A reactive dye mixture is obtained. This mixture 0.1, 0.3 and 0.
6 parts were dissolved in 200 parts of water each, 6 parts of sodium sulfate and 1 piece of cotton
Add 0 parts, raise the temperature to 70 ° C., add 4 parts of sodium carbonate, and dye for 1 hour. Wash, soap, wash and dry. At the time of washing and soaping, the coloring amount of the dyeing wastewater is small. The obtained dyed products were all uniform and dark reddish yellow, and the reactive dye composition 0.6
The dyed product obtained using 0.3 parts was sufficiently thicker than the dyed product obtained using 0.3 parts, and the dyed product obtained using 0.3 parts of the reactive dye composition was obtained using 0.1 part. It is sufficiently darker than the dyed product, and the build-up property of the reactive dye composition used is good. During dyeing, it has excellent exhaustion properties, solubility and leveling properties, and shows a high fixation rate. In addition, the light resistance, sweat resistance, sweat and sunlight resistance, chlorine resistance, acid hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance of the obtained dyed product are all good. is there.

Example 2 Dyeing is carried out in the same manner as in Example 1 except that the amount of sodium sulfate used is changed from 6 parts to 4 parts. Each of the obtained dyed products has the same quality as the dyed product obtained in Example 1.

Example 3 In each of Examples 1 and 2, dyeing is performed in accordance with Examples 1 and 2, except that the dyeing temperature is changed from 70 ° C. to 60 ° C. The obtained dyed products have the same quality as the dyed products obtained in Examples 1 and 2, respectively.

Example 4 Using the reactive dye mixture of Example 1, color pastes having the following compositions were prepared.

Color paste composition Reactive dye mixture 5 parts Urea 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance (water) 13 parts Total 100 parts

Each of the color pastes was 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 to finish. The resulting prints are all uniform, deep reddish yellow, have good build-up properties, and have good overall fastness and storage stability.

Example 5 After 30 parts of the reactive dye mixture of Example 1 were dissolved in hot water, the mixture was cooled to 25 ° C. To this dye solution,
15 parts of a 2.5% aqueous solution of caustic soda and 150 parts of 50 ° Baume water glass are added, and water is further added at 25 ° C. to make the total amount 1000 parts. Immediately after that, the liquid is used as a padding liquid to pad the cotton fabric. 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. The resulting dyed products are all uniform, dark reddish yellow, have good build-up properties,
Its various fastnesses and storage stability are also good.

Example 6 20 parts of the reactive dye mixture in Example 1 were each dissolved in hot water and then cooled to 25 ° C. 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate were added to this dye solution, and water was added at 25 ° C. to make the total amount 1000 parts. Pad the cotton fabric. The padded cotton fabric is dried at 120 ° C. for 2 minutes and then
The dye was fixed by steaming at 00 ° C. for 5 minutes.
Each of the dyed products obtained is uniform, dark reddish yellow, has good build-up properties, and has good fastnesses and storage stability.

In each of Examples 1 to 6, in the reactive dye mixture used, each of the compounds represented by the above structural formulas (1) and (2) was replaced with the compound in the second column and the third column in Tables 1 to 8, respectively. The dyeing is performed according to Examples 1 to 6, except that the composition ratio is changed to Each of the obtained dyed products is shown in Table 1 on cotton.
To 8 shown in the fourth column, all of which have the same quality as the dyed products obtained in Examples 1 to 6.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

Claims (4)

[Claims] 1. A compound of the following general formula (I) in the form of a free acid: (I) wherein R ₁ represents a halogen atom, a C _1-4 alkyl group, a ureido, a C _1-4 alkylcarbonylamino, a C _2-4 alkenylcarbonylamino or an optionally substituted phenylcarbonylamino; R ₂ may represent a hydrogen atom or form a benzene ring together with R _1, and the ring may be substituted with a sulfo group. R ₃ represents a hydrogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group or a sulfo group; R ₄ and R ₅ independently represent a hydrogen atom or an optionally substituted alkyl group; B ₁ and B
₂ independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and Y ₁ and Y ₂ each independently represent -CH ₂ CH ₂ L (L represents a group capable of leaving under the action of an alkali) or a vinyl group, m represents 1 or 2, n represents 0 or 1, and m + n is 2 or 3. And at least one reactive dye represented by the following general formula (II): (II) [wherein, R ₁ , R ₂ , R ₃ , m and n represent the same meaning as above, R ₆ represents a hydrogen atom or an alkyl group which may be substituted, and B ₃ represents a substituent. Represents a phenylene group which may have or a naphthylene group which may have a substituent,
Y ₃ is —CH ₂ CH ₂ L (L is a group which is eliminated by the action of an alkali)
Or a vinyl group. ] A reactive dye mixture comprising at least one reactive dye represented by the formula: 2. The mixture according to claim 1, wherein R ₁ is ureido or acetylamino, and R ₂ and R ₃ are hydrogen atoms. 3. The method according to claim 1, wherein R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, methyl or ethyl, and B ₁ , B ₂ and B ₃ are unsubstituted phenylene. The mixture as described. 4. A method for dyeing or printing a cellulosic fiber material, comprising using the mixture according to claim 1.