JPH04314762A - Reactive dye composition and dyeing or printing of fibrous material therewith - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is useful for dyeing and printing materials containing hydroxyl groups and/or amide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc., and blended fibers thereof. The present invention relates to improved reactive dye compositions which enable suitable, light-fast and wet-fast dyeings, as well as their applications.

0002

[Prior Art] Compounds useful as reactive dyes used for dyeing materials containing hydroxyl groups and/or amide groups, and compounds in which a vinyl sulfone reactive group and a pigment matrix are linked via a triazine ring, for example, are particularly useful as reactive dyes. Kaisho 56-1
It is publicly known as described in Japanese Patent No. 5481 and the like.

0003

Conventionally, this type of reactive dye has been widely used in the fields of dyeing and printing textile materials. However, the current state of the art is not fully satisfactory in view of the high requirements regarding suitability for specific dyeing methods and the increasingly sophisticated requirements regarding the fastness and dyeability of dyed products. It is strongly desired that the above-mentioned known reactive dyes be further improved in terms of build-up properties, solubility, stability over time, and fastness (for example, fastness to acid hydrolysis). The present inventors have completed the present invention as a result of intensive studies aimed at improving the above-mentioned known dyes and finding a new reactive dye that can broadly satisfy the requirements required for dyes.

0004

[Means to solve the problem]

The present invention provides the following general formula (I) in the form of a free acid:

[0005]

[Chemical formula 3]

[In the formula, Z is -CH=CH2 or -CH
It represents 2CH2Z1, and Z1 represents a group that is eliminated by the action of an alkali. ] and a reactive dye represented by the following general formula (I
I)

[0007]

[C4]

[In the formula, Z' is -CH=CH2 or -C
It represents H2CH2Z2, and Z2 represents a group that is eliminated by the action of an alkali. The present invention provides a reactive dye composition characterized by containing the reactive dye shown in the following, and a method for dyeing or printing a fiber material characterized by using the same.

The reactive dyes of the general formulas (I) and (II) in the composition of the invention are present in the form of free acids or in the form of their salts, in particular alkali metal salts and alkaline earth metal salts. Among them, soda salt, potassium salt, and lithium salt are preferred.

The reactive dye represented by the general formula (I) can be produced by the method described in JP-A-56-15481. In addition, the reactive dye represented by the general formula (II) is novel, for example, the reactive dye represented by the general formula (I) in the form of a free acid.
It can be produced by hydrolyzing the reactive dye represented by in an aqueous medium. The dye composition of the present invention is
It can be obtained by mixing the monoazo reactive dyes represented by the general formulas (I) and (II), but the general formula (I)
The amount of the reactive dye represented by I) to be mixed is 1 to 50% by weight, preferably 1 to 20% by weight, based on the reactive dye of general formula (I).
Weight%. In the present invention, the monoazo reactive dyes represented by the general formulas (I) and (II) may be mixed by being synthesized at the same time, or may be synthesized separately and then mixed. May be mixed. Furthermore, they may be mixed during dyeing. Z
Examples of groups that are eliminated by the action of alkali represented by 1 and Z2 include -OSO3H, -OCOCH3,
Examples include -OPO3H2 and -CL, among which -OSO3H is preferred.

The composition of the present invention has fiber reactivity and can be used for dyeing or printing materials containing hydroxy groups or carbonamide groups. Preferably, the material is used in the form of a fibrous material or a blend thereof. Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or regenerated products thereof and polyvinyl alcohol. Preferably, the cellulosic fiber material is cotton or other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers include, for example, viscose staple and filament viscose. Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,6, polyamide-6, polyamide-11.
and polyamide-4.

The composition of the present invention can dye or print the above-mentioned materials, especially the above-mentioned fiber materials, by a method depending on their physical and chemical properties. For example, in the case of exhaust dyeing on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, a neutral salt such as mirabilite or common salt is optionally added, and if desired, a solubilizer is added. , a penetrant or a leveling agent is used in combination, and it is carried out at a relatively low temperature. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions. When dyeing cellulose fibers according to the padding method, it can be padded at room temperature or at an elevated temperature and, after drying, fixed by steaming or dry heat. When printing is carried out on cellulose fibers, it is printed in one phase, for example with a printing paste containing baking soda or other acid condensing agent, and then
By steaming at 0-160°C or in two phases, for example with a neutral or weakly acidic printing paste, which is passed through a hot electrolyte-containing alkaline bath or overpadded with an alkaline electrolyte-containing padding liquid. , steaming or dry heat treatment. Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Acid binders suitable for fixing the dyes of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali when heated. It is. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary, or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate, and the like. The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion under pH control from an acidic or slightly acidic dye bath, and then by changing to a neutral or even alkaline pH value for fixation. I can do it. Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as cyanuric chloride and
It is also possible to use a condensation product with twice the molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or an addition product of, for example, stearylamine with ethylene oxide.

The composition of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials. Particularly suitable for dyeing cellulose fiber materials, with good light fastness and sweat resistance, sunlight resistance, moisture resistance, such as washing resistance, peroxide washing resistance, sweat resistance, chlorine resistance, acid hydrolysis resistance and It is alkaline and has good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, solubility, level dyeing properties, and wash-off properties, as well as good exhaustion and fixation properties, and dyed products with stable quality that are not affected by fluctuations in dyeing temperature or dye bath ratio. It is distinctive in that it is obtained. Another characteristic of the dyed product is that there is little discoloration during fix treatment or resin processing, and there is little change due to contact with basic substances during storage. Hereinafter, the present invention will be explained in detail with reference to Examples. In the examples, parts and % represent parts by weight and % by weight, respectively.

[0015]

[Example] Example 1 The following structural formula (i) in free acid form:

[0016]

[C5]

100 parts of a monoazo reactive dye represented by the following structural formula (ii) in the form of a free acid:

[0018]

[C6]

A dye composition was obtained by blending with 10 parts of the monoazo reactive dye shown below. 0.1, 0.3 and 0.6 parts of this composition were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 60°C, and 4 parts of soda carbonate was added. Stained for 1 hour. After washing with water, soaping, washing with water and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained. The reactive dye represented by structural formula (ii) is prepared by mixing the reactive dye represented by structural formula (i) in an aqueous medium at pH 1 to 3, pH 60 to 80.
Obtained by reaction at ℃.

Example 2 100 parts of the monoazo reactive dye represented by structural formula (i) used in Example 1 and 15 parts of the monoazo reactive dye represented by structural formula (ii) used in Example 1 were blended. A dye composition was obtained, and 0.1, 0.3 and 0.6 parts were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added.
The temperature was raised to 0°C, 4 parts of soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, washing with water and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained.

Example 3 100 parts of the monoazo reactive dye represented by structural formula (i) used in Example 1 and 3 parts of the monoazo reactive dye represented by structural formula (ii) used in Example 1 were blended. A dye composition was obtained, and 0.1, 0.3 and 0.6 parts of the dye composition were added to 2 parts of water, respectively.
00 parts, add 10 parts of Glauber's salt and 10 parts of cotton, and make 60 parts.
The temperature was raised to .degree. C., 4 parts of soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, washing with water and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained.

Example 4 The following structural formula (iii) in free acid form:

[0023]

[C7]

100 parts of a monoazo reactive dye represented by the following structural formula (iv) in the form of a free acid:

[0025]

[Chemical formula 8]

A dye composition is obtained by blending with 5 parts of monoazo reactive dye shown in the following.
200 parts of water, 10 parts of mirabilite and 10 parts of cotton.
1 part, heated to 60°C, added 4 parts of soda carbonate,
Stained for 1 hour. After washing with water, soaping, washing with water and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained. Example 5 The following structural formula (V) in free acid form

[0027]

[Chemical formula 9]

100 parts of a monoazo reactive dye represented by the following structural formula (vi) in the form of a free acid:

[0029]

[Chemical formula 10]

A dye composition is obtained by blending with 10 parts of monoazo reactive dye shown in the following.
6 parts each in 200 parts of water, 10 parts of mirabilite and 1 part of cotton.
0 parts was added, the temperature was raised to 60°C, 4 parts of soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, washing with water and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained. Example 6 Using the reactive dye composition obtained in Example 1, a colored paste having the following composition was made. reactive dye composition
5 part urea

5 parts Sodium alginate (5%) base glue
50 parts boiling water
25 parts baking soda
2 part balance

13 parts This colored paste was printed on mercerized cotton broadcloth, and after intermediate drying, it was steamed at 100° C. for 5 minutes, washed with hot water, soaped, washed with hot water, and dried. The obtained printed material was excellent in various fastnesses and had good build-up properties.

Claims (2)

[Claims] Claim 1: In the form of a free acid, the following general formula [Formula 1] [wherein, Z is -CH=CH2 or -CH2CH2Z1]
, and Z1 represents a group that is eliminated by the action of an alkali. ] and 1 to 5 for the dye.
0% by weight in the form of free acid of the following general formula: [Formula, Z' is -CH=CH2 or -CH2CH2Z
2, and Z2 represents a group that is eliminated by the action of an alkali. ] A reactive dye composition characterized by containing a reactive dye represented by the following. 2. A method for dyeing or printing textile materials, which comprises using the reactive dye composition according to claim 1.