JPH04198277A - Reactive dye composition and method of dyeing or printing fibrous material by using it - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in build-up, solubility, long- term stability, fastness, etc., by mixing two specified reactive dyes. CONSTITUTION:In an aqueous medium, 2-aminonaphthalene-8,6,8-trisulfonic acid is diazotized, coupled with 1,3-diaminobenzene, converted into a ureide by using a cyanate to give a reactive dye (A) of formula I (wherein Z' is -CH=CH2 or -CH2CH2Z2; Z2 is a group eliminable by an alkali) in free acid form. A reactive dye (B) of formula II (wherein Z is -CH=CH2 or -CH2CH2Z1; Z1 is a group eliminable by an alkali) in free acid form is mixed with component A in an amount of 1-30wt.% based on component B to give the title composition. A fibrous material containing OH groups or carboxamido groups is dyed or printed with this composition.

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF APPLICATION ON THE MARKET The present invention is applicable to materials containing hydroxyl groups and/or amide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc. is an improved reactive dye composition which is suitable for dyeing and printing blended fibers thereof and which enables light-fast and wet-fast dyeing;
and its application.

<Conventional technology> Compounds having a vinylsulfone-based reactive group and a monochlorotriazine-based reactive group, which are useful as reactive dyes used for dyeing materials containing hydroxyl groups and/or amide groups, are disclosed in, for example, JP-A No. It is publicly known as described in Japanese Patent No. 56-15481 and the like.

<Problems to be Solved by the Invention> 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 terms of high requirements regarding suitability for specific dyeing methods and increasingly demanding requirements regarding the dullness and dyeability of dyed products.

The above-mentioned known reactive dyes also have adhesive properties, solubility,
Further improvements in terms of stability over time and robustness are strongly desired.

The present inventors improved the above-mentioned known dyes and completed the present invention as a result of intensive studies aimed at finding a reactive dye that can broadly satisfy the requirements required for dyes.

Means for Solving the Problems> The present invention provides the following general formula (1) [wherein Z
Bar CH-CHg Also represents 11-CH2CH* Zl, where zl represents a group that clears by the action of an alkali. ] The reactive dye represented by 1 to 80 times 1 to the dye
% of the free acid form of the following general formula (TI) [wherein Z'
Bar CH-CHz also represents 1d-CH2Ckhz2, and zl represents a group that is eliminated by the action of an alkali. ] Does it contain the reactive dye indicated by ? :44> In contrast to a, the present invention provides a dye composition and a method for dyeing, printing, and printing fiber materials using the dye composition.

The reactive dyes of the general formulas (f) and (It) in the compositions of the invention are present in the form of the free acids or in the form of their salts, in particular alkali metal salts and alkaline earth metal salts,
Among them, powder salts, potassium salts, and lithium salts are preferable.The reactive dye represented by the general formula (1) is, for example,
-15481 and EPC56975.

The reactive dye represented by general formula (II) can be produced, for example, as follows. After diazotization of 2-amitunaphthanone-8,6,8-tris-μphonic acid in an aqueous medium in a conventional manner and subsequent coupling with 1,8-diaminobenzene in a conventional manner, a cyanate salt, e.g. A monoazo compound represented by ureidation is obtained using a cyanate metal salt such as . The resulting monoazo compound has theta chloride μ and taste. ) can be condensed in any order to produce a reactive dye represented by general formula (II). The above-mentioned ureidation reaction is preferably carried out at pH 4.
Preferably at 0 to 70° C., more preferably 10 to 10, more preferably 5 to 8.
It can be carried out at ~40°C. The above-mentioned condensation reaction may also be carried out in an aqueous medium, preferably at -10-50°C, preferably at -30°C, and at a pH of 1-10, preferably 2-50°C.
7, 1.1 While adjusting, secondarily at 0-70℃,
It can be carried out preferably at a temperature of 10 to 50°C while adjusting the pH to 2 to 9, preferably 8 to 6.

The reactive dye represented by the general formula (1) thus obtained is itself useful for dyeing or printing hydroxy group-containing or carbonamide group-containing fiber materials.

The dye composition of the present invention has general formulas (1) and (I
It is obtained by mixing the reactive dye represented by I), and the amount of the reactive dye represented by the general formula 1r) is as follows:
The amount is 1 to 80% by weight, preferably 2 to 15ii%, based on the reactive dye of general formula (1).

In the present invention, the reactive dyes represented by the general formulas (I) and (n) may be mixed by being synthesized at the same time, or may be synthesized separately and then mixed. You can leave it there. Furthermore, even if it is mixed during dyeing, it can be used for dyeing or printing materials containing bonamide groups. Preferably, the material is used in the form of a fibrous material or a blend thereof.

The hydroxyl group-containing material may be a natural or synthetic hydroxyl group-containing material, such as cellulose fiber material or its regenerated material and bolipinia yco. Preferably, the cellulosic fibrous material is cotton or other vegetable fibers such as linen, hemp, shade and fumy fibers. Regenerated cellulose fibers include Tatoeba viscose tape and filament viscose.

Carbonamide-containing materials include, 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 compound 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, when exhaust dyeing is carried out on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, optionally a neutral filler, such as mirabilite or common salt, is added and, if desired, dissolved. Using auxiliary agents, penetrants or leveling agents together,
It is carried out at relatively low temperatures. Neutral salts that promote dye O exhaustion can be added at room temperature or at room temperature when dyeing c/l' loin fibers according to the robbing method, which can optionally be added in portions only after or before the original dyeing temperature is reached. After buffing and drying at elevated temperatures, it can be fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, it can be carried out in one phase, e.g. by printing with a printing paste containing 'ILIM or other acid binders and then steaming at 100-160°C, or in two phases, e.g. Printing can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overbagging with a bagging liquid containing an alkaline electrolyte, followed by steaming or dry heat treatment.

In the printing pastes, thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used, if desired, in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Suitable acid binders for fixing the dye compositions 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. be. Particularly preferred are 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. As such an acid binder,
Examples include caustic soda, caustic potash, baking soda, soda 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 involves first exhaustion under control of the μ■ value from an acidic or slightly acidic dye bath, and then a change to a neutral or sometimes dialkaline pH value for fixation. This can be done by letting 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 a condensation product of theata μ chloride and 8 times the mole of aminobenzenesulfonic acid or amine naphthalenesulfonic acid, are used. Alternatively, an addition product of stearylamine and ethylene oxide can also be used.

The dye composition of the present invention is characterized in that it exhibits excellent performance in dyeing and printing fiber materials. It is particularly suitable for dyeing cellulose fiber materials, and has good light fastness, perspiration and sunlight resistance, moisture resistance, such as washing resistance, peroxidation washing resistance, sweat resistance, chlorine resistance, acid hydrolysis resistance and It has alkali resistance, as well as 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 less affected by fluctuations in dyeing temperature and dye bath. It is characterized by the fact that it is

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, part and % represent Mdan part and left jk%, respectively.

Example 1 A reactive dye was prepared by blending 100 parts of a monoazo reactive dye represented by the following structural formula (1) in the form of a free acid with 10 parts of a monoazo reactive dye represented by the following structural formula (1) in the form of a free acid. A composition was obtained. 0.1, 0.8 and 0.6 parts of each were dissolved in 200 parts of water, 10 parts of Glauber's salt and mlO of wood were added, the temperature was raised to 60°C, 4 parts of sodium hypochlorite was added, and 1 Time stained. After washing with water, soaping, washing with water and drying, a yellow dyed product having excellent tenacity and good build-up properties was obtained.

The monoazo reactive dye represented by the above formula (8) was produced as follows.

2-Aminoaphthalene-8,6,8-)lysulfonic acid 8
After diazotizing 8.8 parts in water in a conventional manner, adding 10.8 parts of K, 1,8-diaminobenzene and coupling in a conventional manner, adding 7.15 parts of sodium cyanate, The ureidation was completed at room temperature while adjusting the pH to γ using a 2N MCI aqueous solution, and 1 g of cyanuric chloride was added.
Complete the first condensation by adding 5 parts of 1-amino-3-
After the second condensation was completed by adding 28.1 parts of β-sulfate ethylsulfonylbenzene, the reaction dye represented by the structural formula (II) was obtained by isolation.

Example 2 100 parts of the monoazo reactive dye represented by the structural formula (1) used in Example 1 and 5 parts of the heptanoazo reactive dye represented by the structural formula (1) used in Example 1 were blended. 0.1, 0.8 and 0.6 parts of the obtained dye compositions were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, the mixture was heated to 60°C, and 4 parts of soda carbonate was added. In addition, staining was carried out for 1 hour. washing with water,
After soaping, rinsing and drying, a yellow dyed product with excellent fastness and good build-up properties was obtained.

Example 8 100 parts of a monoazo reactive dye represented by the following structural formula (1) in the form of a free acid and 10 parts of a monoazo reactive dye represented by the following structural formula (IV) Cj2 (1,) in the form of a free acid were prepared. 0.1, 0.8 and 0.6 parts of the dye composition obtained by blending were added to 20 parts of water, respectively.
0 parts, add 10 parts of Glauber's salt and 10 parts of cotton, and heat at 60°C.
4 parts of I# acid soda were added and dyed 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 4 100 parts of a monoazo dye represented by the following structural formula (V) in the form of a free acid and the following -
Formation (vl) 0.1, 0.8 and 0.6 parts of the dye compositions obtained by blending with 5 parts of heptanoazo reactive dye were added to 200 parts of water, respectively.
10 parts of Glauber's salt and 10 parts of cotton were added to the solution, heated externally to 60°C, added 4 parts of soda carbonate, and dyed 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 Using each of the reactive dye compositions used in Examples 1-4, colored pastes having the following compositions were made.

Reactive dye composition 5 parts urine rice
5 parts Sodium anongate (5%
) Motonori 50 parts (, p n1
25 Part weight o'
2 parts Balance 13 parts This colored paste was printed on broad mercerized wire, dried in medium tiIJ, steamed at 100° C. for 5 minutes, washed with hot water, soaped, washed with hot water and dried. The obtained printed material is
All of them had excellent fastness and good build-up 18E (margins below)

Claims (2)

[Claims] (1) In the form of a free acid, there is the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ “In the formula, Z is -CH=CH_2 or -CH_2CH_2
Z_1 represents a group that is eliminated by the action of an alkali. ] The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available for the reactive dye represented by and 1 to 80% by weight of the dye in the form of free acid. ▼ "In the formula, Z' is -CH= CH_2 or -CH_2CH_
2Z_2, where Z_2 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.