JPH04189872A - Reactive dye composition and method for dyeing or printing fiber material with the same - Google Patents

Abstract

PURPOSE:To provide a reactive dye composition comprising a mixture of plural kinds of specific reactive dyes each having a naphthalene sulfonic acid group, a triazine ring group, etc., and capable of dyeing fibers having hydroxyl groups, amide groups, etc., into dyed products having good color fastness to light and moisture. CONSTITUTION:The objective reactive dye composition comprises a reactive dye of formula I [Z is CH=CH2 or CH2CH2Z1 (Z1 is a group releasable with an alkali) in the form of a free acid, and at least one of reactive dyes of formulas II [one of X, Y is sulfonic acid group, the other is H; Z' is CH=CH2, CH2 CH2Z2 (Z2 is a group releasable with an alkali), II (Q is SO2CH=CH2), and IV [Z'' is CH=CH2, CH2CH2Z3 (Z3 is a group releasable with an alkali)] in the form of free acids in an amount of 1-60wt.% based on the reactive dye of formula I.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is applicable to materials containing hydroquine groups and/or amide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc. The present invention relates to an improved reactive dye composition suitable for dyeing and printing blended fibers and capable of dyeing that is light-fast and wet-fast, and its application.

<Prior art> A compound useful as a reactive dye used for dyeing materials containing a hydrol-l-nor group and/or -mido group, and a compound in which a vinyl sulfone-based reactive group and a dye matrix are linked via a triazine ring. , for example, is described in Japanese Patent Application Laid-Open No. 50-178 and the like.

Problems to be Solved by Polymerization 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 does not fully satisfy the high requirements for suitability for specific dyeing methods and the sophistication of requirements regarding the fastness and dyeability of dyed products. It is strongly desired that reactive dyes be further improved in terms of 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 with the aim of improving the above-mentioned known dyes and also finding a new reactive dye that can broadly satisfy the requirements required for dyes.

(Means for Solving the Problems) The present invention provides the following general formula (I) in the form of a free acid: H: where Z::-C! -I=CHp or 4 CH2koH
2Z, and zl represents a group that is eliminated by the action of an alkali. ] and the following general formulas (n), HIT) and (IV), respectively in the free acid form: where X
and Y, one represents a sulfonic acid group and the other represents hydrogen, and 2° is -CH-CH2 or LJ CH=CH2Z2
and Z2 represents a group that is eliminated by the action of an alkali.

[Among the three major ones, Q represents -5O2CH=Ct12, only in the above general formula (i)), -5O2Z is 7' group, 〇-Cho1 Tamata: Map-position: : When substituting, - is respectively O-, m-tatali p-position 1 = t to be substituted and 1-1 A reactive dye represented by the general formula fil is selected when n B: Also, the above general formula In (■), Z: Ma-CII2[H2
It is Z1. : Three major middle, Z” :i, CH=CH2Also:t CH
=CH2Z3, and z3 represents a group that is eliminated by the action of an alkali. : Containing a reactive dye mixture consisting of at least two reactive dyes selected from the group of reactive dyes represented by: ~6
5. A reactive dye composition containing 0% by weight, and its use. The present invention provides a method for dyeing or printing a fiber material.

General formula (El) in the composition of the present invention.

Reactive dyes denoted as 11) and (■) exist in the form of free acids, in the form of salts of reeds, especially alkali metal salts and alkaline earth metal salts, especially soda salt, potassium salt, and lithium salt are preferred."5-General formula (I
) and (I) are disclosed in Japanese Unexamined Patent Publication No. 50-1
The second method can be produced by the method described in Japanese Patent No. 78.

The reactive dye represented by the general formula (II) is, for example, in the form of a free acid, represented by the following general formula (V): X and Y; 2, and the general formula (■): where, 2
゛ has the above meaning. ], the amine shown as
2 can be prepared by condensing 2 with chloride and 2 in any order.

Tamada, the reactive dye represented by the general formula (■) is new,
For example, a reactive dye represented by the above general formula 1) in the form of a free acid can be produced by removing water from an aqueous medium and decomposing water at the cutting edge.

The uninvented dye composition comprises a reactive dye represented by the general formula (]) and at least two reactive dyes selected from the group of reactive dyes represented by the general formulas <II), ([1) and (TV)]. The amount of the reactive dye mixture is i to 60% by weight, preferably 2 to 41% by weight, based on the reactive dye represented by the general formula (+). ]% by weight.

1. Uninvented. ):) When the reactive dye represented by the general formula (I) is used in the reactive dye mixture, the reactive dye represented by the general formula (I) is -CH2CH,Z as 2.
, (Zl has the above meaning.). The use of the reactive dye represented by the general formula (II[) or the combination thereof with the reactive dye represented by the general formula (II) is preferable from the viewpoint of the build-up property of the reactive dye composition. The use of reactive dyes indicated by (■) is particularly preferred from the viewpoint of solubility in aqueous media.

The reactive dye represented by the general formula (I) and the reactive dye mixture may be mixed by simultaneously producing each reactive dye, or may be carried out after producing each reactive dye separately. Furthermore, it may be carried out at the time of dyeing.

The composition of the present invention can be used for dyeing or printing materials containing hydroxy 7 groups or carbonamide groups. Preferably, the material is used in the form of a fibrous material or a blend thereof.

Hydroquine group-containing materials are natural or synthetic hydroquine group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinymalcol. Preferably, the cellulosic fiber material is cotton or other vegetable fibers, such as cotton, hemp, yarn, and ramie fibers. Regenerated cellulose fibers include, for example, viscose stable and filament viscose.

Carbonamide-based materials: also synthetic and natural polymers and flakes, especially in the form of fibers, such as wool and other animal hairs, silk, threads, polyamide-6,5, boria These include 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 the 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 triphosphate, or caustic soda, if necessary, a neutral salt such as mirabilite or common salt is added.
If desired, solubilizers, penetrants or leveling agents are used in combination and the process is carried out at relatively low temperatures. 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 Panong method, it can be banded and dried at room temperature or elevated temperature and then fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, printing is carried out in the -phase with a printing paste containing e.g. Printing is carried out in two phases, for example with a wide base or a weakly acidic printing base, which is then passed through an alkaline group containing an electrolyte, or by herbaging with a panning solution containing an alkaline electrolyte, steaming or It can be carried out by 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 immobilizing the dye compositions of the invention on cellulose fibers include, for example, alkali metals or alkaline earth metals and inorganic or organic acids. It is a basic salt. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak, moderately strong inorganic or organic acids, of which soda and potash salts are particularly preferred. Examples of suitable acid binders include caustic acid (2nod, causticity), baking soda, soda carbonate, sodium formate, carbonicity 1.1. 1st, 2nd, tertiary sodium phosphate, sodium thiate, 777! Examples include oral acetic acid.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion in an acidic dyebath or in a slightly acidic dye bath at a controlled hpH value, and then at a neutral or sometimes alkaline pH value for fixation. This can be done by changing. Dyeing is usually 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 anuric acid chloride and 3 times the mole of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, it is also possible to use an addition product of stearylamine and 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 alkali resistance,
Furthermore, it has good abrasion resistance and ironing resistance.

; It has excellent build-up properties, solubility, level dyeing support and drying properties, and even better exhaustion and fixation properties;
It is characterized by being less susceptible to fluctuations in dyeing temperature and dye bath ratio and producing dyed products of stable quality.

Further, the resulting dyed product is characterized by little discoloration during finlas treatment or resin processing, and 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.

Example 1 100 parts of a reactive dye shown in the following structural formula in the form of a free acid, 5 parts of a reactive dye shown in the following structural formula in the form of a free acid and the following structural formula in the form of a free acid. A dye composition was obtained by blending with 10 parts of the indicated reactive dye. 01.0.3 and 06 parts of this composition were each added to 2 parts of water.
00 parts, add 10 parts of Glauber's salt and 1° part 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 (71), a red dyed product with excellent fastness and good build-up properties was obtained.

The reactive dye represented by the structural formula 2 is prepared by mixing the reactive dye represented by the structural formula $ in an aqueous medium at a pH of 1 to 3.60. TI-To 8
Obtained by f:i core at 0°C.

Further, the reactive dye represented by the structural formula 2 is prepared by adding the reactive dye represented by the structural formula in an aqueous medium at pH 6 to 3.30 to 5.
Obtained by reaction at 0°C.

Example 2 Reactive dye 10 used in Example 1 and represented by the structural formula $
0 parts, 3 parts of the reactive dye represented by the structural formula ■, and the structural formula ■
A dye composition was obtained by blending 0.1, 0.3 and 0.6 with 20 parts of water, respectively.
10 parts of Glauber's salt and 10 parts of cotton were 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, sowing pink, washing with water and drying ('5), red dyeings with excellent fastness properties and good build-up properties were obtained.

Example 3 Example 2 Example 2 (), the reaction dye 1 shown in the structural formula
00 evil and the structural formula in the form of 10 parts of the reactive dye and the free acid shown in the structural formula■:! A dye composition was obtained by blending 4 parts of the reactive dye shown below. 01.032 and 06 parts of this composition were added to 7 to 20 parts, respectively.
Dissolve in 0 parts, add 10B of Glauber's salt and 1 part of cotton to the blade, 60
The temperature was raised to 0.degree. C., 4 parts of carbonate was added, and staining was carried out for 1 hour. Wash with water, 7 no pink, wash with water and dry)
, dyed products with excellent firmness were obtained.

Example 4 Example 1 Reactive dye 1 represented by the structural formula:
00 parts and a reactive dye whose structural formula is shown by! A dye composition was obtained by blending 5 parts of the reactive dye used in Example 3 and represented by the structural formula (2).

0.3 and 0.6 parts of O, L, each were 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, 4 parts of soda carbonate was added, and the mixture was heated for 1 hour. Stained. (Water washing, 7 noping, water washing and drying were not carried out), respectively, and a red dyed product with excellent build map properties was obtained.

Example 5 100 parts of a reactive dye represented by the following structural formula (■) in the form of a free acid, and a reactive dye I shown by the following structural formula (2) (blank space below) in the form of a free acid and Tenki structure in the form of a free acid. A dye composition is obtained by blending with 5 parts of a reactive dye indicated by 1+(n).
2-01.03 and 06 eaves were each dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the temperature was raised to 60°C.
4 parts of soda carbonate was added and dyed for 1 hour. After washing with water, knoping, washing with water and drying, a red dyed product with excellent firmness and good build-up properties was obtained.

Example 6 Reactive dye 1 represented by structural formula 3
00, 15 parts of a reactive dye represented by the structural formula; and a reactive dye 3 represented by the following structural formula (So3'A) in the form of a free acid to obtain a dye composition,
Dissolve 2002, 03 and 0.6 parts each in 201 parts of water, add 10 parts of sodium sulfate ↓i] J: Add 10 parts of cotton, and add 10 parts of cotton.
4 parts of soda carbonate was added and dyed for a while.

After washing with water, washing with soap pink, washing with step 7 and drying, a red dyed product with excellent fastness and good build-up properties was obtained.

Example 7 100 parts of a reactive dye represented by the following structural formula in free acid form; 5 parts of a reactive dye represented by the following structural formula in free acid form; and 10 parts of a reactive dye represented by the following structural formula in free acid form. and 4 parts of a reactive dye represented by the following structural formula in the form of a free acid to obtain a reactive dye composition. Part 0. Lo, 3 and 0.6 parts each in 20 parts of water
0 parts, add 10 parts of Glauber's salt and 10 parts of cotton, and heat at 60°C.
4 parts of soda carbonate were added and dyed for 1 hour.

After washing with water, washing with water, washing with water and drying, a red dyed product with excellent fastness and good build-up properties was obtained.

Example 8 100 parts of a reactive dye represented by the following structural formula in free acid form; 5 parts of a reactive dye represented by the following structural formula in free acid form; and 10 parts of a reactive dye represented by the following structure in free acid form. A dye composition obtained by blending 2 parts of a reactive dye represented by the following structural formula % in the form of a free acid.
．． 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, and the temperature was raised to 60°C.
4 parts of soda carbonate was added and dyed for 1 hour. (without washing with water, soaping, washing with water and drying), a red dyed product with excellent fastness and good build-up properties was obtained.

Example 9 100 parts of a reactive dye represented by the following structural formula in free acid form, 2 parts of a reactive dye represented by the following structural formula in free acid form, and 15 parts of a reactive dye represented by the following structural formula in free acid form. Dye composition 0 obtained by blending and 4 parts of a reactive dye represented by the following structural formula in the form of a free acid.
．． 1. Dissolve 0.3'J6 and 0.6 parts in 200 parts of water each, add 10 parts of Glauber's salt and 10 parts of cotton, heat to 60°C, add 4 parts of soda carbonate, and dye for 1 hour. did. washing with water,
After soaping, washing with water and drying, a red dyed product with excellent fastness and good build-up properties was obtained.

Example 10 Using each of the reactive dye compositions used in Examples 1-9, colored pastes having the following compositions were made.

Reactive dye composition 5 parts urea
5 parts Sodium alginate (5%)
Motonori 50 parts Boiling water 25
2 parts baking soda 2 parts 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 dyed products obtained were all excellent in various fastnesses and had good build-up properties.

(Margin below)

Claims (2)

[Claims] (1) In the form of free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [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. ], and the following general formulas (II), (III) and (IV), respectively, in the form of free acids [wherein X and Y, one represents a sulfonic acid group and the other represents hydrogen] ,Z
' represents -CH=CH_2 or -CH_2CH_2Z_2, and Z_2 represents a group that is eliminated by the action of an alkali. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, Q represents -SO_2CH=CH_2. However, in the above general formula (I), when -SO_2Z is substituted at the o-, m-, or p-position of the imino group, Q shall be substituted at the o-, m-, or p-position, respectively, and the general formula When the reactive dye represented by (III) is selected, Z in the general formula (I) is -CH_2CH_2Z_1. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [In the formula, Z'' is -CH=CH_2 or -CH_2CH_
2Z_3 represents a group that is eliminated by the action of an alkali. ] Contains a reactive dye mixture consisting of at least two types selected from the reactive dye group represented by the following, and the reactive dye mixture is 1 to 60% of the reactive dye represented by the general formula (I).
A reactive dye composition containing % by weight. (2) A method for dyeing or printing textile materials, which comprises using the reactive dye composition according to claim 1.