JPS63112781A - Dyeing of cellulose-containing fibers - Google Patents

Abstract

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

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for dyeing cellulose-containing fibers, and more specifically, the present invention relates to a method for dyeing cellulose-containing fibers, and more specifically, the present invention relates to a method for dyeing cellulose-containing fibers, and more particularly, the present invention relates to a dyeing method for cellulose-containing fibers, and more particularly, the present invention relates to a dyeing method for cellulose-containing fibers, and more particularly, the present invention relates to a method for dyeing cellulose-containing fibers, and more particularly, the present invention relates to a method for dyeing cellulose-containing fibers, and more particularly, the present invention relates to a method for dyeing cellulose-containing fibers, and more particularly, the present invention relates to a method for dyeing cellulose-containing fibers, and more specifically, the present invention relates to a dyeing method for cellulose-containing fibers, and more specifically, the present invention relates to a dyeing method for cellulose-containing fibers, and more specifically, it relates to a dyeing method for cellulose-containing fibers. In the method of dyeing by exhaustion method, each color component is blended with a specific water-soluble reactive dye having a vinyl sulfone type, monochloro or monofluoro-triacyl reactive group, and dyeing is carried out in the dye bath. This invention relates to an industrially extremely advantageous dyeing method in which good exhaust dyeing can be achieved even when the amount of inorganic salt used is reduced to an unprecedented extent.

Water-soluble reactive dyes have a clear color tone and good wet fastness, and can be reactively fixed to cellulose-containing fibers by various dyeing methods, so they are often used for exhaust dyeing and printing of cellulose-containing fibers. has been done.

(Prior art) Conventionally, in the exhaust dyeing method using water-soluble reactive dyes, inorganic salts such as mirabilite and common salt are added to the dye bath 1 during dyeing as a means to improve dyeing properties in order to obtain richly dyed products. ! Our price is 50~
It is necessary to add 100f, and if this amount is large,
Particularly in dyeing factories, this not only increases dyeing costs, but also creates troublesome problems in the treatment of dyeing wastewater.

Therefore, there has been a demand for water-soluble reactive dyes that can perform good exhaust dyeing even in the presence of small amounts of inorganic salts.

(Problems to be Solved by the Invention) However, for example, when the water-soluble reactive dye represented by the general formula [II] as the red component in the present invention is used alone, even a small amount of inorganic salt is sufficient. Although it can be dyed and satisfies the above-mentioned conventional demands without any problems, when it is used in combination with a yellow component and/or blue component reactive dye, the yellow and/or blue components to be mixed are There is also a problem in that the desirable properties of the red component dye cannot be fully exhibited unless each blue component can be satisfactorily exhaust-dyed with a small amount of inorganic salt.

The present invention can be used in the form of a free acid of the general formula CI , X 1d-CH=C
H2i also shows the -C2H40SO3H group. ) Yellow and blue vinyl sulfone type or monochloro or monofluoro-triazine which, when used in combination with a red water-soluble reactive dye represented by the formula, can provide good exhaust dyeing even in the presence of a small amount of inorganic salt. The object of the present invention is to provide an exhaust dyeing method using a novel combination of water-soluble reactive dyes of three primary colors, which makes it possible to solve the above-mentioned conventional problems by obtaining a reactive dye having type reactive groups.

(Means for Solving the Problems) The present inventors conducted various studies to achieve the above object, and as a result, they arrived at the present invention. That is, the present invention provides a free acid having the general formula (1) (wherein R1 and R2 represent a hydrogen atom or a lower alkyl group which may have a substituent, and R3 represents a hydrogen atom or a lower alkyl group). or represents a halogen atom, X is -CH=CH
2 groups or -C2H40S03H group. ) is used as a red component, and a mixed dye containing yellow and/or blue component water-soluble reactive dyes is used to exhaust cellulose-containing fibers in the presence of inorganic salts and alkalis. In the dyeing method, the yellow component is represented by the general formula (II) in the form of a free acid (wherein 2 represents a chlorine atom or a fluorine atom, and X has the same meaning as in the front nail general formula [I]). ), the blue component is represented by the general formula (III) group or -O^ in the form of a free acid, and R4 is -C
It represents an OOH group, a chlorine atom, or a -○H group, and m and n represent the numbers 0 or 1, but m and n are never O at the same time, and z represents the front nail general formula (II). has the same meaning as The gist of this paper is a method for dyeing cellulose-containing fibers, which is characterized by using a water-soluble reactive dye represented by:

The present invention will be explained in detail below.

The dyeing method of the present invention is based on the use of a water-soluble reactive dye represented by the general formula [I] in the form of a free acid as a red component, and in the general formula CI), R
The lower alkyl group or the lower alkyl group which may have a substituent represented by 1, R2 and R3 is usually
A linear or branched unsubstituted alkyl group having 1 to 4 carbon atoms, or 2-hydroxyethyl, 2-cyanoethyl, cyanomethyl, 2-chloroethyl.

Hydroxyl group, cyan group such as 3-ethoxyglobil.

Examples include a halogen atom and an alkyl group substituted with an alkoxy group, and examples of the halogen atom represented by R3 include a bromine atom and a chlorine atom.

In the dyeing method of the present invention, the yellow component reactive dye represented by the front nail general formula (1) to be blended with the red component reactive dye represented by the front nail general formula (1) and/or the yellow component reactive dye represented by the front nail general formula () I
The usage amount of each blue component reactive dye represented by II is 0 to the red component reactive dye represented by the front nail general formula (1).
．． 05 to 50 times by weight, preferably 0.1 to 10 times by weight. According to the present invention, dyes of various desired tones can be prepared based on red component dyes, and in any case, good dyeing can be achieved in the presence of a small amount of inorganic salt.

All of the water-soluble reactive dyes used in the dyeing method of the present invention exist in the form of free acids or their salts, and the salts are usually alkali metals such as lithium salts, sodium salts, potassium salts, and calcium salts. Salts or alkaline earth metal salts are preferred. In addition, the front claw general formula (1) used in the present invention
The water-soluble reactive dyes represented by (II) can be produced according to known methods.

The cellulose-containing fibers to which the dyeing method of the present invention is applied are usually cellulose fibers such as cotton, viscose rayon, cuproammonium rayon, and hemp, or these cellulose fibers and polyesters, triacetate, diacetate, polyacrylonitrile, etc. Examples include fibers mixed with polyamide, wool, silk, etc.

In order to exhaustively dye cellulose-containing fibers by the dyeing method using the water-soluble reactive dyes of the three primary colors of the present invention, for example, an alkali such as bicarbonate, soda, lithium carbonate, caustic soda, triethylamine, etc. For example, dyeing can be carried out in the presence of an inorganic salt such as mirabilite or common salt.

The amount of alkali used in this case is usually per dye bath IE,
10-302. In addition, the amount of inorganic salt used is
Although it is acceptable to use a large amount of 50 f/l or more, in the case of the dyeing method of the present invention, a small amount of 5 to 40 f/l is sufficient.

More specifically, even within the range of the above-mentioned usage amount of inorganic salt in the case of the present invention, it varies depending on the density of the dyed fabric to be obtained; for example, when the dyeing density is light color, it is about 5 to 159/l. , in the case of medium color, it is about 15 to 30 f/l, and in the case of dark color, it is about 30 to 402/j. In addition, the dyeing temperature is 40~
The temperature is 80°C, preferably 50-60°C. After dyeing, the dyed material is subjected to noping and washing, and then dried.

(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples.

Example 1 0.14 of a reactive dye represented by the following structural formula [a] in the form of free acid as a red component, and 0.14 of a reactive dye represented by the following structural formula (b) SO□C2H40SO3H in the form of a free acid as a yellow component. A dye mixture consisting of 1F and 0.12 of a reactive dye represented by the following structural formula [C] in the form of a free acid as a blue component was dissolved in 200 mJ of water, 5 tons of Glauber's salt was added thereto, and then a cotton cloth 102 was added. The temperature was raised from room temperature (25°C) to 60°C over a period of 30 minutes, anhydrous sodium carbonate 47 was added, and dyeing was carried out at 60°C for 1 hour. Thereafter, the dyed product was washed with water, knoped, washed with water, and dried according to a conventional method to obtain a red-brown dyed product.

In this dyeing, the reactive fixation of each color component dye to the fibers was very good. In addition, in the above staining method,
Reduce the amount of Glauber's salt used from 52 (i.e. 25?/l) to 10f.
(50 r/n) and compared the density and hue of the dyed products, and the results were almost the same.

Examples 2 to 4 In Example 1, the blending amounts of reactive dyes [a] to [c] were changed to the proportions shown in Table 1 below, and similar dyeing was performed, resulting in the color tones shown in Table 1 below. A dyed product was obtained, and in all cases, the reaction fixation of each color component dye to the fiber was very good.

Table 1 Comparative Example 1 In Example 3, the blue component, reactive dye [C], is a known blue dye with the following structural formula (represented in free acid form).

): When similar dyeing was carried out by changing the reactive dye represented by 0.2 f, the color tone of the dyed product obtained was not red but yellowish lupine. This was due to the extremely poor dyeability of the blue dye, and in fact, the dye bath residue had a very strong blue tint.

For reference, in Comparative Example 1, the amount of Glauber's salt used was changed from s y (2s y/g,) to 1 (M'(50
When dyeing was carried out by increasing the amount of the dye, the color tone of the dyed product obtained was almost the same as in Example 3, a dark red color.

Example 5 The method of Example 1 was followed, except that the red component, reactive dye [a], was changed to those of each structural formula (represented in free acid form) shown in Table 2 below. When dyeing was carried out according to the method, in all cases, the reaction fixation of each color component dye to the fibers was good, and a dyed product of a deep red-brown color was obtained.

Example 6 The method of Example 1 was repeated, except that the blue component, reactive dye [C], was changed to those of each structural formula (represented in free acid form) shown in Table 3 below. When dyeing was carried out according to the method, in all cases, the reactive fixity of each color component dye to the fibers was good, and a dyed product of a deep red-brown color was obtained.

Example 7 The method of Example 1 was repeated, except that the yellow component, reactive dye (b), was changed to each structural formula (represented in free acid form) shown in Table 4 below. When dyeing was carried out according to the method, in each case, the reaction and fixation of each color component dye to the fibers was good, and a rich red-brown dyed product was obtained.

Table 4 (Effects of the Invention) As is clear from the above results, the dyeing method for cellulose-containing fibers of the present invention is suitable for dyeing cellulose-containing fibers in the three primary colors of red, yellow, and blue. A combination exhaust dyeing method performed by combining specific water-soluble reactive dyes having a triazine type reactive group,
In particular, the amount of inorganic salt used during dyeing has been reduced to 1/3 to 1/3 of the conventional amount.

Since it is possible to dye with good color tone and density even if the dye is reduced to a certain extent, it is very advantageous not only for dyeing work in dyeing factories but also for dyeing wastewater treatment, saving resources, reducing dyeing costs, etc. It has a remarkable effect of industrial value.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Tsunebe Ogawa Procedural amendment (voluntary) November 22, 1986

Claims (5)

[Claims] (1) In the form of a free acid, the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 and R^2 have a hydrogen atom or a substituent. R^3 represents a hydrogen atom, a lower alkyl group, or a halogen atom, and X represents -CH
=CH_2 group or -C_2H_4OSO_3H group. ) is used as a red component, and a mixed dye containing yellow and/or blue component water-soluble reactive dyes is used to exhaust cellulose-containing fibers in the presence of inorganic salts and alkalis. In the dyeing method,
The yellow component is in the form of a free acid and has the general formula [II] ▲Mathematical formula, chemical formula, table, etc.▼...[II] (In the formula, Z represents a chlorine or fluorine atom, and X represents the general formula shown above. It has the same meaning as in [I]), and the blue component has the general formula [III] in the form of a free acid. ▲Mathematical formula, chemical formula, table, etc.▼...[ III] (In the formula, Y^1 and Y^2 are -CH=CH_2 group, -C
_2H_4OSO_3H group or -OH group, R^4
represents -COOH group, chlorine atom or -OH group, and
m and n indicate the number 0 or 1, but m and n are 0 at the same time
Z has the same meaning as in the above general formula [II]. ) A dyeing method for cellulose-containing fibers characterized by using a water-soluble reactive dye represented by: (2) The dyeing method according to claim 1, wherein the inorganic salt is mirabilite. (3) The dyeing method according to claim 1 or 2, characterized in that the amount of inorganic salt used is 5 to 40 g per liter of dye bath. (4) The dyeing method according to claim 1, wherein the dyeing temperature is 40 to 80°C. (5) The amount of the water-soluble reactive dye represented by the general formula [II] or [III] used is 0.05 to 50 times the weight of the water-soluble reactive dye represented by the general formula [I]. The dyeing method according to claim 1, characterized in that: