JPH01170661A - Water-soluble dye mixture - Google Patents

Abstract

PURPOSE:To obtain the titled yellow-based mixture having excellent various kinds of fastness, level dyeing properties, build-up properties and wash off properties, useful for dyeing cellulose fibers or nitrogen-containing fibers, by blending specific two kinds of yellow reactive dyes. CONSTITUTION:The aimed mixture obtained by blending (A) a yellow reactive dye shown by formula I [X is halogen; R<1> is H or lower alkyl; Y is -SO2CH= CH2, -SO2CH2CH2W (W is group eliminable by action of alkali) or lower alkyl] in the form of a free acid with (B) 0.2-2 pts.wt. based on 1 pt.wt. component A of a yellow reactive dye shown by formula II (Z is -CH=CH2 or -C2H4W; R<2> is H, -OCH3 or -CH3; R<3> is -CH3, -CONH2 or -COOH) in the form of a fee acid.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a water-soluble dye mixture, and more specifically, to a water-soluble dye mixture that exhibits excellent color fastness when used for dyeing cellulose fibers or nitrogen-containing fibers. The present invention relates to a yellow reactive dye mixture that is well-balanced and excellent in level dyeing properties, build-up properties, wash-off properties, and dyeing suitability such as salt concentration dependence and temperature dependence.

[Prior art]

Water-soluble reactive dyes are usually used for dyeing cellulose fibers or nitrogen-containing fibers, but dyes that have excellent color fastness and suitability for various dyeings are desired. Dyeing suitability includes - numerically, level dyeing property, build-up property, wash-off property, salt concentration dependence, temperature dependence, etc., but so far, there has been no product that has good properties for all of these properties. . For example, in the range of reactive dyes with excellent chlorine fastness, sweat fastness to sunlight, and light fastness, if you select a reactive dye with excellent salt concentration dependence and temperature dependence, on the one hand, level dyeing It also has the disadvantage of poor wash-off properties.

For example, the reactive dye represented by the structural formula below (see Tokko Shojter No. 2g, No. 22) has excellent chlorine fastness and sweat/sunlight fastness, as well as excellent salt concentration dependence; Poor properties and wash-off properties.

As a way to improve this level dyeing property and wash-off property, we originally used reactive dyes shown by the forefoot structural formula.
It is conceivable to incorporate another reactive dye with excellent level dyeing properties and wash-off properties. However, reactive dyes with excellent level dyeing properties and wash-off properties have poor salt concentration dependence, and not all of them have good fastness properties. Therefore, when such two types of reactive dyes are used in combination, the physical property values of each are averaged. Incur consequences such as becoming a thing. Therefore, it has been desired to develop a reactive dye that has well-balanced and excellent physical properties.

[Problem that the invention seeks to solve]

In view of the above-mentioned circumstances, the inventors of the present invention have proposed that the yellow reactive dye represented by the structural formula (1) and its similar dyes have level dyeing properties and wash-off properties without significantly impairing chlorine fastness and salt concentration dependence. As a result of various studies on ways to improve this, it was discovered that when used in combination with a specific reactive dye of a similar color, each physical property value shows desirable results above the average, and the present invention was completed.

[Means for solving problems]

The gist of the present invention is to provide the following formula (A) in the form of a free acid: [wherein, X represents a halogen atom, R1 represents a hydrogen atom or a lower alkyl group, and Y represents -8o20H:C! A yellow reactive dye represented by H2 group, -8O2CH2CH2W (where W represents a group that is eliminated by the action of an alkali) or a lower alkyl group] and 0.2 to 2 times the weight of the dye. In the form of free acid, the following - formula CB) [wherein 2 is -CH=CH2 group or -C2H4W group (
However, W is the same as defined above), R2 is a hydrogen atom, -00H3 group or -CH3 group, and R3 is -C
Represents H3 group, -CONH2 group or -C0oH group]
The water-soluble dye mixture is characterized by containing a yellow reactive dye represented by:

The present invention will be explained in detail below.

In the forefoot general formulas (A) and CB) in the present invention,
The groups represented by W that are eliminated by the action of alkali are usually -0SO3H group, -8SO3H group, -0PO
Examples include acid ester groups such as 3H group and -ococn3 group, and halogen atoms, with 08o3H group being particularly representative.

The lower alkyl group represented by R1 and Y usually includes O, to 4 alkyl groups such as methyl, ethyl, n-propyl, and n-butyl. Also, X
The halogen atom represented by is usually a chlorine atom or a fluorine atom.

Foreleg - In formula (A), when Y is a vinyl sulfone type reactive group, its position is preferably at the para or meta position with respect to the amino group of the benzene ring.

In the present invention, all water-soluble reactive dyes are present in the form of free acids or their salts, and generally, the salts are:
Preferred are alkali metal salts or alkaline earth metal salts such as lithium salts, sodium salts, potassium salts, calcium salts.

Further, the water-soluble reactive dyes represented by the general formulas (A) and CB) can be produced according to known methods, and the production method is not particularly limited.

The present invention requires that the reactive dye of the forepaw general formula (A) and the reactive dye of the forepaw general formula CB) be blended; )
of reactive dye, 0.2 to 2 times by weight, preferably 0
．． 6~/, which is twice the weight of Hiro. Even if the amount of the reactive dye represented by the formula [B] is too small or too large, it is not possible to obtain a dye with well-balanced and excellent various fastness properties and dyeing properties, which is the goal of the present invention. In the present invention, both reactive dyes may be mixed in advance or may be mixed during dyeing. In addition, in the present invention, for color matching, a dye as a third component may be blended in an amount of, for example, 70% by weight or less within a range that does not impair the effects of the present invention.

Examples of fibers that can be dyed with the dye mixture of the present invention include cellulose fibers such as cotton, viscose rayon, cuproammonium rayon, and hemp, as well as nitrogen-containing fibers such as polyamide, wool, and silk; is particularly desirable. Furthermore, these fibers may be used as mixed fibers of polyester, triacetate, polyacrylonitrile, and the like.

The dye mixture of the present invention can be applied to various known dyeing methods, and although it is usually desirable to apply it to an exhaust dyeing method, it is also effective to apply it to a cold butt batch method or a pad steam method. be.

For exhaust dyeing of cellulose-containing fibers using the water-soluble dye mixtures of the invention, alkalis such as, for example, bicarbonate of soda, soda of carbonate, lithium carbonate, caustic soda, and
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 1 per dye bath.
0-30? It is. In addition, the amount of inorganic salt used is dye bath/1
per liter, for example, from 30 to 609/l. The dyeing temperature is usually 0°C to 0°C, preferably 0-6θ°C.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the description of the examples unless it exceeds the gist thereof.

Example 1 A dye mixture 0 was prepared by blending parts by weight of a reactive dye SO represented by the following structural formula (a) in the form of a free acid with 50 parts by weight of a reactive dye represented by the following structural formula (b) in the form of a free acid. .22 was dissolved in water 200.1, and mirabilite was added thereto and dissolved.
), unmercerized cotton stockinette 10? The temperature was raised to 60°C over 30 minutes, and then 3% of soda was added. was added and exhaust dyeing was carried out at the same temperature for 1 hour. After dyeing,
The dyed fabric is washed with water, soaked, and dried using conventional methods.
A yellow dyed fabric with good level dyeing properties was obtained.

In addition, in order to investigate the dependence of salt concentration during dyeing of the dye mixture used in this example, the concentration of Glauber's salt in the dye bath was adjusted to 10 r/min.
1 was changed and the same staining was performed, and based on this result,
Glauber's salt concentration is based on the dyeing concentration results at SOt/l (
100), the mirabilite concentration for this is 10. ? /l
The same results were obtained using relative values.

Furthermore, the wash-off property, level dyeing property, chlorine fastness and sweat fastness of the dyed fabric obtained in the above dyeing method were measured by the following methods, and the results are summarized in Table 7.

(2) Wash-off property test After the dyed fabric was squeezed to a squeezing rate of 100%, it was treated as described below, and the degree of coloring of the second no-pinda solution was measured according to the following criteria. As the soaping agent, the product name Diamond Server 5CCT≠Q (manufactured by Mitsubishi Chemical Industries, Ltd.) was used.

Wash with water λj'cX/ 0 minute groove sink
jO"cX 1st soaping for 10 minutes 60°C x 10 minutes 2nd soaping 60°C x 10 minutes Bath ratio /:20 Soaping agent 2?/L [Judgment criteria] ◎... Almost no coloring.

○...There is some coloring.

×・・・・・・The coloring is quite dog-like.

X: Significant coloring.

■ Level dyeing test Dissolve 0.21 part of the reactive dye mixture in 200.1 parts of water, and add 10 parts of Glauber's salt to this. Dye bath prepared by adding and dissolving mirabilite concentration ro
t7t), soak 10f of unmercerized cotton knitted cloth,
After exhaustion treatment is carried out at 60° C. for 30 minutes using a shaking dyeing machine, the exhaustion cloth is squeezed to a squeezing rate of 100% and collected. And this exhaust cloth (hereinafter referred to as A cloth)? and the same kind of white cloth (hereinafter referred to as B cloth) 200ml of water and 10ml of mirabilite.
? After soaking in an aqueous solution consisting of soda ash 3? was added and allowed to react and solidify at this temperature for 60 minutes. After that, both A and B fabrics are processed using the usual method.
Wash with water, soap, and dry to obtain a yellow dyed cloth.

The surface reflectance of the fabric A and fabric B obtained here was measured using a color difference meter (manufactured by Nippon Denshoku Kogyo ■) to determine the surface density, and the dyeing density of the canvas was determined according to the following criteria.

〔Judgment criteria〕

◎・・・・・・The density of cloth A and cloth B is almost the same.

○...A cloth is slightly darker than B cloth.

×・・・・・・　　　　　　　　　　　　Pretty dark.

X...... Significantly dark.

(2) Chlorine fastness Measured according to J Engineering 5L-orru (chlorine concentration 20 ppm).

■ Sweat and sunlight fastness Measured according to JIS L-011rl (7 roof 21J).

Example 2 and Comparative Example/-2 In the method of Example/, the blending ratio of the dye mixture is shown below.
A test was carried out in exactly the same manner as in Example 1, with the changes described in .

The results are shown in Table-/.

Example 3 In the method of Example 1, the reactive dye represented by structural formula [a] was changed to the reactive dye represented by the structural formula in Table 2, and a test was conducted in exactly the same manner as in Example 1. However, in both cases, the salt concentration dependence is 60-70%, and the
It was a well-balanced and overall excellent product with an off property rating of "O", a level dyeing rating of "○", a chlorine fastness of class 3, and a sweat and sunlight fastness of class GS.

Example ψ In the method of Example 1, the reactive dye represented by the structural formula [b] was changed to the reactive dye represented by the structural formula in Table 3, and the test was conducted in the same manner as in Example 1 except for the following: However, in both cases, the salt concentration dependence was 60-70%, and the washability rating was "○".
It was overall excellent with a well-balanced level dyeing rating of "○" and sweat and sunlight fastness of ≠ grade.

〔Effect of the invention〕

According to the present invention, by blending two types of specific reactive dyes, one with excellent chlorine fastness and salt concentration dependence, and the other with excellent wash-off properties and level dyeing properties,
This results in an overall well-balanced dye with each physical property value above average.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/Name

Claims (1)

[Claims] (1) In the form of free acid, the following general formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[A] [In the formula, X represents a halogen atom, R^1 represents a hydrogen atom or a lower alkyl group, and Y represents -SO_2CH=
CH_2 groups, -SO_2CH_2CH_2W (however, W
represents a group that is eliminated by the action of an alkali) or a lower alkyl group] and a free acid of the following general formula [ B]▲There are mathematical formulas, chemical formulas, tables, etc.▼...
...... [B] [In the formula, Z is -CH=CH_2 group or -C_2H_4
Represents a W group (where W is the same as defined above), R^2 represents a hydrogen atom, -OCH_3 group or -CH_3 group, R^3 represents -CH_3 group, -CONH_2 group or -C
A water-soluble dye mixture characterized in that it contains a yellow reactive dye represented by the following formula: OOH group.